CN101045779A - Preparation method of melamine resin double coated Deca-BDE - Google Patents
Preparation method of melamine resin double coated Deca-BDE Download PDFInfo
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- CN101045779A CN101045779A CN 200710048900 CN200710048900A CN101045779A CN 101045779 A CN101045779 A CN 101045779A CN 200710048900 CN200710048900 CN 200710048900 CN 200710048900 A CN200710048900 A CN 200710048900A CN 101045779 A CN101045779 A CN 101045779A
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- formaldehyde resin
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- decabromodiphenyl oxide
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Abstract
This invention relates to a preparation method of melamine formaldehyde resin double deck coating decabromodiphenyl oxide. It takes 20 to 100 shares decabromodiphenyl oxide, dispersant 1 to 20 shares, water 100 to 1000 shares or melamine 5 to 20 shares, 37 percent formalin 10 to 60 shares, water 50 to 150 shares as materials; mix these materials and whip at PH 7 to PH 9 to prepare dispersal liquid or melamine formaldehyde resin prepolymer, then break prepolymer into two shares, add one share to dispersal liquid for blending, then adjust PH value to 3 to 5, whip for 1 to 4 hour for reaction; Then add another share of prepolymer, carry out reaction for 1 to 4 hours, gain white emulsion; finally separate emulsion, dry to gain white mealiness product. This product has good compactness, high initial decomposition temperature, high tensile and compressive strength, good water-proof, can used as additive flame-retardant of polymer that has very high processing temperature, enlarge the field of application of decabromodiphenyl oxide.
Description
Technical field
The invention belongs to the fire retardant preparing technical field, be specifically related to a kind of preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide.
Background technology
Decabromodiphenyl oxide is a white powder, and water insoluble and common organic solvents is a kind of addition type efficient flame-retarding agent.Because its brominated amount height, addition is few, thereby is widely used as polyethylene, polypropylene, ABS resin, polyphenylene oxide, polycarbonate, urethane, polyvinyl chloride, Resins, epoxy, PBT, PET, the fire retardant of macromolecular material such as silicon rubber and terpolymer EP rubber, and rubber conveyor belt, refining of petroleum, the flame-retardant additive of industrial rubber articles.The fire retardant mechanism of decabromodiphenyl oxide is based on gas phase " radical is caught " theory, and promptly decabromodiphenyl oxide can decompose generation HBr under the high temperature of material combustion, and HBr can catch radicals such as OH and O and react with it, thereby reaches the purpose of flame-retarding fire-extinguishing.Simultaneously, non-flammable gases such as the hydrogen halide of generation also can play diluting effect, reduce the concentration of inflammable gas, act synergistically thereby flame-retarding fire-extinguishing brought into play.
But for applying to space flight and aviation, the polymkeric substance that processing temperature in the fields such as electronics is high, in the time of need making fire-retardant finish as polyimide etc., because the decomposition temperature (345 ℃) of traditional bromide fire retardant is lower than the processing temperature of these materials, thereby can be in the course of processing as polyimide materials such as (processing temperature are 380～390 ℃), because of not bearing high processing temperature decomposition failure, do not have due fire retardation, thereby hindered bromide fire retardant such as the application of decabromodiphenyl oxide in these materials.
Summary of the invention
The objective of the invention is to expand the fire-retardant application of decabromodiphenyl oxide in the high polymkeric substance of processing temperature, a kind of preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide is provided in order to overcome the problem that prior art exists.
The preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide provided by the invention, the step of this method and processing condition are:
(1) 20～100 parts of decabromodiphenyl oxides, 1～20 part of dispersion agent, water are mixed for 100～1000 parts together, and be warming up to 70～80 ℃ under low whipping speed 1000～3000rpm and make it to disperse;
(2) 5～20 parts of trimeric cyanamides, 10～60 parts of 37% formalins, water are mixed for 50～150 parts together, and regulate its pH value to 7～9 with alkaline conditioner after being warming up to 70～80 ℃, the restir reaction obtained the terpolycyantoamino-formaldehyde resin prepolymer in 10～30 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, regulate pH value to 3～5 with acid regulator then, stirring reaction adds other a melamino-formaldehyde prepolymer after 1～4 hour again, reacted again 1～4 hour, obtain white milk sap, temperature remains on 70～80 ℃ in this step reaction, and stirring velocity is 1000～3000rpm;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product,
More than form umber and be weight part.
Used dispersion agent is the styrene-maleic anhydride resin in the above method, polyvinyl alcohol, sodium lauryl sulphate, polysorbas20, polysorbate40, polysorbate60, at least a in the tween 80.
Used alkaline conditioner is a trolamine in the above method, yellow soda ash, sodium hydroxide, any in the sodium bicarbonate.
Used acid regulator is an acetic acid in the above method, hydrochloric acid, any in the phosphoric acid.
The present invention has the following advantages:
1, owing to can coat two-layer flame retardant properties terpolycyantoamino-formaldehyde resin preferably on the decabromodiphenyl oxide surface with the inventive method, thereby this fire retardant thermal stability and temperature of initial decomposition (up to 433 ℃) have been improved greatly, make it can apply to the fire-retardant of the high polymkeric substance of processing temperature, expanded its range of application.
2, because the present invention has adopted double-coated on the decabromodiphenyl oxide surface, thereby its compactness is good, coat more fully, can man-hour the coating layer breakage not appear adding simultaneously with polymkeric substance, cause the problem of decomposition failure.
3, since the present invention select coating layer---it is fast that terpolycyantoamino-formaldehyde resin has curing speed, form stretching, the compressive strength height of coating, water-tolerant, thereby not only make the course of processing easy, condition is easy to control, and the fire-retardant particle tolerance good processability that is obtained.
4, since the present invention select coating layer---terpolycyantoamino-formaldehyde resin and most of Compatibility in Plastics are better, thereby can not bring influence to the over-all properties of body material.
5, because the fire retardant median size of the present invention preparation has only about 5 μ m, thereby add to and also can not influence the original performance of body material in the resin.
Description of drawings
This accompanying drawing is the grain size statistics figure before and after the coating of decabromodiphenyl oxide fire retardant, specifically is to measure with the Mastersizer 2000 laser particle size counting instruments that Malvern Tnstruments produces.
Embodiment
Provide embodiment below so that the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area still belongs to protection scope of the present invention according to the content of the invention described above to some nonessential improvement and the adjustment that the present invention makes.
In addition, need to prove that the used umber of following examples is weight part.
Embodiment 1
(1) decabromodiphenyl oxide 20kg, styrene-maleic anhydride resin 0.5kg, polysorbas20 0.5kg, water 100kg are added in the reactor of belt stirrer, thermometer together, be warming up to 80 ℃ under the low whipping speed 3000rpm and make it to disperse;
(2) trimeric cyanamide 15kg, 37% formalin 50kg, water 80kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 8 with yellow soda ash after temperature rises to 80 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 10 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use vinegar acid for adjusting pH value to 5 then, keeping 80 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 2 hours again under the 3000rpm, reacted again 3 hours, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 433.5 ℃.
Embodiment 2
(1) decabromodiphenyl oxide 100kg, polyvinyl alcohol 10kg, polysorbate60 10kg, water 100kg are added in the reactor of belt stirrer, thermometer together, be warming up to 70 ℃ under the low whipping speed 1000rpm and make it to disperse;
(2) trimeric cyanamide 20kg, 37% formalin 60kg, water 150kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 9 with sodium hydroxide after temperature rises to 70 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 30 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use salt acid for adjusting pH value to 3 then, keeping 70 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 1 hour again under the 1000rpm, reacted again 4 hours, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 382 ℃.
Embodiment 3
(1) decabromodiphenyl oxide 40kg, tween 80 5kg, polysorbate40 7kg, water 450kg are added in the reactor of belt stirrer, thermometer together, be warming up to 80 ℃ under the low whipping speed 2500rpm and make it to disperse;
(2) trimeric cyanamide 5kg, 37% formalin 10kg, water 50kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 7 with sodium bicarbonate after temperature rises to 80 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 10 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use vinegar acid for adjusting pH value to 4 then, keeping 80 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 3 hours again under the 2500rpm, reacted again 2 hours, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 399.1 ℃.
(1) decabromodiphenyl oxide 70kg, sodium lauryl sulphate 10kg, water 800kg are added in the reactor of belt stirrer, thermometer together, be warming up to 75 ℃ under the low whipping speed 1500rpm and make it to disperse;
(2) trimeric cyanamide 10kg, 37% formalin 35kg, water 120kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 8 with trolamine after temperature rises to 75 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 20 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use phosphorus acid for adjusting pH value to 4 then, keeping 75 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 4 hours again under the 1500rpm, reacted again 1 hour, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 405 ℃.
(1) decabromodiphenyl oxide 25kg, polyvinyl alcohol 8kg, water 1000kg are added in the reactor of belt stirrer, thermometer together, be warming up to 70 ℃ under the low whipping speed 2000rpm and make it to disperse;
(2) trimeric cyanamide 8kg, 37% formalin 30kg, water 100kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 7 with sodium bicarbonate after temperature rises to 70 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 15 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use phosphorus acid for adjusting pH value to 3 then, keeping 70 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 1 hour again under the 2000rpm, reacted again 3 hours, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 410 ℃.
(1) decabromodiphenyl oxide 90kg, tween 80 15kg, water 900kg are added in the reactor of belt stirrer, thermometer together, be warming up to 75 ℃ under the low whipping speed 3000rpm and make it to disperse;
(2) trimeric cyanamide 17kg, 37% formalin 45kg, water 75kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 8 with sodium hydroxide after temperature rises to 75 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 25 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use salt acid for adjusting pH value to 5 then, keeping 75 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 2 hours again under the 3000rpm, reacted again 2 hours, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 397 ℃.
(1) decabromodiphenyl oxide 50kg, styrene-maleic anhydride resin 5kg, water 300kg are added in the reactor of belt stirrer, thermometer together, be warming up to 75 ℃ under the low whipping speed 2500rpm and make it to disperse;
(2) trimeric cyanamide 9kg, 37% formalin 20kg, water 140kg are added together in the reactor of belt stirrer, thermometer and mix, regulate its pH value to 9 with trolamine after temperature rises to 75 ℃, the restir reaction obtained transparent terpolycyantoamino-formaldehyde resin prepolymer in 20 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is equally divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, use vinegar acid for adjusting pH value to 4 then, keeping 75 ℃ of temperature, stirring velocity is that stirring reaction adds other a melamino-formaldehyde prepolymer after 3 hours again under the 2500rpm, reacted again 4 hours, and obtained white milk sap;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product.
The initial heat decomposition temperature of this product is 435 ℃.
Claims (5)
1, a kind of preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide, the step of this method and processing condition are:
(1) 20～100 parts of decabromodiphenyl oxides, 1～20 part of dispersion agent, water are mixed for 100～1000 parts together, and be warming up to 70～80 ℃ under low whipping speed 1000～3000rpm and make it to disperse;
(2) 5～20 parts of trimeric cyanamides, 10～60 parts of 37% formalins, water are mixed for 50～150 parts together, and regulate its pH value to 7～9 with alkaline conditioner after being warming up to 70～80 ℃, the restir reaction obtained the terpolycyantoamino-formaldehyde resin prepolymer in 10～30 minutes;
(3) the terpolycyantoamino-formaldehyde resin prepolymer that (2) step was obtained is divided into two parts, a copy of it joined in (1) the step gained dispersion liquid mix, regulate pH value to 3～5 with acid regulator then, stirring reaction adds other a melamino-formaldehyde prepolymer after 1～4 hour again, reacted again 1～4 hour, obtain white milk sap, temperature remains on 70～80 ℃ in this step reaction, and stirring velocity is 1000～3000rpm;
(4) with above-mentioned milk sap after filtration or centrifugation, dry back obtain white powder-like product, more than form umber and be weight part.
2, the preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide according to claim 1 is characterized in that used dispersion agent is the styrene-maleic anhydride resin, polyvinyl alcohol, sodium lauryl sulphate, polysorbas20, polysorbate40, polysorbate60, at least a in the tween 80.
3, the preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide according to claim 1 and 2 is characterized in that used alkaline conditioner is a trolamine, yellow soda ash, sodium hydroxide, any in the sodium bicarbonate.
4, the preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide according to claim 1 and 2 is characterized in that used acid regulator is an acetic acid, hydrochloric acid, any in the phosphoric acid.
5, the preparation method of terpolycyantoamino-formaldehyde resin double-coated decabromodiphenyl oxide according to claim 3 is characterized in that used acid regulator is an acetic acid, hydrochloric acid, any in the phosphoric acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200710048900 CN101045779A (en) | 2007-04-19 | 2007-04-19 | Preparation method of melamine resin double coated Deca-BDE |
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| CN 200710048900 CN101045779A (en) | 2007-04-19 | 2007-04-19 | Preparation method of melamine resin double coated Deca-BDE |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071032A (en) * | 2010-12-27 | 2011-05-25 | 北京盛大华源科技有限公司 | Amino resin-containing flame retardant and preparation method thereof |
| CN102250494A (en) * | 2011-05-23 | 2011-11-23 | 河南大学 | Antimony trioxide superfine powder coated by melamino-formaldehyde resin and preparation method thereof |
| CN102796512A (en) * | 2012-05-14 | 2012-11-28 | 西安交通大学 | Method for preparing melamine-formaldehyde resin fluorescent microspheres |
| CN102888021A (en) * | 2012-07-30 | 2013-01-23 | 连云港海水化工有限公司 | Microencapsulated tetrabromobisphenol A bis(propenyl) ether fire retardant and application thereof |
| CN107400373A (en) * | 2016-05-20 | 2017-11-28 | 天津圣工科技有限公司 | A kind of preparation method of the high heat-resisting microcapsules of organo-mineral complexing bilayer wall material for pitch selfreparing |
| CN114957581A (en) * | 2022-07-04 | 2022-08-30 | 珠海格力电器股份有限公司 | Modified melamine resin, preparation method thereof, dust collecting plate and air purifier |
-
2007
- 2007-04-19 CN CN 200710048900 patent/CN101045779A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071032A (en) * | 2010-12-27 | 2011-05-25 | 北京盛大华源科技有限公司 | Amino resin-containing flame retardant and preparation method thereof |
| CN102250494A (en) * | 2011-05-23 | 2011-11-23 | 河南大学 | Antimony trioxide superfine powder coated by melamino-formaldehyde resin and preparation method thereof |
| CN102250494B (en) * | 2011-05-23 | 2013-11-06 | 河南大学 | Antimony trioxide superfine powder coated by melamino-formaldehyde resin and preparation method thereof |
| CN102796512A (en) * | 2012-05-14 | 2012-11-28 | 西安交通大学 | Method for preparing melamine-formaldehyde resin fluorescent microspheres |
| CN102888021A (en) * | 2012-07-30 | 2013-01-23 | 连云港海水化工有限公司 | Microencapsulated tetrabromobisphenol A bis(propenyl) ether fire retardant and application thereof |
| CN102888021B (en) * | 2012-07-30 | 2017-11-14 | 连云港市工投集团利海化工有限公司 | Microencapsulation tetrabromobisphenol A is double（Pi-allyl）Ether flame retardant and its application |
| CN107400373A (en) * | 2016-05-20 | 2017-11-28 | 天津圣工科技有限公司 | A kind of preparation method of the high heat-resisting microcapsules of organo-mineral complexing bilayer wall material for pitch selfreparing |
| CN107400373B (en) * | 2016-05-20 | 2019-05-17 | 天津圣工科技有限公司 | A kind of preparation method of the organo-mineral complexing bilayer wall material high heat resistance microcapsules for pitch selfreparing |
| CN114957581A (en) * | 2022-07-04 | 2022-08-30 | 珠海格力电器股份有限公司 | Modified melamine resin, preparation method thereof, dust collecting plate and air purifier |
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