CN102585498A - Antistatic and anti-flaming phosphorous nitrogen series flame retardant and preparation method thereof - Google Patents
Antistatic and anti-flaming phosphorous nitrogen series flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antistatic and anti-flaming phosphorous nitrogen series flame retardant and a preparation method thereof. The phosphorous nitrogen series flame retardant is characterized in that the phosphorous nitrogen series flame retardant with antistatic and anti-flaming functions is obtained by in-situ polymerization of aniline or derivative thereof in the presence of ammonium polyphosphate. The preparation method comprises the following synthesizing steps of: preparing 1-70% suspended slurry from ammonium polyphosphate and water; adding surfactant, aniline or a derivative thereof and proton acid, slowly dripping an oxidant with continuous stirring, reacting for 1 to 30 hours at the temperature of between 20 DEG C below zero and 50 DEG C; and filtering, dehydrating, washing for 2 to 5 times by using deionized water, and drying to obtain the product. By the method, the production process for preparing the macromolecular composite material with antistatic and anti-flaming functions is simplified, and the consumption amount of filler in the composite material is reduced; and the preparation method of the phosphorous nitrogen series flame retardant is simple in production process, convenient to operate, low in cost and convenient for industrialized production.
Description
Technical field
The present invention relates to a kind of antistatic and fire-retardant phosphorus-nitrogen containing flame retardant and preparation method thereof, belong to functional high polymer material field.
Background technology
Macromolecular material generally all is inflammable or combustible, and easy initiation fire accident has become the material that mainly catches fire of initiation fire.For guaranteeing the safety in utilization of material, the most effectively way is in macromolecular material, to add fire retardant (FR), makes it flammable and reduces, and in combustion processes, suppresses the generation of smog or toxic gas.Fire retardant of a great variety, what wherein consumption was maximum is halogenated flame retardant, particularly bromide fire retardant (BFR).The research institution of Switzerland in 1986 has found halogenated flame retardant De dioxin (Dioxins) problem; Be that polybromodiphenyl ether and fire-retardant superpolymer thereof produce deleterious many bromines dibenzo dioxane (PBDD) and many bromines diphenylene-oxide (PBDF) 510 ℃～630 ℃ following thermolysiss; This brings stern challenge with regard to the development of giving halogenated flame retardant, and impels the researchist to remove to develop low halogen Halogen product innovation to reduce the influence to environment.Therefore the consumption of phosphorus flame retardant obtains rapid growth.Phosphorus flame retardant mostly has advantages such as low cigarette, nontoxic, low halogen, Halogen, meets the developing direction of fire retardant, has good development prospect.
Static has become one of macromolecular material leading cause of fire.Usually macromolecular material has electrical insulating property, is generally 10 like the surface resistivity of Vestolen PP 7052 (PP), Vilaterm (PE)
16～10
20Ω.Therefore, very easily produce static.When accumulation of static electricity is serious, can produces static sparking, thereby may cause accidents such as fire, blast, electric shock.For fear of this type of accident, must do antistatic treatment in the use of a lot of occasion (industries such as colliery, oil) macromolecule material products.Adding static inhibitor is to eliminate the most simple and effective way of macromolecular material electrostatic, and cost is low, practical, uses also general.Traditional method is in macromolecular material, to add low quantity of surfactant or other hydroaropic substances can demonstrate antistatic effect.The major defect of this method has: comparing under the exsiccant condition, because the moisture that the surface absorbs is limited, this method will lose efficacy; Because tensio-active agent or other hydroaropic substances can slowly be moved to material surface; Cause the amount of tensio-active agent or other hydroaropic substances in the material fewer and feweri; The life-span of using the antistatic material of this antistatic technology preparation is limited, is not permanent.The recombining process that various conductive filler materials (metal-powder, steel fiber, carbon black etc.) join in the macromolecular material is simple, can solve two problems that conventional art exists, make permanence antistatic property material.The inorganic conductive filling kind that adopts now is various, but with the most use be graphitized carbon black.In polymkeric substance, add carbon black and still have following problem: add graphitized carbon black in the matrix material, make the mechanical property loss of matrix material serious, especially elongation at break reduces obviously; In the resistivity curve of sooty addition and matrix material, near the curvilinear motion amplitude excess effusion value is big especially, and this just makes that the difficulty of controllability of resistivity of material is very big, and repeatability is also poor.
Adopt the conducting polymer of eigenmode to prepare high molecular matrix material, can solve above-mentioned several problems as conductive filler material.Owing to polyaniline (PANI) has that raw material is easy to get, synthesis technique is simple, chemistry and advantages such as environmental stability is good, price is relatively low, stable performance, good conductivity have obtained extensive studies and exploitation, and demonstrated wide application prospect in a lot of fields.PANI is considered to have a kind of of commercial promise most in numerous conducting polymers.Adopting PANI is that conductive filler material prepares the good PANI matrix material of antistatic property, and the mechanical property of its material does not worsen because of the adding of PANI.In the resistivity curve of the addition of PANI and matrix material, near the curve ratio excess effusion value is milder, thereby makes that the controllability of resistivity of material is better.
The macromolecule material product that uses in a lot of occasions (industries such as colliery, oil, chemical industry, rubber, papermaking printing, powder processing) must have fire-retardant and antistatic property simultaneously.In order to prepare this two anti-functional materials, have in macromolecular material, add simultaneously fire retardant and static inhibitor.Because fire-retardant and antistatic is two relatively independent processes; With fire retardant and static inhibitor compound be a complicated process; Following two problems appear easily: at first; Owing to need introduce the index that fire retardant and static inhibitor just can reach pair anti-functions simultaneously, make that the total filler amount in the base material is very big, influencing each other between the relatively poor or two kinds of fillers of the consistency of two kinds of fillers and base material makes that the dispersion of filler in base material is bad; Finally be prone to cause the mechanical property of matrix material to worsen or unstable properties, the bloom of additive in use occur or ooze out phenomenon.Secondly, the mutual phenomenon that weakens, for example amine static inhibitor and chlorine-containing flame retardant between fire retardant and the static inhibitor appear easily.
Summary of the invention
A kind of antistatic and fire-retardant phosphorus-nitrogen containing flame retardant that the objective of the invention is to be directed against the deficiency of prior art and provide and preparation method thereof; Be characterized in that in the presence of ammonium polyphosphate the in-situ polymerization through the aniline or derivatives thereof obtains having antistatic and fire-retardant bifunctional phosphorus-nitrogen containing flame retardant.
The object of the invention is realized that by following technical measures wherein all raw material marks are weight fraction except that specified otherwise.
Antistatic and fire-retardant phosphorus-nitrogen containing flame retardant is composed of the following components:
1 part of ammonium polyphosphate
0.01～20 part of aniline or derivatives thereof
Wherein, ammonium polyphosphate is at least a in I type, II type, III type, IV type, V-type and the VI N-type waferN.
The preparation method of antistatic and fire-retardant phosphorus-nitrogen containing flame retardant may further comprise the steps:
1) ammonium polyphosphate and water stir together, are mixed with the suspension slip of concentration 1～70%;
2) in above-mentioned slip, add tensio-active agent, add-on is 0～15% of an ammonium polyphosphate, and stirs;
3) in above-mentioned slip, add the aniline or derivatives thereof, add-on is 0.01～20 times of ammonium polyphosphate, and stirs;
4) under continuous stirring condition, in above-mentioned slip, add protonic acid, the equivalence ratio of protonic acid and aniline or derivatives thereof is 0.3～2.0;
5) under continuous stirring condition, dropping oxidizing agent solution in above-mentioned slip, the equivalence ratio of oxygenant and aniline or derivatives thereof is 0.2～1.5; In temperature-20～50 ℃, continue stirring reaction 1～30h;
6) slurry filtration or the centrifuge dehydration above-mentioned reaction accomplished with washed with de-ionized water 2～5 times, are dewatered again, obtain antistatic and fire-retardant phosphorus-nitrogen containing flame retardant.
Tensio-active agent be in AS, nonionogenic tenside, cats product, the amphoterics at least a.
The chemical formula of aniline or derivatives thereof is:
R in the chemical formula is-H ,-C
nH
2n+1,-O C
nH
2n+1,-NO
2,-F ,-Cl ,-Br and-at least a among the I, wherein R can be identical or different, n=1～20.
Protonic acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid, C
6～30Phenylsulfonic acid, C
1～30Carboxylic acid, C
1～30Sulfonic acid at least a.
Oxygenant is at least a in persulphate, dichromate, iodate and the ydrogen peroxide 50.
The present invention has the following advantages
Antistatic and fire-retardant bifunctional phosphorus-nitrogen containing flame retardant; Utilize its conduction and flame retardant properties; Simplified preparation widely and had the production technique of antistatic and fire-retardant difunctional polymer composite, can obviously reduce the consumption of filler in the matrix material, and the production technique of this difunctional phosphorus-nitrogen containing flame retardant has been simple, easy to operate; Cost is low, helps suitability for industrialized production.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; But can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
(1) I type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 70%;
(2) in slip, add nonionogenic tenside OP-10, add-on is 15% of an ammonium polyphosphate, and stirs;
(3) in slip, add aniline, add-on is 20 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add hydrochloric acid, with the equivalence ratio of aniline be 0.6;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 10% ammonium persulfate solution, with the equivalence ratio of aniline be 1.5;
(6) at temperature-20 ℃ reaction 1h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 2
(1) II type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 35%;
(2) in slip, add anionic, add-on is 5% of an ammonium polyphosphate, and stirs;
(3) in slip, add o-toluidine, add-on is 10 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add sulfuric acid, with the equivalence ratio of o-toluidine be 0.3;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 10% ammonium persulfate solution, with the equivalence ratio of o-toluidine be 1.0;
(6) at 20 ℃ of reactions of temperature 15h, constantly stir between the reaction period;
(7) the slip centrifuge dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 3
(1) III type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 1%;
(2) in slip, add the cats product cetyl trimethylammonium bromide, add-on is 0.5% of an ammonium polyphosphate, and stirs;
(3) in slip, add 2, the 5-diethoxy aniline, add-on is 0.01 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add nitric acid, with 2, the equivalence ratio of 5-diethoxy aniline is 2.0;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% potassium bichromate solution, with 2, the equivalence ratio of 5-diethoxy aniline is 0.2;
(6) at 50 ℃ of reactions of temperature 30h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 4
(1) IV type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 20%;
(2) in slip, add amphoterics stearylamide SULPHOSUCCINIC ACID ESTER trimethyl-glycine, add-on is 3% of an ammonium polyphosphate, and stirs;
(3) in slip, add o-Nitraniline, add-on is 1.0 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add phosphoric acid, with the equivalence ratio of o-Nitraniline be 1.0;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% hydrogen peroxide solution, with the equivalence ratio of o-Nitraniline be 1.0;
(6) at 20 ℃ of reactions of temperature 24h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 5
(1) V-type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 10%;
(2) in slip, add m-fluoroaniline, add-on is 0.5 times of ammonium polyphosphate, and stirs;
(3) under continuous stirring condition, in slip, add perchloric acid, with the equivalence ratio of m-fluoroaniline be 1.0;
(4) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% potassium iodate solution, with the equivalence ratio of m-fluoroaniline be 1.5;
(5) at 25 ℃ of reactions of temperature 15h, constantly stir between the reaction period;
(6) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 6
(1) VI type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 25%;
(2) in slip, add nonionogenic tenside OP-10 and amphoterics stearylamide SULPHOSUCCINIC ACID ESTER trimethyl-glycine, both mass ratioes are 1: 1, and add-on is 3% of an ammonium polyphosphate, and stirs;
(3) in slip, add m-chloro aniline, add-on is 1.0 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add Witco 1298 Soft Acid, with the equivalence ratio of m-chloro aniline be 1.0;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% potassium persulfate solution, with the equivalence ratio of m-chloro aniline be 1.0;
(6) at 20 ℃ of reactions of temperature 6h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 7
(1) I type and II type ammonium polyphosphate and water stir together, and both mass ratioes are 1: 1, are mixed with the suspension slip 1000g of concentration 30%;
(2) in slip, add nonionogenic tenside OP-10 and anionic, both mass ratioes are 1: 0.8, and add-on is 4% of an ammonium polyphosphate, and stirs;
(3) in slip, add m-bromoaniline, add-on is 0.7 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add beta-naphthalenesulfonic-acid, with the equivalence ratio of m-bromoaniline be 1.05;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% potassium persulfate solution, with the equivalence ratio of m-bromoaniline be 1.0;
(6) at 20 ℃ of reactions of temperature 6h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 8
(1) I type, II type and V-type ammonium polyphosphate and water stir together, and three's mass ratio is 1: 1: 0.5, are mixed with the suspension slip 1000g of concentration 20%;
(2) in slip, add nonionogenic tenside OP-10 and cats product cetyl trimethylammonium bromide, both mass ratioes are 1: 1, and add-on is 2% of an ammonium polyphosphate, and stirs;
(3) in slip, add between Iodoaniline, add-on is 0.6 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add oxalic acid, and the equivalence ratio of an Iodoaniline is 0.8;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% potassium persulfate solution, and the equivalence ratio of an Iodoaniline is 1.0;
(6) at 20 ℃ of reactions of temperature 6h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 9
(1) II type and V-type ammonium polyphosphate and water stir together, and both mass ratioes are 1: 0.5, are mixed with the suspension slip 1000g of concentration 20%;
(2) in slip, add nonionogenic tenside OP-10 and anionic, both mass ratioes are 1: 0.8, and add-on is 2% of an ammonium polyphosphate, and stirs;
(3) in slip, add aniline, add-on is 0.6 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add hydrofluoric acid, with the equivalence ratio of aniline be 0.8;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% ammonium persulfate solution, with the equivalence ratio of aniline be 1.0;
(6) at 20 ℃ of reactions of temperature 6h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Embodiment 10
(1) II type ammonium polyphosphate and water stir together, are mixed with the suspension slip 1000g of concentration 20%;
(2) in slip, add nonionogenic tenside OP-10 and anionic, both mass ratioes are 1: 0.8, and add-on is 2% of an ammonium polyphosphate, and stirs;
(3) in slip, add aniline, add-on is 0.3 times of ammonium polyphosphate, and stirs;
(4) under continuous stirring condition, in slip, add hydrochloric acid, with the equivalence ratio of aniline be 1.0;
(5) under continuous stirring condition, in above-mentioned slip, slowly splash into concentration and be 5% ammonium persulfate solution, with the equivalence ratio of aniline be 1.0;
(6) at 20 ℃ of reactions of temperature 6h, constantly stir between the reaction period;
(7) the slurry filtration dehydration accomplished of reaction with washed with de-ionized water 2～5 times, and is dewatered again, and final drying obtains product.
Claims (6)
1. an antistatic and fire-retardant phosphorus-nitrogen containing flame retardant is characterized in that this phosphorus-nitrogen containing flame retardant is composed of the following components, counts by weight:
1 part of ammonium polyphosphate
0.01～20 part of aniline or derivatives thereof
Wherein, ammonium polyphosphate is at least a in I type, II type, III type, IV type, V-type and the VI N-type waferN.
2. according to the preparation method of the said antistatic and fire-retardant phosphorus-nitrogen containing flame retardant of claim 1, it is characterized in that this method may further comprise the steps, wherein said raw material umber is parts by weight except that specified otherwise:
1) ammonium polyphosphate and water stir together, are mixed with the suspension slip of concentration 1～70%;
2) in above-mentioned slip, add tensio-active agent, add-on is 0～15% of an ammonium polyphosphate, and stirs;
3) in above-mentioned slip, add the aniline or derivatives thereof, add-on is 0.01～20 times of ammonium polyphosphate, and stirs;
4) under continuous stirring condition, in above-mentioned slip, add protonic acid, the equivalence ratio of protonic acid and aniline or derivatives thereof is 0.3～2.0;
5) under continuous stirring condition, dropping oxidizing agent solution in above-mentioned slip, the equivalence ratio of oxygenant and aniline or derivatives thereof is 0.2～1.5; In temperature-20～50 ℃, continue stirring reaction 1～30h;
6) slurry filtration or the centrifuge dehydration above-mentioned reaction accomplished with washed with de-ionized water 2～5 times, are dewatered again, obtain antistatic and fire-retardant phosphorus-nitrogen containing flame retardant.
3. according to the preparation method of the said antistatic and fire-retardant phosphorus-nitrogen containing flame retardant of claim 2, it is characterized in that tensio-active agent be in AS, nonionogenic tenside, cats product, the amphoterics at least a.
4. according to the preparation method of the said antistatic and fire-retardant phosphorus-nitrogen containing flame retardant of claim 2, it is characterized in that the chemical formula of aniline or derivatives thereof is:
R in the chemical formula is-H ,-C
nH
2n+1,-O C
nH
2n+1,-NO
2,-F ,-Cl ,-Br and-at least a among the I, wherein R can be identical or different, n=1～20.
5. according to the preparation method of the said antistatic and fire-retardant phosphorus-nitrogen containing flame retardant of claim 2, it is characterized in that protonic acid is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydrofluoric acid, C
6～30Phenylsulfonic acid, C
1～30Carboxylic acid, C
1～30Sulfonic acid at least a.
6. according to the preparation method of the said antistatic and fire-retardant phosphorus-nitrogen containing flame retardant of claim 2, it is characterized in that oxygenant is at least a in persulphate, dichromate, iodate and the ydrogen peroxide 50.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850592A (en) * | 2012-08-30 | 2013-01-02 | 西南石油大学 | Preparation method for ammonium polyphosphate/polystyrene core-shell microspheres |
| CN103539942A (en) * | 2013-09-24 | 2014-01-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of poly-2,3,5,6-four-fluoroaniline nano structure |
| CN105085926A (en) * | 2014-05-19 | 2015-11-25 | 中国科学技术大学先进技术研究院 | Synthesis of transparent organophosphorus-nitrogen polymeric flame retardant and application in flame retardation of transparent paint and varnish |
| CN111138713A (en) * | 2019-12-30 | 2020-05-12 | 上海普利特复合材料股份有限公司 | Stearylamine modified ammonium polyphosphate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050075426A1 (en) * | 2003-10-03 | 2005-04-07 | Campbell John Robert | Flame-retardant thermoset composition, method, and article |
| CN1990824A (en) * | 2005-12-30 | 2007-07-04 | 上海杰事杰新材料股份有限公司 | Preparation method of modified non-halogen fire retardant |
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2012
- 2012-02-23 CN CN 201210042870 patent/CN102585498B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050075426A1 (en) * | 2003-10-03 | 2005-04-07 | Campbell John Robert | Flame-retardant thermoset composition, method, and article |
| CN1990824A (en) * | 2005-12-30 | 2007-07-04 | 上海杰事杰新材料股份有限公司 | Preparation method of modified non-halogen fire retardant |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850592A (en) * | 2012-08-30 | 2013-01-02 | 西南石油大学 | Preparation method for ammonium polyphosphate/polystyrene core-shell microspheres |
| CN103539942A (en) * | 2013-09-24 | 2014-01-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of poly-2,3,5,6-four-fluoroaniline nano structure |
| CN103539942B (en) * | 2013-09-24 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of poly-2,3,5,6-tetrafluoroaniline nanostructure |
| CN105085926A (en) * | 2014-05-19 | 2015-11-25 | 中国科学技术大学先进技术研究院 | Synthesis of transparent organophosphorus-nitrogen polymeric flame retardant and application in flame retardation of transparent paint and varnish |
| CN105085926B (en) * | 2014-05-19 | 2018-07-24 | 中国科学技术大学先进技术研究院 | The synthesis of transparent organophosphor-nitrogen high molecular weight flame retardant and its application in celluloid paint and varnish are fire-retardant |
| CN111138713A (en) * | 2019-12-30 | 2020-05-12 | 上海普利特复合材料股份有限公司 | Stearylamine modified ammonium polyphosphate and preparation method and application thereof |
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