CN101691452B - Novel preparation method and application of multicolored ultrafine microencapsulated red phosphorus - Google Patents

Abstract

A novel preparation method for multicolored ultrafine microencapsulated red phosphorus comprises the following steps: carrying out deposition coloring on ultrafine red phosphorus by using organic pigment or organic dye dissolved in organic solvent, carrying out microencapsulated coating treatment by adopting urea resin aqueous solution, melamine resin aqueous solution or phenolic resin aqueous solution to prepare the multicolored microencapsulated ultrafine red phosphorus with the same color as that of the organic pigment or the organic dye. The multicolored microencapsulated ultrafine red phosphorus has the characteristics of high phosphorus content, high thermal stability, high chemical stability, high ignition point and low moisture absorption, and can be used as red phosphorus flame retardant; meanwhile, the ultrafine red phosphorus can also be used as organic dye with pure chroma, and has high color fastness, high resistance transference and low toxicity; when the ultrafine red phosphorus is used together with other dye or pigment for color matching, chemical reaction does not occur between the ultrafine red phosphorus and other dye or pigment, and hue stability of color matching is high; and the ultrafine red phosphorus has excellent compatibility with composite materials and has a wide application range.

Description

Multicolored ultrafine microencapsulated red phosphorus preparation method and application

Technical field

The present invention relates to a kind of synthetic material auxiliary agent, particularly colorful microcapsule red phosphorus and preparation method thereof and application.Colorful microcapsule red phosphorus provided by the invention can directly carry out painted and fire-retardant finish as pigment dyestuff and fire retardant to synthetic materials.

Technical background

Red phosphorus is historical as a kind of use in existing more than 30 year of fire retardant kind of environmental protection.But red phosphorus self has many-sided shortcoming: 1. being prone to the moisture absorption oxidation conversion is the phosphuret-(t)ed hydrogen of phosphorous acid and severe toxicity; 2. the thermostability of red phosphorus self is poor, when in air, heating 240 ℃, dieseling can take place; 3. in order to improve the dispersity of red phosphorus in synthetic materials, red phosphorus is wanted ultrafining treatment, and ultra-fine red phosphorus very easily causes dust explosion risk; 4. the dark violet redness of red phosphorus self seriously causes the aberration of synthetic materials goods.In order to overcome the above problems, it is necessary that red phosphorus is carried out the deep processing processing.

One of deep processing treatment technology of red phosphorus is a super-refinement: red phosphorus is dispersed in water or the ethanol medium; In the presence of dispersion agents such as sodium alkyl benzene sulfonate, colloidal aluminium hydroxide, sodium metnylene bis-naphthalene sulfonate, Z 150PH; Use colloidal mill, ball mill and ultrasonication; The red phosphorus particle diameter can reach 0.05～30 μ m, is equivalent to the dispersion particle diameter of pigment dyestuff in synthetic materials.

Two of the deep processing treatment technology of red phosphorus is that microcapsule coat; Reach the purpose of albefaction or stabilization treatment; For example polymkeric substance such as oxyhydroxide, oxide compound, carbonate or the phosphoric acid salt of US4210630, US4440880, US4853288, US5093199, US5043218, US5292494, US5351596, US6646625, US6765047, US6846854, US7005475, CN1995112A, CN1940014A, CN1632057A, CN101381605A, CN101343542A, CN1995112A or the like use inorganics such as magnesium, aluminium, zinc, tin, nickel, copper, titanium, silicon and urea-formaldehyde resin, melamine resin, resol, urethane, epoxy resin carry out single or multiple lift microcapsule coating processing to super-refinement red phosphorus; Reach the effect of removing the red phosphorus true qualities and obtaining the red phosphorus albefaction; Physical properties, chemical property, the mechanical property and thermally-stabilised of red phosphorus have obviously been improved; Its point of ignition is brought up to more than 350 ℃ from 240 ℃; Water-absorbent and phosphuret-(t)ed hydrogen burst size reduce significantly; Significantly improve with the synthetic materials consistency; Be widely used in thermoplastic's resins such as polyester, polycarbonate, polymeric amide, polyolefine, also can be used for the fire-retardant of thermosetting resins such as epoxy resin, resol, unsaturated polyester resin and cis-1,4-polybutadiene rubber, ethylene-propylene rubber(EPR), scrim.Yet the microencapsulated red phosphorus flame retardant that appears on the market so far still exists dark violet red heavy, perhaps because excessive microcapsule coat the low defective of prepared albefaction red phosphorus content.2009; Application number is that CN2009101408445 has proposed to contain in the molecular structure pigementation that carboxyl or sulfonic water-soluble organic pigment sodium salt, sylvite or ammonium salt and calcium chloride, strontium chloride, Manganous chloride tetrahydrate or bariumchloride reaction generate; The pigementation deposition ultra-fine red phosphorus particle surface that is generated; Use urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution or phenolic resin aqueous solution to carry out microcapsule and coat processing; Process the appearance colour colorize microcapsule red phosphorus identical, realized the effect of red phosphorus combustion inhibitor super-refinement, colorize and stabilization with said color lake color.Yet contain carboxyl or sulfonic water-soluble organic pigment limited amount in the molecular structure that CN2009101408445 proposed; Color lake kind color is not abundant; The industrial application selectable range is little, so have the single problem of color by the red phosphorus combustion inhibitor of color lake colorize.

Summary of the invention

The present invention proposes a kind of novel method for preparing the multicolored ultrafine microencapsulated red phosphorus fire retardant, and defective that purpose is to exist to microencapsulated red phosphorus flame retardant product in the technical background and problem are improved and innovated.

One of skill in the art knows contains carboxyl or sulfonic water-soluble organic pigment limited amount in the molecular structure, and can generate the stable color lake quantity of form and aspect especially less and few with reaction such as calcium chloride, strontium chloride, Manganous chloride tetrahydrate or bariumchloride.And can the dissolved organic pigment in organic solvent and pigment dyestuff quantity kind huge, the industrial application selectable range is very extensive; The color lake deposition that CN2009101408445 proposes is carried out the colorize treatment process to red phosphorus, is that after chemical reaction realizes, must produce colorful wastewater and need decolour and handle or WWT.

Therefore; The inventor select for use in organic solvent can the dissolved organic pigment or pigment dyestuff deposit painted to super-refinement red phosphorus; Then use urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution or phenolic resin aqueous solution to carry out microcapsule and coat processing, process the colored red phosphorus of the appearance colour microcapsule identical with said organic pigment or pigment dyestuff color; Wherein said organic pigment or pigment dyestuff quantity kind are huge; Simultaneously according to the painted needs of synthetic materials; According to the three primary colors color theory; Mix and use two or more organic pigment or pigment dyestuff, can realize the rich color and the tone variation of ultrafine microencapsulated red phosphorus flame retardant product.

Organic solvent of the present invention is characterized in that being selected from one or more mixed solvents in normal hexane, sherwood oil, hexanaphthene, methylcyclohexane, naphthane, perhydronaphthalene, benzene,toluene,xylene, chlorobenzene, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, chloroform, tetracol phenixin, ethylene dichloride, methyl acetate, ETHYLE ACETATE, propyl acetate, butylacetate, ether, dipropyl ether or the dibutyl ether.The mass ratio 5～30: 100 of wherein said organic solvent and organic pigment or pigment dyestuff.

Organic pigment of the present invention or pigment dyestuff refer to:

C.I. Disperse Red 4 (C.I.60755, CAS:2379-90-0),

C.I. dispersion red 11 (C.I.62015, CAS:2872-48-2),

C.I. Red-1 200 5 (C.I.60710, CAS:116-85-8),

C.I. Disperse Red 53 (C.I.60759, CAS:59787-78-9),

C.I. Red-60 200 (C.I.60756, CAS:12223-37-9),

C.I. disperse red 86 (C.I.62175, CAS:12223-43-7),

C.I. Disperse Red 92 (C.I.60752, CAS:12236-11-2),

C.I. Red-1 200 52 (C.I.111905, CAS:78564-86-0),

C.I. Red-1 200 53 (C.I.111370, CAS:78564-87-1),

C.I. Disperse Red 277 (C.I.505720, CAS:70294-19-8)

C.I. disperse Red 35 6 (C.I.571050, CAS:152165-67-8),

C.I. 63 ,DIS,PER,SE ,Vio,let, 63 1 (C.I.61100, CAS:128-95-0),

C.I. 63 ,DIS,PER,SE ,Vio,let, 63 17 (C.I.60712, CAS:12217-92-4),

C.I. 63 ,DIS,PER,SE ,Vio,let, 63 23 (C.I.60724, CAS:12217-94-6),

C.I. 63 ,DIS,PER,SE ,Vio,let, 63 26 (C.I.62025, CAS:12217-95-7),

C.I. 63 ,DIS,PER,SE ,Vio,let, 63 28 (C.I.61102, CAS:81-42-5),

C.I. EX-SF DISPERSE BLUE EX-SF 300 3 (C.I.61505, CAS:2475-46-9),

C.I. EX-SF DISPERSE BLUE EX-SF 300 14 (C.I.61500, CAS:2475-44-7),

C.I. Disperse Blue-56 (C.I.63285, CAS:12217-79-6),

C.I. Disperse Blue-60 (C.I.61104, CAS:12217-80-0),

C.I. EX-SF DISPERSE BLUE EX-SF 300 72 (C.I.60725, CAS:12217-81-1),

C.I. EX-SF DISPERSE BLUE EX-SF 300 73 (C.I.63265, CAS:12222-78-5),

C.I. EX-SF DISPERSE BLUE EX-SF 300 77 (C.I.60766, CAS:20241-76-3),

C.I. EX-SF DISPERSE BLUE EX-SF 300 87 (C.I.668305, CAS:12222-85-4),

C.I. Disperse Green 9 (C.I.110795, CAS:71627-50-9),

C.I. disperse black 1 (C.I.11365, CAS:6054-48-4),

C.I. disperse black 9 (C.I.11301, CAS:12222-69-4),

C.I. solvent red 23 (C.I.26100, CAS:85-86-9),

C.I. solvent red 24 (C.I.26106, CAS:85-83-6),

C.I. solvent red 25 (C.I.26110, CAS:3176-79-2),

C.I. solvent red 26 (C.I.26120, CAS:4477-79-6),

C.I. solvent red 30 (C.I.27291, CAS:6226-87-5),

C.I. solvent red 52 (C.I.68210, CAS:81-39-0),

C.I. solvent red 111 (C.I.60505, CAS:82-38-2),

C.I. solvent of red 135 (C.I.564120, CAS:71902-17-5),

C.I. solvent red 146 (C.I.60756, CAS:70956-30-8),

C.I. solvent red 149 (C.I.674700, CAS:71902-18-6),

C.I. solvent red 168 (C.I.60510, CAS:71832-19-4),

C.I. solvent red 169 (C.I.605060, CAS:27354-18-3),

C.I. solvent red 172 (C.I.607280, CAS:63512-13-0),

C.I. solvent red 179 (C.I.564150, CAS:89106-94-5),

C.I. solvent red 196 (C.I.505700, CAS:52372-36-8),

C.I. solvent red 197 (C.I.505720, CAS:52372-39-1),

C.I. solvent red 207 (C.I.617001, CAS:15958-69-6),

C.I. solvent red 24 2 (C.I.73300, CAS:522-75-8),

C.I. solvent purple 8 (C.I.42535, CAS:52080-58-7),

C.I. solvent purple 31 (C.I.61102, CAS:70956-27-3),

C.I. solvent violet 38 (C.I.615665, CAS:63512-14-1),

C.I. solvent violet 59 (C.I.62025, CAS:6408-72-6),

C.I. solvent blue 4 (C.I.44045, CAS:6786-83-0),

C.I. solvent blue 5 (C.I.42595, CAS:1325-86-6),

C.I. solvent blue 6 (C.I.44040, CAS:6786-84-1),

C.I. solvent blue 19 22 (C.I.60744, CAS:67905-17-3)

C.I. solvent black 3 (C.I.26150, CAS:4197-25-5),

C.I. 3b vat red 3b 10 (C.I.67000, CAS:2379-79-5),

C.I. 3b vat red 3b 13 (C.I.70320, CAS:4203-77-4),

C.I. 3b vat red 3b 14 (C.I.71110, CAS:8005-56-9),

C.I. 3b vat red 3b 15 (C.I.71100, CAS:4216-02-8),

C.I. 3b vat red 3b 23 (C.I.71130, CAS:5521-31-3),

C.I. Vat Red 29 (C.I.71140, CAS:6424-77-7),

C.I. Vat Red 31 (C.I.600300, CAS:12227-47-3),

C.I. 3b vat red 3b 32 (C.I.71135, CAS:2379-77-3),

C.I. 3b vat red 3b 41 (C.I.73300, CAS:522-75-8),

C.I. Vat Violet 1 (C.I.60010, CAS:1324-55-6),

C.I. reduction purple 9 (C.I.60005, CAS:1324-17-0),

C.I. vat blue 1 (C.I.60010, CAS:1324-55-6),

C.I. Vat blue 4 (C.I.69800, CAS:81-77-6),

C.I. vat blue 5 (C.I.73065, CAS:2475-31-2),

C.I. reductive blue 6 (C.I.69825, CAS:130-20-1),

C.I. vat blue 14 (C.I.69810, CAS:1324-27-2),

C.I. vat blue 20 (C.I.59800, CAS:116-71-2),

C.I. reductive blue 64 (C.I.66730, CAS:15935-52-1),

C.I. B150reactive Black B 150 8 (C.I.71000, CAS:2278-50-4),

C.I. Vat Black 25 (C.I.69525, CAS:4395-53-3),

C.I. vat blue 27 (C.I.69005, CAS:2379-81-9),

C.I. vat blue 27 (C.I.65225, CAS:6049-19-0),

The gold-tinted red (C.I.12310, CAS:6041-94-7),

Solid forever pink FB (C.I.12490, CAS:6410-41-9),

Permanent bordeaux F4RH (C.I.12420, CAS:6471-51-8),

Permanent bordeaux FRLL (C.I.12460, CAS:6471-51-8),

Permanent bordeaux FRL (C.I.12440, CAS:6410-35-1),

Solid forever purplish red FRR (C.I.12385, CAS:6410-32-8),

Pigment red FR (C.I.12300, CAS:6410-26-0)

Rubber pigment carbuncle BF (C.I.12320, CAS:6410-29-3),

Pigment red 38 (C.I.21120, CAS:6538-87-8),

The oil purple (C.I.12170, CAS:2653-64-7),

Pigment Red 112 (C.I.12370, CAS:6535-46-2),

Pigment red 170 (C.I.12475, CAS:2786-76-7),

Permanent bordeaux HST (C.I.12513, CAS:6471-51-8),

Pigment red 176 (C.I.12515, CAS:12225-06-8),

Dianthraquinone red (C.I.65300, CAS:4051-63-2),

Pigment red 254 (C.I.56110, CAS:84632-65-5),

Pigment red 255 (C.I.12515, CAS:120500-90-5),

Pigment red 122 (C.I.73915, CAS:980-26-7),

Permanent violet RL (C.I.51319; CAS:6358-30-1) or Pigment red 185 (C.I.73915; CAS:51920-12-8) (the above organic pigment or pigment dyestuff title and call number are taken from " dyestuff " that Yang Xin Wei, Luo Yuyan, Xiao Gang, He Yanbin write, Beijing: Chemical Industry Press, 2005 respectively to one or more mixtures in; The 4th edition, ISBN 7-5025-5971-X/TQ2046; And Han Changri, the little flat sennit of Song " pigment manufacturing and the colorant utilisation technology " write, Beijing: science tech publishing house, calendar year 2001, first version, ISBN 7-5023-3713-X/TQ48).Wherein said organic pigment or pigment dyestuff consumption are 0.5～30% of red phosphorus quality.

Urea-formaldehyde resin aqueous solution of the present invention, the melamine resin aqueous solution or phenolic resin aqueous solution refer to solid content and are controlled at 30～60% commercial goods; Or being the urea-formaldehyde resin aqueous solution of synthetic urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution, phenolic resin aqueous solution or the modification of producing of raw material, the melamine resin aqueous solution and the resin modified phenol resin aqueous solution of modification by urea, trimeric cyanamide, phenol, cresols, formaldehyde and properties-correcting agent etc., its solid content is controlled at 30～50%.The urea-formaldehyde resin aqueous solution of wherein said urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution, phenolic resin aqueous solution or modification, the melamine resin aqueous solution of modification and resin modified phenol resin amount of aqueous solution used are 5～80% of red phosphorus quality.

The present invention proposes to select for use the urea-formaldehyde resin aqueous solution of urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution, phenolic resin aqueous solution or modification, the melamine resin aqueous solution and the resin modified phenol resin aqueous solution of modification that organic pigment or the sedimentary multicolored ultrafine red phosphorus of pigment dyestuff are carried out microcapsule coating processing; Concrete effect is that described resin aqueous solution solidifies the thermosetting resin generation tint retention that the back is generated; Can effectively stop organic pigment or the migration of pigment dyestuff in high temperature plasticizing or sweet refining process of multicolored ultrafine microencapsulated red phosphorus and synthetic materialss such as PS, polyester, polycarbonate, polymeric amide, polyolefine, epoxy resin or rubber, the painted form and aspect of protection synthetic materials goods.Physical properties, chemical property, the mechanical property and thermally-stabilised of red phosphorus have also been improved simultaneously.

Multicolored ultrafine microencapsulated red phosphorus provided by the invention has following characteristic:

1. multicolored ultrafine microencapsulated red phosphorus size distribution of the present invention is between 0.05～30 μ m.

2. multicolored ultrafine microencapsulated red phosphorus of the present invention has the function of pigment dyestuff, can be directly carry out paintedly to synthetic materials as pigment dyestuff, or uses with other colorant color matching.

3. multicolored ultrafine microencapsulated red phosphorus of the present invention has the high characteristic of phosphorus content, and is few as the addition of fire retardant, and flame retardant effect is high.

4. multicolored ultrafine microencapsulated red phosphorus thermostability of the present invention is high, chemicalstability is high, point of ignition is high, water absorbability is low.

5. the colourity of multicolored ultrafine microencapsulated red phosphorus of the present invention is pure, colour fastness is high, resistance to migration is high, toxicity is low, during with other dyestuff or pigment color matching, chemical reaction does not take place each other, and color matching form and aspect stability is high.

6. do not produce three wastes materials such as waste water, waste residue, waste gas in the preparation process of multicolored ultrafine microencapsulated red phosphorus of the present invention, belong to eco-friendly technology of preparing.

The compatibility performance of multicolored ultrafine microencapsulated red phosphorus 7. of the present invention and synthetic materials is good, and applied range is applicable to the plasticizing honey refining machine-shaping process of synthetic materials between 25～300 ℃.

The preparation method of multicolored ultrafine microencapsulated red phosphorus of the present invention, concrete steps are following:

The preparation process of the colorful emulsion of step 1

At ambient temperature, take by weighing organic pigment or pigment dyestuff and be dissolved in the organic solvent, be mixed with organic solution.Organic solution is sent in the water that contains tensio-active agent continuously; Use the emulsor stirring and emulsifying; Prepare colorful emulsion, wherein said organic pigment or pigment dyestuff: organic solvent: water: the mass ratio of tensio-active agent is 5～30: 30～100: 100: 0.05～5.

Organic solvent of the present invention comprises: one or more mixed solvents of normal hexane, sherwood oil, hexanaphthene, methylcyclohexane, naphthane, perhydronaphthalene, benzene,toluene,xylene, chlorobenzene, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, chloroform, tetracol phenixin, ethylene dichloride, methyl acetate, ETHYLE ACETATE, propyl acetate, butylacetate, ether, dipropyl ether or dibutyl ether.

Tensio-active agent of the present invention comprises alkylphenol polyoxyethylene ether; The polyoxyethylene laurate; Polyoxyethylene dehydration sorbic ester; The polyoxyethylene stearate, alkylol amide, Witco 1298 Soft Acid, α-olefin sulfonic acid, dodecyl sodium sulfonate, alkyl alcohol polyoxyethylene sulfonic acid, alkylphenol polyoxyethylene sulfonic acid and stearic sodium salt, sylvite or ammonium salt; Palmityl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, OTAC, positively charged ion silicone oil dimethyl dodecyl amine oxide, one or more mixtures in Varion CDG-K or the carboxylic acid type tetrahydroglyoxaline.

The preparation process of step 2 multicolored ultrafine red phosphorus aqueous dispersion

Median size is in the ultra-fine red phosphorus aqueous dispersion of 0.05～30 μ m; Add the prepared colorful emulsion of step 1, after stirring, 10～150 ℃ of temperature controls; Described organic solvent is reclaimed in distillation; Described organic solvent reclaims and finishes, and make the multicolored ultrafine red phosphorus aqueous dispersion of surperficial uniform deposition organic pigment or pigment dyestuff, wherein said colorful emulsion: red phosphorus: the mass ratio of water is 30～300: 100: 200～500.

The preparation process of step 3 multicolored ultrafine microencapsulated red phosphorus

In the multicolored ultrafine red phosphorus aqueous dispersion that step 2 makes; The solid content that input is equivalent to red phosphorus quality 5～80% is the urea-formaldehyde resin aqueous solution of 30～60% urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution, phenolic resin aqueous solution or modification, the melamine resin aqueous solution or the resin modified phenol resin aqueous solution of modification, and temperature control stirs after 30 minutes for 20～40 ℃, adds solidifying agent such as ammonium chloride, formic acid, acetate or phosphoric acid; And improve 60～80 ℃ of temperature of charge; Stirring reaction solidified 2～8 hours, and standing demix leaches throw out; Wash the bottom throw out 2～3 times with clear water; Throw out is sent into moisture eliminator, and 60～120 ℃ of dryings 3～10 hours make multicolored ultrafine microencapsulated red phosphorus.

Following embodiment further specifies the preparation method and the purposes of multicolored ultrafine microencapsulated red phosphorus provided by the invention; But the embodiment that the present invention enumerates only is the description that the implementation method of optimization of the present invention is carried out; Any distortion and improvement that falls in the plan scope of the present invention, all asking for protection among the interest field in claims record of the present invention.

Embodiment 1

Step 1: take by weighing the C.I. Red-60 200 (C.I.60756, CAS:12223-37-9) 5.8 kilograms with C.I. solvent red 197 (C.I.505720, CAS:52372-39-1) 1.2 kilograms, be dissolved under the room temperature in 35 kilograms of toluene, preparation becomes red toluene solution.Described red toluene solution is sent into the emulsor that 0.1 kilogram of dodecyl benzyl dimethyl ammonium chloride and 0.3 kilogram of dodecanol polyoxyethylene sodium sulfonate and 100 kg of water are housed continuously, and stirring and emulsifying made red emulsion in 1 hour.

Step 2: the red emulsion that step 1 is made slowly flows in the super-refinement red phosphorus aqueous dispersion that median size is 0.05～30 μ m; Stirring at room 30 minutes evenly after; Heat up 85～105 ℃, toluene is reclaimed in distillation, makes vivid red ultra-fine red phosphorus aqueous dispersion.

Step 3: in the vivid red ultra-fine red phosphorus aqueous dispersion that step 2 makes; Dropping into solid content is 40 kilograms of the 48% melamine resin aqueous solution; Stir after 60 minutes; Adding mass percent is 30% acetic acid aqueous solution adjustment pH value=4.5～6.0, improves 60～80 ℃ of temperature of charge, and stirring reaction solidified 1 hour.Leave standstill deposition, divide and remove supernatant water solution, bottom throw out clear water washing 2 times.Leach throw out, send into moisture eliminator, 120 ℃ of dryings 3 hours make 126.8 kilograms of bright red ultrafine microencapsulated red phosphorus flame retardants.

Embodiment 2

According to method and the step among the embodiment 1; With the C.I. Red-60 200 among the embodiment 1 (C.I.607-56, CAS:12223-37-9) 5.8 kilograms with C.I. solvent red 197 (C.I.505720, CAS:52372-39-1) 1.2 kilograms of changes are C.I. EX-SF DISPERSE BLUE EX-SF 300 72 (C.I.60725; CAS:12217-81-1) 5.5 kilograms and C.I. solvent blue 6 (C.I.44040; CAS:6786-84-1) 2.5 kilograms, make the mazarine ultrafine microencapsulated red phosphorus flame retardant, each item performance analysis and detected result are seen table 1.

Embodiment 3

According to method and the step among the embodiment 1; With the C.I. solvent red 197 (C.I.505720 among the embodiment 1; CAS:52372-39-1) 1.2 kilograms of changes are C.I. solvent red 197 (C.I.505720, CAS:52372-39-1) 1.2 kilograms and C.I. solvent blue 6 (C.I.44040, CAS:6786-84-1) 1.8 kilograms; Make light violet red ultrafine microencapsulated red phosphorus flame retardant, each item performance analysis and detected result are seen table 1.

Embodiment 4

According to method and the step among the embodiment 1; With the C.I. Red-60 200 (C.I.607-56 among the embodiment 1; CAS:12223-37-9) 5.8 kilograms with C.I. solvent red 197 (C.I.505720, CAS:52372-39-1) 1.2 kilograms of changes are C.I. 3b vat red 3b 41 (C.I.73300, CAS:522-75-8) 7.2 kilograms; Make the shiny red ultrafine microencapsulated red phosphorus flame retardant, each item performance analysis and detected result are seen table 1.

Embodiment 5

According to method and the step among the embodiment 1; With the C.I. Red-60 200 (C.I.607-56 among the embodiment 1; CAS:12223-37-9) 5.8 kilograms with C.I. solvent red 197 (C.I.505720, CAS:52372-39-1) 1.2 kilograms of changes are C.I. vat blue 5 (C.I.73065, CAS:2475-31-2) 8 kilograms; Make the mazarine ultrafine microencapsulated red phosphorus flame retardant, each item performance analysis and detected result are seen table 1.

Embodiment 6

According to method and the step among the embodiment 1, with step 3 schedule of operation change among the embodiment 1 be: in the vivid red ultra-fine red phosphorus aqueous dispersion that step 3 makes, drop into 13 kilograms of trimeric cyanamides; Mass percent is 35 kilograms of 37% formalins; Functional quality percentage ratio is 30% caustic-soda aqueous solution adjustment material pH value=8.5, heats up 60～80 ℃, stirs after 60 minutes; Add 30% acetic acid aqueous solution adjustment pH value=4.5～6.0, stirring reaction solidified 2 hours.Leave standstill deposition, divide and remove supernatant water solution, bottom throw out clear water washing 2 times.Leach throw out, send into moisture eliminator, 120 ℃ of dryings 3 hours make the bright red ultrafine microencapsulated red phosphorus flame retardant, and each item performance analysis and detected result are seen table 1.

Embodiment 7

According to method and the step among the embodiment 1; Step 3 schedule of operation among the embodiment 1 changed be: in reactor drum, add 4 kilograms in urea, 10 kilograms of phenol, mass percent and be 12 kilograms in 37% 15 kilograms of formalins and water, stir; Regulate pH=8.0 with urotropine; Heat up 80～85 ℃, stir after 2 hours, make urea-modified phenolic resin aqueous solution.The prepared urea modified phenolic resin aqueous solution is sneaked in the vivid red ultra-fine red phosphorus aqueous dispersion that embodiment 1 step 3 makes, with phosphoric acid adjustment pH value=2.0～4.0, stirring reaction curing 4 hours.Leave standstill deposition, divide and remove supernatant water solution, bottom throw out clear water washing 2 times.Leach throw out, send into moisture eliminator, 120 ℃ of dryings 3 hours make the bright red ultrafine microencapsulated red phosphorus flame retardant, and each item performance analysis and detected result are seen table 1.

Embodiment 8

Get 10 kilograms of bright red ultra-fine red phosphorus fire retardants, 100 kilograms of nylon-6s and 0.2 kilogram of oxidation inhibitor that embodiment 1 makes and send into pre-mixing in the plasticizing machine; Then send in the extruding machine 210～260 ℃ and melt extrude granulation; Make test piece and present redness, each item performance analysis and detected result are seen table 1.

Embodiment 9

Get 10 kilograms of light violet red ultrafine microencapsulated red phosphorus flame retardants, 100 kilograms of polyethylene terephthalates, 5 kilograms of triphenylphosphates and 0.2 kilogram of oxidation inhibitor that embodiment 3 makes and send into 260～280 ℃ of melt blendings in the plasticizing machine; The blend mold pressing is made test piece and is presented red-purple, and each item performance analysis and detected result are seen table 1.

Embodiment 10

Getting 10 kilograms of mazarine ultrafine microencapsulated red phosphorus flame retardants, 100 kilograms of epoxy resin E-44s, 10 kilograms in solidifying agent, triphenylphosphates that embodiment 5 makes stirs for 10 kilograms; Blend is brushed the making test piece and is presented blueness, and each item performance analysis and detected result are seen table 1.

Each item performance analysis among embodiment 1～embodiment 10 according to the invention is carried out according to following method with detecting respectively:

Particle size analysis: get multicolored ultrafine microencapsulated red phosphorus 2 grams, put into 500 milliliters of Erlenmeyer flasks, add 200 milliliters of zero(ppm) water, in KQ-118 type ultrasonic cleaner, disperse, BT-1500 particle size analyzer test particle diameter is adopted in the back, and analytical results is seen table 1.

Analysis of phosphorus contents: adopt the GB4947-2003 method to measure the phosphorus content of multicolored ultrafine microencapsulated red phosphorus, analytical results is seen table 1.

The water absorbability test: get 2.000 gram multicolored ultrafine microencapsulated red phosphorus and evenly put into petridish, insert the moisture eliminator upper strata that saturated aqueous sodium sulfate is housed, weightening finish is measured in airtight preservation 10 days, and with weightening finish percentage number scale water absorbability, analytical results is seen table 1.

The point of ignition test: adopt TGS-2 type thermogravimetric analyzer, measure the multicolored ultrafine microencapsulated red phosphorus kindling temperature, test result is seen table 1.

The color heat stability test: adopt HG/T3853-2006 pigment dry powder thermotolerance assay method, test multicolored ultrafine microencapsulated red phosphorus discoloring temperature, the result sees table 1.

The test of synthetic materials test piece flame retardant properties: adopt GB/T2406-1993 plastics combustionproperty assay method, the synthetic materials limiting oxygen index(LOI) (LOI) of multicolored ultrafine microencapsulated red phosphorus is added in test, and the result sees table 1.

Each item performance analysis of table 1 multicolored ultrafine microencapsulated red phosphorus fire retardant and detected result

?	Phosphorus content %	Median size μ m	Water absorbability %	Point of ignition ℃	Discoloring temperature ℃	Limiting oxygen index(LOI) LOI
							Embodiment 1	78.74	9	0.43	335	300	?
Embodiment 2	76.98	37	0.66	330	300	?
							Embodiment 3	76.43	4	0.57	335	300	?
Embodiment 4	78.56	9	0.28	340	300	?
							Embodiment 5	78.66	21	0.47	330	300	?
Embodiment 6	81.15	13	0.21	335	300	?
							Embodiment 7	80.96	14	0.27	340	310	?
Embodiment 8	7.12	?	?	?	?	28
							Embodiment 9	7.13	?	?	?	?	29
Embodiment 10	6.27	?	?	?	?	34

Claims (3)

1. the preparation method of a multicolored ultrafine microencapsulated red phosphorus is characterized in that comprising the steps:

The preparation process of the colorful emulsion of step 1

At ambient temperature; Taking by weighing organic pigment or pigment dyestuff is dissolved in the organic solvent; Be mixed with organic solution, described organic solution sent into continuously in the water that contains tensio-active agent, use the emulsor stirring and emulsifying; Make colorful emulsion, wherein said organic pigment or pigment dyestuff: organic solvent: water: the mass ratio of tensio-active agent is 5～30: 30～100: 100: 0.05～5;

Step 2 multicolored ultrafine red phosphorus aqueous dispersion prepares process

In median size is to add the prepared colorful emulsion of step 1 in the ultra-fine red phosphorus aqueous dispersion of 0.05～30 μ m; After stirring; 10～150 ℃ of temperature controls, described organic solvent is reclaimed in distillation, and described organic solvent reclaims and finishes; Make the multicolored ultrafine red phosphorus aqueous dispersion of surperficial uniform deposition organic pigment or pigment dyestuff, wherein said colorful emulsion: red phosphorus: the mass ratio of water is 30～300: 100: 200～500;

Step 3 multicolored ultrafine microencapsulated red phosphorus prepares process

In the multicolored ultrafine red phosphorus aqueous dispersion that step 2 makes; The solid content that input is equivalent to red phosphorus quality 5～80% is the urea-formaldehyde resin aqueous solution of 30～60% urea-formaldehyde resin aqueous solution, the melamine resin aqueous solution, phenolic resin aqueous solution or modification, the melamine resin aqueous solution or the resin modified phenol resin aqueous solution of modification, and temperature control stirs after 30 minutes for 20～40 ℃, adds ammonium chloride, formic acid, acetate or phosphoric acid solidifying agent; And improve 60～80 ℃ of temperature of charge; Stirring reaction solidified 2～8 hours, and standing demix leaches throw out; Wash the bottom throw out 2～3 times with clear water; Throw out is sent into moisture eliminator, and 60～120 ℃ of dryings 3～10 hours make multicolored ultrafine microencapsulated red phosphorus.

2. according to the preparation method of the described multicolored ultrafine microencapsulated red phosphorus of claim 1, it is characterized in that described organic solvent is selected from one or more mixed solvents in normal hexane, sherwood oil, hexanaphthene, methylcyclohexane, naphthane, perhydronaphthalene, benzene,toluene,xylene, chlorobenzene, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, chloroform, tetracol phenixin, ethylene dichloride, methyl acetate, ETHYLE ACETATE, propyl acetate, butylacetate, ether, dipropyl ether or the dibutyl ether.

3. the preparation method who accordings to the described multicolored ultrafine microencapsulated red phosphorus of claim 1; It is characterized in that described tensio-active agent is selected from alkylphenol polyoxyethylene ether, polyoxyethylene laurate, polyoxyethylene stearate; Alkylol amide; Witco 1298 Soft Acid, α-olefin sulfonic acid, dodecyl sodium sulfonate, alkyl alcohol polyoxyethylene sulfonic acid, alkylphenol polyoxyethylene sulfonic acid and stearic sodium salt, sylvite or ammonium salt, palmityl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride; OTAC, one or more mixtures in Varion CDG-K or the carboxylic acid type tetrahydroglyoxaline.