CN103030836A - Halogen-free flame retardant and preparation method thereof - Google Patents
Halogen-free flame retardant and preparation method thereof Download PDFInfo
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- CN103030836A CN103030836A CN2012105704632A CN201210570463A CN103030836A CN 103030836 A CN103030836 A CN 103030836A CN 2012105704632 A CN2012105704632 A CN 2012105704632A CN 201210570463 A CN201210570463 A CN 201210570463A CN 103030836 A CN103030836 A CN 103030836A
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Abstract
The invention relates to a halogen-free flame retardant and a preparation method thereof. The flame retardant is formed by combining one or two of the following three organic hypophosphite compounds containing triazine ring structures at any mass ratio. The preparation method of the halogen-free flame retardant comprises the following steps of adding triglycidyl isocyanurate and hypophosphite into a reaction vessel, taking ethanol, ethylene glycol or glacial acetic acid as a solvent, heating slowly and maintaining a reaction, conducting suction filtration, washing and drying after the reaction is finished, and obtaining the halogen-free flame retardant. The halogen-free flame retardant is prepared by taking hypophosphite and triglycidyl isocyanurate (TGIC) as main raw materials, and has the characteristics that the raw materials are easy to obtain, a process is simple and easy to run, and the production and the operation are safe. The prepared halogen-free flame retardant and a composition are good in thermostability and excellent in comprehensive property; various colors can be blended; the halogen-free flame retardant and the composition can be applied to flame retarding PBT (polybutylece terephthalate) engineering plastics, PA6 (polyamide6) or PET(polyethylene terephthalate) and the like, and are good in application prospect.
Description
Technical field
The present invention relates to a kind of halogen-free flame retardants and preparation method thereof, particularly relate to halogen-free flame retardants of a kind of organic secondary phosphine acid salt that contains triazine ring structure and preparation method thereof.
Background technology
In recent years, strengthen the fire-resistant engineering plastics material increasing at the application quantity of electronic apparatus and other industrial circles, its characteristic of property has: shaping speed is fast, electrical property is excellent, chemical resistance is good and the physical strength advantages of higher, shows wide market application foreground.But it is flame-retardant system that traditional fire-retardant enhancement engineering plastic material is all selected bromine, and the release of high, the toxic gas of the amount of being fuming during burning is so that it faces more and more stricter environmental protection and safety requirements.
Since WEEE and two instructions of RoHS are issued in succession, various countries have strengthened the exploitation to halogen-free flame retardants, but halogen-free expansion fire retardant still faces many deficiencies so far, and addition is still too high, is still perplexing current academia with the relatively poor problem of separating out of bringing of the consistency of material.
The halogen-free enhanced flame-retardant engineering plastic materials mainly is red phosphorus flame-retardant at present, it is product colour that there is maximum problem in the red phosphorus flame-retardant engineering plastic materials, make it can only do redness or black product, particularly when the product requirement was light even white, red phosphorus flame-retardant enhancement engineering plastic material just seemed helpless; And red phosphorus flame-retardant enhancement engineering plastics are easy to occur the red phosphorus dieseling in extrusion, cause raw-material a large amount of waste; Moreover red phosphorus combustion inhibitor is easily emitted very hypertoxic PH under oxidizing condition
3Gas all is huge potential safety hazard to direct labor even human consumer, and therefore, market seems more urgent to the cry of halogen-free non-red-phosphorus flame-retardant enhancement engineering plastic material.
At present, Clariant company (Clariant) has released since the agent of OP fire-retardant, this fire retardant is making considerable progress aspect glass fiber enhanced nylon and the polyester, but the price of fire retardant costliness makes the fire retardant PBT with no halogen material cost high, has greatly limited the marketing of halogen-free flameproof enhancement engineering plastics.And the agent of OP fire-retardant also faces the shortcomings such as mechanical property loss is obvious, with bromine be in the competition of fire-retardant enhancement engineering plastic material, if the pressure that can't advise promotes, fully at a disadvantage.
Recently, a lot of companies and scholar are devoted to the exploitation that fiberglass reinforced engineering plastics is used halogen-free flame retardants, fire retardant or the flame-retardant system of a lot of patents and bibliographical information, all there is two large problems: first, the fire retardant thermostability is not high, add the man-hour fire retardant and just begin to decompose extruding, cause extruding material strip foaming embrittlement, even the generation of dieseling; The second, the mechanical property loss of flame retardant products is serious, and a lot of halogen-free flame retardants additions are high, cause the rigidity of fire-resistant engineering plastics material and toughness all to descend much, can't satisfy the requirement of moulding, use and do not know where to begin especially.
Summary of the invention
The purpose of this invention is to provide a kind of halogen-free flame retardants and preparation method thereof, particularly halogen-free flame retardants of a kind of organic secondary phosphine acid salt that contains triazine ring structure and preparation method thereof.Adopting fire retardant of the present invention is main body, and composite other fire retardants improve flame retarding efficiency, reduce the mechanicalness loss of energy, reach the product requirement of modifying material terminal client fully.More estimable is, can reduce cost, and market is accepted possibility and increased, and can allot shades of colour, and especially light product has very large feasibility.
A kind of halogen-free flame retardants of the present invention, by the combination of any mass ratio of one or both or three kinds in following three kinds of compounds:
Wherein, n=1,2,3 or 4;
Wherein, n=1,2,3 or 4,2n=am;
Wherein, n=1,2,3 or 4,3n=am;
M is sodium Metal 99.5, potassium, magnesium, calcium, barium, zinc, tin, titanium, zirconium, iron or aluminium, and n is the valency of M.
The present invention also provides a kind of preparation method of halogen-free flame retardants, may further comprise the steps: it is that the isocyanuric acid three-glycidyl ester of 1:1 ~ 3.5 and hypophosphite drop into reaction vessel that molar weight is compared, take ethanol, ethylene glycol or Glacial acetic acid as solvent, slowly be heated to 70 ~ 150 ℃ and keep reaction 4 ~ 10h, react complete by suction filtration, washing namely gets described halogen-free flame retardants after the drying.
The composition of target compound is different and different according to the equivalence ratio of isocyanuric acid three-glycidyl ester and hypophosphite, a kind of compound before equivalence ratio mainly generates when 1:1-1.2, be designated as I, the sort of compound in the middle of mainly generating when being in 1:1.9-2.2, be designated as II, a kind of compound after mainly generating when 1:3-3.5 is designated as III, detailed process is: by rising progressively of equivalence ratio, product is respectively I, I and II, II, I and II and III, II and III, III.
As preferred technical scheme:
The preparation method of aforesaid a kind of halogen-free flame retardants, described hypophosphite is sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium propionate, barium hypophosphite, zinc hypophosphite, Hypophosporous Acid, 50 tin, Hypophosporous Acid, 50 titanium, Hypophosporous Acid, 50 zirconium, ferric hypophosphite or hypo-aluminum orthophosphate.
The preparation method of aforesaid a kind of halogen-free flame retardants, the mol ratio of described isocyanuric acid three-glycidyl ester and hypophosphite are 1:3.5.
Beneficial effect:
A kind of halogen-free flame retardants of the present invention, good flame retardation effect, flame-proof composite material can pass through the UL94V-0 level, and 1.6mm is not halogen-containing, meets the non-halogen trend of current fire retardant material, and can allot light color product, and this is that red phosphorus combustion inhibitor institute is inaccessiable.The preparation method of a kind of halogen-free flame retardants of the present invention, step is succinct, successful.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Chemical compounds I
Wherein, n=1,2,3 or 4;
Compound ii
Wherein, n=1,2,3 or 4,2n=am;
The compound III
Wherein, n=1,2,3 or 4,3n=am;
M is sodium Metal 99.5, potassium, magnesium, calcium, barium, zinc, tin, titanium, zirconium, iron or aluminium, and n is the valency of M.
Embodiment 1
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:1 and magnesium hypophosphite drop into reaction vessel with equivalence ratio, take ethanol as solvent, slowly be heated to 70 ℃ of heated and stirred backflow 10h, the cooling suction filtration, washing, drying obtain the target compound I.
Embodiment 2
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:2 and sodium hypophosphite drop into reaction vessel with equivalence ratio, take ethylene glycol as solvent, slowly be heated to 150 ℃ of heated and stirred backflow 4h,, the cooling suction filtration, washing, drying obtain the target compound II.
Embodiment 3
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:3.5 and potassium hypophosphite drop into reaction vessel with equivalence ratio, take ethanol as solvent, slowly be heated to 100 ℃ of heated and stirred backflow 6h, the cooling suction filtration, washing, drying obtain the target compound III.
Embodiment 4
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:3.2 and hypo-aluminum orthophosphate drop into reaction vessel with equivalence ratio, take ethylene glycol as solvent, slowly be heated to 90 ℃ of heated and stirred backflow 8h, the cooling suction filtration, washing, drying obtain the target compound III.
Embodiment 5
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:3 and calcium propionate drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 100 ℃ of heated and stirred backflow 10h, the cooling suction filtration, washing, drying obtain the target compound III.
Embodiment 6
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:1.5 and barium hypophosphite drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 110 ℃ of heated and stirred backflow 5h, the cooling suction filtration, washing, drying obtain the mixture of target compound I and II.
Embodiment 7
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:2.5 and zinc hypophosphite drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 105 ℃ of heated and stirred backflow 8h, the cooling suction filtration, washing, drying obtain the mixture of target compound I and II and III.
Embodiment 8
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:2.8 and Hypophosporous Acid, 50 tin drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 115 ℃ of heated and stirred backflow 6h, the cooling suction filtration, washing, drying obtain the mixture of target compound II and III.
Embodiment 9
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:3 and Hypophosporous Acid, 50 titanium drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 89 ℃ of heated and stirred backflow 10h, the cooling suction filtration, washing, drying obtain the target compound III.
Embodiment 10
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:3 and Hypophosporous Acid, 50 zirconium drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 140 ℃ of heated and stirred backflow 6h, the cooling suction filtration, washing, drying obtain the target compound III.
Embodiment 11
Be that the TGIC (isocyanuric acid three-glycidyl ester) of 1:3.1 and ferric hypophosphite drop into reaction vessel with equivalence ratio, take Glacial acetic acid as solvent, slowly be heated to 120 ℃ of heated and stirred backflow 6h, the cooling suction filtration, washing, drying obtain the target compound III.
Claims (4)
1. halogen-free flame retardants is characterized in that: described halogen-free flame retardants is by the combination of any mass ratio of one or both or three kinds in following three kinds of compounds:
Wherein, n=1,2,3 or 4;
Wherein, n=1,2,3 or 4,2n=am;
Wherein, n=1,2,3 or 4,3n=am;
M is sodium Metal 99.5, potassium, magnesium, calcium, barium, zinc, tin, titanium, zirconium, iron or aluminium, and n is the valency of M.
2. the preparation method of a kind of halogen-free flame retardants as claimed in claim 1, it is characterized in that may further comprise the steps: it is that the isocyanuric acid three-glycidyl ester of 1:1 ~ 3.5 and hypophosphite drop into reaction vessel that molar weight is compared, take ethanol, ethylene glycol or Glacial acetic acid as solvent, slowly be heated to 70 ~ 150 ℃ and keep reaction 4 ~ 10h, react complete by suction filtration, washing namely gets described halogen-free flame retardants after the drying.
3. the preparation method of a kind of halogen-free flame retardants according to claim 2, it is characterized in that, described hypophosphite is sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium propionate, barium hypophosphite, zinc hypophosphite, Hypophosporous Acid, 50 tin, Hypophosporous Acid, 50 titanium, Hypophosporous Acid, 50 zirconium, ferric hypophosphite or hypo-aluminum orthophosphate.
4. the preparation method of a kind of halogen-free flame retardants according to claim 2 is characterized in that, the mol ratio of described isocyanuric acid three-glycidyl ester and hypophosphite is 1:3.5.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646581A (en) * | 2016-02-18 | 2016-06-08 | 厦门大学 | Halogen-free and ketone-containing intumescent flame retardant adopting cyanuric acid structure and synthetic method |
| CN105860067A (en) * | 2016-06-08 | 2016-08-17 | 浙江旭森非卤消烟阻燃剂有限公司 | Nitrogen-series macromolecular halogen-free flame-retardant char-forming agent compound and preparation method thereof |
| CN105885045A (en) * | 2016-06-08 | 2016-08-24 | 浙江旭森非卤消烟阻燃剂有限公司 | Organic selenium triazine polymer and preparation method thereof |
| CN105968351A (en) * | 2016-06-08 | 2016-09-28 | 浙江旭森非卤消烟阻燃剂有限公司 | Sulfur-containing macromolecule triazine polymer and preparation method thereof |
| CN106084286A (en) * | 2016-06-08 | 2016-11-09 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of halogen-free expansion type flame-proof carbon forming agent compound and preparation method thereof |
| CN106084287A (en) * | 2016-06-08 | 2016-11-09 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of sulfur-bearing macro molecular triazine class fire-retardant carbon forming agent compound and preparation method thereof |
| CN107629806A (en) * | 2017-09-14 | 2018-01-26 | 绵竹耀隆化工有限公司 | A kind of basic zirconium phosphate fire retardant and preparation method thereof |
| CN106009037B (en) * | 2016-06-08 | 2018-10-30 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof |
| CN106084289B (en) * | 2016-06-08 | 2018-10-30 | 浙江旭森非卤消烟阻燃剂有限公司 | One kind macromolecular fire retardant compound of triazines containing selenium and preparation method thereof |
| CN111234312A (en) * | 2020-03-27 | 2020-06-05 | 北京理工大学 | Aluminum hypophosphite composite halogen-free flame retardant, preparation and application thereof |
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| CN102229622A (en) * | 2011-04-20 | 2011-11-02 | 苏州科技学院 | Organic phosphinic acid metal salt containing triazine ring and preparation method thereof |
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| CN101362819A (en) * | 2008-09-10 | 2009-02-11 | 华南理工大学 | Triazines cross-linking compounds, preparation method and application thereof |
| CN101712807A (en) * | 2008-09-29 | 2010-05-26 | 富士电机机器制御株式会社 | Flame-resistant resin composition |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646581A (en) * | 2016-02-18 | 2016-06-08 | 厦门大学 | Halogen-free and ketone-containing intumescent flame retardant adopting cyanuric acid structure and synthetic method |
| CN106084289B (en) * | 2016-06-08 | 2018-10-30 | 浙江旭森非卤消烟阻燃剂有限公司 | One kind macromolecular fire retardant compound of triazines containing selenium and preparation method thereof |
| CN105885045A (en) * | 2016-06-08 | 2016-08-24 | 浙江旭森非卤消烟阻燃剂有限公司 | Organic selenium triazine polymer and preparation method thereof |
| CN105968351A (en) * | 2016-06-08 | 2016-09-28 | 浙江旭森非卤消烟阻燃剂有限公司 | Sulfur-containing macromolecule triazine polymer and preparation method thereof |
| CN106084286A (en) * | 2016-06-08 | 2016-11-09 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of halogen-free expansion type flame-proof carbon forming agent compound and preparation method thereof |
| CN106084287A (en) * | 2016-06-08 | 2016-11-09 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of sulfur-bearing macro molecular triazine class fire-retardant carbon forming agent compound and preparation method thereof |
| CN106009037B (en) * | 2016-06-08 | 2018-10-30 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof |
| CN106084287B (en) * | 2016-06-08 | 2018-10-30 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class and preparation method thereof |
| CN105860067A (en) * | 2016-06-08 | 2016-08-17 | 浙江旭森非卤消烟阻燃剂有限公司 | Nitrogen-series macromolecular halogen-free flame-retardant char-forming agent compound and preparation method thereof |
| CN106084286B (en) * | 2016-06-08 | 2018-10-30 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of halogen-free expansion type flame-proof carbon forming agent compound and preparation method thereof |
| CN105885045B (en) * | 2016-06-08 | 2019-03-08 | 浙江旭森非卤消烟阻燃剂有限公司 | A kind of organic selenium class aerotex and preparation method thereof |
| CN107629806A (en) * | 2017-09-14 | 2018-01-26 | 绵竹耀隆化工有限公司 | A kind of basic zirconium phosphate fire retardant and preparation method thereof |
| CN111234312A (en) * | 2020-03-27 | 2020-06-05 | 北京理工大学 | Aluminum hypophosphite composite halogen-free flame retardant, preparation and application thereof |
| CN111234312B (en) * | 2020-03-27 | 2020-11-10 | 北京理工大学 | Aluminum hypophosphite composite halogen-free flame retardant, preparation and application thereof |
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Effective date of registration: 20200814 Address after: 201613, Songjiang District, China Road, No. 68, 13, 5, Shanghai Patentee after: Shanghai Li Dao new material Polytron Technologies Inc. Address before: 425300, Hunan, Daoxian County province Yongzhou Industrial Park, East Ring Road Patentee before: HUNAN MEILAIPO SCIENCE AND TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20210611 Address after: 425300 East 1st ring road, Daoxian Industrial Park, Yongzhou City, Hunan Province Patentee after: HUNAN MEILAIPO SCIENCE AND TECHNOLOGY Co.,Ltd. Address before: 5 / F, building 13, No. 68, Zhongchuang Road, Songjiang District, Shanghai, 201613 Patentee before: Shanghai Li Dao new material Polytron Technologies Inc. |