CN108440731A - A kind of preparation method of lignin-base expansion type flame retardant - Google Patents
A kind of preparation method of lignin-base expansion type flame retardant Download PDFInfo
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- CN108440731A CN108440731A CN201810200344.5A CN201810200344A CN108440731A CN 108440731 A CN108440731 A CN 108440731A CN 201810200344 A CN201810200344 A CN 201810200344A CN 108440731 A CN108440731 A CN 108440731A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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Abstract
The invention discloses a kind of preparation methods of lignin-base expansion type flame retardant.Alkaline lignin is placed in enough water, melamine is added in heating, stirring heating, formalin reaction is added dropwise, plant acid solution is proportionally added dropwise to addition again, product, which is put into centrifuge, carries out centrifugally operated, and white precipitate is removed, then remaining liq is dry in vacuum drying chamber, until product quality no longer changes.It does not produce thick smoke and poisonous and harmful irritant smell product when fire retardant burning of the present invention, environmental-friendly, simultaneously synthesizing fire retardant material requested is renewable resource, and raw material is easy to get and is easily handled, and does not generate burden to environment.
Description
Technical field
The invention belongs to a kind of fire retardant preparation methods of field of fire-proof technology, and in particular to a kind of lignin-base intumescent
The preparation method of fire retardant.
Background technology
With the development of science and technology, low cost, high-performance and environmental-friendly oil based polyalcohol receive looking steadily for people
Mesh.Since the polymer industry of the nonrenewable resources such as oil consumes excessively in global resources under the background constantly deteriorated with environment
Sight is turned to renewable resource by dim future, people.For example, preparing the modeling of the biology bases such as polylactic acid and poly butylene succinate
The raw material sources of material are in the crops such as corn and beet, it has high intensity, high transparency, easily processed into type and good in addition
The good characteristics such as biodegradation, compatibility, be now widely used in the fields such as food packaging and weaving.But these are given birth to
Object base plastics are extremely inflammable, and limit oxygen index is less than 20%, strongly limits it in fields such as electronic apparatus, automobile and steamers
Application.Therefore, solve that the inflammability of bio-based plastics, to improve its fire safety performance extremely necessary and urgent.
Addition fire retardant is the most easy method for improving bio-based plastics flame retardant property.Currently, the comparative maturity of development
And occupy most of market is halogenated flame retardant, although its flame retarding efficiency is high, can be caused seriously to environment after burning
It destroys, therefore is gradually eliminated.And in all kinds of halogen-free flame retardants, phosphorus flame retardant is because of its low cigarette, minuent, non-corrosive gas
The advantages that generation and be widely used.In contrast, phosphorous simultaneously, nitrogen fire retardant is with lower toxicity and preferably
Thermal stability, and phosphorus, nitrogen have cooperative flame retardant effect.Zhu Xueyuan (CN10172426A) has studied a kind of inorganic fire-retarded
Agent carries out melting using the metal oxide mixture of zinc, potassium, lithium to the flame retardant effect of polylactic acid according to different ratio, by
Glass powder is made in cooling crush, and the flame retardant property of the polylactic acid fire proofing is not less than V-2；(three (the hexichol of fire retardant such as Jiang Ming visits
Base phosphoric acid isocyanide arteries and veins acid) synthesis and its application in polyurethane.Plastics industry .2014,42 (12):103-106) synthesize
Three (diphenyl phosphoester) isocyanuric acid ester (P-THEIC) fire retardants simultaneously apply it in polyurethane, and result of study shows P-
THEIC has higher processing temperature, and when its additive amount is 20wt%, the oxygen index (OI) of resistance combustion polyurethane foam can be improved
26%, and can be tested by UL-94V-0 grades；Wang Huiya (the synthesis chemical research of novel one pack system phosphorus nitrogen expanding fire retardant
.2010,21(1):32-35) using neopentyl glycol, phosphorus oxychloride, benzimidizole derivatives as a kind of novel single group of Material synthesis
Divide phosphorus nitrogen expanding fire retardant that can effectively improve polyolefin the study found that the thermal stability and charring rate of the fire retardant are higher
Molten drop phenomenon is to prevent the sprawling of fire；Wang Xinlong (CN104927061A) devises a kind of high molecular weight flame retardant of the key containing P-N,
It is obtained by the reaction with dichloro-phenyl phosphate by 1,3-PD bis- (4-aminobenzoic acid esters), due to containing in high molecular weight flame retardant
Multiple phenyl ring, therefore flame retardant effect is excellent, and soft segment is contained in main chain, can be used as a kind of nucleating agent, and can effectively improve
The crystallinity of polylactic acid.Although however, fire retardant excellent fireproof performance described above, its synthesis material is based primarily upon can not
There is biodegradable sex chromosome mosaicism in biodegradable and increasingly depleted fossil resources, therefore, the based flame retardant, a large amount of using undoubtedly
Immeasurable negative effect and burden can be generated to environment.
On the other hand, in nature, the reserves of lignin are only second to cellulose, and annual all with 50,000,000,000 tons or so
Speed regeneration, pulp and paper industry also produces 50,000,000 tons every year from plant while 1.4 hundred million tons of celluloses of sub-department
The lignin byproduct of left and right.But so far, rivers are burnt up or are discharged into after the separating lignin concentration more than 95%, this
Sample not only causes the great wasting of resources, but also polluted environment.Therefore, biodegradable lignin-base intumescent resistance is prepared
Firing agent has important social effect and economic value.
Invention content
In order to improve the biological degradability of expansion type flame retardant, reduce its environmental pressure, the present invention provides a kind of lignin
The preparation method of base expansion type flame retardant.
Realize that technical solution of the invention is：
The expansion type flame retardant be by alkali lignin, melamine and formaldehyde reaction then and plant acid solution be mixed into salt
It prepares.
Method preparation process is：
(1) alkaline lignin is placed in enough water, is warming up to 70 DEG C, melamine is added, stir 5-10min, temperature
90 DEG C are risen to, formalin is added dropwise, is reacted 5-7 hours；
(2) plant acid solution is proportionally added dropwise to addition again；
(3) product is put into centrifuge and carries out centrifugally operated, white precipitate is removed, then does remaining liq in vacuum
It is dry in dry case, it is 12-36 hours dry at 80 DEG C, until product quality no longer changes.
Further product is ground, place into ball mill carry out particle it is levigate, finally obtain with excellent flame
Phosphorous, nitrogen the expansion type flame retardant of performance.
Obtained expansion type flame retardant is black powder.
The quality rate of charge of the melamine, alkaline lignin and formaldehyde is 1.6：1：0.6.
The quality rate of charge of the melamine and plant acid solution (Solute mass fraction 50wt%) is 1：1.746~1：
10.476。
Formalin in the step (1) is added dropwise in 1-2h.
Enough water in the step (1) refers to 60% -80% that the content of water is alkaline lignin and water gross mass.
The route that the present invention is synthetically prepared is as follows：
(1) production of melamine modified lignin resin
(2) the cyanurotriamide modified lignin of synthesis and phytic acid are re-dubbed salt
The molecule of fire retardant of the present invention contains the elements such as phosphorus, nitrogen simultaneously, has very strong flame retardant effect, and not halogen
Element, the influence to human body and environment drop to extremely low level.
The present invention by be added alkali lignin, melamine and formaldehyde reaction after again with plant acid solution hybrid shaping at production
Object has fire-retardant, thermal stability, hydrolytic stability, due to during MOLECULE DESIGN, introducing melamine in the synthesis process,
Melamine is six-membered ring structure, which has extremely strong thermal stability；Contain the hexa-atomic of benzene in the molecular structure of lignin
Ring structure, the structure have extremely strong thermal stability as melamine；Phytic acid in molecule contains great amount of hydroxy group group,
In hydrolytic process in molecule nitrogen and oxygen formed hydrogen bond, therefore have good thermal stability.This fire retardant itself provides
Carbon source, air source and acid source, and rich in phosphorus, nitrogen, therefore considerable flame retardant effect can be reached.
Compared with prior art, the present invention having the following advantages that：
(1) expansion type flame retardant disclosed by the invention is halogen-free, and toxicity is low, and no harmful products of combustion generates.
(2) molecular structure contains hexatomic ring in expansion type flame retardant disclosed by the invention, thermal stability and good at charcoal,
TGA test results show that product charring rate is high, possess excellent flame retardant effect.
(3) P element is combined with P-C keys or P=O keys with other groups in molecule, has higher hydrolytic stability, in material
It is not easy to decompose diffusion from material and reduce flame retardant property during use.
(4) raw material object of the present invention is rich inexpensive, and synthesis technology is simple, is well suited for industrialized production.
(5) raw material of the present invention is renewable raw materials, and the fire retardant of synthesis is degradable, therefore the influence caused by environment
It is small.
Description of the drawings
The infrared spectrum of expansion type flame retardant in Fig. 1 present invention.
Thermogravimetric analysis (TGA) spectrogram of expansion type flame retardant in nitrogen in Fig. 2 present invention.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and examples.
The embodiment of the present invention is as follows：
Embodiment 1：
8.07g alkali lignins are put into 500ml there-necked flasks to and are added 80g deionized waters, lead to condensed water, are stirred, are risen
12.906g melamines are added in system by temperature to 70 DEG C, stir 10min；90 DEG C are warming up to, by 13.08g formalins
(37wt%) is slowly dropped in there-necked flask, time for adding 1h, keeps temperature, reacts 6h.After reaction, in there-necked flask
20.88g plant acid solutions (50wt%) are added, filter residue is washed with deionized 3 times, then filter residue is dried, puts by filtering
Under setting in 80 DEG C of vacuum drying chamber for 24 hours.Product is ground, then product is put into ball mill ball milling 24 hours, finally
Obtain phosphorous, nitrogen expansion type flame retardant.
Embodiment 2：
16.14 alkali lignins are put into 500ml there-necked flasks to and are added 160g deionized waters, lead to condensed water, are stirred, are risen
25.818g melamines are added in system by temperature to 70 DEG C, stir 10min；90 DEG C are warming up to, by 26.16g formalins
(37wt%) is slowly dropped in there-necked flask, time for adding 2h, keeps temperature, reacts 7h.After reaction, in there-necked flask
83.52g plant acid solutions (50wt%) are added, filter residue is washed with deionized 3 times, then filter residue is dried, puts by filtering
Under setting in 80 DEG C of vacuum drying chamber for 24 hours.Product is ground, then product is put into ball mill ball milling 36 hours, finally
Obtain phosphorous, nitrogen expansion type flame retardant.
Embodiment 3：
8.07g alkali lignins are put into there-necked flask and be added 80g deionized waters, lead to condensed water, are stirred, are stirred, heating
To 70 DEG C, 12.906g melamines are added in system, stir 10min；90 DEG C are warming up to, by 13.08g formalins
(37wt%) is slowly dropped in there-necked flask, time for adding 1h, keeps temperature, reacts 6h.After reaction, in there-necked flask
41.76g plant acid solutions (50wt%) are added, filter residue is washed with deionized 3 times, then filter residue is dried, puts by filtering
Under setting in 80 DEG C of vacuum drying chamber for 24 hours.Product is ground, then product is put into ball mill ball milling 24 hours, finally
Obtain phosphorous, nitrogen expansion type flame retardant.
Embodiment 4：
16.14 alkali lignins are put into 500ml there-necked flasks to and are added 160g deionized waters, lead to condensed water, are stirred, are risen
25.818g melamines are added in system by temperature to 70 DEG C, stir 10min；90 DEG C are warming up to, by 26.16g formalins
(37wt%) is slowly dropped in there-necked flask, time for adding 3h, keeps temperature, reacts 8h.After reaction, in there-necked flask
83.52g plant acid solutions (50wt%) are added, filter residue is washed with deionized 3 times, then filter residue is dried, puts by filtering
Set the lower 36h in 80 DEG C of vacuum drying chamber.Product is ground, then product is put into ball mill ball milling 36 hours, finally
Obtain phosphorous, nitrogen expansion type flame retardant.
Embodiment 5：
16.14 alkali lignins are put into 500ml there-necked flasks to and are added 160g deionized waters, lead to condensed water, are stirred, are risen
25.818g melamines are added in system by temperature to 70 DEG C, stir 10min；90 DEG C are warming up to, by 26.16g formalins
(37wt%) is slowly dropped in there-necked flask, time for adding 3h, keeps temperature, reacts 6h.After reaction, in there-necked flask
83.52g plant acid solutions (50wt%) are added, filter residue is washed with deionized 3 times, then filter residue is dried, puts by filtering
Set the lower 36h in 80 DEG C of vacuum drying chamber.Product is ground, then product is put into ball mill ball milling 48 hours, finally
Obtain phosphorous, nitrogen expansion type flame retardant.
The flame retardant product of embodiment 1 is tested through thermogravimetic analysis (TGA) (TGA) and obtains initial decomposition temperature in the present invention
(Tonset) and the carbon left under 700 degree, such as the following table 1：
In 1 present invention of table the initial decomposition temperature (Tonset) of 1 neutral and alkali lignin-base expansion type flame retardant of embodiment and
Carbon left under 700 degree
| Decomposition temperature | Carbon left | |
| Expansion type flame retardant | 203℃ | 37.73% |
As it can be seen that initial decomposition temperature (the T of neutral and alkali lignin-base expansion type flame retardant of the present invention in upper tableonset) it is 203
Remaining carbon at DEG C 700 DEG C is 37.73%.
The flame retardant product of each embodiment is as follows through elemental analysis test acquisition element composition result in the present invention：
The elemental analysis test result of expansion type flame retardant in 2 present invention of table
| C | O | H | N | P | |
| Embodiment 1 | 40.00% | 38.11% | 2.43% | 7.57% | 11.89% |
| Embodiment 2 | 39.83% | 38.20% | 3.66% | 6.28% | 12.03% |
| Embodiment 3 | 40.30% | 37.91% | 2.76% | 7.29% | 11.74% |
| Embodiment 4 | 40.01% | 38.34% | 1.92% | 6.84% | 12.89% |
| Embodiment 5 | 39.96% | 38.15% | 2.92% | 7.06% | 12.01% |
As it can be seen that the phosphorus element content of expansion type flame retardant is about 12% in the present invention in upper table, nitrogen element content is about
7%.
Fig. 1 is the infrared spectrum of 1 expansion type flame retardant of embodiment in the present invention, there it can be seen that in 3362cm-1Place has
Apparent absorption peak illustrates to contain secondary amine structure (- NH -), 1629cm in the molecular structure of fire retardant-1、1151cm-1Place
Absorption peak shows to further illustrate actual reaction route containing P=O and O=P-O-C-structure in the flame retardant molecule respectively
With being consistent for design.
Fig. 2 is thermogravimetric analysis (TGA) spectrogram of expansion type flame retardant in nitrogen in the present invention.Show the expansion of the preparation
Carbon left under the initial decomposition temperature (Tonset) of type fire retardant and 700 degree.
Claims (7)
1. a kind of preparation method of lignin-base expansion type flame retardant, it is characterised in that include the following steps：
(1) alkaline lignin is placed in enough water, is warming up to 70 DEG C, melamine is added, stir 5-10min, temperature rises to
90 DEG C, formalin is added dropwise, reacts 5-7 hours；
(2) plant acid solution is proportionally added dropwise to addition again；
(3) product is put into centrifuge and carries out centrifugally operated, white precipitate removed, then by remaining liq in vacuum drying chamber
Middle drying, it is 12-36 hours dry at 80 DEG C, until product quality no longer changes.
2. a kind of preparation method of lignin-base expansion type flame retardant according to claim 1, it is characterised in that：Further
Ground grinds product, places into ball mill and carries out that particle is levigate, it is first to finally obtain the phosphorous, nitrogen with excellent fire-retardancy
The expansion type flame retardant of element.
3. a kind of preparation method of lignin-base expansion type flame retardant according to claim 2, it is characterised in that：It is acquired
Expansion type flame retardant be black powder.
4. a kind of preparation method of lignin-base expansion type flame retardant according to claim 1, it is characterised in that：Described three
The quality rate of charge of poly cyanamid, alkaline lignin and formaldehyde is 1.6：1：0.6.
5. a kind of preparation method of lignin-base expansion type flame retardant according to claim 1, it is characterised in that：Described three
The quality rate of charge of poly cyanamid and plant acid solution is 1：1.746~1：10.476.
6. a kind of preparation method of lignin-base expansion type flame retardant according to claim 1, it is characterised in that：The step
Suddenly the formalin in (1) is added dropwise in 1-2h.
7. a kind of preparation method of lignin-base expansion type flame retardant according to claim 1, it is characterised in that：The step
Suddenly it is 60%-the 80% of alkalinity lignin and water gross mass that the enough water in (1), which refers to the content of water,.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105626A (en) * | 2019-05-04 | 2019-08-09 | 武汉理工大学 | Supramolecular Assembling ammonium polyphosphate modifying and preparation method thereof |
| CN111848977A (en) * | 2020-08-06 | 2020-10-30 | 江南大学 | Modified lignin, preparation method and application thereof in toughening flame-retardant composite material |
| CN112143215A (en) * | 2020-10-16 | 2020-12-29 | 界首市宏达塑业有限公司 | High-flame-retardant polyurethane plastic particle and preparation method thereof |
| CN114874357A (en) * | 2022-06-28 | 2022-08-09 | 河北科技大学 | Hemicellulose-based intumescent flame retardant and preparation method thereof |
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| CN101735278A (en) * | 2009-12-09 | 2010-06-16 | 湖北兴发化工集团股份有限公司 | Method for synthesizing P-N-containing intumescent flame retardant |
| US20130292615A1 (en) * | 2012-05-03 | 2013-11-07 | Empire Technology Development Llc | Phosphonate-substituted lignin as a flame retardant |
| CN105504309A (en) * | 2015-12-31 | 2016-04-20 | 浙江农林大学 | Halogen-free flame retardant modified industrial lignin of wood-plastic section as well as preparation method and application |
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2018
- 2018-03-12 CN CN201810200344.5A patent/CN108440731B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735278A (en) * | 2009-12-09 | 2010-06-16 | 湖北兴发化工集团股份有限公司 | Method for synthesizing P-N-containing intumescent flame retardant |
| US20130292615A1 (en) * | 2012-05-03 | 2013-11-07 | Empire Technology Development Llc | Phosphonate-substituted lignin as a flame retardant |
| CN105504309A (en) * | 2015-12-31 | 2016-04-20 | 浙江农林大学 | Halogen-free flame retardant modified industrial lignin of wood-plastic section as well as preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105626A (en) * | 2019-05-04 | 2019-08-09 | 武汉理工大学 | Supramolecular Assembling ammonium polyphosphate modifying and preparation method thereof |
| CN110105626B (en) * | 2019-05-04 | 2021-02-26 | 武汉理工大学 | Supermolecular assembly modified ammonium polyphosphate and preparation method thereof |
| CN111848977A (en) * | 2020-08-06 | 2020-10-30 | 江南大学 | Modified lignin, preparation method and application thereof in toughening flame-retardant composite material |
| CN112143215A (en) * | 2020-10-16 | 2020-12-29 | 界首市宏达塑业有限公司 | High-flame-retardant polyurethane plastic particle and preparation method thereof |
| CN114874357A (en) * | 2022-06-28 | 2022-08-09 | 河北科技大学 | Hemicellulose-based intumescent flame retardant and preparation method thereof |
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