CN106349178A - Preparation method of macromolecular three-element-integrated low-smoke halogen-free intumescent flame retardant - Google Patents
Preparation method of macromolecular three-element-integrated low-smoke halogen-free intumescent flame retardant Download PDFInfo
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- CN106349178A CN106349178A CN201610662119.4A CN201610662119A CN106349178A CN 106349178 A CN106349178 A CN 106349178A CN 201610662119 A CN201610662119 A CN 201610662119A CN 106349178 A CN106349178 A CN 106349178A
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- preparation
- flame retardant
- water
- smoke halogen
- flame
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
Abstract
The invention discloses a preparation method of a macromolecular three-element-integrated low-smoke halogen-free intumescent flame retardant. The preparation method includes following steps: (1), enabling phosphoric acid to react with a multi-amino compound in a water solution for 1-2h, and controlling temperature of the water solution to 70-90 DEG C; (2), adding a water solution of triglycidyl isocyanurate into a reaction solution above, holding the temperature, continuing reacting for 1-2h, cooling, filtering, and drying to obtain the macromolecular integrated intumescent flame retardant. Nitrogen, phosphor and carbon are introduced into a same molecular structure at the same time, and the macromolecular intumescent flame retardant having a branched structure and integrating three elements is formed, so that thermostability, waterproofness and compatibility with high-molecular polymer of the flame retardant are improved.
Description
Technical field
The invention belongs to flame retardant area, low-smoke halogen-free expansion flame-retarded dose of the three-source integrated formula of more particularly, to a kind of macromole type
Preparation method.
Background technology
, mainly with phosphorus, nitrogen as main component, it is typically by " carbon source, source of the gas, acid source " three source institute for expansion type flame retardant (ifr)
Composition, this based flame retardant when being heated between " three sources " pass through chemical reaction, quickly form have heat-insulated, every matter function cellular
Charcoal barrier layer, this barrier layer can stop flame transmission, makes polymeric substrate avoid degrading further or burning, so that poly-
Compound base material obtains good flame retardant effect.Ifr system main release water outlet and ammonia under burning condition, simultaneously because surface
The iris action of cystose layer of charcoal is it is suppressed that the effusion .ifr of flammable escaping gas in polymer base material catabolic process has
Flame retarding efficiency is high, no molten drop, low cigarette, the advantages of nontoxic, non-corrosiveness gas is released, meet country's close friend's flame-retardant system will
Ask it is considered to be one of current important developing direction of bittern-free flame-proof material.
Ifr mainly has mixed type and integral type type (three sources are concurrently present in same molecule) at present.Currently engage in trade
The ifr of product mostly is mixed type, generally individually using APP as acid source with source of the gas add another become carbonization compound as carbon source,
As tetramethylolmethane etc., however this kind of ifr to there is heat stability low, poor water resistance, to polymeric matrix Effect on Mechanical Properties phase
To larger the shortcomings of (cn01128575.3, us3936416).
Chinese patent cn20089810198458.7 reports with multiamino compound and isocyanuric acid three-glycidyl ester
For raw material, polyreaction is prepared for a kind of cross-linking type triazines carbon forming agent in the molten state, and it is steady that this carbon forming agent has good heat
Qualitative and resistance to water, it is combined with APP and constitutes expansion type flame retardant, show good resistance for polypropylene flame redardant
Combustion performance, and the production preparation process Organic substance zero-emission of fire retardant.But, the preparation of this fire retardant first is by by instead
Answer under thing molten condition in screw extruder or banbury reaction 3h, then institute after high temperature drying case total ripening 4-6h
Obtain, carried out with the method producing on the one hand due to screw extruder or banbury machine limited volume, on the other hand due to anti-
Need 3h between seasonable, along with the 4-6h of ripening, lead to the method production efficiency extremely inefficient, be not suitable for industrialization life at all
Produce.Secondly it is known that the water resistance of APP is still poor although this carbon forming agent has higher heat stability and resistance to
Aqueouss, but with APP be combined after overall flame agent heat stability and water-fast still do not solve, this is also triazines
The common fault of fire retardant.
With respect to mixed type expansion type flame retardant, the expansion type flame retardant of " three-source integrated formula " be fire retardant technology particularly
Important developing direction.This expansion type flame retardant advantage the most prominent is to significantly reduce moisture absorption, good weatherability, with high score
The compatibility between son is preferable.What integral type ifr was reported at present mainly has tetramethylolmethane melamine phosphate etc., and it is mainly
With phosphorus oxychloride, Phosphorous chloride. or phosphorus pentachloride for raw material react in organic solvent prepared (cn1135755a,
Cn1281861a), but this reaction not only consumes a large amount of organic solvents, pollute environment, and complex operation post processing trouble.China
Patent cn201020124603.4 discloses a kind of preparation method of three-source integrated microcapsule expanding fire retardant, and preparation process is
APP is dispersed in poly ethyldiol modified carbamide prepolymer solution, then carries out micro encapsulation, products obtained therefrom
Excellent flame retardancy.But micro-encapsulation technology generally there are " technology controlling and process is difficult, need high-speed stirred, high energy consumption, high cost " etc. to be lacked
Point, also exists simultaneously and coats incomplete problem.
Content of the invention
Present invention aim at customer service prior art shortcoming, provide a kind of collection with good thermal stability and resistance to water
" acid source, source of the gas, charcoal source " three comes from low-smoke halogen-free expansion flame-retarded dose of the macromole type of one.
Another object of the present invention is to provide a kind of integral type macromole type discharging without organic solvent, unharmful substance
Low-smoke halogen-free expansion flame-retarded dose of preparation method.
The technical solution used in the present invention is: by multiamino compound, phosphoric acid and isocyanuric acid three-glycidyl ester
Reacted in aqueous, synthesized the macromole type expandable flame retardant that a kind of collection " acid source, source of the gas, charcoal source " three comes from one
Agent, this fire retardant has excellent fire resistance and heat stability and resistance to water, and entirely preparation is simple, in nothing
Mesosome separation process, the whole response time is only 3 hours, and with water as solvent, without other organic solvents, course of reaction zero is organic
Thing discharges.When using it for polyolefin flame-retardant modification, prepared fire retardant polyolefin composite material shows excellent fire-retardant effect
Fruit and resistance to water, neat coal amout is high and layer of charcoal is fine and close.
Specific embodiments of the present invention are as follows:
A kind of preparation method of low-smoke halogen-free expansion flame-retarded dose of the three-source integrated formula of macromole type it is characterised in that:
Comprise the following steps:
(1) phosphoric acid is reacted in aqueous with multiamino compound, reacted 1-2 hour, aqueous temperature is controlled in 70-
90℃；
(2) add the aqueous solution of isocyanuric acid three-glycidyl ester in above-mentioned reaction solution, insulation continues reaction 1-2h, subsequently
Cool down, filter, being dried to obtain macromole integral type expansion type flame retardant.
A kind of preparation method of low-smoke halogen-free expansion flame-retarded dose described of the three-source integrated formula of macromole type it is characterised in that:
Described multiamino compound can be one of cyanuric acid, tripolycyanamide, 2- imidazolidinone, hydantoin.
A kind of preparation method of low-smoke halogen-free expansion flame-retarded dose described of the three-source integrated formula of macromole type it is characterised in that:
Phosphoric acid is controlled in 1:3～1:0.8 with the mol ratio of multiamino compound.
A kind of preparation method of low-smoke halogen-free expansion flame-retarded dose described of the three-source integrated formula of macromole type it is characterised in that:
Isocyanuric acid three-glycidyl ester is controlled in 1:5～1:1 with the mol ratio of multiamino compound.
The present invention first passes through phosphoric acid and reacts formation phosphate with multiamino compound, adds isocyanuric acid three-glycidyl
Ester and unreacted amino carry out epoxy ring opening reaction, define a kind of simultaneously containing nitrogen, phosphorus, carbon three element there is branched knot
The macromole type compound flame retardant of structure.
Wherein said multiamino compound can be cyanuric acid, tripolycyanamide, 2- imidazolidinone, hydantoin.With three
As a example poly cyanamid, its reactive chemistry formula such as Fig. 1.
The present invention compared with prior art has advantages below and a beneficial effect:
(1) nitrogen, phosphorus, carbon three element are simultaneously introduced in same molecular structure, and define the collection with branched structure by the present invention
" three sources ", in the macromole type expanding fire retardant of one, improves heat stability, resistance to water and and the polyphosphazene polymer of fire retardant
The compatibility of compound；
(2) present invention is with water as solvent, without organic solvent, and no coupling product produces, and water can recycle, it is to avoid right
Environment and equipment impact；
(3) reaction is not related to the separation of intermediate product, and process is simple is with short production cycle.
Brief description
Fig. 1 is described multiamino compound；
Fig. 2 be embodiment gained macromole expanding fire retardant heat decomposition curve (temperature of initial decomposition reaches 290oC).
Specific embodiment
Example below is that the present invention is described in detail.But embodiments of the present invention are not limited to that.
Embodiment 1
Add 250ml water in the there-necked flask of 500ml, and 40 g phosphoric acid solutions (85 %, about 0.35mol), after stirring,
Heating in water bath is to 80oC, is dividedly in some parts 44g tripolycyanamide (about 0.35mol), and quick stirring, 80o2h. is reacted under c
By 29.7g(about 0.1mol) isocyanuric acid three-glycidyl ester is placed in 150ml water, is heated to 80oC is allowed to be completely dissolved
Transparent shape solution, is then poured in above-mentioned there-necked flask, quick stirring, and continues insulation reaction 1.5h.Cooled and filtered, does
Dry obtain product 93g, yield 92%.
Water solublity measures: weighs fire-retardant powder 0.5g, is wrapped with filter paper, is placed in 500ml water, 70oC insulation 72h takes
Go out, 120oC is dried and is weighed, and recording water solublity is 0.015g/100ml water.
Embodiment 2
In addition 250ml water in the there-necked flask of 500ml, and 20g phosphoric acid solution (85 %, about 0.175mol), stir
Afterwards, heating in water bath is to 90oC, is dividedly in some parts 37.8g tripolycyanamide (about 0.3mol), and quick stirring, 90o1h. is reacted under c
By 44.5g(about 0.15mol) isocyanuric acid three-glycidyl ester is placed in 150ml water, is heated to 80oC is allowed to completely molten
Solve transparent shape solution, be then poured in above-mentioned there-necked flask, quick stirring, and continue insulation reaction 2h.Cooled and filtered, does
Dry obtain product 86g, yield 95%.
Water solublity measures: weighs fire-retardant powder 0.5g, is wrapped with filter paper, is placed in 500ml water, 70oC insulation 72h takes
Go out, 120oC is dried and is weighed, and recording water solublity is 0.014g/100ml water.
Embodiment 3
Add 250ml water in the there-necked flask of 500ml, and 57.6g phosphoric acid solution (85 %, about 0.5mol), after stirring,
Heating in water bath is to 80oC, is dividedly in some parts 50.5g tripolycyanamide (about 0.4mol), and quick stirring, 80o2h. is reacted under c
By 29.7g(about 0.1mol) isocyanuric acid three-glycidyl ester is placed in 150ml water, is heated to 80oC is allowed to be completely dissolved
Transparent shape solution, is then poured in above-mentioned there-necked flask, quick stirring, and continues insulation reaction 1.5h.Cooled and filtered, does
Dry obtain product 99g, yield 94%.
Water solublity measures: weighs fire-retardant powder 0.5g, is wrapped with filter paper, is placed in 500ml water, 70oC insulation 72h takes
Go out, 120oC is dried and is weighed, and recording water solublity is 0.019g/100ml water.
Embodiment 4
Add 250ml water in the there-necked flask of 500ml, and 40 g phosphoric acid solutions (85 %, about 0.35 mol), after stirring,
Heating in water bath is to 80oC, is dividedly in some parts 34.5g 2- imidazolidinone (about 0.4 mol), and quick stirring, 80o2h. is reacted under c
By 44.5 g(about 0.15mol) isocyanuric acid three-glycidyl ester is placed in 150ml water, is heated to 80oC is allowed to completely molten
Solve transparent shape solution, be then poured in above-mentioned there-necked flask, quick stirring, and continue insulation reaction 1.5h.Cooled and filtered,
It is dried to obtain product 104 g, yield 92%.
Water solublity measures: weighs fire-retardant powder 0.5g, is wrapped with filter paper, is placed in 500ml water, 70oC insulation 72h takes
Go out, 120oC is dried and is weighed, and recording water solublity is 0.017g/100ml water.
Embodiment 5
Add 250ml water in the there-necked flask of 500ml, and 80.5 g phosphoric acid (85 %, about 0.7mol), after stirring, water-bath
It is heated to 80oC, is dividedly in some parts 45g cyanuric acid (about 0.35mol), and quick stirring, 80o2h. is reacted under c
By 29.7g(about 0.1mol) isocyanuric acid three-glycidyl ester is placed in 150ml water, is heated to 80oC is allowed to be completely dissolved
Transparent shape solution, is then poured in above-mentioned there-necked flask, quick stirring, and continues insulation reaction 1.5h.Cooled and filtered, does
Dry obtain product 137g, yield 96%.
Water solublity measures: weighs fire-retardant powder 0.5g, is wrapped with filter paper, is placed in 500ml water, 70oC insulation 72h takes
Go out, 120oC is dried and is weighed, and recording water solublity is 0.015g/100ml water.
Embodiment 6
Add 250ml water in the there-necked flask of 500ml, and 46 g phosphoric acid (85 %, about 0.4mol), after stirring, water-bath adds
Heat is to 80oC, is dividedly in some parts 151g tripolycyanamide (about 1.2 mol), and quick stirring, 80o2h. is reacted under c
By 59.5 g(about 0.2mol) isocyanuric acid three-glycidyl ester is placed in 150 ml water, is heated to 80oC is allowed to completely molten
Solve transparent shape solution, be then poured in above-mentioned there-necked flask, quick stirring, and continue insulation reaction 1.5h.Cooled and filtered,
It is dried to obtain product 237 g, yield 95 %.
Water solublity measures: weighs fire-retardant powder 0.5g, is wrapped with filter paper, is placed in 500ml water, 70oC insulation 72h takes
Go out, 120oC is dried and is weighed, and recording water solublity is 0.012g/100ml water.
Respectively the expansion type flame retardant prepared by embodiment 1-6 is added in acrylic resin according to 20 wt % additions,
It is prepared into standard specimen, respectively test oxygen index (OI) (loi) and vertical combustion (ul-94) experiment after 180oc mixing 15min.Result
It is as follows:
| Sample | Ifr content (wt%) | Loi (%) | ul-94 |
| Ifr embodiment 1 | 20 | 32 | v-0 |
| Ifr embodiment 2 | 20 | 31 | v-0 |
| Ifr embodiment 3 | 20 | 30 | v-0 |
| Ifr embodiment 4 | 20 | 30 | v-0 |
| Ifr embodiment 5 | 20 | 33 | v-0 |
| Ifr embodiment 6 | 20 | 32 | v-0 |
Claims (4)
1. a kind of low-smoke halogen-free expansion flame-retarded dose of the three-source integrated formula of macromole type preparation method it is characterised in that:
Comprise the following steps:
(1) phosphoric acid is reacted in aqueous with multiamino compound, reacted 1-2 hour, aqueous temperature is controlled in 70-
90℃；
(2) add the aqueous solution of isocyanuric acid three-glycidyl ester in above-mentioned reaction solution, insulation continues reaction 1-2h, subsequently
Cool down, filter, being dried to obtain macromole integral type expansion type flame retardant.
2. the preparation method of low-smoke halogen-free expansion flame-retarded dose of the three-source integrated formula of a kind of macromole type according to claim 1,
It is characterized in that: described multiamino compound can be cyanuric acid, tripolycyanamide, 2- imidazolidinone, in hydantoin one
Kind.
3. the preparation method of low-smoke halogen-free expansion flame-retarded dose of the three-source integrated formula of a kind of macromole type according to claim 1,
It is characterized in that: phosphoric acid is controlled in 1:3～1:0.8 with the mol ratio of multiamino compound.
4. the preparation method of low-smoke halogen-free expansion flame-retarded dose of the three-source integrated formula of a kind of macromole type according to claim 1,
It is characterized in that: isocyanuric acid three-glycidyl ester is controlled in 1:5～1:1 with the mol ratio of multiamino compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201654A (en) * | 2017-06-30 | 2017-09-26 | 四川东方绝缘材料股份有限公司 | A kind of washable fire-retardant polyester cotton and preparation method thereof |
| CN107602839A (en) * | 2017-10-16 | 2018-01-19 | 中山康诺德新材料有限公司 | A kind of water resistance halogen-free expansion fire retardant and preparation method thereof |
| CN116284132A (en) * | 2023-02-28 | 2023-06-23 | 苏州大学 | Phosphorus/nitrogen flame retardant, preparation method thereof and application thereof in protein fiber product finishing |
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| CN102585292A (en) * | 2012-02-28 | 2012-07-18 | 中科院广州化学有限公司 | Epoxy resin reaction-type microcapsule fire retardant and preparation method thereof |
| CN104693485A (en) * | 2015-03-18 | 2015-06-10 | 苏州安鸿泰新材料有限公司 | Halogen-free intumescent compound flame retardant and application thereof in high-density polyethylene |
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2016
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| CN101362819B (en) * | 2008-09-10 | 2011-04-27 | 华南理工大学 | Triazines cross-linking compounds, preparation method and application thereof |
| CN102585292A (en) * | 2012-02-28 | 2012-07-18 | 中科院广州化学有限公司 | Epoxy resin reaction-type microcapsule fire retardant and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107201654A (en) * | 2017-06-30 | 2017-09-26 | 四川东方绝缘材料股份有限公司 | A kind of washable fire-retardant polyester cotton and preparation method thereof |
| CN107602839A (en) * | 2017-10-16 | 2018-01-19 | 中山康诺德新材料有限公司 | A kind of water resistance halogen-free expansion fire retardant and preparation method thereof |
| CN116284132A (en) * | 2023-02-28 | 2023-06-23 | 苏州大学 | Phosphorus/nitrogen flame retardant, preparation method thereof and application thereof in protein fiber product finishing |
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Application publication date: 20170125 |