CN105440572B - Phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion and preparation method thereof - Google Patents
Phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion and preparation method thereof.Its preparation method is：After acrylate monomer, 2 hydroxyethyl meth acrylate phosphates, emulsifying agent DNS 86, water are mixed, high-speed stirred carries out pre-emulsification, and the pre-emulsification time is 15min~30min, then adds organically-modified phosphoric acid hydrogen zirconium thereto, continue pre-emulsification 10min~20min, obtain pre-emulsion；Phosphoric acid hydrogen modified zirconia polyacrylate dispersion is prepared by semicontinuous pre-emulsification emulsion polymerization；The pH to 8~9 of emulsion is adjusted, the Nitrogen-containing Phenolic Resins aqueous solution is added, after being well mixed, that is, phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion is obtained.Phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion stability prepared by the present invention is good, and cost is low, while having good fire resistance and mechanical property.
Description
Technical field
The present invention relates to a kind of flame-proof acrylic ester emulsion, more particularly to a kind of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins
Extinguishing waterborn polyacrylate dispersion and preparation method thereof.
Background technology
Water polyacrylic acid emulsion has the advantages that environmental protection, weatherability and good mechanical performance, has been widely used at present
In fields such as building coating, industrial coating and car paints.However, acrylic polymer has inflammability, once occur
The life and property that fire will give people cause grave danger.Therefore the fire-retardant research for acrylic acid ester emulsion has very
Important meaning.
Some conventional flame retardants such as APP, melamine, metal hydroxides etc. are added in acrylic acid ester emulsion
Its fire resistance can be effectively improved.Chinese invention patent application CN103254711A discloses a kind of water polyacrylic acid and is combined
Fireproof coating and preparation method thereof, this method adds melamine, inorganic composite flame retardants etc. in acrylic acid ester emulsion, prepares
There is the water polyacrylic acid fireproof coating of preferable fire resistance.But this method fire retardant addition is big, with base material phase
Capacitive is poor, deteriorates its mechanical property.
With add fire retardant method compared with, by reactive flame retardant with chemical bonds on acrylate polymeric chain
Method can overcome the shortcoming of fire retardant and substrate compatibility difference.Chinese invention patent application CN102408513A is in acrylic acid
Reactive flame retardant phosphate is introduced in ester emulsion building-up process, passes through comonomer acrylic acid hydroxyl Ester and phosphate
Ester exchange reaction, is prepared for the phosphate modified acrylic acid ester emulsion with preferable fire resistance.But this method works as response type
When amount of flame-retardant agent is less, then preferable flame retardant effect is unable to reach；When consumption is more, shadow can be caused to emulsion intercalation method
Ring, and it is costly be difficult to industrialization.Chinese invention patent application CN102964514A is in polyacrylate dispersion
Silicon, fluorine and phosphate group are introduced, three has cooperative flame retardant effect, effectively increases the anti-flammability of polyacrylate dispersion
Can, but equally there is also the higher shortcoming of cost for this method.Chinese invention patent application CN1024311725A is prepared for one kind
Flame-retardant polypropelene acid esters emulsion, while using reactive flame retardant, adds a small amount of antimony class compound as fire-retardant association
Agent is imitated, relatively good flame retardant effect, but antimony class compound bad dispersibility in emulsion has been reached, the stable storing of emulsion is influenceed
Property.Therefore a kind of low cost, stable storing and the novel acrylic ester emulsion with preferable fire resistance and mechanical property are studied
Tool is of great significance.
The content of the invention
It is an object of the invention to the defect existed for existing polypropylene flame redardant acid esters emulsion there is provided a kind of cost it is low,
Stable storing, and there is good flame-retardance can gather with the phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn of mechanical property simultaneously
Acrylic acid ester emulsion and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion, including following step
Suddenly：
(1) by acrylate monomer, HEMA phosphate, emulsifying agent propoxyl group polyoxyethylene nonyl phenyl second
After alkene (10) ether ammonium sulfate (DNS-86), water mixing, high-speed stirred carries out pre-emulsification, and the pre-emulsification time is 15min~30min,
Add organically-modified phosphoric acid hydrogen zirconium thereto again, continue pre-emulsification 10min~20min, obtain pre-emulsion；
(2) pH buffer sodium acid carbonate is dissolved in water, stirs and raise temperature to 75 DEG C~85 DEG C；It is synchronous thereto
The initiator potassium persulfate aqueous solution and the pre-emulsion is added dropwise, control time for adding reacts after 3.0h~5.0h, completion of dropping
30min~90min, then be warming up to after 85 DEG C~90 DEG C continuation reaction 30min~90min, cold filtration, obtain phosphoric acid hydrogen zirconium and change
Property polyacrylate dispersion；
(3) pH to 8~9 of phosphoric acid hydrogen modified zirconia polyacrylate dispersion is adjusted with methylamine, Nitrogen-containing Phenolic Resins water is added
Solution, is well mixed, that is, obtains phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion.
Further to realize the object of the invention, it is preferable that be calculated in mass percent, raw material composition bag in above-mentioned preparation method
Include：
Preferably, described acrylate monomer is made up of methyl methacrylate, butyl acrylate and acrylic acid, its matter
Amount is than being 49.0:49.0:2.0.
Preferably, the mass percent that described methylamine accounts for raw material is 1.0%~5.0%.
Preferably, described organically-modified phosphoric acid hydrogen zirconium is prepared via a method which：At room temperature, by the phosphoric acid of 1 mass parts
Hydrogen zirconium is scattered in 80~120 mass parts water, ultrasonic disperse, then adds TBAH aqueous solution progress intercalation thereto
It is modified, continue ultrasonic disperse, be stirred for 6~8h, by being centrifuged at a high speed, drying, obtain organically-modified phosphoric acid hydrogen zirconium, it is described
The mol ratio of TBAH and phosphoric acid hydrogen zirconium is 0.6:1.0~1.0:1.0.
Preferably, the time of the ultrasonic disperse and continuation ultrasonic disperse is all 30min~60min.
Preferably, the described Nitrogen-containing Phenolic Resins aqueous solution is the melamine modified phenolic resin aqueous solution.
A kind of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion, by above-mentioned preparation method system
.
In the present invention, organically-modified phosphoric acid hydrogen zirconium and the Nitrogen-containing Phenolic Resins aqueous solution have to water polyacrylic acid emulsion
Good synergistic fire retardation.This is probably that, because phosphoric acid hydrogen zirconium is nano-lamellar structure, after organically-modified, can compare
Good is dispersed in polyacrylate base material, forms barrier layer on surface in combustion, plays heat-insulated oxygen barrier effect；And
Phosphoric acid hydrogen zirconium is a kind of lewis acid again simultaneously, with acid catalysis, in combustion phosphoric acid hydrogen zirconium catalysed phenolic resin
Charcoal is cross-linked into polyacrylate, more abundant and fine and close layer of charcoal is advantageously formed, the anti-flammability of material is further increased
Energy.Because phosphoric acid hydrogen zirconium nano-lamellar structure is after organically-modified, it can be dispersed in relatively good in polyacrylate base material,
Avoid disperseing the bad influence to material mechanical performance, and used is water soluble phenol resin, with polyacrylate breast
Liquid has preferable compatibility, overcomes conventional flame retardant and substrate compatibility difference and deteriorates the shortcoming of material mechanical performance.
Compared with prior art, the present invention has advantages below：
(1) organically-modified phosphoric acid hydrogen zirconium and the Nitrogen-containing Phenolic Resins aqueous solution have preferable to water polyacrylic acid emulsion
Synergistic fire retardation, oxygen index (OI) is improved to 22.5% during single addition organic modified phosphate hydrogen zirconium (comparative example 2)；Single addition water
Oxygen index (OI) is improved to 27.0% during property Nitrogen-containing Phenolic Resins (comparative example 3).It is generally acknowledged that oxygen index (OI) is easy less than 22% in this area
Combustible material, is combustible material between 22% to 27%, is nonflammable material more than 27%.The organic modified phosphate hydrogen zirconium of single addition or
Aqueous Nitrogen-containing Phenolic Resins polyacrylate dispersion is still combustible material.However, adding 1.0wt% organically-modified phosphoric acid simultaneously
The aqueous Nitrogen-containing Phenolic Resins of hydrogen zirconium and 35.0wt%, the limited oxygen index of polyacrylate dispersion is brought up to from 22.0%
30.5%, fire retardant rank is reached, illustrates that the two has preferable synergistic fire retardation.
(2) Nitrogen-containing Phenolic Resins in phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion of the present invention
The aqueous solution is good with emulsion compatibility, thus the water polyacrylic acid emulsion prepared has good fire resistance while also having
Good mechanical property, particularly pencil hardness bring up to H from HB, in the application with more preferable wearability, illustrate that addition has
Machine modified phosphate hydrogen zirconium does not reduce the mechanical property of energy polyacrylate dispersion not only, and improves polyacrylate dispersion
Mechanical property.
(3) Nitrogen-containing Phenolic Resins in phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion of the present invention
The aqueous solution is good with emulsion compatibility, thus the water polyacrylic acid emulsion stable storing prepared.
(4) raw material are cheap and easy to get, preparation technology is simple, reaction condition is gentle, be easily achieved industrialization.
Embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is further described, but the implementation of the present invention
Mode is not limited to this.
Embodiment 1
3g phosphoric acid hydrogen zirconiums are taken to be scattered in the beaker equipped with 300g water, ultrasonic disperse 30min, then 11.92g is added thereto
TBAH (TBA, mass fraction be about 25%) aqueous solution carry out intercalation modifying.Continue ultrasonic disperse 30min, then stir
Mix after 8h, by being centrifuged at a high speed, drying, obtain organically-modified phosphoric acid hydrogen zirconium.
By 30g water, 1.42g emulsifying agent propoxyl group Nonyl pheno (10) ether ammonium sulfate (DNS-86), 7.12g 2-
Hydroxyethyl meth acrylate phosphate (learning Materials Co., Ltd in PM-1500, essence Dehua, Guangzhou), which is placed in 500ml beakers, to be mixed
Uniformly.It is slowly added thereto after being again well mixed 30g methyl methacrylates, 30g butyl acrylates and 1.32g acrylic acid,
Pre-emulsification is carried out by high speed homogeneous dispersion machine, the pre-emulsification time is 20min.The organically-modified phosphoric acid hydrogen zirconiums of 0.68g are disperseed again
In 20g water, it is added drop-wise to after ultrasonic disperse 30min in pre-emulsion, continues pre-emulsification 10min, obtain pre-emulsion.
Take 40g water, 0.72g sodium acid carbonates to be placed in 500ml four-hole boiling flasks, stir and raise temperature to 80 DEG C.By 0.57g
Potassium peroxydisulfate is dissolved in 20g water.Pre-emulsion and persulfate aqueous solution are synchronously added dropwise into four-hole boiling flask, time for adding is controlled
60min is reacted after 4.0h or so, completion of dropping.85 DEG C are warming up to again to continue to react after 60min, cold filtration, are adjusted with methylamine
Emulsion pH is saved to 9, adding the aqueous Nitrogen-containing Phenolic Resins of 80.11g, (solid content is 46%, and nitrogen content is 5.25%, and Guangzhou is too
That adhesive Co., Ltd), stir, that is, obtain phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate breast
Liquid, carries out mechanical property and limited oxygen index test.As a result it is as shown in table 1.
As can be seen that oxygen index (OI) is improved to 22.5% during single addition organic modified phosphate hydrogen zirconium (comparative example 2)；It is single to add
Oxygen index (OI) is improved to 27.0% during adding water property Nitrogen-containing Phenolic Resins (comparative example 3).It is generally acknowledged that oxygen index (OI) is less than 22% in this area
It is combustible material between 22% to 27% for combustible material, is nonflammable material more than 27%.The single organic modified phosphate hydrogen of addition
Zirconium or aqueous Nitrogen-containing Phenolic Resins polyacrylate dispersion are still combustible material.However, adding the organically-modified of 1.0wt% simultaneously
The aqueous Nitrogen-containing Phenolic Resins of phosphoric acid hydrogen zirconium and 35.0wt%, the limited oxygen index of polyacrylate dispersion is brought up to from 22.0%
30.5%, fire retardant rank is reached, illustrates that the two has preferable synergistic fire retardation.And it is worth noting that, the material is same
When maintain excellent mechanical property, particularly pencil hardness and bring up to H from HB, in the application with more preferable wearability, say
The bright organically-modified phosphoric acid hydrogen zirconium of addition does not reduce the mechanical property of energy polyacrylate dispersion not only, and improves polypropylene
The mechanical property of acid esters emulsion.
Embodiment 2
The present embodiment and the difference of embodiment 1 are that the consumption of aqueous Nitrogen-containing Phenolic Resins is reduced to 57.22g
(25wt%).Mechanical property and limited oxygen index test result are as shown in table 1.As can be seen that manufactured in the present embodiment aqueous poly-
The limited oxygen index of acrylic acid ester emulsion is 28.5%, has been declined compared with embodiment 1, but still with relatively good fire resistance,
Illustrate that the consumption of aqueous Nitrogen-containing Phenolic Resins has a certain impact to the fire resistance of material.And contrasted with comparative example 3, it can see
Go out, add a small amount of synergist, the consumption of fire retardant can be reduced, reduce cost.
Embodiment 3
The present embodiment and the difference of embodiment 1 are that the consumption of organically-modified phosphoric acid hydrogen zirconium is reduced to 0.34g
(0.5wt%).Mechanical property and limited oxygen index test result are as shown in table 1.As can be seen that aqueous prepared by the present embodiment
The limited oxygen index of polyacrylate dispersion is 29.0%, has been declined compared with embodiment 1, but still with relatively good anti-flammability
Can, illustrate that the consumption of organically-modified phosphoric acid hydrogen zirconium also has a certain impact to the fire resistance of material.
Embodiment 4
The present embodiment and the difference of embodiment 1 are to carry out intercalation modifying to phosphoric acid hydrogen zirconium with TBAH
When, the consumption of TBAH is reduced to 7.15g, and the mol ratio with phosphoric acid hydrogen zirconium is 0.6:1.0, organically-modified phosphoric acid hydrogen
The consumption of zirconium is 0.68g.Mechanical property and limited oxygen index test result are as shown in table 1.As can be seen that prepared by the present embodiment
The limited oxygen index of water polyacrylic acid emulsion be 29.5%, declined compared with embodiment 1, but still with relatively good resistance
Fire performance.Illustrate during organically-modified phosphoric acid hydrogen zirconium is prepared, reduce the consumption of intercalator, phosphoric acid hydrogen zirconium may be unfavorable for
Intercalation modifying, influence organically-modified phosphoric acid hydrogen zirconium scattered in emulsion, therefore fire resistance is affected.
Comparative example 1
By 30g water, 1.42g emulsifying agents, 7.12g HEMAs phosphate (PM-1500, Guangzhou essence moral
Chemical material Co., Ltd) it is placed in 500ml beakers and is well mixed, then by 30g methyl methacrylates, 30g butyl acrylates
It is slowly added thereto after being well mixed with 1.32g acrylic acid.By high speed homogeneous dispersion machine progress pre-emulsification, the pre-emulsification time is
30min, obtains pre-emulsion.
Take 40g water, 0.72g sodium acid carbonates to be placed in 500ml four-hole boiling flasks, stir and raise temperature to 80 DEG C.By 0.57g
Potassium peroxydisulfate is dissolved in 20g water.Pre-emulsion and persulfate aqueous solution are synchronously added dropwise into four-hole boiling flask, time for adding is controlled
60min is reacted after 4.0h or so, completion of dropping.It is warming up to 85 DEG C again to continue to react 60min, cold filtration obtains poly- third
Olefin(e) acid ester emulsion.This method using prior art (preparation of phosphoric acrylic ester emulsion and performance study, chemistry with bonding,
2012,34 (6):7-9) reactive flame retardant is prepared in method of the chemical bonds on acrylate polymeric chain aqueous poly-
Acrylic acid ester emulsion, overcomes fire retardant and the shortcoming of substrate compatibility difference, but in order to keep stability of emulsion, reaction-type flame-retarding
Agent addition is less, and fire resistance improves limited.Mechanical property and limited oxygen index test result are as shown in table 1.
Comparative example 2
3g phosphoric acid hydrogen zirconiums are taken to be scattered in the beaker equipped with 300g water, ultrasonic disperse 30min, then 11.92g is added thereto
TBAH (TBA, mass fraction be about 25%) aqueous solution carry out intercalation modifying, continue ultrasound 30min, be stirred for 8h
Afterwards, by being centrifuged at a high speed, drying, organically-modified phosphoric acid hydrogen zirconium is obtained.
30g water, 1.42g emulsifying agents, 7.12g HEMA phosphates are placed in 500ml beakers and mixed
Close uniform, then by 30g methyl methacrylates, 30g butyl acrylates and 1.32g acrylic acid it is well mixed after be slowly added to it
In.Pre-emulsification is carried out by high speed homogeneous dispersion machine, the pre-emulsification time is 20min, then the organically-modified phosphoric acid hydrogen zirconiums of 0.68g are divided
Dissipate in 20g water, be added drop-wise to after ultrasonic 30min in pre-emulsion, continue pre-emulsification 10min, obtain pre-emulsion.
Take 40g water, 0.72g sodium acid carbonates to be placed in 500ml four-hole boiling flasks, stir and raise temperature to 80 DEG C.By 0.57g
Potassium peroxydisulfate is dissolved in 20g water.Pre-emulsion and persulfate aqueous solution are synchronously added dropwise into four-hole boiling flask, time for adding is controlled
60min is reacted after 4.0h or so, completion of dropping.It is warming up to 85 DEG C again to continue to react 60min, cold filtration obtains poly- third
Olefin(e) acid ester emulsion.Mechanical property and limited oxygen index test result are as shown in table 1.
Comparative example 3
30g water, 1.42g emulsifying agents, 7.12g HEMA phosphates are placed in 500ml beakers and mixed
Close uniform, then by 30g methyl methacrylates, 30g butyl acrylates and 1.32g acrylic acid it is well mixed after be slowly added to it
In.Pre-emulsification is carried out by high speed homogeneous dispersion machine, the pre-emulsification time is 30min, obtains pre-emulsion.
Take 40g water, 0.72g sodium acid carbonates to be placed in 500ml four-hole boiling flasks, stir and raise temperature to 80 DEG C.By 0.57g
Potassium peroxydisulfate is dissolved in 20g water.Pre-emulsion and persulfate aqueous solution are synchronously added dropwise into four mouthfuls of beakers, time for adding is controlled
60min is reacted after 4.0h or so, completion of dropping.85 DEG C are warming up to again to continue to react after 60min, cold filtration, are adjusted with methylamine
Emulsion pH is saved to 9, adding the aqueous Nitrogen-containing Phenolic Resins of 80.11g, (solid content is 46%, and nitrogen content is 5.25%, and Guangzhou is too
That adhesive Co., Ltd), stir, obtain Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion.Mechanical property and
Limited oxygen index test result is as shown in table 1.
Method of testing
1. Mechanics Performance Testing：
Sample is provided according to GB/T 1727-1992, using tinplate as base material, is prepared using knife coating.
Impact strength performance provides to test according to GB/T 1732-1993；
Flexility provides to test according to GB/T 1731-1993；
Adhesive force provides to test according to GB/T 9286-1998；
Pencil hardness provides to test according to GB/T 6739-2006.
2. fire resistance is tested：
A certain amount of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion is weighed in polytetrafluoroethylene (PTFE)
Die for molding, is first dried, then dried in 75 DEG C of baking oven to constant weight at room temperature.
Provide to test according to GB/T 2406-1993, test bars size is 100mm × 6.5mm × 1.6mm.
The mechanical property and limited oxygen index of the water polyacrylic acid emulsion of table 1
As it can be seen from table 1 organically-modified phosphoric acid hydrogen zirconium of the invention and the Nitrogen-containing Phenolic Resins aqueous solution are to aqueous polyacrylamide
Acid esters emulsion has a preferable synergistic fire retardation, and oxygen index (OI) is improved during single addition organic modified phosphate hydrogen zirconium (comparative example 2)
To 22.5%；Oxygen index (OI) is improved to 27.0% during single addition aqueous Nitrogen-containing Phenolic Resins (comparative example 3).It is generally acknowledged that this area
Oxygen index (OI) is combustible material less than 22%, is combustible material between 22% to 27%, is nonflammable material more than 27%.Single addition
Organically-modified phosphoric acid hydrogen zirconium or aqueous Nitrogen-containing Phenolic Resins polyacrylate dispersion are still combustible material.The present invention simultaneously added with
Machine modified phosphate hydrogen zirconium and aqueous Nitrogen-containing Phenolic Resins, the limited oxygen index of polyacrylate dispersion are brought up to from 22.0%
More than 28.54, and reach 30.5%, fire retardant rank has been reached, has illustrated that the two has preferable synergistic fire retardation.Meanwhile,
The Nitrogen-containing Phenolic Resins aqueous solution and breast in phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion of the present invention
Liquid phase capacitive is good, thus the water polyacrylic acid emulsion prepared has good fire resistance while also having good mechanics
Performance, particularly pencil hardness bring up to H from HB, in the application with more preferable wearability, illustrate to add organically-modified phosphoric acid
Hydrogen zirconium does not reduce the mechanical property of energy polyacrylate dispersion not only, and improves the mechanical property of polyacrylate dispersion
Energy.
Claims (6)
1. the preparation method of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion, it is characterised in that including
Following steps：
(1) acrylic acid and acrylate monomer, HEMA phosphate, emulsifying agent DNS-86, water are mixed
Afterwards, high-speed stirred carries out pre-emulsification, and the pre-emulsification time is 15min~30min, then adds organically-modified phosphoric acid hydrogen zirconium thereto,
Continue pre-emulsification 10min~20min, obtain pre-emulsion；Described acrylic acid and acrylate monomer by methyl methacrylate,
Butyl acrylate and acrylic acid composition, its mass ratio is 49.0:49.0:2.0；
Described organically-modified phosphoric acid hydrogen zirconium is prepared via a method which：At room temperature, the phosphoric acid hydrogen zirconium of 1 mass parts is scattered in 80
In~120 mass parts water, ultrasonic disperse, then TBAH aqueous solution progress intercalation modifying is added thereto, continue super
Sound disperses, and is stirred for 6~8h, by being centrifuged at a high speed, drying, obtains organically-modified phosphoric acid hydrogen zirconium, the tetrabutyl hydrogen-oxygen
The mol ratio for changing ammonium and phosphoric acid hydrogen zirconium is 0.6:1.0~1.0:1.0；
(2) pH buffer sodium acid carbonate is dissolved in water, stirs and raise temperature to 75 DEG C~85 DEG C；It is synchronous thereto to be added dropwise
The initiator potassium persulfate aqueous solution and the pre-emulsion, control time for adding react 30min after 3.0h~5.0h, completion of dropping
~90min, then be warming up to after 85 DEG C~90 DEG C continuation reaction 30min~90min, cold filtration, obtain phosphoric acid hydrogen modified zirconia and gather
Acrylic acid ester emulsion；
(3) pH to 8~9 of phosphoric acid hydrogen modified zirconia polyacrylate dispersion is adjusted with methylamine, the Nitrogen-containing Phenolic Resins aqueous solution is added,
It is well mixed, that is, obtain phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion.
2. the preparation of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion according to claim 1
Method, it is characterised in that be calculated in mass percent, its raw material composition includes：
3. the preparation of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion according to claim 1
Method, it is characterised in that the mass percent that described methylamine accounts for raw material is 1.0%~5.0%.
4. the preparation of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion according to claim 1
Method, it is characterised in that the time of the ultrasonic disperse and continuation ultrasonic disperse is all 30min~60min.
5. the preparation of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion according to claim 1
Method, it is characterised in that the described Nitrogen-containing Phenolic Resins aqueous solution is the melamine modified phenolic resin aqueous solution.
6. a kind of phosphoric acid hydrogen zirconium synergistic Nitrogen-containing Phenolic Resins extinguishing waterborn polyacrylate dispersion, it is characterised in that it will by right
Preparation method described in 1 is asked to be made.
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