CN103992293A - Preparation method for halogen-free flame retardant and flame retardant polyolefin composition thereof - Google Patents
Preparation method for halogen-free flame retardant and flame retardant polyolefin composition thereof Download PDFInfo
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- CN103992293A CN103992293A CN201410190249.3A CN201410190249A CN103992293A CN 103992293 A CN103992293 A CN 103992293A CN 201410190249 A CN201410190249 A CN 201410190249A CN 103992293 A CN103992293 A CN 103992293A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
Belonging to the field of flame retardant preparation, the invention discloses a preparation method for a halogen-free flame retardant and a flame retardant polyolefin composition thereof. Specifically, piperazine diphosphate is prepared by reacting phosphoric acid with piperazine in proportion, and then performing spray drying treatment; and piperazine pyrophosphate is prepared by combining the preparation method of the piperazine diphosphate, and subjecting the obtained piperazine diphosphate to dehydration condensation reaction under an inert atmosphere or vacuum condition. The invention also provides the flame-retardant polyolefin composition, which comprises 100 parts by mass of polyolefin resin, 10-100 parts by mass of the piperazine pyrophosphate prepared by the method and the like. The yield of the piperazine diphosphate prepared by the method is over 95%, and the piperazine pyrophosphate has a W value represented whiteness of over 90. The flame retardant polyolefin composition has the advantages of excellent flame retardant properties, small adding amount of piperazine pyrophosphate, and excellent coloring properties, thus having terrific industrial application prospects.
Description
Technical field
The invention belongs to fire retardant preparation field, more specifically, relate to a kind of preparation method and flame retardant polyolefin compound thereof of halogen-free flame retardants.
Background technology
The halogen-free flameproof character of fluoropolymer resin is the problem that paid close attention to by flame retardant industry.In existing flame-retardant modified polyolefine, in order to meet non-halogen requirement, need to select to add the fire retardant of phosphorous, nitrogen or its compound system.Use now the most general phosphonium flame retardant and composition thereof to mainly contain micro encapsulation red phosphorus, phosphoric acid ester, Intumscent Flame Retardant System taking ammonium polyphosphate as main body etc.But, there is the shortcomings such as addition is large, flame retarding efficiency is low in these flame-retardant systems and the comparison of traditional bromine ~ antimony compositional flame-retardant system.
Piperazine pyrophosphate (Piperazine Pyrophosphate), as phosphorus-nitrogen-containing halogen-free flame retardant, has extremely excellent flame retardant properties, is the novel halogen-free flame-retardant agent that has market potential.For many years, also there is more report about its preparation method, US Patent No. 3810850 and US4599375 as far back as 70 ~ eighties of last century just disclose respectively, under acidic conditions, utilize sodium pyrophosphate decahydrate and Piperazine anhydrous reaction to generate the sedimentary method of water-fast piperazine pyrophosphate, but the method has been used salt acid sodium-salt, cause containing in product a large amount of chlorions and sodium ion, and be difficult to remove completely, the purity of the piperazine pyrophosphate of preparation cannot be ensured, and affect its flame retarding efficiency, limit the industrial applications of the method.
Chinese patent 200480025664.8 and 201080035352.0 discloses respectively the method that uses bisphosphate piperazine dehydrating condensation to prepare piperazine pyrophosphate.The method can effectively be controlled the content of chlorine, sodium element, improves the purity of piperazine pyrophosphate.The method needs first in aqueous solvent, to prepare bisphosphate piperazine, but because bisphosphate piperazine has larger solubleness in the aqueous solution, thereby make its yield lower.In addition, bisphosphate piperazine is prepared easily variable color in the process of piperazine pyrophosphate at dehydrating condensation, makes its painted generation detrimentally affect to the finished product, these drawbacks limit the purposes of piperazine pyrophosphate as fire retardant.
Summary of the invention
Goal of the invention of the present invention is to overcome the low problem of yield in existing bisphosphate piperazine preparation, and a kind of preparation method of bisphosphate piperazine is provided.The method can effectively improve the yield of bisphosphate piperazine.
Another goal of the invention of the present invention is that to overcome in existing piperazine pyrophosphate preparation method productive rate low, holds allochroic problem, and a kind of preparation method of piperazine pyrophosphate is provided.The method can effectively improve the yield of intermediate product bisphosphate piperazine and the whiteness of piperazine pyrophosphate.
Another object of the present invention is to provide a kind of flame retardant polyolefin compound that contains piperazine pyrophosphate prepared by present method.
Above-mentioned purpose of the present invention solves by following technological method:
The preparation method of bisphosphate piperazine is taking water as a solvent, and phosphoric acid and piperazine, according to 2 ~ 2.2:1 mixed in molar ratio, after stirring reaction 1 ~ 12h, are heated to 50 ~ 80 DEG C, more spray-dried, obtains bisphosphate piperazine.
The stoichiometric ratio that generates the 1 required phosphoric acid of stoichiometric bisphosphate piperazine and piperazine is 2:1.React completely in order to ensure piperazine, accelerate speed of reaction simultaneously, therefore the consumption of phosphoric acid can be slightly more than required by the consumption of stoichiometric ratio.
It is transformation efficiency and the crystallization rate in order to control reaction that the time of stirring reaction is controlled.
Phosphoric acid carries out with reacting at normal temperatures of piperazine, and it is to be the dry preheating preparation of doing of spraying that reacted system is heated to 50 ~ 80 DEG C.
Preferably, the mol ratio of described phosphoric acid and piperazine is 2 ~ 2.1:1.
Preferably, the described stirring reaction time is 2 ~ 6h, and after heating, reacting liquid temperature is preferably 60 ~ 70 DEG C.
Because bisphosphate piperazine has larger solubleness in the aqueous solution, make its yield lower.Prior art in the time preparing bisphosphate piperazine, only from reaction system by bisphosphate piperazine crystal separation out, drier with common drying means, cause like this yield lower.And in the application, adopt spray-drying process, by reaction solution, in kiln after atomization, with the contacting of warm air, moisture is vaporized rapidly, obtains dry bisphosphate piperazine.This drying means is easy to control surface property and the size of product, has overcome common process and has prepared the low shortcoming of bisphosphate piperazine yield, and do not affected the character of bisphosphate piperazine.
Described spray-drying process is the conventional spray-drying processes such as pressure spray dryer method, centrifugal spray drying method or pneumatic spray drying method.
Preferably, described spray-drying process is preferably centrifugal spray drying method.
Preferably, the technique of described spray-drying process is: phosphoric acid and piperazine reaction solution, after thermal pretreatment, enter the high speed rotating centrifugal energy nozzle at spray-dryer top by pump, be dispersed into little droplet under centrifugal action; On the other hand, dry air heater via is heated to 130-170 DEG C, enters spray-dryer top subsequently by hot-air distributor; Droplet fully contacts in moisture eliminator with hot blast, carries out being dried to as product after heat exchange, then realizes separation by cyclonic separator, and solid materials is collected, and gaseous media is discharged from after filtering again.
Preferably, the rotating speed of the centrifugal energy nozzle of described centrifugal spraying is 8000～18000r/min.
A preparation method for piperazine pyrophosphate, comprises following reactions steps:
S1. by phosphoric acid and piperazine according to 2 ~ 2.2:1 mixed in molar ratio, after stirring reaction 1 ~ 12h, be heated to 50 ~ 80 DEG C, more spray-dried, obtain bisphosphate piperazine;
S2. described bisphosphate piperazine is carried out to dehydration condensation and prepare piperazine pyrophosphate, the processing condition of described dehydration condensation are under inert atmosphere or vacuum condition, at the dehydrating condensation temperature heating 1 ~ 12h of 200 ~ 280 DEG C.
Described inert atmosphere is not particularly limited, and can be nitrogen, argon, helium, carbonic acid gas etc.Consider from the viewpoint of product whiteness, be preferably argon gas, more preferably pure more than 99.999% high-purity argon gas.
Described vacuum condition, more excellent is 0.02 ~ 0.03MPa, more preferably 0.02 ~ 0.025MPa.
Described dehydrating condensation temperature, more excellent is 200 ~ 260 DEG C, further more excellent is 220 ~ 250 DEG C.
Described heat-up time, more excellent is 2 ~ 10h, and further more excellent is 4 ~ 8h.
For the equipment of dehydrating condensation that carries out above-mentioned bisphosphate piperazine, as long as heating and dewater, and can under inert atmosphere or vacuum condition, carry out conversion unit.Can complete dehydrating condensation operation with equipment such as heating mixing facilities, warm air drying equipment.
Particularly, use the method for above-mentioned heating mixing facilities preferably to use vacuum condition, specifically by the following method: with 200～280 DEG C of Heating temperatures, rate of feeding 20 ~ 200kg/h, revolution 20～1000rpm, bisphosphate piperazine is carried out to dehydrating condensation.Be not particularly limited as above-mentioned heating mixing facilities, can use common mixing facilities, such as twin screw, single screw extrusion machine, Henschel mixing tank, Banbury mixing tank, vacuum kneader etc.In these equipment, Banbury mixing tank and vacuum kneader can make reaction effectively carry out, and drop temperature is effectively controlled, is therefore preferred.
Particularly, using the method for above-mentioned warm air drying equipment preferably to use inert atmosphere protection, is the method for with 200～280 DEG C of hot blast temperatures, bisphosphate piperazine being carried out dehydrating condensation.As above-mentioned warm braw drying plant, as long as volume production piperazine pyrophosphate is just not particularly limited economically, can be pneumatic drier, throughcirculation dryer, shelf dryer, atmosphere rotary kiln, atmosphere pusher furnace, moving-bed dryer, atmosphere tube furnace etc.In these equipment, consider from quantity-produced feasibility and product property controllability, preferably use atmosphere rotary kiln and atmosphere pusher furnace.
The material that a kind of flame retardant polyolefin compound provided by the invention contains following mass fraction:
The polyolefin resin of 100 mass parts;
Piperazine pyrophosphate prepared by 10 ~ 100 mass parts the inventive method;
The melamine compound of 10 ~ 100 mass parts;
1 ~ 10 mass parts nano-oxide fire retarding synergist;
0.1 ~ 1 mass parts anti-dripping agent;
0.1 ~ 1 mass parts processing aid.
Described polyolefin resin is optional conventional polyolefine, from range of application and use properties angle, is preferably polypropylene and polyethylene, further preferably uses acrylic resin, is further preferably homopolymer polypropylene.
The consumption of piperazine pyrophosphate prepared by described the inventive method, rationalizes angle from cost and performance, is preferably 10 ~ 50 mass parts, more preferably 15 ~ 40 mass parts.
Described melamine compound is trimeric cyanamide phosphoric acid, melamine pyrophosphate or melamine polyphosphate.Consider from thermal characteristics angle, be preferably melamine pyrophosphate.For its consumption, be preferably 10 ~ 50 mass parts, more a step is preferably 10 ~ 30 mass parts.
Preferably, the mass ratio of piperazine pyrophosphate and melamine compound is 3 ~ 1:1.
Described nano-oxide is one or more mixture of zinc oxide, magnesium oxide, titanium oxide, silicon-dioxide etc.More excellent is zinc oxide and silicon-dioxide, more preferably silicon-dioxide.For its consumption, be more preferably 1 ~ 6 mass parts, more preferably 2 ~ 5 mass parts.
Described anti-dripping agent is teflon resin, is preferably powdered samples, and consumption is preferably 0.1 ~ 0.5 mass parts.
Described processing aid comprises oxidation inhibitor, lubricant etc.Described oxidation inhibitor is selected from one or more mixture of phenols, amine, phosphorous acid esters, half Hinered phenols, calixarene kind and Tyox B etc.Described processing and lubrication auxiliary agent is selected from one or more mixture of glyceryl stearate point, metal soap, stearic acid complex ester class, amides etc.
Compared with prior art, the present invention has following beneficial effect:
1. the preparation method of bisphosphate piperazine of the present invention, its product yield reaches more than 95%, has overcome common process and has prepared the low shortcoming of bisphosphate piperazine yield, and do not affected the character of bisphosphate piperazine, has obtained significant technique effect.
2. the preparation method of piperazine pyrophosphate of the present invention, the yield (calculating according to the consumption of the phosphoric acid using and piperazine) of its product reaches more than 95%, and purity is high, the not impurity such as sodium chloride-containing and piperazine pyrophosphate sodium salt, the physical properties excellent such as thermotolerance, water tolerance.
3. the preparation method of piperazine pyrophosphate of the present invention, the piperazine pyrophosphate of its production has the whiteness with W value representation of >90, and use procedure does not affect the tinctorial property of product, is very suitable for the fire-retardant purposes of resin.
4. flame retardant polyolefin compound provided by the invention has high water-fast resistance toheat and flame retardant properties, and has excellent tinctorial property, can be according to without purposes component design, and make various moulding products, there is splendid prospects for commercial application.
5. flame retardant polyolefin compound provided by the invention, adds a small amount of piperazine pyrophosphate and just can obtain good flame retardant effect.
Embodiment
Below in conjunction with some embodiments to the bisphosphate piperazine the present invention relates to, piperazine pyrophosphate preparation method and the flame retardant polyolefin compound that contains piperazine pyrophosphate prepared by the method be described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.Unless stated otherwise, the method that the embodiment of the present invention adopts is this area ordinary method.
In specification sheets of the present invention, W value refers to the value of whiteness index.Whiteness index (W value) is to be to red sensing value based on three primary colors (red, green, blue) values X, Y, Z(X, and Y is to green sensing value, and Z is to blue sensing value), calculated by following formula.This whiteness index can use colour-difference meter automatically to measure.The numerical value of whiteness index is higher, represents that whiteness is higher.
Whiteness index (W value)=Y+800 (x
n-x)+1700 (y
n-y)
In above formula, the tristimulus coordinates in the XYZ colorimetric system that x, y are sample, x
n, y
nfor the value (with reference to CIE1983) of the tristimulus coordinates in the XYZ colorimetric system of persect reflecting diffuser.
embodiment
By the following examples the present invention is described in detail.But the present invention is not subject to any restriction of following examples.
the preparation method of bisphosphate piperazine
The spray-dryer using in following examples is centrifugal spray-dryer, and model is LPG-50, and manufacturer is Changzhou power horse.
In embodiment, phosphoric acid solution used is the phosphoric acid solution that commercially available phosphoric acid quality concentration is 85%.
Embodiment 1
Take 23kg phosphoric acid solution and join in 20L water, join in phosphoric acid solution by feeding tube after 8.6kg piperazine is dissolved in 30L water, stirring at normal temperature reaction 4h.Then be warming up to 60 DEG C, reaction solution materials pipe be communicated to the feeding pump of spray-dryer, enter subsequently in spray-dryer, centrifugal spray drying under the rotating speed of 18000r/min, heated drying air temperature is 150 DEG C, obtains 28.0kg bisphosphate piperazine.
Embodiment 2
Take 25.4kg phosphoric acid solution and join in 20L water, join in phosphoric acid solution by feeding tube after 8.6kg piperazine is dissolved in 30L water, stirring at normal temperature reaction 4h.Then be warming up to 60 DEG C, reaction solution materials pipe be communicated to the feeding pump of spray-dryer, enter subsequently in spray-dryer, centrifugal spray drying under the rotating speed of 8000r/min, heated drying air temperature is 160 DEG C, obtains 27.8kg bisphosphate piperazine.
Embodiment 3
Take 23kg phosphoric acid solution and join in 20L water, join in phosphoric acid solution by feeding tube after 8.6kg piperazine is dissolved in 30L water, stirring at normal temperature reaction 2h.Then be warming up to 70 DEG C, reaction solution materials pipe be communicated to the feeding pump of spray-dryer, enter subsequently in spray-dryer, centrifugal spray drying under the rotating speed of 10000r/min, heated drying air temperature is 140 DEG C, obtains 27.5kg bisphosphate piperazine.
Embodiment 4
Take 25.4kg phosphoric acid solution and join in 20L water, join in phosphoric acid solution by feeding tube after 8.6kg piperazine is dissolved in 30L water, stirring at normal temperature reaction 6h.Then be warming up to 65 DEG C, reaction solution materials pipe be communicated to the feeding pump of spray-dryer, enter subsequently in spray-dryer, centrifugal spray drying under the rotating speed of 15000r/min, heated drying air temperature is 165 DEG C, obtains 28.3kg bisphosphate piperazine.
Comparative example 1
Take 23kg phosphoric acid solution and join in 20L water, join in phosphoric acid solution by feeding tube after 8.6kg piperazine is dissolved in 30L water, stirring at normal temperature reaction 4h.Then be cooled to 4 DEG C, by reacting liquid filtering, product after dry 6h, obtained to 20.5kg bisphosphate piperazine at 80 DEG C.
Yield and the phosphorus content thereof of the bisphosphate piperazine to above-described embodiment and comparative example are added up, and the results are shown in Table 1.
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Yield | 99% | 98% | 97% | 99% | 73% |
| Phosphorus content | 21.8% | 22.1% | 21.7% | 21.9% | 21.7% |
As shown in Table 1, the yield of preparing bisphosphate piperazine of embodiments of the invention 1 to 4 all reaches more than 95%, exceeds comparative example 1 and reaches 26% left and right, has obtained significance effect.
the preparation method of piperazine pyrophosphate
Embodiment 5
Use Banbury mixer, Heating temperature is 250 DEG C, and vacuum degree control is at 0.025MPa, and rotating speed is 20rpm, and bisphosphate piperazine reacting by heating 4h prepared by 2kg embodiment 1, obtains 1.84kg white powder piperazine pyrophosphate.
Embodiment 6
Use vacuum kneader, Heating temperature is 250 DEG C, and vacuum degree control is at 0.025MPa, and rotating speed is 20rpm, and bisphosphate piperazine reacting by heating 4h prepared by 2kg embodiment 1, obtains 1.86kg white powder piperazine pyrophosphate.
Embodiment 7
Use atmosphere protection type rotary kiln, Heating temperature is set as 250 DEG C, passes to high-purity argon gas for protection gas, and rotating speed is 10rpm, and bisphosphate piperazine reacting by heating 6h prepared by 2kg embodiment 1 obtains 1.83kg white powder piperazine pyrophosphate.
Embodiment 8
Use atmosphere protection type rotary kiln, Heating temperature is set as 200 DEG C, passes to high-purity argon gas for protection gas, and rotating speed is 10rpm, and bisphosphate piperazine reacting by heating 12h prepared by 2kg embodiment 1 obtains 1.82kg white powder piperazine pyrophosphate.
Comparative example 2
Use Banbury mixer, Heating temperature is 250 DEG C, does not vacuumize, and rotating speed is 20rpm, and bisphosphate piperazine reacting by heating 4h prepared by 2kg embodiment 1, obtains the Powdered piperazine pyrophosphate of 1.86kg black gray expandable.
Comparative example 3
Use atmosphere protection type rotary kiln, Heating temperature is set as 250 DEG C, passes to air atmosphere, and rotating speed is 10rpm, and bisphosphate piperazine reacting by heating 6h prepared by 2kg embodiment 1, obtains the Powdered piperazine pyrophosphate of 1.82kg black gray expandable.
Outward appearance, yield, phosphorus content and product whiteness to embodiment 5 ~ 8 and comparative example 2 ~ 3 are tested, and the results are shown in Table 2.
Table 2
| ? | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 2 | Comparative example 3 |
| Whiteness (W value) | 97 | 93 | 97 | 96 | 63 | 70 |
| Outward appearance | White | White | White | White | Black gray expandable | Black gray expandable |
| Yield | 98% | 99% | 98% | 97% | 99% | 97% |
| Phosphorus content | 23.3% | 23.2% | 23.4% | 22.7 | 22.8% | 22.5% |
As shown in Table 2, the whiteness W value of the piperazine pyrophosphate that the inventive method prepares is up to more than 90%, exceeds comparative example 2 and comparative example 3 reaches 45%, obtained significant effect.
flame retardant polyolefin compound
Application examples 1 ~ 3
According to the proportioning of table 3, piperazine pyrophosphate, melamine pyrophosphate, nano silicon, tetrafluoroethylene and processing aid prepared by acrylic resin, embodiment 5 are after high-speed mixer mixes, by twin screw extruder extruding pelletization at 200 DEG C, and then injection moulding at 200 DEG C, evaluate its flame retardant properties with UL-94.
Application comparative example 1 ~ 3
According to the proportioning of table 3, by acrylic resin, commercially available high molecular ammonium polyphosphate flame retardant, commercially available piperazine pyrophosphate fire retardant, nano silicon, tetrafluoroethylene and processing aid after high-speed mixer mixes, by twin screw extruder extruding pelletization at 200 DEG C, and then injection moulding at 200 DEG C, evaluate its flame retardant properties with UL-94.
Table 3
As shown in Table 3, flame retardant polyolefin compound disclosed by the invention, in the situation that fire retardant usage quantity is less, has still obtained than the better flame retardant effect of existing composition.
Claims (10)
1. a preparation method for bisphosphate piperazine, is characterized in that, described preparation method comprises the following steps:
Phosphoric acid and piperazine, according to 2 ~ 2.2:1 mixed in molar ratio, after stirring reaction 1 ~ 12h, are heated to 50 ~ 80 DEG C, more spray-dried, obtain bisphosphate piperazine.
2. a preparation method for piperazine pyrophosphate, is characterized in that, described preparation method comprises the following steps:
S1. by phosphoric acid and piperazine according to 2 ~ 2.2:1 mixed in molar ratio, after stirring reaction 1 ~ 12h, be heated to 50 ~ 80 DEG C, more spray-dried, obtain bisphosphate piperazine;
S2. described bisphosphate piperazine is carried out to dehydration condensation and prepare piperazine pyrophosphate, the processing condition of described dehydration condensation are at 200 ~ 280 DEG C of heating 1 ~ 12h under inert atmosphere or vacuum condition.
3. according to preparation method described in claim 1 or 2, it is characterized in that, described phosphoric acid mixes according to mol ratio 2:1 with piperazine.
4. according to preparation method described in claim 1 or 2, it is characterized in that, the described stirring reaction time is 2 ~ 6h; Temperature after described heating is 60 ~ 70 DEG C.
5. according to preparation method described in claim 1 or 2, it is characterized in that, described spraying is dried as pressure spray dryer method, centrifugal spray drying method or pneumatic spray drying method.
6. the preparation method of piperazine pyrophosphate according to claim 2, is characterized in that, described inert atmosphere is argon gas; Described vacuum condition is 0.02 ~ 0.05MPa.
7. a flame retardant polyolefin compound, is characterized in that, the material that described flame retardant polyolefin compound contains following mass fraction:
The polyolefin resin of 100 mass parts;
The piperazine pyrophosphate that described in claim 2 to 6 any one of 10 ~ 100 mass parts prepared by preparation method;
The melamine compound of 10 ~ 100 mass parts;
1 ~ 10 mass parts nano-oxide fire retarding synergist;
0.1 ~ 1 mass parts anti-dripping agent;
0.1 ~ 1 mass parts processing aid.
8. flame retardant polyolefin compound according to claim 7, is characterized in that, described melamine compound is one or more mixture of trimeric cyanamide phosphoric acid, melamine pyrophosphate, melamine polyphosphate.
9. flame retardant polyolefin compound according to claim 7, is characterized in that, described nano-oxide fire retarding synergist is one or more mixture of zinc oxide, magnesium oxide, titanium oxide, silicon-dioxide.
10. flame retardant polyolefin compound according to claim 7, is characterized in that, described anti-dripping agent is teflon resin; Described processing aid comprises oxidation inhibitor, lubricant.
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| CN105017563A (en) * | 2015-07-09 | 2015-11-04 | 金发科技股份有限公司 | Preparation method of halogen-free flame-retardant composition and flame-retardant polyolefin composition consisting of same |
| CN105541758A (en) * | 2015-12-31 | 2016-05-04 | 中山康诺德新材料有限公司 | Method for preparing high-purity and high-yield pyrophosphoric acid piperazine and application thereof |
| CN105837855A (en) * | 2016-05-10 | 2016-08-10 | 金发科技股份有限公司 | Halogen-free flame retardant and preparation method thereof and flame-retardant polyolefin composition composed of same |
| CN106316983A (en) * | 2016-08-24 | 2017-01-11 | 浙江万盛股份有限公司 | Microwave-assisted synthetic method of pyrophosphate piperazine |
| CN106633420A (en) * | 2016-09-19 | 2017-05-10 | 广东省石油化工研究院 | Halogen-free flame-retardation thermoplastic dynamic sulfurated ethylene-propylene-diene monomer rubber/polypropylene composition and preparation method thereof |
| CN107207806A (en) * | 2015-02-06 | 2017-09-26 | 株式会社艾迪科 | Anti-flaming polypropylene composition |
| CN108947936A (en) * | 2018-07-27 | 2018-12-07 | 台启龙 | Graphene/piperazine pyrophosphate nano-complex and preparation method thereof |
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| CN109181003A (en) * | 2018-08-06 | 2019-01-11 | 台启龙 | The preparation method of Flame-retardant low-smoke functional master batch and the functional master batch |
| CN109722000A (en) * | 2018-11-22 | 2019-05-07 | 东莞捷佳塑胶科技有限公司 | The polyurethane of imitative silica gel feel and the manufacture craft of polyether thermoplastic elastomer alloy |
| CN109735031A (en) * | 2019-01-11 | 2019-05-10 | 浦江金鑫塑业股份有限公司 | A kind of multicomponent collaboration halogen-free flame-retardant system and its application |
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| CN111004285A (en) * | 2019-11-29 | 2020-04-14 | 湖北航天化学技术研究所 | Preparation method of fine-grained piperazine polyphosphate |
| CN112341405A (en) * | 2020-11-16 | 2021-02-09 | 清远市普塞呋磷化学有限公司 | Preparation method of fine-particle-size high-whiteness piperazine pyrophosphate flame retardant |
| CN112679740A (en) * | 2021-01-07 | 2021-04-20 | 浙江富锦新材料有限公司 | Novel piperazine pyrophosphate flame retardant and preparation method thereof |
| CN113402715A (en) * | 2020-11-06 | 2021-09-17 | 江苏集萃先进高分子材料研究所有限公司 | Novel phosphorus-nitrogen flame retardant and preparation method thereof |
| CN114015115A (en) * | 2021-10-25 | 2022-02-08 | 沈阳工业大学 | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate |
| CN114181431A (en) * | 2021-12-21 | 2022-03-15 | 包头稀土研究院 | Flame retardant, preparation method and application thereof and polyolefin composition |
| CN114605353A (en) * | 2022-03-15 | 2022-06-10 | 山东迈特新材料科技有限公司 | Preparation method of piperazine pyrophosphate |
| CN115385869A (en) * | 2021-05-25 | 2022-11-25 | 金发科技股份有限公司 | High-whiteness piperazine pyrophosphate and preparation method and application thereof |
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| CN107207806A (en) * | 2015-02-06 | 2017-09-26 | 株式会社艾迪科 | Anti-flaming polypropylene composition |
| CN105017563A (en) * | 2015-07-09 | 2015-11-04 | 金发科技股份有限公司 | Preparation method of halogen-free flame-retardant composition and flame-retardant polyolefin composition consisting of same |
| CN105541758A (en) * | 2015-12-31 | 2016-05-04 | 中山康诺德新材料有限公司 | Method for preparing high-purity and high-yield pyrophosphoric acid piperazine and application thereof |
| CN105837855A (en) * | 2016-05-10 | 2016-08-10 | 金发科技股份有限公司 | Halogen-free flame retardant and preparation method thereof and flame-retardant polyolefin composition composed of same |
| CN105837855B (en) * | 2016-05-10 | 2018-09-28 | 金发科技股份有限公司 | A kind of halogen-free flame retardants and preparation method thereof and the flame retardant polyolefin compound being made from it |
| CN106316983A (en) * | 2016-08-24 | 2017-01-11 | 浙江万盛股份有限公司 | Microwave-assisted synthetic method of pyrophosphate piperazine |
| CN106633420A (en) * | 2016-09-19 | 2017-05-10 | 广东省石油化工研究院 | Halogen-free flame-retardation thermoplastic dynamic sulfurated ethylene-propylene-diene monomer rubber/polypropylene composition and preparation method thereof |
| CN108947936A (en) * | 2018-07-27 | 2018-12-07 | 台启龙 | Graphene/piperazine pyrophosphate nano-complex and preparation method thereof |
| CN109135057A (en) * | 2018-07-27 | 2019-01-04 | 台启龙 | Heat conductive flame-retarding polyolefin resin composite and formed body |
| CN109135057B (en) * | 2018-07-27 | 2021-03-09 | 苏州和塑美科技有限公司 | Heat-conductive flame-retardant polyolefin resin composition and molded article |
| CN109181003A (en) * | 2018-08-06 | 2019-01-11 | 台启龙 | The preparation method of Flame-retardant low-smoke functional master batch and the functional master batch |
| CN109722000A (en) * | 2018-11-22 | 2019-05-07 | 东莞捷佳塑胶科技有限公司 | The polyurethane of imitative silica gel feel and the manufacture craft of polyether thermoplastic elastomer alloy |
| CN109749244A (en) * | 2019-01-11 | 2019-05-14 | 浦江金鑫塑业股份有限公司 | A kind of halogen-free flame-retardant polypropylene composition and its preparation method and application |
| CN109735031A (en) * | 2019-01-11 | 2019-05-10 | 浦江金鑫塑业股份有限公司 | A kind of multicomponent collaboration halogen-free flame-retardant system and its application |
| CN111004285B (en) * | 2019-11-29 | 2022-06-17 | 湖北航天化学技术研究所 | Preparation method of fine-grained piperazine polyphosphate |
| CN111004285A (en) * | 2019-11-29 | 2020-04-14 | 湖北航天化学技术研究所 | Preparation method of fine-grained piperazine polyphosphate |
| CN113402715A (en) * | 2020-11-06 | 2021-09-17 | 江苏集萃先进高分子材料研究所有限公司 | Novel phosphorus-nitrogen flame retardant and preparation method thereof |
| CN112341405A (en) * | 2020-11-16 | 2021-02-09 | 清远市普塞呋磷化学有限公司 | Preparation method of fine-particle-size high-whiteness piperazine pyrophosphate flame retardant |
| CN112679740A (en) * | 2021-01-07 | 2021-04-20 | 浙江富锦新材料有限公司 | Novel piperazine pyrophosphate flame retardant and preparation method thereof |
| CN115385869A (en) * | 2021-05-25 | 2022-11-25 | 金发科技股份有限公司 | High-whiteness piperazine pyrophosphate and preparation method and application thereof |
| CN114015115A (en) * | 2021-10-25 | 2022-02-08 | 沈阳工业大学 | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate |
| CN114015115B (en) * | 2021-10-25 | 2023-03-28 | 沈阳工业大学 | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate |
| CN114181431A (en) * | 2021-12-21 | 2022-03-15 | 包头稀土研究院 | Flame retardant, preparation method and application thereof and polyolefin composition |
| CN114181431B (en) * | 2021-12-21 | 2023-08-15 | 包头稀土研究院 | Flame retardant, preparation method and application thereof and polyolefin composition |
| CN114605353A (en) * | 2022-03-15 | 2022-06-10 | 山东迈特新材料科技有限公司 | Preparation method of piperazine pyrophosphate |
| CN114605353B (en) * | 2022-03-15 | 2024-03-15 | 山东迈特新材料科技有限公司 | Preparation method of piperazine pyrophosphate |
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