CN104098775B - A kind of halogen-free expansion fire retardant of resistance to migration and preparation method and application - Google Patents
A kind of halogen-free expansion fire retardant of resistance to migration and preparation method and application Download PDFInfo
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Abstract
The present invention relates to technical field of flame retardant agent preparation, for solving the easy moisture absorption of halogen-free expansion fire retardant, poor water resistance, poor compatibility in the polymer such as polyolefin, in hot and humid lower easy migration and precipitation, it is low that surface processes treatment effeciency, the easily problem such as destroyed, the present invention proposes a kind of halogen-free expansion fire retardant of resistance to migration and preparation method and application, and the halogen-free expansion fire retardant of resistance to migration structural formula is as shown in (I):
Description
Technical field
The present invention relates to technical field of flame retardant agent preparation, relate in particular to a kind of halogen-free expansion fire retardant of resistance to migration and
Its preparation method and application.
Background technology
Halogen-free expansible halogen-free flame retardants based on ammonium polyphosphate has become current industrialization more successfully nothing
Halogen fire retardant kind, is widely used in polyolefin such as polypropylene, polyethylene, EVA, EPDM, POE, thermoplastic elastomer (TPE) as and poly-ammonia
In ester elastomer, TPE, TPV, there is preferable flame retarding efficiency and good processing characteristics, the mechanical property of material is also had order
The result that people is satisfied.But it is as the polymer of a kind of phosphorus, and the problem that there is easy moisture absorption, facile hydrolysis, particularly hot and humid
Under the conditions of easily migration precipitation, additionally the best with in the non-polar material compatibility such as polyolefin, when extrusion, screw speed is subject to
To limiting, affect production efficiency.Research at present is concentrated mainly on and improves fire retardant itself by the method for surface modification and cladding
Resistance to water and with the compatibility of polymer, typically use silane, melamine resin (MF resin), epoxy resin etc. to enter
Row surface processes, but it is all heat cured, and fire-retardant particles can be caused in processing procedure to bond, and granule is excessive, once enters
Row is pulverized, and surface breakdown additionally under screw rod Strong shear, also can destroy covered effect, it is impossible to obtain stable water-fast effect.
Patent CN103265500A proposes and uses formaldehyde to make the intermolecular generation crosslinking of fire retardant as cross-linking agent, come
The method improving the resistance to water of fire retardant, but there is a drawback in the method, owing to using formaldehyde as cross-linking agent, cross-linking process
-the CH of middle formation2-O-CH2-key, can be converted into-CH during being heated and using2-, methylenation, simultaneously release formaldehyde, this
Performance, the environment of material is exerted an adverse impact.
Summary of the invention
For solving the easy moisture absorption of halogen-free expansion fire retardant, poor water resistance, poor compatibility in the polymer such as polyolefin, at height
Easily migrating under temperature high humidity and separate out, the problems such as it is low that surface processes treatment effeciency, the most destroyed, the present invention proposes a kind of resistance to migration
Halogen-free expansion fire retardant and preparation method and application, present invention achieves the crosslinking between flame retardant molecule, improves resistance to water,
Particularly in resistance to migration and the precipitation performance of hot and humid condition.
The present invention is achieved by the following technical solutions: a kind of halogen-free expansion fire retardant of resistance to migration has-Si-O-R-
The cross-linked structure of O-Si-, structural formula is as shown in (I):
Wherein: R1Selected from CH3Or C6H5, positive integer in n=1～10000, m=1～100, b=1～500, M is selected from three
In poly cyanamid and derivant, morpholine, piperidines, piperazine, alkyl hydroxyl polyamines, nitrogenous aerotex one or several
Kind.M is preferably tripolycyanamide and derivant thereof, alkyl hydroxyl polyamines, in nitrogenous aerotex one or more, its
In nitrogenous aerotex there is following chemical constitution:
Wherein, D=heterocycle, piperazine, polyamine.
The present invention uses and introduces siloxanes in the P-O chain of fire retardant polyphosphoric acid, improves fire-retardant by alkyl on siloxanes
Agent itself and the compatibility of polymer.Utilize the alkoxyl of reservation simultaneously, by self dealcoholysis, form Si-OH, then contract
Close, formation-Si-O-Si-, it is achieved the crosslinking between flame retardant molecule, improve resistance to water, particularly move the resistance to of hot and humid condition
Move and separate out performance.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration of the present invention is following steps:
(1) preparation of phosphorus silicon compound
By reactor nitrogen charging-evacuation, after circulation several times, add diammonium phosphate under nitrogen protection, 30～150
DEG C, preferably 60～-120 DEG C, stir 1～3 hour after stirring lower spraying alkylsiloxane, be then warmed up to 50～250 DEG C, excellent
Electing 80～230 DEG C as, start evacuation devolatilization, vacuum is 0.005～0.08MPa continuation reaction 0.5～15 hour, is preferably
1～12 hour, obtain phosphorus silicon compound；The synthesis type of phosphorus silicon compound is as follows:
As preferably, in step (1), the cycle-index of reactor nitrogen charging-evacuation is more than 1～5 time.
Described alkylsiloxane is selected from MTMS, MTES, phenyl trimethoxy silicon
Alkane, phenyl triethoxysilane one or more.It is preferably MTMS, the one of phenyltrimethoxysila,e
Or it is several.
The moisture of described diammonium phosphate is less than 0.1%, the mol ratio of diammonium phosphate and alkylsiloxane be 1: 0.1～
3, preferred molar ratio is 1: 0.3～1.5.
(2) preparation of polymer A
In mediating reactor, put into phosphorus silicon compound and diammonium phosphate stirring prepared by step (1), be subsequently adding water
Stir 1～3 hour, add phosphorus pentoxide stirring, start to warm up logical ammonia, react 1 hour～5 at 200 DEG C～350 DEG C
Hour, wherein the ratio of ammonia intake and reactant is that to lead to ammonia amount be 0.5-5m to 100 kilograms of reactants3/ hour, then at 200-
At 280 DEG C, every 100 kilograms of reactants 0.1～2.0m3/ hour logical ammonia amount under continue reaction 0.5～5 hour after stop logical ammonia
Heating, then lead to 0.1-0.5m3/ hour N2, be cooled to 40～60 DEG C, pulverize and sieve, obtain polymer A, polymer A have as
(II) structural formula shown in:
Wherein: R1Selected from CH3Or C6H5；
As preferably, the rotating speed mediating reactor is 40～80 revs/min；
The mol ratio of described phosphorus silicon compound and diammonium phosphate is 1: 0.01～1, preferred molar ratio be 1: 0.03～-
0.3, the usage amount of water is the 0.1～-0.6% of the 0.05～1% of phosphorus silicon compound weight, preferably phosphorus silicon compound weight,
The usage amount of phosphorus pentoxide is the molal quantity sum of diammonium phosphate and phosphorus silicon compound.
(3) preparation of polymer B
In mediating reactor, it is passed through drying nitrogen, polymer A and M prepared by step (2) will be added under nitrogen protection,
Reacting 1～10 hour under 80～250 DEG C (preferably 100～-220 DEG C), obtain polymer B, polymer B has such as (III)
Shown structural formula:
Reaction equation is as follows:
Wherein M gathers selected from tripolycyanamide and derivant thereof, morpholine, piperidines, piperazine, alkyl hydroxyl polyamines, nitrogenous triazine
In compound one or more；The usage amount of M is the 0.5～50% of polymer A weight.
(4) cross-linking reaction
In mediating reactor, add polymer B prepared by step (3), add water stirring, heat up, at 60～100 DEG C
Reacting 0.2～4 hour, then vacuum volatilization, vacuum is 0.005～0.08Mpa, then is warmed up to 110～180 DEG C, continues anti-
Answer 0.5～8 hour, obtain the halogen-free expansion fire retardant of resistance to migration.Reaction equation is as follows:
The usage amount of described water is the 0.2～2% of polymer B weight.
The one halogen-free expansion fire retardant of resistance to migration of the present invention is Halogen resistance on polyolefin and thermoplastic elastomer (TPE)
The application of combustion.The prepared halogen-free expansion fire retardant of resistance to migration is applied to the halogen-free flameproof of polyolefin and thermoplastic elastomer (TPE),
There are the excellent compatibility, resistance to migration and precipitation with polymer, in the case of hot and humid, particularly have good resistance to precipitation performance.
Described polyolefin is polypropylene, polyethylene, EVA, EPDM, POE；Described thermoplastic elastomer (TPE) is that polyurethane thermoplastic is elastic
Body, SEBE base TPE thermoplastic elastomer (TPE), TPV.
Compared with prior art, the invention has the beneficial effects as follows: the crosslinking that present invention achieves between flame retardant molecule, carry
Enhanced water resistance, particularly in resistance to migration and the precipitation performance of hot and humid condition.
Detailed description of the invention
Below by following example, this explanation is described in further details, but the present invention is not limited to these enforcement
Example.In embodiment raw materials used the most commercially available.
Embodiment 1
(1) preparation of phosphorus silicon compound
Horizontal reactor nitrogen charging-evacuation, after circulating three times, adds diammonium phosphate under nitrogen protection and (requires water
Point < 0.1%) 132 kilograms, at 85 DEG C (preferably 60-120 DEG C), stirring is lower sprays MTMS 136 kilograms, stirs
Mix 2 hours.It is warmed up to 90 DEG C, starts evacuation devolatilization, vacuum 0.05Mpa, continue reaction 10 hours, obtain phosphorus silicon compound
1。
(2) preparation of polymer A
In mediating reactor, put into phosphorus silicon compound 1 and the diammonium phosphate (DAP) 105.6 kilograms of 23.6 kilograms, stir
Mix uniformly, add 0.10 kilogram of water, stir 2 hours, add phosphorus pentoxide (P2O5) 142 kilograms, stir, start to warm up
Logical ammonia.Reacting at 200 DEG C-280 DEG C 4 hours, wherein ammonia intake is that 100 kilograms of reactants lead to ammonia amount with the ratio of reactant
For 3m3/ hour.At 250 DEG C, every 100 kilograms of reactant 1.0m3/ hour logical ammonia amount under continue reaction 2 hours, obtain white
Pressed powder.Stop logical ammonia heating, logical 0.3m3/ hour N2, it is cooled to 50 DEG C, pulverizes and sieves, obtain polymer A 1.
(3) preparation of polymer B
In mediating reactor, it is passed through drying nitrogen, under nitrogen protection, adds 150 kg polymer A1 and tripolycyanamide
5 kilograms, nitrogenous aerotex 45 kilograms, 110 DEG C of reactions, after being raised to 200 DEG C in 2 hours, continue reaction 4 hours,
To polymer B 1.
(4) cross-linking reaction
In mediating reactor, add polymer B 1, add the water of its weight 1%, stir, heat up, anti-at 90 DEG C
Answering 2 hours, start vacuum volatilization, vacuum is 0.05Mpa, is warmed up to 160 DEG C, continues reaction 2 hours, obtains the Halogen of resistance to migration
Expansion type flame retardant 1.
Embodiment 2
The step of embodiment 2, with embodiment 1, puts into phosphorus silicon compound 1 and the phosphoric acid hydrogen two of 11.8 kilograms in step (2)
Ammonium (DAP) 119 kilograms, prepares the halogen-free expansion fire retardant of resistance to migration 2.
Embodiment 3
(1) preparation of phosphorus silicon compound
Horizontal reactor nitrogen charging-evacuation, after circulating three times, adds diammonium phosphate under nitrogen protection and (requires water
Point < 0.1%) 132 kilograms, at 100 DEG C, stirring is lower sprays phenyltrimethoxysila,e 198 kilograms, stirs 2 hours.It is warmed up to
180 DEG C, start evacuation devolatilization, vacuum 0.05Mpa, continue reaction 8 hours, obtain phosphorus silicon compound 3.
(2) preparation of polymer A
Phosphorus silicon compound 3 and the diammonium phosphate (DAP) 105.6 kilograms of 34.2 kilograms is put in mediating reactor.Its
Remaining preparation method, with embodiment 1, prepares the halogen-free expansion fire retardant of resistance to migration 3.
Embodiment 4
The step of embodiment 4, with embodiment 1, puts into phosphorus silicon compound 1 and the phosphoric acid hydrogen two of 17.1 kilograms in step (2)
Ammonium (DAP) 119 kilograms, prepares the halogen-free expansion fire retardant of resistance to migration 4.
Embodiment 5
The step of embodiment 54, with embodiment 1, puts into the phosphorus silicon compound 1,17.1 kilograms of 11.8 kilograms in step (2)
Phosphorus silicon compound 3, diammonium phosphate (DAP) 105.6 kilograms, prepare the halogen-free expansion fire retardant of resistance to migration 5.
Test case
The prepared halogen-free expansion fire retardant of resistance to migration 1～5 properties of product that embodiment 1～5 prepares contrast table such as table 1 institute
Show:
Table 1:
Table 1 data show, the difference of 1% is less.Thermal weight loss temperature from 2% finds the heat stability of phenyl, and whiteness is good.
Application examples 1～5
Carrying out extruding pelletization processing, extruder 5 district on Ф 36 twin screw, processing temperature is 120-160-180-190-
160 DEG C, screw speed is 300RPM.Following formula is carried out extruding pelletization processing, obtains the fire-retardant PP of formula.Performance such as table
Shown in 2:
Table 2:
Remarks:
1, PP: homopolymerization, MI=2.3, raises sub-petrochemical industry
2, antioxidant: 1010:168=2:1
3, glass fibre: the short fibre of alkali-free, 12mm
4, fire retardant flame retardant amount 0.5% VTES processes
Comparative example
Using tradition halogen-free expanded flame-retardant agent, JLS-PNP1, Hangzhou JLS Flame Retardants Chemical Co., Ltd. produces.Performance is such as
Shown in table 3:
Table 3:
| Comparative example | PP | JLS-PNP1 | Glass fibre | Antioxidant | Calcium stearate |
| Comparative example 1 | 74 | 26 | 0 | 0.2 | 0.2 |
| Comparative example 2 | 65 | 35 | 0 | 0.2 | 0.2 |
| Comparative example 3 | 61 | 24 | 15 | 0.2 | 0.2 |
Application examples is as shown in table 4 with the Performance comparision of comparative example:
Table 4:
1. water extraction yield test condition: 10cm X5cm, thickness is that the plate of 0.4mm soaks 168 hours in the water of 70 DEG C
2. disruptive test: 20cm X20cm, thickness be the plate of 0.4mm at 80 DEG C, the climatic chamber of 85 humidity is put
72 hours, blot surface moisture, carry out proof voltage test.
From table 4, it appeared that silicon content has negative effect to fire-retardant, increase resistance to water with silicon content and be significantly improved.
Additionally somewhat not good enough than methyl of phenyl fire resistance, but compare first in resistance to water, the most hot and humid rear proof voltage performance
Base good, has remarkable result in mechanical performance and hot and humid rear proof voltage performance after coupling agent treatment.Use phenyl and first
The anti-dripping melt of base mixing is good, can reach UL94V00.8mm.After having added glass, water-fast extractibility is decreased obviously simultaneously, mainly
Being in soak test, water adds internal causing along glass, and immersion is it is apparent that thin-line-shaped white vestige occurs in surface.
Not having siloxanes to participate in polymerization, the JLS-PNP1 without cross-linked structure is serious in hot and humid lower migration precipitation, resistance to
Voltage performance is very poor, and processing characteristics, mechanical property are the most bad.
Claims (9)
1. the halogen-free expansion fire retardant of resistance to migration, it is characterised in that the described one halogen-free expansion fire retardant of resistance to migration
Having the cross-linked structure of-Si-O-R-O-Si-, structural formula is as shown in (I):
(I),
Wherein: R1 is selected from CH3Or C6H5, n=1 ~ 10000, m=1 ~ 100, positive integer in b=1 ~ 500, M selected from tripolycyanamide and
One or more in derivant, morpholine, piperidines, piperazine, alkyl hydroxyl polyamines, nitrogenous aerotex.
2. the preparation method of a kind of halogen-free expansion fire retardant of resistance to migration as claimed in claim 1, it is characterised in that institute
The preparation method stated is following steps:
(1) preparation of phosphorus silicon compound
By reactor nitrogen charging-evacuation, after circulation several times, add diammonium phosphate under nitrogen protection, at 30 ~ 150 DEG C,
Stirring 1 ~ 3 hour after stirring lower sprinkling alkylsiloxane, be then warmed up to 50 ~ 250 DEG C, start evacuation devolatilization, vacuum is
0.005 ~ 0.08MPa continues reaction 0.5 ~ 15 hour, obtains phosphorus silicon compound；
Described alkylsiloxane is selected from MTMS, MTES, phenyltrimethoxysila,e, benzene
One or more of ethyl triethoxy silicane alkane；
(2) preparation of polymer A
In mediating reactor, put into phosphorus silicon compound and diammonium phosphate stirring prepared by step (1), be subsequently adding water stirring 1
~ 3 hours, add phosphorus pentoxide stirring, start to warm up logical ammonia, react 1 hour～5 hours at 200 DEG C ~ 350 DEG C, its
The ratio of middle ammonia intake and reactant is that to lead to ammonia amount be 0.5-5m to 100 kilograms of reactants3/ hour, then at 200-280 DEG C,
Every 100 kilograms of reactant 0.1 ~ 2.0 m3/ hour logical ammonia amount under continue reaction 0.5 ~ 5 hour after stop logical ammonia heating, then lead to
0.1-0.5 m3/ hour N2, it being cooled to 40 ~ 60 DEG C, pulverize and sieve, obtain polymer A, polymer A has as shown in (II)
Structural formula:
(II),
Wherein: R1Selected from CH3Or C6H5；
(3) preparation of polymer B
In mediating reactor, it is passed through drying nitrogen, polymer A and M will be added under nitrogen protection, at 80 ~ 250 DEG C, react 1
~ 10 hours, obtaining polymer B, polymer B has a structural formula as shown in (III):
(III)；
Wherein M is selected from tripolycyanamide and derivant, morpholine, piperidines, piperazine, alkyl hydroxyl polyamines, nitrogenous aerotex
In one or more；
(4) cross-linking reaction
In kneading reactor, add polymer B, add water stirring, heat up, reaction 0.2 ~ 4 hour at 60 ~ 100 DEG C, then
Vacuum volatilization, vacuum is 0.005 ~ 0.08MPa, then is warmed up to 110 ~ 180 DEG C, continues reaction 0.5 ~ 8 hour, obtains resistance to migration
Halogen-free expansion fire retardant.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration the most according to claim 2, it is characterised in that step
(1) in, the cycle-index of reactor nitrogen charging-evacuation is 1 ~ 5 time.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration the most according to claim 2, it is characterised in that step
(1) moisture of diammonium phosphate described in is less than 0.1%, and diammonium phosphate is 1:0.1 ~ 3 with the mol ratio of alkylsiloxane.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration the most according to claim 2, it is characterised in that step
(2) rotating speed mediating reactor in is 40 ~ 80 revs/min.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration the most according to claim 2, it is characterised in that step
(2) in, phosphorus silicon compound is 1:0.01 ~ 1 with the mol ratio of diammonium phosphate, and the usage amount of water is phosphorus silicon compound weight
0.05 ~ 1%, the usage amount of phosphorus pentoxide is the molal quantity sum of diammonium phosphate and phosphorus silicon compound.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration the most according to claim 2, it is characterised in that step
(3) in, the usage amount of M is the 0.5 ~ 50% of polymer A weight.
The preparation method of a kind of halogen-free expansion fire retardant of resistance to migration the most according to claim 2, it is characterised in that step
Suddenly in (4) usage amount is polymer B weight the 0.2 ~ 2% of water.
9. the one halogen-free expansion fire retardant of resistance to migration as claimed in claim 1 is on polyolefin and thermoplastic elastomer (TPE)
The application of halogen-free flameproof.
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| CN107286342B (en) * | 2017-08-07 | 2019-08-16 | 顺德职业技术学院 | " phosphorus-silicon-nitrogen " oligomer formula expansion type flame retardant and its synthetic method containing triazine ring |
| CN109096616B (en) * | 2018-08-30 | 2021-08-31 | 杭州捷尔思阻燃化工有限公司 | Long glass fiber reinforced halogen-free flame-retardant polypropylene battery jar material and preparation method thereof |
| CN110229415B (en) * | 2019-05-27 | 2021-11-19 | 中广核俊尔(浙江)新材料有限公司 | Flame-retardant-grade continuous glass fiber reinforced polypropylene prepreg tape material and preparation method thereof |
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| CN1834138A (en) * | 2005-03-20 | 2006-09-20 | 杭州捷尔思阻燃化工有限公司 | Prepn. of expanding halide-free fire-retardant and products thereof |
| CN101597044A (en) * | 2009-07-15 | 2009-12-09 | 广东聚石化学股份有限公司 | The preparation method of the crystal II-type ammonium polyphosphate of high-polymerization degree narrow molecular weight distributions |
| CN101987728A (en) * | 2010-11-15 | 2011-03-23 | 华东理工大学 | Method for preparing crystal V-type ammonium polyphosphate by phosphorus pentoxide material route |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834138A (en) * | 2005-03-20 | 2006-09-20 | 杭州捷尔思阻燃化工有限公司 | Prepn. of expanding halide-free fire-retardant and products thereof |
| CN101597044A (en) * | 2009-07-15 | 2009-12-09 | 广东聚石化学股份有限公司 | The preparation method of the crystal II-type ammonium polyphosphate of high-polymerization degree narrow molecular weight distributions |
| CN101987728A (en) * | 2010-11-15 | 2011-03-23 | 华东理工大学 | Method for preparing crystal V-type ammonium polyphosphate by phosphorus pentoxide material route |
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