CN107629086B - A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants - Google Patents
A kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants Download PDFInfo
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Abstract
The invention belongs to application project plastics arts, and in particular to a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants.This method is reacted using phenol with phosphorus oxychloride under louis catalyst effect, decompression steams extra phosphorus oxychloride, obtain mixture intermediate, mixture intermediate and hydroquinone carry out in condensation reaction, it is first reacted with appropriate hydroquinone using mixing intermediate, the high vacuum dehydrochlorination after the hydroquinone fully reacting of part, it is reacted again plus under triethylamine and remaining hydroquinone lower temperature, the raising of low triphenyl phosphate content is greatly dropped, reduce the murder by poisoning to human body, the purity and yield of product are improved simultaneously, its technological operation is easy, it is with short production cycle, it is economic and environment-friendly, it is able to satisfy the requirement of industrial scale production, suitable for industrial application.
Description
Technical field
The invention belongs to fine chemistry industry production technical fields, and in particular to a kind of low triphenyl phosphate engineering plastics Halogen resistance
Fire the preparation method of agent.
Background technique
Halogen armaticity phosphoric acid ester hinders right agent since with efficient and convenient flame retardant property, the market space is very big, with
Rapid growth is increased production capacity by the market demand of phosphate flame retardant, the bigger industrialization rule of its formation of the right to use
Mould meets the market demand, takes part in international competition, and becomes the task of top priority.
The patent CN200810063129 of traditional our company invention is first reacted using phosphorus oxychloride with to biphenol, then with
Phenol carries out the oligomer that obtains of condensation reaction, and pyrocondensation reaction could completely, and the process of high temperature is easy to produce disproportionation,
It is generated in reaction preparation process and is more toxic triphenyl phosphate, and the process of high temperature, the color of product is easy to deepen.Our company's hair
Bright patent CN201510517986, CN201510517984 prepare low triphenyl phosphate technique BDP technique, and triphenyl phosphate contains
Amount is all to be reacted using phosphorus oxychloride with Resorcino, the method for last phenol pyrocondensation, phosphorus oxychloride is except dry less than 3%
Net method achieves the goal.In order to overcome above-mentioned disadvantage, using inventing new synthetic route preparation method, first phosphorus oxychloride with
Phenol carries out esterification and prepares mixture intermediate, and mixture intermediate carries out condensation reaction prior to part hydroquinone, instead
Then dehydrochlorination after answering is added under organic base and remaining hydroquinone lower temperature and is reacted.Avoid the disproportionation of high temperature
Reaction, control are more toxic triphenyl phosphate content, carry out condensation reaction at lower temperature, solve the color of product, and phosphorus
Triphenyl phosphate ester is controlled less than 1% or less.The present invention overcomes deficiency in the prior art, provide it is a kind of it is with short production cycle, economical,
And environmental protection meets the requirement of commercial scale, reasonable preparation method, the hydroquinone bis phosphoric acid phenyl ester being prepared by it
Oligomer product quality gets a greater increase.
Summary of the invention
For the defect that product made from traditional hydroquinone bis phosphoric acid phenyl ester oligomer preparation method occurs, the present invention is mentioned
For a kind of preparation method of new low triphenyl phosphate engineering plastics halogen-free flame retardants, this method is easy to operate, reaction temperature is low,
Requirement that is economic and environment-friendly, being able to satisfy industrial scale production, the specific technical solution of the present invention elder generation phosphorus oxychloride and phenol carry out
Esterification prepares mixture intermediate, and mixture intermediate first carries out condensation reaction, dechlorination after reaction with part hydroquinone
Change hydrogen, is then added under organic base and remaining hydroquinone lower temperature and carries out condensation reaction.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that by trichlorine oxygen
Phosphorus react under lewis acid catalyst effect with phenol prepares mixture intermediate, and mixture intermediate is right with part again
Benzenediol carry out condensation reaction, after hydroquinone fully reacting high vacuum remove hydrogen chloride, Tuo Wanhou add organic base and
Remaining hydroquinone carries out condensation reaction at low temperature, and after reaction, cooling, solidification obtains crude product, after crude product crushes
Reason is washed, and washing is neutralized, and drying obtains the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product, chemical equation
It is as follows:
0≤n≤6 in above formula, n=1 therein, 2,3,4,5,6 finished product contain different contents, and n=0 mass percentage contains
Compound when measuring less than 1%, n=0 is triphenyl phosphate.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that including as follows
Step:
1) phosphorus oxychloride and phenol esterif iotacation step: are carried out to esterification under the catalysis of lewis acid catalyst to no chlorine
Until changing hydrogen releasing, phosphorus oxychloride is removed and recycled under reduced pressure, obtain among a substitution and disubstituted mixture for phosphorus oxychloride
Body；
2) condensation polymerization step: under the catalysis of lewis acid catalyst, first plus part hydroquinone is added to step 1)
Mixing intermediate in carry out primary condensation polymerization reaction, detect the content of hydroquinone to fully reacting, dechlorination under vacuum
Hydrogen, then plus organic base and remaining hydroquinone to carry out secondary condensation polymerization reaction complete to mixing intermediate reaction, obtain ester
Change crude product；
3) purification step: the esterification crude product that step 2) is obtained is through cooling, solidification, pulverization process, smashed product
Through washing, alkali cleaning, washing, drying obtains the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 1)
Esterification reaction temperature be 80-90 DEG C, preferably 85-90 DEG C, the reaction time be 3-10 hours, preferably 4-6 hours.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 1)
The molar ratio of phosphorus oxychloride and phenol is 1:0.8-1.5, temperature of the preferably 1:1 vacuum distillation except remaining a small amount of phosphorus oxychloride
Degree is 90~120 DEG C, and preferably 85-90 DEG C of vacuum degree is 30~60KPa.
A kind of preparation method of the low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that step 1) and
Lewis acid catalyst in step 2) is respectively titanium tetrachloride, alchlor or magnesium chloride, preferably magnesium chloride, and catalyst is used
Amount be phosphorus oxychloride weight 0.001-0.5%, preferably 0.01%.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 2)
Mixture intermediate and the molar ratio of total hydroquinone be 1:1.1-2.0, preferably 1:1.5 moles, primary condensation is poly-
The hydroquinone put into when conjunction accounts for the 55-65% of total amount, preferably 60%, and the hydroquinone Zhan that secondary condensation is put into when polymerizeing is total
The 35-45% of amount, preferably 40%, primary condensation polymeric reaction temperature be 100~150 DEG C, preferably 140 DEG C, primary condensation
Polymerization time is 3-10 hours, preferably 3-5 hours.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 2)
Dehydrochlorination temperature is 60~100 DEG C, and preferably 65-90 DEG C, vacuum degree is 30~60KPa.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 2)
Organic base be triethylamine, diethylamine, ammonia or pyridine, preferably triethylamine, the amount that organic base is added is mixture intermediate
The 2-5% of weight, preferably 2%.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 2)
Except the secondary condensation polymeric reaction temperature after de-chlorine hydride is 60~100 DEG C, preferably 80-90 DEG C, the reaction time is that 4-13 is small
When, preferably 4-10 hours.
The preparation method of a kind of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that in step 3)
Using alkaline weak solution alkali cleaning, alkaline weak solution is any in sodium hydroxide solution, sodium carbonate liquor or sodium bicarbonate solution
One kind, preferably sodium hydroxide solution, the mass concentration 3~5% of alkaline weak solution, alkali cleaning temperature are 60~80 DEG C, when alkali cleaning
Between be 25-35min, preferably 30min separates water, is then washed to neutrality.
Phosphorus oxychloride is first carried out esterification preparation with phenol and mixes intermediate by the present invention by using above-mentioned technology,
It mixes intermediate and first carries out condensation reaction with part hydroquinone, then organic base and remaining is added in dehydrochlorination after reaction
Condensation reaction is carried out under hydroquinone lower temperature, it is post-treated to obtain low triphenyl phosphate engineering plastics halogen-free flame retardants.This hair
It is bright it is easy to operate, reaction temperature is low, it is with short production cycle, economic and environment-friendly, be able to satisfy industrial scale production requirement, obtained production
Product purity is high, triphenyl phosphate content greatly reduce, and are suitable for industrial application.
Specific embodiment
The invention will be further described with reference to embodiments, but protection scope of the present invention is not limited to that:
Embodiment 1:
Respectively by 78g (0.5mol) phosphorus oxychloride, it is 70-80 DEG C that magnesium chloride 0.1g, which is added in four-hole boiling flask and rises to temperature,
Slowly be added dropwise 50g (0.55mol) phenol, time for adding be 2.5 hours, after dripping 80-90 DEG C insulation reaction 5 hours, until
After no hydrogen chloride is released, reaction is completed, and it is 30-100KPa, vapo(u)rizing temperature 30- that phosphorus oxychloride vacuum degree is evaporated under reduced pressure after reaction
100 DEG C, obtain mixture intermediate after vacuum distillation, i.e. the one of phosphorus oxychloride replaces and disubstituted mixture, one replace and
Two replace the ratio of mixture to be 4:6, and the yield 95% of mixture intermediate, the rate of recovery of phosphorus oxychloride is 95% (with trichlorine
Oxygen phosphorus calculates)；
Mixture intermediate is added in four-hole boiling flask, magnesium chloride 0.1g is added, hydroquinone 60g is first added, slowly rises
For temperature to 130-140 DEG C of reaction, the reaction time is 6 hours, until after being released without hydrogen chloride, vacuum distillation deacidification, vacuum degree 30-
60KPa, decompression temperature are 85-90 DEG C, and decompression removes hydrogen chloride 1 hour, then triethylamine 20g is slowly added dropwise, and feed liquid is neutrality, are added
Remaining hydroquinone 20g is reacted, and reaction temperature is 90-100 DEG C, and the reaction time is 4 hours, and it is anti-that liquid phase detects intermediate
It should be complete.Liquid cooling and solidifying is poured out after reaction to smash, and 150g water is added in the solid 100g after smashing, with 30g 3%
Sodium hydroxide solution is washed, and then washing is neutral, and material drying, which smashes, obtains finished product, the total recovery of two-step reaction about 93%,
Fusing point: 100-103 DEG C, triphenyl phosphate accounts for the 0.5% of total amount, obtains white crystalline powder.
Does is (difference with embodiment 1 that hydroquinone is added at one time to comparative test test example 1? yes)
Respectively by 78g (0.5mol) phosphorus oxychloride, magnesium chloride 0.1g, which is added in four-hole boiling flask, to be reacted, and rising to temperature is
70-80 DEG C, phenol 50g (0.55mol) phenol is slowly added dropwise, it is time for adding 2-3 hours, anti-in 80-90 DEG C of heat preservation after dripping
It answers 3-5 hours, until reaction is completed after releasing without hydrogen chloride, it is 30- that phosphorus oxychloride tower vacuum degree is evaporated under reduced pressure after reaction
100KPa, vapo(u)rizing temperature are 30-100 DEG C, mixture intermediate are obtained after vacuum distillation, the one of phosphorus oxychloride replaces and two replace
Mixture, the ratio of mixture is 4:6, and gas phase analysis obtains mixture intermediate, the yield 95% of intermediate, trichlorine oxygen
The rate of recovery of phosphorus is 95% (being calculated with phosphorus oxychloride).
Mixture intermediate is added in four-hole boiling flask, magnesium chloride 0.1g is added, part hydroquinone 80g is first added, is delayed
Slowly it is warming up to 115-150 DEG C of reaction, the reaction time is 14 hours, until it is cold to pour out liquid after reaction after releasing without hydrogen chloride
But solidification smashes, and 150g water is added in the solid 100g after smashing, is washed with 3% sodium hydroxide solution of 30g, then water
Neutrality is washed, material drying, which smashes, obtains finished product, the total recovery of two-step reaction about 80%, fusing point: 100-103 DEG C, triphenyl phosphate
5.0%, obtain white crystalline powder.
Embodiment 2:
Respectively by 160g (1mol) phosphorus oxychloride, titanium tetrachloride 1g, which is added in four-hole boiling flask, to be reacted, and rising to temperature is
70-80 DEG C, phenol 94g (1mol) slowly is added dropwise, phenol time for adding about 2-3 hours, in 80-90 DEG C of insulation reaction after dripping
3-5 hours, until reaction is completed after releasing without hydrogen chloride, phosphorus oxychloride is evaporated under reduced pressure after reaction, vacuum degree 30-100KPa steams
Evaporating temperature is 30-100 DEG C, and mixture intermediate is obtained after vacuum distillation, and the one of phosphorus oxychloride replaces and disubstituted mixture,
The ratio of mixture is 5:5, and gas phase analysis obtains mixture intermediate, the yield 95% of intermediate, the rate of recovery of phosphorus oxychloride
For 95% (being calculated with phosphorus oxychloride)；
Mixture intermediate is added in four-hole boiling flask, titanium tetrachloride 1g is added, part hydroquinone 100g is first added, is delayed
Slowly it is warming up to 130-140 DEG C of reaction, the reaction time is 4-6 hours, until after being released without hydrogen chloride, vacuum distillation deacidification, vacuum degree
For 30-100KPa, depressurizing temperature is 85-90 DEG C, and triethylamine 50g is slowly added dropwise in decompression deacidification 1 hour, and feed liquid is neutrality, is added
Remaining hydroquinone 65g is reacted, and reaction temperature is 90-100 DEG C, and the reaction time is 3-4 hours, and liquid phase detects intermediate
Fully reacting.Liquid cooling and solidifying is poured out after reaction to smash, and 300g water is added in the solid 100g after smashing, uses 100g
3% sodium hydroxide solution is washed, and then washing is neutral, and material drying, which smashes, obtains finished product, and the total recovery of two-step reaction is about
94%, fusing point: 100-103 DEG C, triphenyl phosphate 0.5% obtains white crystalline powder.
Comparative experimental example 2
Respectively by 160g (1mol) phosphorus oxychloride, titanium tetrachloride 1g, which is added in four-hole boiling flask, to be reacted, and rising to temperature is
70-80 DEG C, phenol 94g (1mol) slowly is added dropwise, phenol time for adding about 2-3 hours, in 80-90 DEG C of insulation reaction after dripping
4-5 hours, until reaction is completed after releasing without hydrogen chloride, it was 30-100KPa that phosphorus oxychloride tower vacuum degree is evaporated under reduced pressure after reaction,
Vapo(u)rizing temperature is 30-100 DEG C, mixture intermediate is obtained after vacuum distillation, the one of phosphorus oxychloride replaces and disubstituted mixing
Object, the ratio of mixture are 5:5, and gas phase analysis obtains mixture intermediate, the yield 95% of intermediate, and phosphorus oxychloride is returned
Yield is 95% (being calculated with phosphorus oxychloride)；
Mixture intermediate is added in four-hole boiling flask, titanium tetrachloride 1g is added, part hydroquinone 165g is first added, is delayed
Slowly it is warming up to 115-145 DEG C of reaction, the reaction time is 4-10 hours, until pouring out liquid after reaction after releasing without hydrogen chloride
Cooling and solidifying smashes, and 300g water is added in the solid 100g after smashing, is washed with 3% sodium hydroxide solution of 100g, then
Washing is neutral, and material drying, which smashes, obtains finished product, the total recovery of two-step reaction about 84%, fusing point: 100-103 DEG C, triphenyl phosphate
5.5%, obtain white crystalline powder.
Embodiment 3:
Respectively by 1600g (1mol) phosphorus oxychloride, alchlor 10g, which is added in four-hole boiling flask, to be reacted, and rises to temperature
It is 70-80 DEG C, phenol 1120g (1.1mol) slowly is added dropwise, phenol time for adding about 2-3 hours, is protected after dripping at 80-90 DEG C
Temperature reaction 3-5 hours, until reaction is completed after releasing without hydrogen chloride, it is 30- that phosphorus oxychloride tower vacuum degree is evaporated under reduced pressure after reaction
100KPa, vapo(u)rizing temperature are 30-100 DEG C, mixture intermediate are obtained after vacuum distillation, the one of phosphorus oxychloride replaces and two replace
Mixture, the ratio of mixture is 4:6, and gas phase analysis obtains mixture intermediate, the yield 95% of intermediate, trichlorine oxygen
The rate of recovery of phosphorus is 95% (being calculated with phosphorus oxychloride).
Mixture intermediate is added in four-hole boiling flask, alchlor 10g is added, part hydroquinone 1000g is first added,
It is to slowly warm up to 130-145 DEG C of reaction, the reaction time is 4-6 hours, until after being released without hydrogen chloride, vacuum distillation deacidification, vacuum
Degree is 30-100KPa, and decompression temperature is 85-90 DEG C, decompression deacidification 1 hour, and triethylamine 500g is slowly added dropwise, and feed liquid is neutrality,
It adds remaining hydroquinone 650g to be reacted, reaction temperature is 90-100 DEG C, and the reaction time is 3-4 hours, liquid phase detection
Intermediate reaction is complete.Liquid cooling and solidifying is poured out after reaction to smash, and 300g water is added in the solid 100g after smashing, is used
3% sodium hydroxide solution of 100g is washed, and then washing is neutral, and material drying, which smashes, obtains finished product, the total recovery of two-step reaction
About 94%, fusing point: 100-103 DEG C, triphenyl phosphate 0.5% obtains white crystalline powder.
Embodiment 4:
Respectively by 80g (0.5mol) phosphorus oxychloride, 70g (1.5mol) phenol, butyl titanate 0.1g is added in four-hole boiling flask
It is reacted, reaction temperature is 70-80 DEG C, it reacts 6 hours, is evaporated under reduced pressure phosphorus oxychloride after reaction, vacuum degree 40-60KPa,
Vapo(u)rizing temperature is 80-90 DEG C, mixture intermediate after vacuum distillation, and the one of phosphorus oxychloride replaces and disubstituted mixture, is mixed
The ratio for closing object is 4:6, gas phase analysis.
Mixture intermediate is added in four-hole boiling flask, titanium tetrachloride 1g is added, part hydroquinone 100g is first added, is delayed
Slowly it is warming up to 130-140 DEG C of reaction, the reaction time is 5 hours, vacuum distillation deacidification, vacuum degree after detection hydroquinone has reacted
For 30-60KPa, depressurizing temperature is 85-90 DEG C, and triethylamine 6g is slowly added dropwise in decompression deacidification 2 hours, and feed liquid is neutrality, is added surplus
Under hydroquinone 65g reacted, reaction temperature be 85-100 DEG C, the reaction time be 3-4 hour, liquid phase detection intermediate it is anti-
It should be complete.Liquid cooling and solidifying is poured out after reaction to smash, and 150g water is added in the solid 105g after smashing, with 3% hydrogen of 3g
Sodium hydroxide solution is washed, and washing is neutral, and material drying, which smashes, obtains finished product.Total recovery: 94%, fusing point: 100-103 DEG C, phosphorus
Triphenyl phosphate ester 0.9%, obtains white crystalline powder.
Example 5:
Respectively by 88g (0.55mol) phosphorus oxychloride, magnesium chloride 0.5g, which is added in four-hole boiling flask, to be reacted, and 94g is added dropwise
(1mol) phenol, reaction temperature are 70-80 DEG C, are reacted 6 hours, and it is 40- that phosphorus oxychloride tower vacuum degree is evaporated under reduced pressure after reaction
60KPa, vapo(u)rizing temperature are 80-90 DEG C, and mixture intermediate after vacuum distillation, the one of phosphorus oxychloride replaces and disubstituted mixing
Object, the ratio of mixture are 4.5:5.5, gas phase analysis.
Mixture intermediate is added in four-hole boiling flask, titanium tetrachloride 1g is added, hydroquinone 100g is to slowly warm up to
130-140 DEG C of reaction, reaction time are 4 hours, vacuum distillation deacidification, vacuum degree 30- after detection hydroquinone has reacted
60KPa, decompression temperature are 85-90 DEG C, and triethylamine 6g is slowly added dropwise in decompression deacidification 30 minutes, and feed liquid is neutrality, are added remaining
Hydroquinone 60g is reacted, and the reaction time is 3-4 hours, and reaction temperature is 85-100 DEG C, and it is complete that liquid phase detects intermediate reaction
Entirely.Liquid cooling and solidifying is poured out after reaction to smash, and 150g water is added in the solid 100g after smashing, with 3g3% hydroxide
Sodium solution is washed, and washing is neutral, and material drying, which smashes, obtains finished product.Total recovery: 94%, fusing point: 100-103 DEG C, tricresyl phosphate
Phenyl ester 1.0%, obtains white crystalline powder.
In terms of comparative test, product made from the preparation method using low triphenyl phosphate engineering plastics halogen-free flame retardants
In, the content of toxicant triphenyl phosphate greatly reduces, and the time reacted shortens, stable product quality.
Claims (17)
1. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants, it is characterised in that include the following steps:
1) phosphorus oxychloride and phenol esterif iotacation step: are carried out to esterification under the catalysis of lewis acid catalyst to no hydrogen chloride
Until releasing, phosphorus oxychloride is removed and recycled under reduced pressure, obtain phosphorus oxychloride one replaces and disubstituted mixture intermediate；
2) condensation polymerization step: under the catalysis of lewis acid catalyst, first plus part hydroquinone is added to the mixed of step 1)
It closes and carries out primary condensation polymerization reaction in intermediate, detect the content of hydroquinone to fully reacting, dehydrochlorination under vacuum, then
Add organic base and remaining hydroquinone progress secondary condensation polymerization reaction complete to mixing intermediate reaction, obtains being esterified thick production
Object；
3) purification step: the esterification crude product that step 2) is obtained is through cooling, solidification, pulverization process, and smashed product is through water
It washes, alkali cleaning, washing, drying obtains the low triphenyl phosphate engineering plastics halogen-free flame retardants of finished product；
Its chemical equation is as follows:
0≤n≤6 in above formula, n=1 therein, 2,3,4,5,6 finished product contain different contents, and n=0 mass percentage is small
In 1%.
2. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is that the esterification reaction temperature in step 1) is 80-90 DEG C, the reaction time is 3-10 hours.
3. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 1) that the molar ratio of phosphorus oxychloride and phenol is 1:0.8-1.5；Vacuum distillation is except remaining a small amount of phosphorus oxychloride
Temperature be 90~120 DEG C；Vacuum degree is 30~60KPa.
4. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is that the lewis acid catalyst in step 1) and step 2) is respectively titanium tetrachloride, alchlor or magnesium chloride, catalyst is used
Amount is the 0.001-0.5% of the weight of phosphorus oxychloride.
5. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
The molar ratio for being mixture intermediate and total hydroquinone in step 2) is 1:1.1-2.0, when primary condensation polymerize
The hydroquinone of investment accounts for the 55-65% of total amount, and the hydroquinone that secondary condensation is put into when polymerizeing accounts for the 35-45% of total amount, and one
Secondary condensation polymerization reaction temperature is 100~150 DEG C, and primary condensation polymerization time is 3-10 hours.
6. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 2) that dehydrochlorination temperature is 60~100 DEG C, vacuum degree is 30~60KPa.
7. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is that the organic base in step 2) is triethylamine, diethylamine, ammonia or pyridine, the amount that organic base is added is weight among mixture
The 2-5% of amount.
8. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 2) except the secondary condensation polymeric reaction temperature after de-chlorine hydride to be 60~100 DEG C, the reaction time is 4-13 hours.
9. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 3) that using alkaline weak solution alkali cleaning, alkaline weak solution is sodium hydroxide solution, sodium carbonate liquor or sodium bicarbonate
Any one in solution, the mass concentration 3~5% of alkaline weak solution, alkali cleaning temperature are 60~80 DEG C, and the alkali cleaning time is 25-
35min separates water, is then washed to neutrality.
10. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is that the esterification reaction temperature in step 1) is 85-90 DEG C, the reaction time is 4-6 hours.
11. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 1) that the molar ratio of phosphorus oxychloride and phenol is 1:1；Temperature of the vacuum distillation except remaining a small amount of phosphorus oxychloride
It is 85-90 DEG C.
12. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is that the lewis acid catalyst in step 1) and step 2) is respectively magnesium chloride, catalyst amount is the weight of phosphorus oxychloride
0.01%.
13. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
The molar ratio for being mixture intermediate and total hydroquinone in step 2) is 1:1.5, and primary condensation is put into when polymerizeing
Hydroquinone account for the 60% of total amount, the hydroquinone that secondary condensation is put into when polymerizeing accounts for the 40% of total amount, primary condensation polymerization
Reaction temperature is 140 DEG C, and primary comprehensive polymerization time is 3-5 hours.
14. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 2) that dehydrochlorination temperature is 65-90 DEG C.
15. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is that the organic base in step 2) is triethylamine, the amount that organic base is added is 2% of body weight among mixture.
16. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 2) except the secondary condensation polymeric reaction temperature after de-chlorine hydride to be 80-90 DEG C, the reaction time is 4-10 hours.
17. a kind of preparation method of low triphenyl phosphate engineering plastics halogen-free flame retardants according to claim 1, feature
It is in step 3) using alkaline weak solution alkali cleaning, alkaline weak solution is sodium hydroxide solution, and the alkali cleaning time is 30min.
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| CN111808319A (en) * | 2020-08-07 | 2020-10-23 | 宁波耀众模塑科技有限公司 | Aluminum hydroxide composite material of polyurethane foaming product |
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| CN113185547B (en) * | 2021-04-25 | 2022-05-20 | 广州银塑阻燃新材料股份有限公司 | Preparation method of compound with flame retardant property |
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