CN102040744B - Mixed salt flame retardant of phosphoric acid, gluconic acid and melamine and preparation method thereof - Google Patents
Mixed salt flame retardant of phosphoric acid, gluconic acid and melamine and preparation method thereof Download PDFInfo
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- CN102040744B CN102040744B CN2010105832190A CN201010583219A CN102040744B CN 102040744 B CN102040744 B CN 102040744B CN 2010105832190 A CN2010105832190 A CN 2010105832190A CN 201010583219 A CN201010583219 A CN 201010583219A CN 102040744 B CN102040744 B CN 102040744B
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- fire retardant
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Abstract
The invention discloses a method for preparing a mixed salt flame retardant of phosphoric acid, gluconic acid and melamine. The method is characterized by comprising the following steps of: adding 0.4 to 0.9 mole of phosphoric acid and 1.8 to 0.3 mole of gluconic acid in a mixed acid mole charging ratio of 0.222 to 3.00 based on calculated amount and deionized water in an amount which is 4 times the weight of mixed acid into a reactor with heating and stirring, slowly adding the melamine equivalent to the total equivalent weight of the mixed acid with stirring at the temperature of between 75 and 95 DEG C, performing heat insulation reaction for 3 to 6 hours, then stopping heating and stirring, putting the reactant system into a standing tank, cooling to room temperature, standing for 24 hours, separating out mixed salt sediment, and filtering and drying the sediment to obtain the mixed salt flame retardant. The average grain diameter of the mixed salt flame retardant is 10 to 20 microns by milling with a ball mill and grading treatment; when 25 to 45 weight percent of mixed salt flame retardant is added into an epoxy resin system using low molecular weight polyamide as a curing agent, the mixed salt flame retardant reaches V-1 to V-0 level by UL-94 measurement; the raw materials have wide source and are cheap; the operation is easy; the mixed salt preparation reaction is performed in an aqueous system; and the wastewater reaches pollution-free discharge after acid and alkali neutralizing treatment, so the method is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of phosphoric acid and glucono-and trimeric cyanamide mixed salt and preparation method thereof, belong to macromolecular material flame-retarded technology field.
Background technology
The epoxy resin macromolecular material has excellent physical and mechanical properties and performances such as heat-resisting, weather-proof, corrosion-resistant and insulation, thereby is widely used in various fields such as mechanical engineering, construction work, electric, shipping vehicles.Yet epoxy resin is again easy incendiary material, in numerous practical applications, mostly relates to the fire-retardant requirement to material.Therefore, when using as engineering plastics, epoxy resin must pass through fire-retardant finish.
Have the fire-retardant and halogen-free flameproof two big classes of halogen fire-retardant roughly being divided into of macromolecular material.Have the time of the fire-retardant development of halogen longer, the application of related prods is ripe, and relevant document is also very many.Its principal character through in macromolecular material, adding the halogen-containing organic cpds of some amount (also adding other synergy materials sometimes simultaneously), is perhaps introduced halogen-containing structure exactly in polymer, make material obtain flame retardant resistance.With regard to epoxy resin, can when resin is synthetic, replace common dihydroxyphenyl propane through the Halogen dihydroxyphenyl propane, perhaps adopt halogen-containing anhydride curing agent to replace measure such as common acid anhydride curing agents to reach fire-retardant purpose.Although halogen-containing fire retardant or the flame-retarded technology technology maturation in the numerous macromolecular materials that comprise epoxy resin are fire-retardant is respond well, be based on following reason, there is the halogen flame-retarded technology to face industry more and more intensive query and blame in recent years.
1) adds halogen-containing flame retardant or macromolecular material in the macromolecular material and comprised organic halogen structure; When fire takes place; Material thermolysis meeting discharges a large amount of smog, wherein comprises poisonous and hazardous hydrogen halide, to the fire-fighting field staff sue and labour and work such as withdraw causes difficulty.
2) no matter the macromolecular material of halogen-containing based flame retardant is in follow-up recycling process or be mixed in the rubbish via burning disposal, all can produce dioxin, and thus environment polluted.Dioxin has been proved to be the intensive carcinogenic substance to Er.
Therefore, making great efforts not halogen-containing fire retardant of development and correlation technique, is people in the industry's responsibility, also is the only way of fire-retardant science.
Halogen-free flameproof is having halogen to grow up gradually after fire-retardant, and this type technology adopts not halogen-containing fire retardant, and addition is general more than halogen fire retardant is arranged.The macromolecular material of halogen-free flameproof just can not cause the problem of the fire-retardant that kind of halogen.Generally speaking, different macromolecular materials, its fire-retardant scheme is different.Specific to the halogen-free flameproof of epoxy resin, mainly be to realize at present through in epoxy-resin systems, introducing the organophosphorus structure.As, (DOPO), its structural formula is in the epoxy resin molecular structure, to introduce " 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound " through chemical reaction:
(structure of DOPO)
Chinese patent CN01802749.0, CN02146356.5, U.S. Pat 2010/0130698A1, documents such as " thermosetting resin, 2008,23 (6) " is reported this type of technology.Phosphorous organic structure such as the DOPO formation compact carbon layer of under combustion conditions, can dewatering rapidly effectively delays and stops the burning of resin.In view of this type of technological safety and validity, in recent years, development contains the epoxy resin or the solidifying agent of DOPO structure, becomes an emphasis direction of epoxy resin Non-halogen Flame Retardant Technology.
Yet it is very easy in the macromolecular chain of epoxy resin, to introduce DOPO organophosphorus structure.At first, DOPO is got through polystep reaction by rare and expensive orthoxenol and phosphorus trichloride, and the technological operation more complicated also relates to the discharging of a large amount of corrodibility hydrogen chloride gas and the problem of processing therebetween; Secondly; DOPO also must combine with suitable conversion linking group; As with additions such as para benzoquinone or unsaturated polyprotonic acid; Acquisition contains the diphenol or the diprotic acid of DOPO structure, and these materials curing reaction synthetic through participation epoxy resin or the participation resin is attached in the middle of the resin system, to reach fire-retardant purpose at last.This shows, be attached to the such organophosphorus structure of DOPO in the epoxy resin Polymer Systems that need to experience a plurality of complicated operations processes through the multistep chemical reaction, the required Financial cost of paying is very high therebetween.
Summary of the invention
The mixed salt that the objective of the invention is to be directed against the deficiency of prior art and one type of phosphoric acid and glucono-and trimeric cyanamide are provided; Be characterized in that the mixed acid and the trimeric cyanamide that form through phosphoric acid and glucono-react, and prepare and contain phosphoric, nitrogen element and polyhydric mixed salt in the molecular structure simultaneously.This compounds added to suitable proportion have good flame-retardant effect in the epoxy resin.The preparation feedback of this type mixed salt carries out in water-based system, and raw material is easy to get, and cost is low, simple to operate, safety, and do not have the discharging of corrodibility hydrogen chloride gas, environmentally friendly.
The object of the invention is realized that by following technical measures wherein said raw material umber is molfraction except that specified otherwise.
The reaction formula of phosphoric acid and glucono-and trimeric cyanamide generation mixed salt fire retardant is following:
xH
3PO
4+yHOCH
2(CHOH)
4COOH+C
3N
6H
6→
〔(H
3PO
4)
x[HOCH
2(CHOH)
4COOH]
y〕.[C
3N
6H
6]
More than in the reaction, the common trimeric cyanamide generation acid-base neutralisation with alkalescence of phosphoric acid and glucono-reacts, and forms mixed salt.In order to obtain neutral mixed salt product, when raw material fed intake, the total yield of nitration mixture (phosphoric acid and glucono-) should equate with the equivalent of trimeric cyanamide.According to the upper mattress formula, if the mole charging capacity of trimeric cyanamide is m, then the mole charging capacity of phosphoric acid is xm, and the mole charging capacity of glucono-is ym (m, x and y are positive number); Therefore; If confirmed trimeric cyanamide mole charging capacity in advance; Then, can calculate the batch charging coefficient x and the y of phosphoric acid and glucono-, thereby confirm that mixed salt prepares needed phosphoric acid and glucono-mole charging capacity according to above reaction formula corresponding to any nitration mixture molar feed ratio x/y.But, although according to nitration mixture arbitrarily than all making corresponding mixed salt, the mixed salt product that only prepares in than scope at suitable nitration mixture just has the desired phosphorus of fire retardant, nitrogen, hydroxy radical content and ratio.The suitable nitration mixture mol ratio x/y of the present invention is 0.222～3.00.
The starting raw material of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant is made up of following, counts by the mole umber:
0.4～0.9 mole of phosphoric acid
1.8～0.3 moles of glucono-s
1 mole of trimeric cyanamide
The preparation method of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant may further comprise the steps:
(1) preparation of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant
By 0.222～3.00 nitration mixture molar feed ratio deionized water with 4 times of 0.4～0.9 mole of the phosphoric acid of calculated amount and 1.80～0.3 moles of glucono-s and nitration mixture weight; Add in the reactor drum that has heating and stir; In 75～95 ℃ of temperature; 1 mole of the trimeric cyanamide that under agitation slow adding equates with the nitration mixture total yield, insulation reaction 3～6h.Stop heating and stirring then, reactant system is put into left standstill groove, be chilled to room temperature, leave standstill 24h, separate out the mixed salt deposition,, obtain the mixed salt fire retardant through filtration, drying.
(2) the mixed salt fire retardant is to the fire-retardant finish of epoxy resin
Make the mixed salt fire retardant more than inciting somebody to action, it is 10～20 μ m that process ball mill grinding and stage treatment make its median size, and adding to the low molecular polyamides with 0～45wt% is in the epoxy-resin systems of solidifying agent again; The weight ratio of epoxy resin and solidifying agent is 100: 50～100; Stir at temperature 40-50 ℃, again the mixture melt is poured in the dull and stereotyped test piece mould, solidify 1h in 100 ℃ of reactions of temperature; Place 48h in room temperature again, obtain dull and stereotyped test piece.
Performance test:
Test piece is cut into the standard batten, press the material vertical combustion method of UL-94 standard code, flame retardant performance of the present invention is tested, see for details shown in table 1～3.The result shows that phosphoric acid that the present invention makes and glucono-and trimeric cyanamide mixed salt fire retardant are used for the fire-retardant of epoxy resin, and addition is in 25～45wt% scope, and the UL-94 test can reach V-1 level even V-0 level.
The present invention has following advantage:
1. the fire retardant raw material is inexpensive, wide material sources;
2. the mixed salt preparation feedback carries out in water-based system, processing ease; The acid-base neutralisation that waste water passes through reaches nuisanceless discharging after handling, and is environmentally friendly.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for further specifying what the present invention carried out; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
The preparation method of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant may further comprise the steps:
(1) preparation of phosphoric acid and glucono-and trimeric cyanamide mixed salt
Press nitration mixture feed ratio 0.222 with phosphatase 24 6.1g (concentration 85%, totally 0.4 mole), glucono-353.1g (1.8 moles); Deionized water 1596g; Adding has in the reactor drum of whisking appliance and TM, to 75 ℃ of temperature, keeps this temperature; Under agitation begin slowly to add trimeric cyanamide 126.2g (1 mole), adition process is 0.5h.Trimeric cyanamide is reinforced to finish, and keeps this temperature 5.5h again.Stop heating and stirring, reaction system is transferred to and leaves standstill groove, is chilled to room temperature, leaves standstill 24h, separates out the product deposition, and through filtering, drying obtains mixed salt fire retardant 445g.
(2) the mixed salt fire retardant is to the fire-retardant finish of epoxy resin
Through ball mill grinding, making its median size is 10 μ m with above-mentioned gained mixed salt solid.E-44 type epoxy resin and low molecular polyamides solidifying agent are mixed by 100: 50 weight ratio; Join above-mentioned obtained flame-retardant agent powder in the mixture of epoxy resin and solidifying agent by 0～45wt% again; Stir rapidly at 40-50 ℃, be poured in the dull and stereotyped test piece mould, solidify 1h in 100 ℃ of reactions of temperature with being about to the mixture melt; Place 48h in room temperature again, obtain dull and stereotyped test piece.Then test piece is cut into the standard batten, and carry out the material vertical combustion by the UL-94 standard and measure.The result sees for details shown in the table 1.
Embodiment 2
The preparation method of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant may further comprise the steps:
(1) preparation of phosphoric acid and glucono-and trimeric cyanamide mixed salt
Press nitration mixture feed ratio 0.777 with phosphoric acid 80.7g (concentration 85%, totally 0.7 mole), glucono-176.5g (0.9 mole); Deionized water 1030g; Adding has in the reactor drum of whisking appliance and TM, to 85 ℃ of temperature, keeps this temperature; Stir the slow down trimeric cyanamide 126.2g (1 mole) of adding, adition process is 0.5h.Trimeric cyanamide is reinforced to finish, and keeps this temperature 3.5h again.At last, stop heating and stirring, reaction system is transferred to and leaves standstill groove, is chilled to room temperature, leaves standstill 24h, separates out the product deposition, and through filtering, drying obtains mixed salt fire retardant 315g.
(2) the mixed salt fire retardant is to the fire-retardant finish of epoxy resin
Through ball mill grinding, making its median size is 15 μ m with above-mentioned gained mixed salt solid.E-44 type epoxy resin and low molecular polyamides solidifying agent are mixed by 100: 75 part by weight; Again above-mentioned obtained flame-retardant agent powder is joined in the mixture of epoxy resin and solidifying agent by 0～45% weight proportion; Stir rapidly at temperature 40-50 ℃, the mixture melt is poured in the dull and stereotyped test piece mould, solidify 1h 100 ℃ of reactions; Place 48h in room temperature again, obtain dull and stereotyped test piece.Then test piece is cut into the standard batten, and carry out the material vertical combustion by the UL-94 standard and measure.The result sees for details shown in the table 2.
Embodiment 3
The preparation method of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant may further comprise the steps:
(1) preparation of phosphoric acid and glucono-and trimeric cyanamide mixed salt
Press nitration mixture feed ratio 3.00 with phosphatase 11 03.8g (concentration 85%, totally 0.9 mole), glucono-58.8g (0.3 mole); Zero(ppm) water 652g; Adding has in the reactor drum of whisking appliance and TM, to 95 ℃ of temperature, keeps this temperature; Under agitation slowly add trimeric cyanamide 126.2g (1 mole), adition process is 0.5h.Trimeric cyanamide is reinforced to finish, and keeps this temperature 2.5h again.At last, stop heating and stirring, reaction system is transferred to and leaves standstill groove, is chilled to room temperature, leaves standstill 24h, separates out product, and through filtering, drying obtains mixed salt fire retardant 234g.
(2) the mixed salt fire retardant is to the fire-retardant finish of epoxy resin
Through ball mill grinding, making its median size is 20 μ m with above-mentioned gained mixed salt solid.E-44 type epoxy resin and the low molecular polyamides solidifying agent part by weight by 100: 100 is mixed; Again above-mentioned obtained flame-retardant agent powder is joined in the mixture of epoxy resin and solidifying agent by 0～35% weight proportion; Stir rapidly at temperature 40-50 ℃, be poured in the dull and stereotyped test piece mould, solidify 1h in 100 ℃ of reactions of temperature with being about to the mixture melt; Place 48h in room temperature again, obtain dull and stereotyped test piece.Then test piece is cut into the standard batten, and carry out the material vertical combustion by the UL-94 standard and measure.The result sees for details shown in the table 3.
The fire-retardant situation of table 1 fire retardant of the present invention in epoxy resin
The fire-retardant situation of table 2 fire retardant of the present invention in epoxy resin
The fire-retardant situation of table 3 fire retardant of the present invention in epoxy resin
Claims (4)
1. phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant is characterized in that the reaction formula of this fire retardant is:
x?H
3PO
4+y?HOCH
2(CHOH)
4COOH+C
3N
6H
6→
〔(H
3PO
4)
X?[HOCH
2(CHOH)
4COOH]
y〕.[C
3N
6H
6]
Wherein, the mol ratio x/y=0.222 of nitration mixture～3.00.
2. phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant according to claim 1 is characterized in that the starting raw material of this fire retardant is composed of the following components, count by the mole umber:
0.4～0.9 mole of phosphoric acid
1.8～0.3 moles of glucono-s
1 mole of trimeric cyanamide.
3. the mixed salt fire retardant preparation method of phosphoric acid and glucono-and trimeric cyanamide according to claim 1 or claim 2 is characterized in that this method may further comprise the steps:
By 0.222～3.00 nitration mixture molar feed ratio deionized water, add in the reactor drum that has heating and stir, in 75～95 ℃ of temperature with 4 times of 0.4～0.9 mole of the phosphoric acid of calculated amount and 1.8～0.3 moles of glucono-s and nitration mixture weight; Under agitation slowly add the trimeric cyanamide that equates with the nitration mixture total yield, insulation reaction 3～6h stops heating and stirring then; Reactant system put into leave standstill groove; Be chilled to room temperature, leave standstill 24h, separate out the mixed salt deposition; Through filtration, drying, obtain the mixed salt fire retardant.
4. the purposes of phosphoric acid and glucono-and trimeric cyanamide mixed salt fire retardant according to claim 1 is characterized in that this mixed salt fire retardant is used for ethoxyline resin antiflaming.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105832190A CN102040744B (en) | 2010-12-10 | 2010-12-10 | Mixed salt flame retardant of phosphoric acid, gluconic acid and melamine and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105832190A CN102040744B (en) | 2010-12-10 | 2010-12-10 | Mixed salt flame retardant of phosphoric acid, gluconic acid and melamine and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102040744A CN102040744A (en) | 2011-05-04 |
| CN102040744B true CN102040744B (en) | 2012-03-21 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3103795B2 (en) * | 1998-10-16 | 2000-10-30 | 株式会社三清 | Flame retardant, refractory material using the same and method for producing flame retardant |
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
| CN2775094Y (en) * | 2004-05-20 | 2006-04-26 | 赵全玺 | Anti-corrosion fire-proof cable |
| CN101792465A (en) * | 2009-12-11 | 2010-08-04 | 四川大学 | Modifier of polyol ester phosphate and polyisocyanate, preparation method and application thereof |
-
2010
- 2010-12-10 CN CN2010105832190A patent/CN102040744B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3103795B2 (en) * | 1998-10-16 | 2000-10-30 | 株式会社三清 | Flame retardant, refractory material using the same and method for producing flame retardant |
| CN2775094Y (en) * | 2004-05-20 | 2006-04-26 | 赵全玺 | Anti-corrosion fire-proof cable |
| CN1757667A (en) * | 2005-11-08 | 2006-04-12 | 四川大学 | Halogen-free expansion type retardant polyethylene contg. organic metal complex |
| CN101792465A (en) * | 2009-12-11 | 2010-08-04 | 四川大学 | Modifier of polyol ester phosphate and polyisocyanate, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵国明等.用于环氧树脂不饱和聚酯的聚合物型磷系阻燃剂.《热固性树脂》.2005,第20卷(第4期),8-10，20. * |
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