CN105646936B - A kind of halogen-free expansion type flame retardant carbon forming agent and preparation method thereof - Google Patents
A kind of halogen-free expansion type flame retardant carbon forming agent and preparation method thereof Download PDFInfo
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- CN105646936B CN105646936B CN201610146593.1A CN201610146593A CN105646936B CN 105646936 B CN105646936 B CN 105646936B CN 201610146593 A CN201610146593 A CN 201610146593A CN 105646936 B CN105646936 B CN 105646936B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
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Abstract
The present invention relates to a kind of halogen-free expansion type flame retardant carbon forming agent ABR-660 and preparation method thereof, with Cyanuric Chloride, piperazine with, ammonium hydroxide and sodium hydroxide are that primary raw material by substitution reaction prepares above compound, it is easy to get with raw material, produce stable feature, carbon source and two component of gas source are integrated in a molecular structure by the carbon forming agent of the resulting piperazine-triazine ring structure of the present invention, it is formed centered on triazine ring, bridged piperazine derivatives are the single molecule structure of end group, current triazine carbon forming agent polymer molecular weight is overcome to be unevenly distributed, the unstable disadvantage of flame retardant property, the carbon forming agent has good acid-resistant property simultaneously, it is insoluble in common organic and inorganic acid, it can be used as the fire retardant of most of high molecular materials, it has a good application prospect.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of halogen expansion type flame retardant.
Background technique
With the rapid development of high molecular material, people have higher requirement to the flame retardant property of such material.In early days
Using it is more be halogenated flame retardant.The based flame retardant has additive amount few, and flame retardant effect is obvious, and wide in variety, applicability is extensive
The advantages that, but toxic and corrosive gas can be released when their burnings, generate biggish smog；Make in daily necessities
Used time, the precipitation of the based flame retardant and catabolite also bring along new harm, are gradually eliminated.In recent years, with Israel
Dead Sea bromine company improves the price of bromine raw material, leads to the rapid rise of price of halogenated flame retardant.Under the pressure of environmental requirement and cost factor,
Each state all is seeking to develop multifunctional and composite type fire retardant and environmental protection fire retarding agent.Wherein expansion type flame retardant is to be widely used at present
One of type.Originally, expansion type flame retardant is used primarily in fireproof coating field, because addition score is high, inorganic component is compatible
Property the reasons such as difference in high polymer using not very extensive.But Intumscent Flame Retardant System is ground recently as people
Study carefully, various countries are proposed the expansion type flame retardant that can be used in the high polymers such as polypropylene, polyethylene, EVA, polycarbonate, quotient
The products of product for example, Clariant Corporation AP-750/760 system, 3167 system of Budit of Budenheim company, Adeka
FP-2100/2200 system of company etc..
Currently, theoretical and experiment shows that expansion type flame retardant is needed by containing carbon source (also known as carbon forming agent or at carbon compound
Object), acid source, gas source component be combined, between each component decomposition temperature, in terms of to play synergistic effect.
The system of a variety of mixture compositions will necessarily have the characteristics that each component is unevenly distributed, then in order to ensure flame retardant property just must
Dosage of the fire retardant in high molecular material must be increased.The increase of dosage, and the machinery of material, mechanical property will necessarily be made bright
Aobvious decline.Meanwhile each component of intumescent system, there is also the easy moisture absorption, it is easy to migrate and be precipitated the problem of.
Under the pressure of the above reason, thinking is turned to the thinking that " two sources " is unified by researcher.Mainly include thinking below:
(1) carbon source-acid source " two sources " is unified, representative products such as 1- oxygroup phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclo [2.2.2]
Octane (abbreviation PEPA, the trade names of Biglake chemical Corp, the U.S. are CN-1197), domestic Ou Yuxiang, Peng Zhihan et al. are released
Trimer etc.；(2) acid source-gas source " two sources " is unified, and representative products product are ammonium polyphosphate (APP), melamine phosphate
(MPP), cyanuric acid pyrophosphate etc.；(3) carbon source-gas source " two sources " is unified, as reported in Scientific Articles and domestic and international patent
With Cyanuric Chloride, diamine (such as ethylenediamine, hexamethylene diamine, piperazine), monoamine (such as diethylamine, methylamine, ammonium hydroxide, morpholine
Deng) and acid binding agent be raw material, manufactured triazine ring macromolecular or aggretion type intumescent carbon forming agent.Due in experimental raw
Limitation on deficient and synthesis technology, carbon source-acid source, two class of acid source-gas source " two sources " unify new product negligible amounts.Therefore,
The research and development that carbon source-gas source " two sources " unifies product just become emphasis of the people in the research and development of expansion type flame retardant component.The U.S. is special
Sharp US8444884B2, US8940818B2, Chinese patent 201410016870.8, CN102161763B, 200710170519.4,
201410417817.9 etc., it was recently reported that the synthesis of the pyrrolotriazine derivatives of a major class carbon source-gas source " two sources " unification and its as at
The application of carbon agent.Wherein, in order to reduce the water solubility and its compatibility in macromolecule of triazines carbon forming agent, in report three
Oxazine derivatives are mostly oligomeric high score subclass.And in actual production, with the increase of molecular weight, pyrrolotriazine derivatives it is resistance to
Aqueous enhancing, but the problem of reaction efficiency declines is brought simultaneously, the extent of polymerization for eventually leading to reaction product is uneven, product
Often occurs the unstable phenomenon of performance in fire retardancy test.Therefore, synthesis unimolecule triazine carbon forming agent still has real meaning
Justice.
Summary of the invention
The present invention provides a kind of halogen-free expansion type flame retardant carbonific (hereinafter referred to as ABR-660) and its systems
Preparation Method.The problems such as present invention is uneven for the dispersion of three components existing for Compositional type expansion type flame retardant, synthesizes a kind of carbon source-gas
Product, theoretical carbon content 43.63% are unified in source " two sources ", and theoretical nitrogen content is 50.88%, and remaining carbon is at 750 DEG C
40.08%, carbon forming rate 91.86%, at carbon efficiencies height.Wherein triazine ring plays the role of reducing foaming, and piperazine ring plays into carbon
Fire retardation, raw material are easy to get, reaction system organic solvent-free, industrialization easy to accomplish.The carbon forming agent that the present invention synthesizes can answer
Fire retardant for synthetic materials such as all kinds of polyolefin, nylon, polyester and all kinds of elastomers.
A kind of halogen-free expansion type flame retardant carbon forming agent of the invention, structural formula are as follows:
Wherein phosphorus content 43.63%, nitrogen content 50.88%.
The carbon forming agent is carried out in aqueous solution by piperazine, ammonium hydroxide, Cyanuric Chloride and sodium hydroxide, as preferred
Technical solution, synthesis step include:
(1) concentrated ammonia liquor of 20-28% concentration is diluted with distilled water, is cooled to 0-5 DEG C, is vigorously stirred down, is added portionwise three
Polychlorostyrene cyanogen solid powder controls charging rate, so that the temperature of reaction system is at 10 DEG C or less；After Cyanuric Chloride adds, continue
After the thermotonus 1-2.5 hours, it is warming up to 45-50 DEG C, after stirring lower reaction 2-4 hours, filters, obtains at 45-50 DEG C
Aqueous filter cake；
(2) Piperazine anhydrous is added in distilled water, is warming up to 90-95 DEG C, be vigorously stirred down that (1) step is added portionwise is anti-
The filter cake that should be obtained after adding material, after continuation is stirred to react 2-3 hours at such a temperature, is added dropwise sodium hydroxide solution, continues
Obtain the solution system comprising intermediate 2 within heating reflux reaction 2 hours；
(3) above-mentioned solution is cooled to 0-5 DEG C, be vigorously stirred down, Cyanuric Chloride solid powder is added portionwise, controlled
Charging rate processed, so that the temperature of reaction system is at 10 DEG C or less；After Cyanuric Chloride adds, continue in thermotonus 1-2.5
After hour, sodium hydroxide solution is added dropwise and is warming up to 45-50 DEG C, after stirring lower reaction 2-4 hours, sodium hydroxide solution heating is added dropwise
To 90-95 DEG C, stirs lower reaction 2-4 hours, obtain white slightly solubility precipitating, filter, wash, it is dry, obtain final product (one
Become ABR-660 down).
Further, ammonium hydroxide and distilled water volume ratio are 2:1-2:5 in step (1)；Amino molecule and Cyanuric Chloride molar ratio
For 4:1-5:1.
Further, Piperazine anhydrous and distilled water mass ratio are 1:5-1:10 in step (2)；Piperazine anhydrous and three polychlorostyrene
Cyanogen molar ratio is 1:1；Sodium hydroxide and Cyanuric Chloride molar ratio are 1:1.
Further, Cyanuric Chloride and Cyanuric Chloride molar ratio in step (3) are 3:1 in step (1).
Further, sodium hydroxide is added dropwise before 45-50 DEG C is warming up in step (3) and Cyanuric Chloride molar ratio is 1:1；
The sodium hydroxide and Cyanuric Chloride molar ratio being added dropwise before being warming up to 90-95 DEG C are 2:1.
Further, concentration of sodium hydroxide solution is 10-25% in step (1) (2) (3).
Carbon left is 40.08% when temperature when obtained carbon forming agent weightlessness 5% is 322.4 DEG C, 750 DEG C.
Following formula is synthesis step signal:
Detailed description of the invention
Fig. 1 is carbon forming agent ABR-660 infrared spectroscopy (FT-IR)；
Fig. 2 is the XRD spectra of carbon forming agent ABR-660；
Fig. 3 is carbon forming agent ABR-660 Thermogravimetric Data.
Specific embodiment:
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright and do not have to limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modification to the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
A kind of halogen-free expansion type flame retardant carbon forming agent of the invention, structural formula are as follows:
Embodiment 1
(1) concentrated ammonia liquor of 25% concentration of 120mL is diluted with 120mL distilled water, is cooled to 0-5 DEG C, is vigorously stirred down, point
It criticizes and 55.5g Cyanuric Chloride solid powder is added, charging rate is controlled, so that the temperature of reaction system is at 10 DEG C or less；Three polychlorostyrene
After cyanogen adds, continue after the thermotonus 1 hour, be warming up to 45 DEG C, after stirring lower reaction 2 hours, filters, contained while hot
The filter cake of water；
(2) 26g Piperazine anhydrous is added in 230mL distilled water, is warming up to 90-95 DEG C, be vigorously stirred down and be added portionwise
After adding material, after continuation is stirred to react 2 hours at such a temperature, it is molten that sodium hydroxide is added dropwise in the filter cake that (1) step is reacted
Liquid (12g sodium hydroxide+60mL water), continues to obtain the solution system comprising intermediate 2 in heating reflux reaction 2 hours；
(3) above-mentioned solution is cooled to 0-5 DEG C, be vigorously stirred down, 18.5g Cyanuric Chloride solid powder is added portionwise
End controls charging rate, so that the temperature of reaction system is at 10 DEG C or less；After Cyanuric Chloride adds, continue in the thermotonus 1
After hour, sodium hydroxide solution (4g sodium hydroxide+20mL water) is added dropwise and is warming up to 45 DEG C, after stirring lower reaction 2 hours, hydrogen is added dropwise
Sodium hydroxide solution (8g sodium hydroxide+40mL water) is warming up to 90-95 DEG C, stirs lower reaction 2 hours, it is heavy to obtain white slightly solubility
It forms sediment, filters, wash, it is dry, obtain final product ABR-660.
Embodiment 2
(1) concentrated ammonia liquor of 28% concentration of 120mL is diluted with 160mL distilled water, is cooled to 0-5 DEG C, is vigorously stirred down, point
It criticizes and 55.5g Cyanuric Chloride solid powder is added, charging rate is controlled, so that the temperature of reaction system is at 10 DEG C or less；Three polychlorostyrene
After cyanogen adds, continue after the thermotonus 2.5 hours, be warming up to 50 DEG C, after stirring lower reaction 4 hours, filters, obtain while hot
Aqueous filter cake；
(2) 26g Piperazine anhydrous is added in 200mL distilled water, is warming up to 90-95 DEG C, be vigorously stirred down and be added portionwise
After adding material, after continuation is stirred to react 3 hours at such a temperature, it is molten that sodium hydroxide is added dropwise in the filter cake that (1) step is reacted
Liquid (12g sodium hydroxide+70mL water), continues to obtain the solution system comprising intermediate 2 in heating reflux reaction 2 hours；
(3) above-mentioned solution is cooled to 0-5 DEG C, be vigorously stirred down, 18.5g Cyanuric Chloride solid powder is added portionwise
End controls charging rate, so that the temperature of reaction system is at 10 DEG C or less；After Cyanuric Chloride adds, continue in the thermotonus
After 1-2.5 hours, sodium hydroxide solution (4g sodium hydroxide+25mL water) is added dropwise and is warming up to 50 DEG C, after stirring lower reaction 4 hours,
Sodium hydroxide solution (8g sodium hydroxide+50mL water) is added dropwise and is warming up to 90-95 DEG C, stirs lower reaction 4 hours, obtains white indissoluble
Property precipitating, filter, wash, it is dry, obtain final product ABR-660.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (6)
1. a kind of halogen-free expansion type flame retardant carbon forming agent preparation method, it is characterized in that the halogen-free expanded flame-retardant agent at
The molecular structure of carbon compound is as shown below:
Wherein phosphorus content 43.63%, nitrogen content 50.88%；
Preparation step are as follows:
(1) concentrated ammonia liquor of 20-28% concentration is diluted with distilled water, is cooled to 0-5 DEG C, is vigorously stirred down, and three polychlorostyrene are added portionwise
Cyanogen solid powder controls charging rate, so that the temperature of reaction system is at 10 DEG C or less；After Cyanuric Chloride adds, continue at this
After thermotonus 1-2.5 hours, it is warming up to 45-50 DEG C, after stirring lower reaction 2-4 hours, filters, obtains aqueous at 45-50 DEG C
Filter cake；
(2) Piperazine anhydrous is added in distilled water, is warming up to 90-95 DEG C, be vigorously stirred down and (1) step is added portionwise reacts
The filter cake arrived after adding material, after continuation is stirred to react 2-3 hours at such a temperature, is added dropwise sodium hydroxide solution, continues to heat
Back flow reaction 2 hours；
(3) above-mentioned solution is cooled to 0-5 DEG C, be vigorously stirred down, Cyanuric Chloride solid powder is added portionwise, control adds
Speed is expected, so that the temperature of reaction system is at 10 DEG C or less；After Cyanuric Chloride adds, continue at the thermotonus 1-2.5 hours
Afterwards, sodium hydroxide solution is added dropwise and is warming up to 45-50 DEG C, after stirring lower reaction 2-4 hours, sodium hydroxide solution is added dropwise and is warming up to
It 90-95 DEG C, stirs lower reaction 2-4 hours, obtains white slightly solubility precipitating, filter, wash, it is dry, obtain final product.
2. a kind of halogen-free expansion type flame retardant carbon forming agent preparation method as described in claim 1, which is characterized in that step
(1) ammonium hydroxide and distilled water volume ratio are 2:1-2:5 in；Amino molecule and Cyanuric Chloride molar ratio are 4:1-5:1.
3. a kind of halogen-free expansion type flame retardant carbon forming agent preparation method as described in claim 1, which is characterized in that step
(2) Piperazine anhydrous and distilled water mass ratio are 1:5-1:10 in；Piperazine anhydrous and Cyanuric Chloride molar ratio are 1:1；Sodium hydroxide
It is 1:1 with Cyanuric Chloride molar ratio.
4. a kind of halogen-free expansion type flame retardant carbon forming agent preparation method as described in claim 1, which is characterized in that step
(1) Cyanuric Chloride and Cyanuric Chloride molar ratio in step (3) are 3:1 in.
5. a kind of halogen-free expansion type flame retardant carbon forming agent preparation method as described in claim 1, which is characterized in that heating
Sodium hydroxide is added dropwise before to 45-50 DEG C and Cyanuric Chloride molar ratio is 1:1；The hydroxide being added dropwise before being warming up to 90-95 DEG C
Sodium and Cyanuric Chloride molar ratio are 2:1.
6. a kind of halogen-free expansion type flame retardant carbon forming agent preparation method as described in claim 1, which is characterized in that hydrogen-oxygen
Change sodium solution concentration is 10-25%.
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| CN106939095A (en) * | 2017-03-31 | 2017-07-11 | 江苏坤宇集团有限公司 | Flame-retardant compounds based on three piperazine triazine carbon forming agents |
| CN108997240A (en) * | 2018-07-24 | 2018-12-14 | 中山苏特宝新材料有限公司 | A kind of production method of high-purity triazines carbon forming agent |
| CN110330643B (en) * | 2019-06-24 | 2021-12-07 | 北京工商大学 | Macromolecular char forming agent CPCA with high thermal stability, preparation method and composition thereof, and application thereof |
| CN113845725B (en) * | 2021-10-19 | 2023-03-21 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
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| IT1240630B (en) * | 1990-04-11 | 1993-12-17 | Ministero Del Uni E Della Rice | SALTS OF TRIAZINIC COMPOUNDS WITH OXYGENATED ACIDS OF PHOSPHORUS |
| IT1259408B (en) * | 1991-12-04 | 1996-03-18 | Roberto Cipolli | SALTS OF TRIAZINIC COMPOUNDS WITH CYANURIC ACID AS ANTI-FLAME ADDITIVES FOR POLYMERS |
| CN103333336B (en) * | 2013-06-04 | 2015-12-02 | 合肥安聚达新材料科技有限公司 | A kind of preparation method of hyperbranched triazine char-forming agent |
| CN103524788A (en) * | 2013-10-18 | 2014-01-22 | 上海美莱珀化工材料科技有限公司 | Carbonizing agent for halogen-free expansion flame-retardant system and preparation method of carbonizing agent |
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Effective date of registration: 20190912 Address after: 511520 Yinying Highway, Shengping Industrial Park, Feilaixia Town, Qingcheng District, Qingyuan City, Guangdong Province Patentee after: QINGYUAN CITY YICHENG FLAME RETARDANT MATERIALS CO., LTD. Address before: 730000 Gansu Province Chengguan District of Lanzhou city of Tianshui Road No. 222 Patentee before: Lanzhou University |
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