CN102086401A - Organic aluminum phosphate fire retardant and preparation method and use thereof - Google Patents

Organic aluminum phosphate fire retardant and preparation method and use thereof Download PDF

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CN102086401A
CN102086401A CN2009102204500A CN200910220450A CN102086401A CN 102086401 A CN102086401 A CN 102086401A CN 2009102204500 A CN2009102204500 A CN 2009102204500A CN 200910220450 A CN200910220450 A CN 200910220450A CN 102086401 A CN102086401 A CN 102086401A
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reaction
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mmp
aluminum
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余正坤
刘冰
夏世勇
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a preparation method and use of an organic aluminum phosphate fire retardant. The method comprises: hydrolyzing dimethylmethylphosphonate under the action of sodium hydroxide or potassium hydroxide to form the sodium or potassium salt of dimethylmethylphosphonate, wherein the molar ratio of the dimethylmethylphosphonate to the sodium hydroxide or potassium hydroxide is 1:1; and reacting the aqueous solution of the sodium or potassium salt of dimethylmethylphosphonate with aluminum sulfate under heating and violently stirring CONDITIONS according to a molar ratio of 6:1 to form aluminum methyl methyl phosphonate. The aluminum methyl methyl phosphonate prepared by the invention only is formed by only reactions both of which are performed by using water as reaction medium, the process is simple and the efficiency is high. The thermal decomposition temperature of the aluminum methyl methyl phosphonate prepared by the method is above 325 DEG C, and the aluminum methyl methyl phosphonate can be used as V-0 grade fire retardant for thermoplastic plastics such as poly butylenes terephthalate (PBT) resin, poly(ethylene terephthate) (PET) resin, polyamide PA66 resin and poly(p-phenylene oxide) (PPO) resin.

Description

A kind of organic phospho acid aluminium fire retardant and preparation and application
Technical field
The present invention relates to a kind of organic phospho acid aluminium fire retardant preparation method and application, the sodium salt or the sylvite aqueous solution that promptly prepare methyl methylphosphonic acid (MMP) via dimethyl methyl phosphonate (DMMP) hydrolysis under the effect of equimolar amount alkali perhaps prepare the two-step reaction process that the sodium salt of MMP or the sylvite aqueous solution and this salt brine solution and reacting aluminum sulfate generate organic phospho acid aluminium fire retardant by methyl methylphosphonic acid and equimolar amount alkali reaction.The characteristics of this method are that two-step reaction is reaction medium with water all, avoid using a large amount of organic solvents, and technology are simple, efficient is high.
Technical background
Macromolecular material (plastics, rubber, chemical fibre etc.) is widely used in fields such as building trade, automotive industry, health care, household electrical appliance.Macromolecular material is inflammable or flammable usually, and real world applications is more and more higher to the requirement of its flame retardant properties.The security of using in order to ensure synthetic materials, effective means is to add fire retardant in its course of processing.Fire retardant is of a great variety, according to contained ignition-proof element, is broadly divided into inorganic combustion inhibitor, halogenated flame retardant, phosphorus and Phosphorates phosphorus Halides flame retardant, and phosphorus system also can be referred to as organic fire-retardant with halogenated flame retardant.Halogen containing flame-retardant, flame retarding efficiency height, consumption are few, but tend to discharge poisonous or mordant gas during its burning, and the person and environment are damaged.The great advantage of inorganic combustion inhibitor such as magnesium hydroxide and aluminium hydroxide and antimonous oxide etc. is low toxicity, low cigarette or presses down cigarette, low corrosion, and cheap, but the heat decomposition temperature of inorganic combustion inhibitor is mostly on the low side.
Phosphorus flame retardant is widely used, and Chinese patent (CN1827624) has been reported a kind of two (diphenyl phosphate) piperazines flame retardants and preparation methods.Chinese patent (CN1362413) discloses a kind of melamine polymetaphosphate fire retardant and preparation method thereof.About the aluminum phosphate based flame retardant, also not a large amount of at present relevant patent reports.German Patent in 1998 (DE19708725A1) and its correspondence calendar year 2001 laid-open U.S. Patents (US6303674B1) reported that general structure is [HOCH 2-P (O) (R ')-O] 3The hydroxymethyl phosphonic acid alkyl ester aluminium salt fire retardant of Al (R '=C 1-8Straight-chain alkyl).2007, Italian Italmatch Chemicals S P A disclosed hypo-aluminum orthophosphate Al (H at Chinese patent (CN1926192) with (CN1997698) 2PO 2) 3Do the application of fire retardant.Report about the preparation method of organic phospho acid aluminium fire retardant I is existing: by aluminium hydroxide (Al (OH) 3) react (U.S. Pat 4973727) with dimethyl methyl phosphonate (DMMP), aluminum chloride and DMMP reaction or aluminium carbonate and methyl-phosphorous acid reaction (European patent EP 0245207, U.S. Pat 4972011).
Summary of the invention
The purpose of this invention is to provide the preparation method that a kind of heat decomposition temperature is higher than 325 ℃, can be applied to the fire-retardant organic phospho acid aluminium fire retardant of thermoplastic macromolecule material.
The fire retardant of the present invention's preparation consists of C 6H 18O 9P 3Al, its molecular structure characteristic formula is as follows:
Figure G2009102204500D00021
I (aluminum methyl methylphosphonic acid)
The method of the above-mentioned fire retardant of preparation provided by the invention realizes by two-step reaction, that is: at first dimethyl methyl phosphonate (DMMP) hydrolysis under the effect that waits mol alkali is generated the sodium salt of methyl methylphosphonic acid (MMP) or the aqueous solution (reaction formula 1) of sylvite II, perhaps by with MMP with etc. mol alkali reaction make the aqueous solution (reaction formula 2) of its sodium salt or sylvite II, then the aqueous solution of prepared II and Tai-Ace S 150 are being heated, are making aluminum methyl methylphosphonic acid I (reaction formula 3) by 6: 1 molar ratio reactions under the intense agitation.
Figure G2009102204500D00022
The method that specific descriptions the present invention prepares fire retardant I is:
(a) dimethyl methyl phosphonate (DMMP) is pressed 1: 1 mol ratio room temperature-100 ℃ following reaction 1-10 hour with alkali aqueous solution, obtains the sodium salt of methyl methylphosphonic acid (MMP) or the aqueous solution of sylvite II (reaction formula 1); Perhaps methyl methylphosphonic acid (MMP) and alkali aqueous solution were at room temperature reacted 0.5 hour by 1: 1 mol ratio, obtain the aqueous solution (reaction formula 2) of II.
(b) aqueous solution of the II that will be obtained by step (a) and Tai-Ace S 150 is under vigorous stirring, by 6: 1 mol ratios in 80-140 ℃ of reaction 7-144 hour.Then reaction mixture is cooled to room temperature, filters, washing gets aluminum methyl methylphosphonic acid I after the vacuum-drying.
The used alkali of the present invention is sodium hydroxide or potassium hydroxide.Alkali aqueous solution concentration can be 0.2-8M; The concentration of aluminum sulfate aqueous solution can be 0.2-3M.
The mol ratio of alkali and DMMP or MMP reaction is 1: 1 in the step (a).
Being reflected under the room temperature-100 ℃ of alkali and DMMP carried out in the step (a), preferably from room temperature-60 ℃.Reaction times is 1-10 hour, is preferably 4-8 hour, transforms the back stopped reaction fully until raw material DMMP.
The mol ratio of II and Tai-Ace S 150 is 6: 1 in the step (b).
Stirring velocity in the step (b)＞250 rev/mins.
Being reflected at 80-200 ℃ and carrying out of II and Tai-Ace S 150 in the step (b), preferably temperature is 100-120 ℃, effect is best during 110 ℃ of temperature of reaction.
The reaction times of II and Tai-Ace S 150 is 7-144 hour in the step (b), is preferably 12-24 hour, and the result was best in 24 hours.
The methyl alcohol that generates by reaction formula (1) in the step (a) does not separate and is brought in the step (b), and methyl alcohol can be in step (b) be distilled out in II and the reacting aluminum sulfate, reduces the solubleness of target product I in reaction system thus, reclaims methyl alcohol simultaneously.
Thick product dries in room temperature earlier, promptly obtains target product I at vacuum (15-30mmHg)/160 a ℃ following heat drying to anhydrous state then.
The present invention has the following advantages:
1, the process of preparation target product I has only two-step reaction, is reaction medium with water all, avoids having eco-friendly characteristics because of using a large amount of volatile organic solvents to cause environmental pollution.
2, the first step DMMP hydrolysis reaction mild condition in alkaline aqueous solution is reflected at normal pressure, room temperature is carried out.
3, second step reaction technique is simple, and is easy to operate, only needs after reaction finishes can obtain target product through overcooling, filtration, washing and drying, avoided relating to the operations such as distillation, product extracting and recrystallization in organic solvent process.
4, the yield height of target product I in second step can reach more than 88%.
5, product Heat stability is good, initial heat decomposition temperature are higher than 325 ℃.
6, by mixing the flame retardant effect test shows of carrying out behind the I of 13-20% respectively in thermoplastic materials PBT resin, PET resin, PA66 resin and PPO resin, the flame retardant properties of aluminum methyl methylphosphonic acid I is the V-0 level.
Embodiment
The present invention prepares aluminum methyl methylphosphonic acid and only needs two-step reaction, is reaction medium with water all, and technology is simple, efficient is high.Aluminum methyl methylphosphonic acid prepared by this method can be as the V-0 level fire retardant of THERMOPLASTIC RESINS.
Help further to understand the present invention by following embodiment, but content of the present invention is not limited to this, and wherein each embodiment is made up of two-step reaction: synthetic (reaction formula 3) of the preparation (reaction formula 1 or 2) of methyl methylphosphonic acid (MMP) sodium salt or the sylvite II aqueous solution and aluminum methyl methylphosphonic acid I.
Embodiment 1
The first step: equipped in three mouthfuls of round-bottomed flasks of 3000mL of mechanical stirring, tap water prolong and constant pressure funnel one and to add dimethyl methyl phosphonate (DMMP) (372.3g successively, 3.0mol) and with sodium hydroxide (120.0g, 3.0mol) with the concentration of 1500mL water preparation be the aqueous sodium hydroxide solution of 2mol/L, stirred 6 hours under the room temperature, obtain the aqueous solution of methyl methylphosphonic acid (MMP) sodium salt II.
Second step: one equipped add in the 5000mL four-hole bottle round-bottomed flask of mechanical stirring, tap water prolong, built-in temperature meter and constant pressure funnel Patent alum (333.2g, 0.5mol) and 500mL water, stirring and dissolving.In 3 hours,, in the reinforced process oil bath temperature is risen to 90 ℃ in batches toward the aqueous solution that wherein adds the MMP sodium salt II that obtains by the first step reaction.Oil bath is warming up to 110 ℃ then, continues reaction to 48 hours, the limit coronite will steam from the methyl alcohol that the first step reaction is brought into, reclaims methyl alcohol 60mL, aqueous methanol 70mL (methanol content about 60%).Reaction mixture is chilled to room temperature, filtration, water (5 * 400mL) bubble filter wash cakes, suction filtration, thick product dries in air, (15-30mmHg) drying is removed moisture in the product under 160 ℃ of vacuum then, obtaining the 306g white powder is target product aluminum methyl methylphosphonic acid I, yield 86.4%.Initial heat decomposition temperature (thermogravimetic analysis (TGA) TGA): 325 ℃.Infrared spectra (KBr compressing tablet, cm -1): v 2999.1,2952.9, and 2852.6,1467.7,1307.7,1170.7,1107.1,1045.4,906.5,804.3,756.1,576.7,480.2.Ultimate analysis value: C, 20.25%; H, 5.10%; Al, 7.56%; P, 26.10%.The re-set target product C 6H 18O 9P 3The ultimate analysis theoretical value of Al: C, 20.35%; H, 5.12%; Al, 7.62%; P, 26.24%.
Thermogravimetic analysis (TGA) spectrogram and the infrared spectrogram with embodiment 1 products therefrom is identical respectively with infrared spectrogram for the thermogravimetic analysis (TGA) spectrogram of embodiment 2-11 products therefrom, illustrates that embodiment 1-10 products therefrom is a same substance, i.e. aluminum methyl methylphosphonic acid I.
Embodiment 2
The first step reaction is with embodiment 1, and difference from Example 1 is that the second step reaction 7 hours obtains 299g target product I, and yield is 84.5%.
Embodiment 3
The first step reaction is with embodiment 1, and difference from Example 1 is that the second step reaction 10 hours obtains 300g target product I, and yield is 84.8%.
Embodiment 4
The first step reaction is with embodiment 1, and difference from Example 1 is that the second step reaction 24 hours obtains 307g target product I, and yield is 86.7%.
Embodiment 5
The first step reaction is with embodiment 1, and difference from Example 1 is that the second step reaction 72 hours obtains 308g target product I, and yield is 86.9%.
Embodiment 6
The first step reaction is with embodiment 1, and difference from Example 1 is that the second step reaction 144 hours obtains 313g target product I, and yield is 88.4%.
Embodiment 7
After the first step reaction of embodiment 1 finishes, reaction mixture is removed out most of methyl alcohol that generates under 30-40 ℃ of water-bath/rotary evaporation reduced pressure, carry out second step reaction (operation is with embodiment 1) then, obtain 306g target product I, yield is 86.4%.。
Embodiment 8
The first step reaction is with embodiment 1, and difference from Example 1 is that the aqueous solution of the second step MMP sodium salt II drips the back and continues reaction to 24 hours at 120 ℃, obtains 307g target product I, yield 86.7%.
Embodiment 9
Operation is with embodiment 1, and difference from Example 1 is, the first step DMMP hydrolysis reaction in the second 24 hours reaction times of step, obtains 305g target product I, yield 86.2% at 100 ℃ but not carried out under the room temperature 4 hours.
Embodiment 10
Operation is with embodiment 1, and difference from Example 1 is, the used alkali sodium hydroxide of the first step reaction among the embodiment 1 is substituted with potassium hydroxide, obtains 275g target product I, yield 77.7%.
Embodiment 11
The first step: under agitation, in a 3000mL round-bottomed flask, add methyl methylphosphonic acid (MMP) (330.2g successively, 3.0mol) and use sodium hydroxide (120.0g, 3.0mol) and the concentration that is made into of 1500mL water be the aqueous sodium hydroxide solution of 2mol/L, stirred 30 minutes, and obtained the aqueous solution of MMP sodium salt II.
Second step: one equipped add in the 5000mL four-hole bottle round-bottomed flask of mechanical stirring, tap water prolong, built-in temperature meter and constant pressure funnel Patent alum (333.2g, 0.5mol) and 450mL water, stirring and dissolving.In 2 hours,, in the reinforced process oil bath temperature is risen to about 90 ℃ in batches toward the aqueous solution that wherein adds the MMP sodium salt II that obtains by the first step reaction.Oil bath is warming up to 110 ℃ then, continue reaction to 24 hours, reaction mixture is cooled to room temperature, filtration, water (5 * 200mL) bubble filter wash cakes, thick product dries in air, (15-30mmHg) drying is removed moisture in the product under 160 ℃ of vacuum then, obtains 308g white powder target product aluminum methyl methylphosphonic acid I, yield 87.0%.
Embodiment 12
With THERMOPLASTIC RESINS sample, aluminum methyl methylphosphonic acid fire retardant I, glass fibre and a little processing aid 230 ℃ of hybrid process moulding, carry out the testing vertical flammability of sample then by the flammable bioassay standard method of plastics UL 94, measure the flame retardant properties of aluminum methyl methylphosphonic acid fire retardant I, the results are shown in Table 1 THERMOPLASTIC RESINS polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), PA 66 (PA66 resin) and polyphenylene oxide (PPO resin).Aluminum methyl methylphosphonic acid I is the V-0 level to the flame retardant effect of above-mentioned THERMOPLASTIC RESINS.
Table 1. aluminum methyl methylphosphonic acid I flame retardant effect
Figure G2009102204500D00051

Claims (9)

1. an organic phospho acid aluminium fire retardant consists of C 6H 18O 9P 3Al, molecular structural formula is as follows:
Figure F2009102204500C00011
Its Chinese name is called: aluminum methyl methylphosphonic acid.
2. the preparation method of the described organic phospho acid aluminium of claim 1 fire retardant is characterized in that:
1) A. is with the sodium salt or the sylvite II of dimethyl methyl phosphonate (DMMP) hydrolysis generation methyl methylphosphonic acid (MMP) under alkaline condition, and the aqueous solution that contains II that generates directly uses;
Perhaps B. is with sodium salt or the sylvite II of methyl methylphosphonic acid and alkali effect generation MMP, and the aqueous solution of the II that generates directly uses;
Used alkali is sodium hydroxide or potassium hydroxide;
2) aqueous solution and the Tai-Ace S 150 reaction under heating, intense agitation with II generates aluminum methyl methylphosphonic acid I.
3. according to the described preparation method of claim 2, it is characterized in that:
Concrete steps are:
1) the A. dimethyl methyl phosphonate with etc. the aqueous solution of mol alkali in room temperature-100 ℃ reaction 1-10 hour down, make the sodium salt of methyl methylphosphonic acid or the aqueous solution of sylvite II;
Perhaps B. with MMP with etc. the aqueous solution of mol alkali at room temperature reaction 1-10 hour, make the sodium salt of MMP or the aqueous solution of sylvite II;
Used alkali is sodium hydroxide or potassium hydroxide;
Figure F2009102204500C00012
Dimethyl methyl phosphonate methyl methylphosphonic acid II (methyl methylphosphonic acid sodium or sylvite)
(DMMP) (MMP) (M=Na or K)
2) aqueous solution of the II that will be obtained by step (1) is added drop-wise in the aluminum sulfate aqueous solution, and powerful the stirring was in room temperature-200 ℃ reaction 7-144 hour; Then, reaction mixture is chilled to room temperature, obtains target product aluminum methyl methylphosphonic acid I after filtration, washing, the drying.
4. according to the described preparation method of claim 3, it is characterized in that the mol ratio of DMMP or MMP and alkali sodium hydroxide or potassium hydroxide is 1: 1 in the step (1); The sodium salt of MMP or the mol ratio of sylvite II and Tai-Ace S 150 are 6: 1 in the step (2).
5. according to the described preparation method of claim 3, it is characterized in that: DMMP or MMP and alkali sodium hydroxide or potassium hydroxide reacts on 20-30 ℃ for best among step (1) A.
6. according to the described preparation method of claim 3, it is characterized in that: temperature of reaction is 80-200 ℃ in the step (2).
7. according to the described preparation method of claim 3, it is characterized in that: it is best that the middle temperature of reaction of step (2) is 110 ℃, and the reaction times is 24 hours.
8. according to the described preparation method of claim 3, it is characterized in that: drying temperature is a room temperature-200 ℃ in the step (2), and vacuum tightness 15-30mm Hg is the best with 160 ℃.
9. the described organic phospho acid aluminium of claim 1 fire retardant can be used as the V-O level fire retardant of thermoplastic plastic polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET resin), PA 66 (PA66 resin) or polyphenylene oxide (PPO resin).
CN2009102204500A 2009-12-04 2009-12-04 Organic aluminum phosphate fire retardant and preparation method and use thereof Pending CN102086401A (en)

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CN102146205A (en) * 2011-01-10 2011-08-10 杭州捷尔思阻燃化工有限公司 Halogen-free flame retardant polyether polyurethane thermoplastic elastomer capable of resisting high temperature and high humidity
CN102850392A (en) * 2012-06-07 2013-01-02 叶金标 Organic rare earth metal phosphinate or polymer thereof, and preparation method and application thereof
CN103003289A (en) * 2010-06-24 2013-03-27 Icl-Ip美国公司 Metal Phosphonate Flame Retardant And Method Producing Thereof
CN105199144A (en) * 2015-09-10 2015-12-30 北京理工大学 Submicron organic spiro aluminum phosphate flame retardant and preparation method thereof
WO2023054663A1 (en) * 2021-10-01 2023-04-06 国立大学法人福井大学 Method for producing vinylphosphonic acid monoester

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103003289A (en) * 2010-06-24 2013-03-27 Icl-Ip美国公司 Metal Phosphonate Flame Retardant And Method Producing Thereof
CN103003289B (en) * 2010-06-24 2016-02-10 Icl-Ip美国公司 Metal phosphinate acid esters salt fire retardant and manufacture method thereof
CN102146205A (en) * 2011-01-10 2011-08-10 杭州捷尔思阻燃化工有限公司 Halogen-free flame retardant polyether polyurethane thermoplastic elastomer capable of resisting high temperature and high humidity
CN102146205B (en) * 2011-01-10 2013-02-06 杭州捷尔思阻燃化工有限公司 Halogen-free flame retardant polyether polyurethane thermoplastic elastomer capable of resisting high temperature and high humidity
CN102850392A (en) * 2012-06-07 2013-01-02 叶金标 Organic rare earth metal phosphinate or polymer thereof, and preparation method and application thereof
CN102850392B (en) * 2012-06-07 2015-08-05 叶金标 A kind of organophosphinic acids rare earth metal salt or its polymkeric substance and preparation method thereof and application
CN105199144A (en) * 2015-09-10 2015-12-30 北京理工大学 Submicron organic spiro aluminum phosphate flame retardant and preparation method thereof
CN105199144B (en) * 2015-09-10 2018-03-02 北京理工大学 A kind of organic loop coil aluminum phosphate fire retardant of submicron order and preparation method thereof
WO2023054663A1 (en) * 2021-10-01 2023-04-06 国立大学法人福井大学 Method for producing vinylphosphonic acid monoester

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Application publication date: 20110608