CN110183774A - A kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material - Google Patents
A kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material Download PDFInfo
- Publication number
- CN110183774A CN110183774A CN201910617246.6A CN201910617246A CN110183774A CN 110183774 A CN110183774 A CN 110183774A CN 201910617246 A CN201910617246 A CN 201910617246A CN 110183774 A CN110183774 A CN 110183774A
- Authority
- CN
- China
- Prior art keywords
- composite material
- smoke
- flame retardant
- phosphorus
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material, it is that organic phospho acid is dissolved in distilled water, inorganic particle is added at 80 ~ 100 DEG C, after being stirred to react 6 ~ 10h, filtering, is washed repeatedly with distilled water and obtains a modified product；A modified product is mixed with nitrogenous compound again, 3 ~ 5 h are stirred to react at 80 ~ 100 DEG C, filters, obtains the inorganic fire retardants of organic functional；Dry EVA particle and expansible graphite, organic functional inorganic fire retardants are placed on mixer after being kneaded in compression moulding on cold press to get EVA composite material.Test shows that the oxygen index (OI) of EVA composite material may be up to 32.0, and cigarette yield only has 4.0 m2, there is good flame-retardant smoke inhibition effect, and composite material is still able to maintain excellent mechanical property.
Description
Technical field
The present invention relates to a kind of preparation method of LSOH anti-flaming EVA composite material more particularly to a kind of phosphorus-nitrogen type without
The preparation method of halogen low-smoke and flame retardant EVA composite material, belongs to fire proofing technical field and technical field of polymer materials.
Background technique
Ethylene-vinyl acetate copolymer (EVA) is a kind of thermoplastic macromolecule material, because it is with light, resistance to ag(e)ing
And good impact resistance and excellent electrical insulation capability, and it is widely used in the fields such as traffic, building, household electrical appliance.But
The limit oxygen index (LOI) for being EVA is only 18, belongs to combustible material, and thermal discharge and smoke amount are big and adjoint in combustion
Serious melting drip phenomenon, spread fire-propagation and discharge toxic gas.Therefore prepare Halogen, low cigarette environmental protection it is fire-retardant
Type EVA material has become an important developing direction.
By ignition-proof element type, fire retardant be often divided into halogen system, organic phosphorus and halogen-phosphorus system, nitrogen system, phosphorus-nitrogen system, antimony system,
Phos system, boron system, molybdenum system, metal hydroxides etc..Former classes belong to organic fire-retardant, and rear several classes belong to inorganic fire retardants.
Wherein, halogenated flame retardant has a very high flame retarding efficiency, but can be discharged in view of halogenated flame retardant in burning a large amount of smog with
And toxic gas, the health and property safety of the mankind are severely compromised, so being gradually eliminated.To reduce or eliminating pair
The pollution of environment and harm to the mankind, Halogen, low cigarette, low toxicity environment friendly flame retardant have become the target of people's pursuit.
Halogen-free flame retardants principal item is phosphorus flame retardant and metal hydroxides, additionally some nitrogenous, silicon etc..Metal hydroxides
Mainly include aluminium hydroxide, magnesium hydroxide and modified material such as hydrotalcite etc., mainly by it is heated when the cooling quilt of endothermic decomposition
Fire-retardant matrix, make its temperature be down to maintain to burn necessary to temperature hereinafter, in addition, generating during endothermic decomposition
As middle combustible concentration, the residue thermally decomposed to generate can be used as again for vapor and other non-combustible gas energy carrier gas
Effective barrier prevents underlying substrate from further decomposing under heat effect.But it since inorganic particle surfaces can be high, is easily gathered into
Group, at the same it is very poor with high polymer binding ability, boundary defect is easily caused, causes Properties of Polymer suppression ratio more, therefore is needed
It is modified that surface is carried out to it, also improve the dispersibility of inorganic particle in the base while improving matrix anti-flammability.
Summary of the invention
The purpose of the present invention is aiming at the problem that EVA exists in practical applications, provide a kind of phosphorus-nitrogen type halogen-free low cigarette resistance
Fire the preparation method of EVA composite material.
One, the preparation of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material
The method that the present invention prepares phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material, comprising the following steps:
(1) preparation of organic functional inorganic fire retardants: organic phospho acid is dissolved in distilled water, and nothing is added at 80 ~ 100 DEG C
Machine particle, after being stirred to react 6 ~ 10h, filtering is washed repeatedly with distilled water and obtains a modified product；Again by a modified product
It is mixed with nitrogenous compound, 3 ~ 5 h is stirred to react at 80 ~ 100 DEG C, filtered, obtain the inorganic fire retardants of organic functional；
Wherein, organic phospho acid is diethylene triamine pentamethylene phosphonic, phenyl-phosphonic acid, ethylenediamine tetramethylene phosphonic acid, amino trimethylene
Methylphosphonic acid；Inorganic particle is magnesium hydroxide, aluminium hydroxide, palygorskite, hydrotalcite or the montmorillonite of 400 ~ 600 nm of partial size, and
The mass ratio of organic phospho acid and inorganic particles is 1:1 ~ 6:1.Nitrogenous compound is melamine, urea, p-phenylenediamine, polyethylene
Imines etc.；The mass ratio of nitrogenous compound and inorganic particles is 1:1 ~ 5:1.
In order to improve the oxygen index (OI) of composite material, the compatibility of fire retardant and EVA is improved, by the nothing of the machine functionalization of synthesis
Machine fire retardant is in the ball mill with 1 ~ 3 h of revolving speed ball milling of 300 ~ 800 r/min.
(2) synthesis of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material: by dry EVA particle and expansible graphite, on
The organic functional inorganic fire retardants for stating preparation is placed in mixer, is kneaded the min of 10 min ~ 30 after mixing at 120 ~ 150 DEG C；
Then in cold press, compression moulding is at 150 ~ 180 DEG C, 8 ~ 10 MPa to get EVA composite material.
Expansible graphite and mass percent of the organic functional inorganic fire retardants in EVA composite material are 10% ~ 20%；
The inorganic fire retardants of organic functional and the mass ratio of expansible graphite are 1:1 ~ 1:11.
Two, the characterization of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material
Below by taking inorganic particles magnesium hydroxide as an example, to its structure and phosphorus nitrogen after carrying out organic functional with phenyl-phosphonic acid
The preparation of type LSOH anti-flaming EVA composite material and performance are illustrated.
Fig. 1 is the infrared absorption spectrum curve of inorganic particles magnesium hydroxide organic functional.From curve MH(magnesium hydroxide)
In as can be seen that 3695 cm-1For the OH of magnesium hydroxide-Stretching vibration peak, curve BPA(phosphenylic acid) in 1145 cm-1、
1595 cm-1And 1438 cm-1There is the stretching vibration peak of P=O key, O-H key and P-Ar respectively in place, in curve fire retardant
In 1595 cm in BM-MA-1The absorption peak at place disappears, and illustrates that O-H key is reacted, and in 3466 cm-1With 3133 cm-1Place
There is the stretching vibration absworption peak of N-H, and in 1664 cm-1There is the characteristic absorption peak of melamine C=N in place, can determine whether
It has successfully been prepared through the modified fire retardant of two steps.
Fig. 2 is the heat release rate figure of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material prepared by the present invention.As a result table
Bright, the peak value heat release rate of pure EVA reaches 1586.4 kW/m2, and it is being added to fire retardant and the inflatable stone of flame retardant
Mo Hou, the peak value heat release rate and heat release rate of low smoke, zero halogen EVA composite material all significantly decrease, wherein sample
EVA-1-1 peak value heat release rate is 185.2 kW/m288.3% is reduced compared with pure sample, the EVA composite material of other ratios
Also it has dropped very much.The reduction of heat release rate can effectively weaken flame intensity when burning, and it is compound significantly to reduce EVA
Brought harm when material combustion.
Fig. 3 is total release thermal map of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material prepared by the present invention.Rate of heat release peak
Value (PHRR) and total heat (THR) that discharges are to assess the most important parameters of security against fire.The result shows that total release heat of pure EVA is high
Up to 124.9 MJ/m2, add different proportion fire retardant all significantly reduce EVA composite material total release heat, EVA-1-11
Total rate of release be reduced to 68.2 MJ/m2, total heat release rate reduces 45.4%.
Fig. 4 is that total cigarette of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material prepared by the present invention generates spirogram.As a result table
Bright, total cigarette production quantity of pure EVA is up to 12.8 m2, the fire retardant for adding different proportion all significantly reduces EVA composite material
Total cigarette yield, total cigarette yield of EVA-1-7 are reduced to 4.0 m2, total cigarette rate of release reduces 68.8%.
Fig. 5 is the remaining digital photograph of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA post combustion carbon, wherein figure (a) is logical for pure EVA
The remaining photo of carbon after crossing taper calorimetric test, figure (b), figure (c) are to be added to fire retardant BM-MA and inflatable stone respectively
By the digital photograph figure of remaining a front surface and a side surface of carbon after taper calorimetric after black EG, from figure 5 it can be seen that compared to pure
The burning of EVA has not a particle of carbon residue, and joined the carbon of the composite material of EVA after fire retardant and expansible graphite
It remains thicker and expands, transmitting of the heat to polymer when these residues can effectively slow down burning, to slow down
The pyrolytic process of EVA composite material.
Fig. 6 is the scanning electron microscope (SEM) photograph of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA post combustion carbon layer surface.Scheming (a) is that only addition is closed
At the electron microscope of fire retardant, hole structure in figure, it may be possible to due to the fire retardant of synthesis releases in decomposable process can not
Combustion gas body is to dilute the combustible in air, to slow down the combustion process of EVA.Scheming (b) is addition synthesis fire retardant
It is remained with the carbon of the electron microscope of expansible graphite, the EVA after it can be seen that addition fire retardant and expansible graphite in figure (b)
In honeycomb reticular structure, heat be difficult to rapidly to material internal permeate, also it is effectively completely cut off material with it is flammable in air
The contact of object, therefore good physical barriers together are provided in EVA rouge combustion process, it can also play heat-insulated, oxygen barrier, suppression cigarette
Effect, can not only effectively improve the anti-flammability of composite material, while can also prevent the further degradation of internal material.
Three, phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite property is tested
Using GB/T2460-93 standard testing.Table 1 is that the LOI(limit oxygen of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material refers to
Number) value.From table 1 it follows that obtained phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA is blended using fire retardant with EVA by the present invention
Composite material, anti-flammability are greatly improved.When the compound proportion of fire retardant BM-MA and expansible graphite EG is 1:1,
The oxygen index (OI) of EVA composite material may be up to 32.0, and the flame retardant property for improving 50%, EVA has the promotion of highly significant.
Table 2 be phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material HRR(heat release rate), PHRR(peak heat release speed
Rate), the total cigarette yield of TSP(), av-CO2The average production quantity of Y(carbon dioxide) specific data.Can be prepared from table 2
The all data of EVA composite material is all far below pure EVA, and the peak value heat release rate of pure EVA is up to 1586.4 kW/m2, belong to
Combustible material, the peak value heat release rate of the EVA composite material after being added to fire retardant and expansible graphite have very big
The reduction of amplitude significantly reduces the heat discharged when burning.Total cigarette yield of the EVA composite material of preparation reduces
68.8%, low-smoke can reduce people in the case of fire and because of smog asphyxia lose a possibility that escaping ability, table two
Data all show preparation EVA composite material have good flame retardant effect.
2, Mechanics Performance Testing
Using GB/T1040-1992 standard testing.Table 3 is the mechanical performance of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material.By
Table 3 is it is found that phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material prepared by the present invention still has good mechanical property: fracture
Elongation: 630.1% ~ 805.9% tensile strength: 8.9 ~ 16.6 MPa.
Detailed description of the invention
Fig. 1 is the infrared absorption spectrum curve of inorganic particles magnesium hydroxide organic functional.
Fig. 2 is the heat release rate figure of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material.
Fig. 3 is total release thermal map of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material.
Fig. 4 is that total cigarette of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material generates spirogram.
Fig. 5 is the remaining digital photograph of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material post combustion carbon.
Fig. 6 is the scanning electron microscope (SEM) photograph of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material post combustion carbon layer surface.
Specific embodiment
Below by specific embodiment to the preparation method and resistance of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material of the present invention
Combustion performance is described further.
Embodiment 1
(1) preparation of organic functional inorganic fire retardants: 100 mL distilled water are measured in round-bottomed flask, weigh 10g hydroxide
20g phenyl-phosphonic acid is added after pouring into wherein ultrasound in magnesium, and 5 h of magnetic agitation at 80 DEG C is filtered while hot and repeatedly washed with distilled water
It washs to obtain white powdery solids to be a modified product BM；The product BM for taking 10g to be once modified is dissolved in 300 mL distilled water
In, it is heated to that 20g melamine is added after 100 DEG C thereto, magnetic agitation 3h, filters and washed with hot water to remove not while hot
The melamine of reaction, then in 80 DEG C of dry 24 h, the powder for obtaining white is functionalization inorganic fire retardant BM-MA；It will
BM-MA is spare in the ball mill with the revolving speed ball milling 3h of 500 r/min；
(2) preparation of low-smoke and flame retardant EVA composite material: taking the EVA master batch that 10gBM-MA, 10g expansible graphite, 80g are dried,
It is placed on mixer, is heated to be put into mold after 130 DEG C of mixing 20min to be placed on hot press, 4 min of hot pressing at 10 MPa
Corresponding testing standard is made it have, then cooling, demoulding are compound to get phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA on cold press
Material；
(3) flame retardant property of low-smoke and flame retardant EVA composite material: LOI=32.0%；THR= 76.0MJ/m2, the kW/ of PHRR=185.2
m2, av-CO2Y=2.8 kg/kg, TSP=6.5 m2。
Embodiment 2
(1) preparation of organic functional inorganic fire retardants: measuring 100 mL distilled water in round-bottomed flask, is warming up to 100 DEG C and adds
Enter 30 min of ethylenediamine tetramethylene phosphoric acid magnetic agitation of 10g, is added 40g magnesium hydroxide, 5 h of magnetic agitation at 100 DEG C,
It filters and is repeatedly washed with distilled water while hot and obtain white powdery solids as a modified product EDM；10g is taken once to be modified
Product EDM is dissolved in 300 mL distilled water, is heated to that 40g melamine is added after 100 DEG C thereto, 3 h of magnetic agitation takes advantage of
Heat, which filters, simultaneously wash with hot water to remove unreacted melamine, 80 DEG C it is dry for 24 hours, it is as organic to obtain white powder
Functionalization inorganic fire retardant EDM-MA；It is spare by EDM-MA in the ball mill with the revolving speed ball milling 3h of 500 r/min；
(2) preparation of low-smoke and flame retardant EVA composite material: the EVA for taking 10gEDM-MA, 10g expansible graphite, 80g dried is female
Grain is placed on mixer and is heated to 130 DEG C, is put into mold after 20 min of mixing and is placed on hot press the hot pressing 4 at 10 MPa
Min makes it have corresponding testing standard, and then cooling on cold press, demoulding is multiple to get phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA
Condensation material；
(3) flame retardant property of low-smoke and flame retardant EVA composite material: LOI=28.1%；THR=98.3 MJ/m2, the kW/ of PHRR=280.1
m2, av-CO2P=3.3 kg/kg, TSP=10.7 m2。
Embodiment 3
(1) preparation of organic functional inorganic fire retardants: 100 mL distilled water are measured in round-bottomed flask, weigh 20g hydroxide
10g 1-hydroxy ethylidene-1,1-diphosphonic acid is added after pouring into wherein ultrasound in magnesium, and the magnetic agitation 5h at 80 DEG C is filtered and more with distilled water while hot
It is a modified product HM that secondary washing, which obtains white powdery solids,；The product HM for taking 10g to be once modified is dissolved in 300 mL steaming
After being heated to 100 DEG C in distilled water, 20g p-phenylenediamine is added thereto, magnetic agitation 3h is filtered while hot and repeatedly washed with hot water
It washs, in 80 DEG C of dry 24 h, obtained white powder is organic functional inorganic fire retardants HM-PPD；By HM-PPD in ball milling
It is spare with the revolving speed ball milling 3h of 500 r/min in machine；
(2) preparation of low-smoke and flame retardant EVA composite material: the EVA for taking the expansible graphite of 10gHM-PPD, 10g, 80 g dried
Master batch is placed on mixer and is heated to 130 DEG C, is put into mold after 20 min of mixing and is placed on hot press the hot pressing at 10 MPa
4 min make it have corresponding testing standard, then cooling on cold press, demould to get phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA
Composite material；
(3) flame retardant property of low-smoke and flame retardant EVA composite material: LOI=27.5%；THR=107.4 MJ/m2, the kW/ of PHRR=303.6
m2, av-CO2P=3.2 kg/kg, TSP=10.9 m2。
Embodiment 4
(1) preparation of organic functional inorganic fire retardants: 100 mL distilled water are measured in round-bottomed flask, weigh 30g hydroxide
10g aminotrimethylenephosphonic acid is added after pouring into wherein ultrasound in magnesium, and magnetic agitation 5h, filters while hot and use distilled water at 80 DEG C
It is a modified product ATM that repeatedly washing, which obtains white powdery solids,；Modified product HM of 10g is taken to be dissolved in 300 mL steaming
It in distilled water, is heated to that 30g polyethyleneimine is added after 100 DEG C thereto, 3 h of magnetic agitation, filter while hot and with distilled water water
Repeatedly washing, in 80 DEG C of dry 24 h, obtained white powder is organic functional inorganic fire retardants ATM-PEI；By ATM-
PEI is spare in the ball mill with the revolving speed ball milling 3h of 500 r/min；
(2) 10gATM-PEI, 10g expansible graphite, 80g dried EVA the preparation of low-smoke and flame retardant EVA composite material: are taken
Master batch is placed on mixer and is heated to 130 DEG C, is put into mold after 20 min of mixing and is placed on hot press the hot pressing at 10 MPa
4 min make it have corresponding testing standard, then cooling on cold press, demould to get phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA
Composite material；
(3) flame retardant property of low-smoke and flame retardant EVA composite material: LOI=30.0%；THR=85.6 MJ/m2, the kW/ of PHRR=204.3
m2, av-CO2P=2.5 kg/kg, TSP=7.9 m2。
Claims (9)
1. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material, comprising the following steps:
(1) preparation of organic functional inorganic fire retardants: organic phospho acid is dissolved in distilled water, and nothing is added at 80 ~ 100 DEG C
Machine particle, after being stirred to react 6 ~ 10h, filtering is washed repeatedly with distilled water and obtains a modified product；Again by a modified product
It is mixed with nitrogenous compound, 3 ~ 5 h is stirred to react at 80 ~ 100 DEG C, filtered, obtain the inorganic fire retardants of organic functional；
(2) synthesis of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material: by dry EVA particle and expansible graphite, above-mentioned system
Standby organic functional inorganic fire retardants is placed in mixer, is kneaded 10 ~ 30 min after mixing at 120 ~ 150 DEG C；Then in cold
In press, compression moulding is at 150 ~ 180 DEG C, 8 ~ 10 MPa to get EVA composite material.
2. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (1), organic phospho acid is diethylene triamine pentamethylene phosphonic, phenyl-phosphonic acid, ethylenediamine tetramethylene phosphonic acid, amino trimethylene
Methylphosphonic acid.
3. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (1), inorganic particle is magnesium hydroxide, aluminium hydroxide, palygorskite, hydrotalcite or the montmorillonite of 400 ~ 600 nm of partial size.
4. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (1), the mass ratio of organic phospho acid and inorganic particles is 1:1 ~ 6:1.
5. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (1), nitrogenous compound is melamine, urea, p-phenylenediamine, polyethyleneimine.
6. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (1), the mass ratio of nitrogenous compound and inorganic particles is 1:1 ~ 5:1.
7. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
By the inorganic fire retardants of the organic functional of step (1) preparation in the ball mill with the revolving speed ball milling 1 ~ 3 of 300 ~ 800 r/min
h。
8. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (2), expansible graphite and mass percent of the organic functional inorganic fire retardants in EVA composite material be 10% ~
20%。
9. a kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material as described in claim 1, it is characterised in that:
In step (2), the inorganic fire retardants of organic functional and the mass ratio of expansible graphite are 1:1 ~ 1:11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617246.6A CN110183774A (en) | 2019-07-10 | 2019-07-10 | A kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617246.6A CN110183774A (en) | 2019-07-10 | 2019-07-10 | A kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110183774A true CN110183774A (en) | 2019-08-30 |
Family
ID=67725379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910617246.6A Pending CN110183774A (en) | 2019-07-10 | 2019-07-10 | A kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110183774A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558375A (en) * | 2022-10-19 | 2023-01-03 | 西华大学 | Metal-doped intumescent flame-retardant coating liquid, flame retardant, and preparation and application thereof |
| CN116063690A (en) * | 2022-12-29 | 2023-05-05 | 浙大宁波理工学院 | DOPO modified two-dimensional (Zn/Cu) 2 (bIm) 4 Composite material and high-efficiency flame-retardant EVA (ethylene vinyl acetate) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868281A (en) * | 2017-11-28 | 2018-04-03 | 西北师范大学 | A kind of preparation of hypo-aluminum orthophosphate doping vario-property palygorskite and the application as fire retardant |
| CN109438925A (en) * | 2018-11-15 | 2019-03-08 | 西北师范大学 | A kind of preparation method of Intrinsical LSOH anti-flaming epoxy resin composite material |
-
2019
- 2019-07-10 CN CN201910617246.6A patent/CN110183774A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868281A (en) * | 2017-11-28 | 2018-04-03 | 西北师范大学 | A kind of preparation of hypo-aluminum orthophosphate doping vario-property palygorskite and the application as fire retardant |
| CN109438925A (en) * | 2018-11-15 | 2019-03-08 | 西北师范大学 | A kind of preparation method of Intrinsical LSOH anti-flaming epoxy resin composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558375A (en) * | 2022-10-19 | 2023-01-03 | 西华大学 | Metal-doped intumescent flame-retardant coating liquid, flame retardant, and preparation and application thereof |
| CN115558375B (en) * | 2022-10-19 | 2023-09-29 | 西华大学 | Metal doped intumescent flame retardant coating liquid, flame retardant, preparation and application thereof |
| CN116063690A (en) * | 2022-12-29 | 2023-05-05 | 浙大宁波理工学院 | DOPO modified two-dimensional (Zn/Cu) 2 (bIm) 4 Composite material and high-efficiency flame-retardant EVA (ethylene vinyl acetate) |
| CN116063690B (en) * | 2022-12-29 | 2024-04-30 | 浙大宁波理工学院 | DOPO modified two-dimensional (Zn/Cu)2(bIm)4Composite material and high-efficiency flame-retardant EVA (ethylene vinyl acetate) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Microencapsulation of ammonium polyphosphate with PVA–melamine–formaldehyde resin and its flame retardance in polypropylene | |
| Tawiah et al. | Microporous boron based intumescent macrocycle flame retardant for poly (lactic acid) with excellent UV protection | |
| Nie et al. | Synergistic effect between a char forming agent (CFA) and microencapsulated ammonium polyphosphate on the thermal and flame retardant properties of polypropylene | |
| Wu et al. | Microencapsulated ammonium polyphosphate with urea–melamine–formaldehyde shell: preparation, characterization, and its flame retardance in polypropylene | |
| Wang et al. | Synergistic effect of expandable graphite and melamine phosphate on flame‐retardant polystyrene | |
| Wang et al. | A new intumescent flame‐retardant: preparation, surface modification, and its application in polypropylene | |
| Zhong et al. | Thermal degradation behaviors and flame retardancy of PC/ABS with novel silicon‐containing flame retardant | |
| Pallmann et al. | Phosphorylated sodium alginate/APP/DPER intumescent flame retardant used for polypropylene | |
| Duquesne et al. | Influence of talc on the fire retardant properties of highly filled intumescent polypropylene composites | |
| CN110041612A (en) | Oligomeric silsesquioxane increase-volume and synergistic halogen-free flame retardant polypropylene composite material and preparation method thereof | |
| Ji et al. | Toward an understanding of how red phosphorus and expandable graphite enhance the fire resistance of expandable polystyrene foams | |
| Wang et al. | Flame‐retardant mechanism of expandable polystyrene foam with a macromolecular nitrogen–phosphorus intumescent flame retardant | |
| CN101982497B (en) | Flame-retardant acrylonitrile-butadiene-styrene (ABS) composite material | |
| CN110183774A (en) | A kind of preparation method of phosphorus-nitrogen type halogen-free low-smoke and flame retardant EVA composite material | |
| Li et al. | Preparation and properties of polybutylene‐terephthalate/graphene oxide in situ flame‐retardant material | |
| CN109912799A (en) | A kind of phosphorus-containing organosilicon flame retardant and its preparation and application | |
| CN113717511A (en) | Mxene-based flame-retardant unsaturated resin material and preparation method thereof | |
| CN111690202A (en) | High-flame-retardance high-crust-forming low-smoke halogen-free flame-retardant oxygen-insulating layer cable material | |
| Pham et al. | Thermal properties and fire retardancy of polypropylene/wood flour composites containing eco-friendly flame retardants | |
| CN108503895B (en) | Preparation method of lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and flame-retardant modified ABS thereof | |
| Huang et al. | Flame retardant polypropylene with a single molecule intumescent flame retardant based on chitosan | |
| Liu et al. | Preparation of melamine borate coated red phosphorus microcapsules and use of zinc borate as synergistic flame retardant in polyethylene | |
| Tian et al. | Mechanical, flammability, and thermal properties of polyvinyl chloride‐wood composites with carbide slag | |
| Xu et al. | Preparation of a cobalt metal-organic framework (Co-MOF) and its application as a polypropylene flame retardant by compounding with melamine polyphosphate | |
| Mu et al. | Synergistic effect of intumescent flame retardant and zinc borate on linear low‐density polyethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190830 |
|
| RJ01 | Rejection of invention patent application after publication |