CN107325367A - A kind of flame retardant plastics and preparation method thereof - Google Patents

A kind of flame retardant plastics and preparation method thereof Download PDF

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Publication number
CN107325367A
CN107325367A CN201710512895.0A CN201710512895A CN107325367A CN 107325367 A CN107325367 A CN 107325367A CN 201710512895 A CN201710512895 A CN 201710512895A CN 107325367 A CN107325367 A CN 107325367A
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particle
tio
nano
colloidal sol
flame
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付忠河
冯兆海
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Tianjin Promise Plastics Co Ltd
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Tianjin Promise Plastics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a kind of flame retardant plastics and preparation method thereof, flame retardant plastics includes the material of following parts by weight：High-density polyethylene resin, composite flame-retardant agent, coupling agent, dispersant and haloflex；Composite flame-retardant agent is that will contain TiO2@Al(OH)3The alcohol phase colloidal sol of nano-particle is added in liquid halogenated phosphate and constitutes composite flame-retardant agent, and wherein halogenated phosphate can be adsorbed in TiO2@Al(OH)3On the core-shell structure of nano-particle, TiO is formed2@Al(OH)3Identical collaboration, effectively improves the flame retardant effect of composite flame-retardant agent between the double-deck core-shell structure of@halogenated phosphates, three, can also effectively reduce the addition of fire proofing.The flame retardant plastics of the present invention uses composite flame-retardant agent, has given full play to the synergy between inorganic nano-particle and halogenated phosphate, with excellent processability, anti-flammability and ageing resistace.

Description

A kind of flame retardant plastics and preparation method thereof
Technical field
The invention belongs to plastic applications, and in particular to a kind of flame retardant plastics and preparation method thereof.
Background technology
High density polyethylene (HDPE) (High Density Polyethylene, referred to as " HDPE ") is also known as low-pressure polyethylene, is A kind of crystallinity is high, non-polar plane is in a certain degree of translucent.HDPE is that a kind of crystallinity is high, nonpolar thermoplastic resin Fat.
HDPE (high density polyethylene (HDPE)) has excellent combination property：Good resisting environmental stress and cracking, endurance, height is anti- Punching etc..But HDPE oxygen index (OI) is low to belong to inflammable high polymer material, there is significant limitation the field such as using and studying, meet Easily burnt in heat and discharge process.By adding fire retardant to reach fire-retardant purpose.Fire retardant is roughly divided into halogen flame With two kinds of halogen-free flame retardants.Bromide fire retardant is using the class that most wide anti-flammability is high in halogen flame, to the physics of product Influence small with mechanical performance.
Halogen-free flame retardants mainly includes inorganic hydroxide fire retardant, inorganic phosphorus flame retardant, antimony oxide flame retardant, molybdenum Compound etc..Wherein consumption of the aluminium hydroxide in halogen-free flame retardants is maximum.Inorganic hydroxide flame retardant materials are in burning Fire retardant is produced hydrone by thermal decomposition, and absorbing a large amount of latent heat makes depolymerization slow down into low molecular speed, reduces The generation of fuel gas, reaches flame retardant effect.Wherein Al (OH)3Fire retardant, which is quickly grown, is widely used in various materials, coating, In polyolefin and partial rubber product.China progressively starts to develop and produce efficient Al (OH)3Fire retardant.Mg(OH)2Than same More preferably, strong adaptability can be widely used in polyolefin, copolymer the smoke suppressing effect of class halogen-free flame retardants.Mg(OH)2It is fire-retardant Smoke suppressing, heat endurance etc. are all higher than the Al (OH) of current usage amount maximum3Fire retardant.
The flame-retardant system is added to inorganic phase and high polymer material poor compatibility, addition in material as inorganic powdered filler The more flame retardant effects of amount of fire retardant are better.But its deficiency is, may cause the mechanical property of material reduces, and largely fills energy The mechanical performances such as the intensity and toughness of material are reduced, while the viscosity of fire proofing system can be very big, molding process is made Into very big difficulty.To ensure that the flame retardant effect and mechanical property of material should add the auxiliary agents such as the coupling agent of respective amount, dispersant.It is even The interaction force that connection agent titanate esters can increase two-phase interface improves compatibility.
Therefore, while flame retardant effect is ensured, the addition for reducing fire proofing is that the current technology for needing to solve is asked Topic.
The content of the invention
The purpose of the present invention is that there is provided a kind of flame retardant plastics and preparation method thereof in view of the shortcomings of the prior art.The present invention Flame retardant plastics use composite flame-retardant agent, composite flame-retardant agent is will to contain TiO2@Al(OH)3The alcohol phase colloidal sol of nano-particle is added Composite flame-retardant agent is constituted in liquid halogenated phosphate, wherein halogenated phosphate can be adsorbed in TiO2@Al(OH)3The shell of nano-particle On nuclear structure, TiO is formed2@Al(OH)3Identical collaboration between the double-deck core-shell structure of@halogenated phosphates, three, is effectively improved multiple The flame retardant effect of fire retardant is closed, the addition of fire proofing can also be effectively reduced.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of flame retardant plastics, the flame retardant plastics is made by following raw material blending extrusion, and the raw material is specially：
50~80 parts of high-density polyethylene resin；
10~20 parts of composite flame-retardant agent；
0.2~0.4 part of coupling agent；
10~15 parts of dispersant；
0.1~0.2 part of haloflex；
The composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid halophosphoric acid Composite flame-retardant agent is constituted in ester, wherein halogenated phosphate can be adsorbed in TiO2@Al(OH)3On core-shell structure.
Wherein, TiO2@Al(OH)3The particle diameter of nano-particle is 50-600nm；TiO2@Al(OH)3The alcohol of nano-particle mixes The addition of glue is 4-8 parts；TiO2@Al(OH)3The solid content of the alcohol phase colloidal sol of nano-particle is 40-60%.
It is preferred that, the composite flame-retardant agent also includes TiO2@Mg(OH)2The alcohol phase colloidal sol of nano-particle；Wherein, TiO2@Mg (OH)2The particle diameter of nano-particle is 100-700nm；TiO2@Mg(OH)2The alcohol phase colloidal sol addition of nano-particle is 2-4 parts； TiO2@Mg(OH)2The solid content of the alcohol phase colloidal sol of nano-particle is 40-60%.Wherein halogenated phosphate can be adsorbed in TiO2@Mg (OH)2On the core-shell structure of nano-particle.
It is preferred that, the liquid halogenated phosphate is tricresyl phosphate (2- chloropropyls) ester, tricresyl phosphate (2- chloroethyls) ester, phosphoric acid One kind in three (two chloropropyls) esters or tricresyl phosphate (propylene bromide) ester.
It is preferred that, the coupling agent is monoalkoxytitanates；
The dispersant is one kind in ethylene group bis-stearamides, glyceryl monostearate or glyceryl tristearate.
The present invention also provides a kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 55-105 DEG C；
(3) after heating 10-25 minutes, high-speed mixer is shut down and is cooled to after room temperature, is added double screw extruder extrusion, is made Grain, is made flame retardant plastics.
It is preferred that, the preparation method of the composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle After adding in liquid halogenated phosphate, stirred 5-10 minutes under ultrasonication, composite flame-retardant agent is made；
Or TiO will be contained2@Al(OH)3After the alcohol phase colloidal sol of nano-particle is added in liquid halogenated phosphate, in ultrasound Effect lower stirring 5-10 minutes, then adds TiO2@Mg(OH)2The alcohol phase colloidal sol of nano-particle, 3- is stirred under ultrasonication 5 minutes, composite flame-retardant agent is made.The present invention is halo phosphorus on this condition using the purpose being stirred under ultrasonication Acid esters can be adsorbed in TiO2@Mg(OH)2And TiO2@Al(OH)3Adsorption effect on nano-particle is more preferable.
It is preferred that, TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.5-0.8mol/L's AlCl3The aqueous solution is added to 40-60mmol/L TiCl4Mixed 2-4 minutes in the aqueous solution, then by above-mentioned mixed solution It is placed in after being incubated 1 hour under 80 degree, obtains TiO2@Al(OH)3The aqueous phase colloidal sol of nano-particle, then puts above-mentioned aqueous phase colloidal sol In ethanol after commutation, TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
It is preferred that, the TiCl4The preparation method of the aqueous solution is：According to the speed of 1-3 seconds/drop by TiCl4Slowly drop in ice In aqueous mixtures, 15-30 minutes then are stood, TiCl is made4The aqueous solution.The present invention is by the TiCl configured4Solution left standstill 15- The purpose of 30 minutes is to first allow TiCl4The less TiO of particle diameter is made in hydrolysis2Particle, is used as nucleator.
It is preferred that, TiO2@Mg(OH)2The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.4-0.7mol/L's MgCl2Alcoholic solution is added to 50-70mmol/L TiCl4Mixed 1-2 minutes in the aqueous solution, then by above-mentioned mixed solution It is placed in after standing 5-10 minutes under normal temperature, obtains TiO2@Mg(OH)2The colloidal sol of nano-particle, is then placed in ethanol by above-mentioned colloidal sol After middle commutation, TiO is made in concentration2@Mg(OH)2The alcohol phase colloidal sol of nano-particle.
It is preferred that, the MgCl2The preparation method of alcoholic solution is：By MgCl2Add in ethanol, in the heating temperature of 30-40 degree Under degree, stir 30-40 minutes, MgCl is made2Alcoholic solution.
Inventive principle：The flame retardant plastics of the present invention uses composite flame-retardant agent, will also contain TiO2@Mg(OH)2Nano-particle Alcohol phase colloidal sol adds in liquid halogenated phosphate and constitutes composite flame-retardant agent, and the fire retardant mechanism of inorganic hydroxide fire retardant is fire-retardant The hydrolysis generation crystallization water and oxide occur after agent is heated, the crystallization water steaming thermally decomposed out is absorbed heat by thermal evaporation and steamed as water Gas reduction material surface ignition temperature dilutes fuel gas simultaneously, and oxide can completely cut off air and prevent burning from carrying out and with suppression The effect of cigarette.Al(OH)3By three parts of crystallization water good flame retardation effects of thermal decomposition, Mg (OH)2Smoke elimination effect by thermal decomposition MgO is notable, Therefore Al (OH) is selected3With Mg (OH)2Cooperative flame retardant can reach the fire-retardant effect of LSZH simultaneously.
The flame retardant plastics of the present invention uses composite flame-retardant agent, and composite flame-retardant agent is will to contain TiO2@Al(OH)3Nano-particle Alcohol phase colloidal sol add liquid halogenated phosphate in constitute composite flame-retardant agent, wherein halogenated phosphate can be adsorbed in TiO2@Al (OH)3On the core-shell structure of nano-particle, similar TiO is formed2@Al(OH)3The double-deck core-shell structure of@halogenated phosphates, wherein, TiO2@Al(OH)3Nano-particle can generate TiO under the high temperature action in burning2And Al2O3The compound of nano-particle, due to Al2O3The agglomeration of nano-particle, can expose TiO2The surface of nano-particle, TiO2Nano-particle has effectively capture certainly By the ability of base, it coordinates the free radical that common capture burning is produced with halogen in halogenated phosphate, makes the quantity of free radical sharp Subtract, so as to quickly block combustion reaction, identical collaboration, effectively improves the flame retardant effect of composite flame-retardant agent between three.
The flame retardant plastics of the present invention is used in composite flame-retardant agent, the inorganic combustion inhibitor of use, in TiO2@Al(OH)3Nanoparticle Son and TiO2@Mg(OH)2Coated one layer of halogenated phosphate is distinguished on the surface of nano-particle, can increase the reprimand between nano-particle Power, reduces the reunion between nano-particle, improves dispersing uniformity of the inorganic nano-particle in flame retardant plastics.
The flame retardant plastics of the present invention uses composite flame-retardant agent, is that inorganic combustion inhibitor is added into height in the form of mellowness colloidal sol In Density Polyethylene Resin, form in high-density polyethylene resin is added directly into compared to common inorganic powder, this use More preferably, the chance reunited between particle is smaller for dispersing uniformity of the inorganic combustion inhibitor in flame retardant plastics, more favourable to improve material Hardness and toughness.
The flame retardant plastics of the present invention uses titanium dioxide in composite flame-retardant agent, the inorganic combustion inhibitor of use inherently good Antioxidant and antistatic additive, it is to avoid it is possible to additionally incorporate new material, to keep the original material of plastic material have very big side Help.
Finally, fire retardant is inorganic filler, the poor compatibility with HDPE, and the viscosity that a large amount of fillings can increase material causes to add Work difficult forming influences material property.The composite flame-retardant agent of the present invention effectively reduces fire retardant while flame retardant effect is ensured Addition, advantageously ensure that the mechanical property of material；It is additionally added appropriate coupling agent and dispersant, coupling agent and dispersant energy Significantly improve the compatibility of flame-retardant system.
Performance test：Plastics in embodiment 1-6 are made into standard batten to carry out according to national similar plastics all standard Performance test, the main performance for the material prepared is as follows：Tensile strength MPa (GB/T1040-2006)：35-39, notch shock Intensity kJ/m2(GB/T1043-2008)：30-49；Oxygen index (OI) % (GB/T2406-2008)：30-32, vertical combustion rank UL- 94：V-0；500h light aging impact strength conservation rates：100%.
Beneficial effect：
The flame retardant plastics of the present invention does not allow easy firing in high temperature or other dangerous situations, using safer insurance, and bullet Uniformly, stably, long-term use will not be deformed power, and have the premium properties of other high polymer materials concurrently, and such as intensity is high, tough The advantages of good, cold resistance of property is good.
The flame retardant plastics of the present invention uses composite flame-retardant agent, has given full play between inorganic nano-particle and halogenated phosphate Synergy, with excellent processability, anti-flammability and ageing resistace.
Flame retardant plastics produced by the present invention has good anti-aging and anti-flaming function；And do not influence the machinery of plastics strong Degree；The compatibility with resin will get well simultaneously, do not migrate, do not separate out, be not extracted in plastic products.
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Fixed scope.
Embodiment 1-6
A kind of flame retardant plastics, the flame retardant plastics is made by following raw material blending extrusion, and the raw material is specially：
50~80 parts of high-density polyethylene resin；
10~20 parts of composite flame-retardant agent；
0.2~0.4 part of coupling agent；
10~15 parts of dispersant；
0.1~0.2 part of haloflex；
Composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle is added in liquid halogenated phosphate Composite flame-retardant agent is constituted, wherein halogenated phosphate can be adsorbed in TiO2@Al(OH)3On core-shell structure.
Wherein, TiO2@Al(OH)3The particle diameter of nano-particle is 50-600nm；TiO2@Al(OH)3The alcohol of nano-particle mixes The addition of glue is 4-8 parts；TiO2@Al(OH)3The solid content of the alcohol phase colloidal sol of nano-particle is 40-60%.
It is preferred that, composite flame-retardant agent also includes TiO2@Mg(OH)2The alcohol phase colloidal sol of nano-particle；Wherein, TiO2@Mg (OH)2The particle diameter of nano-particle is 100-700nm；TiO2@Mg(OH)2The alcohol phase colloidal sol addition of nano-particle is 2-4 parts； TiO2@Mg(OH)2The solid content of the alcohol phase colloidal sol of nano-particle is 40-60%.Wherein halogenated phosphate can be adsorbed in TiO2@Mg (OH)2On the core-shell structure of nano-particle.
It is preferred that, liquid halogenated phosphate is tricresyl phosphate (2- chloropropyls) ester, tricresyl phosphate (2- chloroethyls) ester, tricresyl phosphate One kind in (two chloropropyls) ester or tricresyl phosphate (propylene bromide) ester.
It is preferred that, coupling agent is monoalkoxytitanates；
Dispersant is one kind in ethylene group bis-stearamides, glyceryl monostearate or glyceryl tristearate.
1-6 of the embodiment of the present invention flame retardant plastics for preparing adds the component detail of raw material as shown in table 1.
The 1-6's of the embodiment of the present invention of table 1 prepares the component detail that flame retardant plastics adds raw material
1-6 of the embodiment of the present invention preparation method for preparing flame retardant plastics is as follows.
Embodiment 1
A kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 55 DEG C；
(3) after heating 25 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
Wherein, the preparation method of composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid After in state halogenated phosphate, stirred 10 minutes under ultrasonication, supersonic frequency is 1000W, composite flame-retardant agent is made；
TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.5mol/L AlCl3The aqueous solution is added To 40mmol/L TiCl4Mixed in the aqueous solution 2 minutes, then above-mentioned mixed solution is placed under 80 degree and is incubated 1 hour Afterwards, TiO is obtained2@Al(OH)3Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation, commutation by the aqueous phase colloidal sol of nano-particle Using bag filter commutation, TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
TiCl4The preparation method of the aqueous solution is：According to the speed of 1 second/drop by TiCl4Slowly drop in mixture of ice and water, so 30 minutes are stood afterwards, TiCl is made4The aqueous solution.
Embodiment 2
A kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 105 DEG C；
(3) after heating 10 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
Wherein, the preparation method of composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid After in state halogenated phosphate, stirred 5 minutes under ultrasonication, supersonic frequency is 1000 KHzs, and composite flame-retardant agent is made；
TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.8mol/L AlCl3The aqueous solution is added To 60mmol/L TiCl4Mixed in the aqueous solution 4 minutes, then above-mentioned mixed solution is placed under 80 degree and is incubated 1 hour Afterwards, TiO is obtained2@Al(OH)3Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation, commutation by the aqueous phase colloidal sol of nano-particle Using bag filter commutation, TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
TiCl4The preparation method of the aqueous solution is：According to the speed of 3 seconds/drop by TiCl4Slowly drop in mixture of ice and water, so 150 minutes are stood afterwards, TiCl is made4The aqueous solution.
Embodiment 3
A kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 85 DEG C；
(3) after heating 15 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
Wherein, the preparation method of composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid After in state halogenated phosphate, stirred 8 minutes under ultrasonication, then add TiO2@Mg(OH)2The alcohol of nano-particle mixes Glue, is stirred 4 minutes under ultrasonication, and supersonic frequency is 1200 KHzs, and composite flame-retardant agent is made.
TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.7mol/L AlCl3The aqueous solution is added To 50mmol/L TiCl4Mixed in the aqueous solution 3 minutes, then above-mentioned mixed solution is placed under 80 degree and is incubated 1 hour Afterwards, TiO is obtained2@Al(OH)3Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation, commutation by the aqueous phase colloidal sol of nano-particle Using bag filter commutation, TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
TiCl4The preparation method of the aqueous solution is：According to the speed of 2 seconds/drop by TiCl4Slowly drop in mixture of ice and water, so 20 minutes are stood afterwards, TiCl is made4The aqueous solution.
TiO2@Mg(OH)2The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.6mol/L MgCl2Alcoholic solution is added To 55mmol/L TiCl4Mixed in the aqueous solution 2 minutes, then above-mentioned mixed solution is placed under normal temperature and stands 8 minutes Afterwards, TiO is obtained2@Mg(OH)2Above-mentioned colloidal sol, is then placed in ethanol after commutation by the colloidal sol of nano-particle, and commutation is using dialysis TiO is made in bag commutation, concentration2@Mg(OH)2The alcohol phase colloidal sol of nano-particle.
MgCl2The preparation method of alcoholic solution is：By MgCl2Add in ethanol, under 30 degree of heating-up temperature, stir 40 points Clock, is made MgCl2Alcoholic solution.
Embodiment 4
A kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 75 DEG C；
(3) after heating 14 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
Wherein, the preparation method of composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid After in state halogenated phosphate, stirred 6 minutes under ultrasonication, then add TiO2@Mg(OH)2The alcohol of nano-particle mixes Glue, is stirred 4 minutes under ultrasonication, and supersonic frequency is 1000 KHzs, and composite flame-retardant agent is made.
TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.65mol/L AlCl3The aqueous solution adds Enter the TiCl to 55mmol/L4Mixed in the aqueous solution 3 minutes, above-mentioned mixed solution is then placed in insulation 1 under 80 degree small Shi Hou, obtains TiO2@Al(OH)3Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation, changes by the aqueous phase colloidal sol of nano-particle Bag filter commutation is mutually used, TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
TiCl4The preparation method of the aqueous solution is：According to the speed of 2 seconds/drop by TiCl4Slowly drop in mixture of ice and water, so 25 minutes are stood afterwards, TiCl is made4The aqueous solution.
TiO2@Mg(OH)2The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.6mol/L MgCl2Alcoholic solution is added To 65mmol/L TiCl4Mixed in the aqueous solution 1 minute, then above-mentioned mixed solution is placed under normal temperature and stands 7 minutes Afterwards, TiO is obtained2@Mg(OH)2Above-mentioned colloidal sol, is then placed in ethanol after commutation by the colloidal sol of nano-particle, and commutation is using dialysis TiO is made in bag commutation, concentration2@Mg(OH)2The alcohol phase colloidal sol of nano-particle.
MgCl2The preparation method of alcoholic solution is：By MgCl2Add in ethanol, under 35 degree of heating-up temperature, stir 33 points Clock, is made MgCl2Alcoholic solution.
Embodiment 5
A kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 70 DEG C；
(3) after heating 19 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
Wherein, the preparation method of composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid After in state halogenated phosphate, stirred 9 minutes under ultrasonication, then add TiO2@Mg(OH)2The alcohol of nano-particle mixes Glue, is stirred 4.5 minutes under ultrasonication, and supersonic frequency is 1500 KHzs, and composite flame-retardant agent is made.
TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.7mol/L AlCl3The aqueous solution is added To 55mmol/L TiCl4Mixed in the aqueous solution 3 minutes, then above-mentioned mixed solution is placed under 80 degree and is incubated 1 hour Afterwards, TiO is obtained2@Al(OH)3Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation, commutation by the aqueous phase colloidal sol of nano-particle Using bag filter commutation, TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
TiCl4The preparation method of the aqueous solution is：According to the speed of 2 seconds/drop by TiCl4Slowly drop in mixture of ice and water, so 26 minutes are stood afterwards, TiCl is made4The aqueous solution.
TiO2@Mg(OH)2The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.58mol/L MgCl2Alcoholic solution adds Enter the TiCl to 60mmol/L4Mixed 1.5 minutes in the aqueous solution, then above-mentioned mixed solution is placed under normal temperature and stands 8 After minute, TiO is obtained2@Mg(OH)2Above-mentioned colloidal sol, is then placed in ethanol after commutation by the colloidal sol of nano-particle, and commutation is used TiO is made in bag filter commutation, concentration2@Mg(OH)2The alcohol phase colloidal sol of nano-particle.
MgCl2The preparation method of alcoholic solution is：By MgCl2Add in ethanol, under 36 degree of heating-up temperature, stir 38 points Clock, is made MgCl2Alcoholic solution.
Embodiment 6
A kind of preparation method of flame retardant plastics, comprises the following steps：
(1) high density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
(2) coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, makes high-speed mixer liter Temperature heating, temperature range is 95 DEG C；
(3) after heating 15 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
Wherein, the preparation method of composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle adds liquid After in state halogenated phosphate, stirred 6 minutes under ultrasonication, then add TiO2@Mg(OH)2The alcohol of nano-particle mixes Glue, is stirred 4 minutes under ultrasonication, and supersonic frequency is 1600 KHzs, and composite flame-retardant agent is made.
TiO2@Al(OH)3The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.75mol/L AlCl3The aqueous solution adds Enter the TiCl to 55mmol/L4Mixed 3.5 minutes in the aqueous solution, then above-mentioned mixed solution is placed under 80 degree and is incubated 1 After hour, TiO is obtained2@Al(OH)3Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation by the aqueous phase colloidal sol of nano-particle, Commutation uses bag filter commutation, and TiO is made in concentration2@Al(OH)3The alcohol phase colloidal sol of nano-particle.
TiCl4The preparation method of the aqueous solution is：According to the speed of 2.5 seconds/drop by TiCl4Slowly drop in mixture of ice and water, Then 25 minutes are stood, TiCl is made4The aqueous solution.
TiO2@Mg(OH)2The preparation method of the alcohol phase colloidal sol of nano-particle is：By 0.65mol/L MgCl2Alcoholic solution adds Enter the TiCl to 60mmol/L4Mixed in the aqueous solution 1 minute, then above-mentioned mixed solution is placed under normal temperature and stands 7 points Zhong Hou, obtains TiO2@Mg(OH)2Above-mentioned colloidal sol, is then placed in ethanol after commutation by the colloidal sol of nano-particle, and commutation is using saturating Bag commutation is analysed, TiO is made in concentration2@Mg(OH)2The alcohol phase colloidal sol of nano-particle.
MgCl2The preparation method of alcoholic solution is：By MgCl2Add in ethanol, under 33 degree of heating-up temperature, stir 34 points Clock, is made MgCl2Alcoholic solution.
2nd, performance detection
Performance test：Plastics in embodiment 1-6 are made into standard batten to carry out according to national similar plastics all standard Performance test, the main performance for the material prepared is as follows：Tensile strength MPa (GB/T1040-2006)：35-39, notch shock Intensity kJ/m2(GB/T1043-2008)：30-49；Oxygen index (OI) % (GB/T2406-2008)：30-32, vertical combustion rank UL- 94：V-0；500h light aging impact strength conservation rates：100%, glossiness (60 °) (GB/T8807-1988).
1-6 of the embodiment of the present invention performance parameter for preparing flame retardant plastics is as shown in table 2.
The 1-6 of the embodiment of the present invention of table 1 performance parameter for preparing flame retardant plastics

Claims (10)

1. a kind of flame retardant plastics, it is characterized in that, the flame retardant plastics is made by following raw material blending extrusion, and the raw material is specific For：
50 ~ 80 parts of high-density polyethylene resin；
10 ~ 20 parts of composite flame-retardant agent；
0.2 ~ 0.4 part of coupling agent；
10 ~ 15 parts of dispersant；
0.1 ~ 0.2 part of haloflex；
The composite flame-retardant agent is：TiO will be contained2@Al(OH)3The alcohol phase colloidal sol of nano-particle is added in liquid halogenated phosphate Constitute composite flame-retardant agent；
Wherein, TiO2@Al(OH)3The particle diameter of nano-particle is 50-600nm；TiO2@Al(OH)3The alcohol phase colloidal sol of nano-particle Addition is 4-8 parts；TiO2@Al(OH)3The solid content of the alcohol phase colloidal sol of nano-particle is 40-60%.
2. a kind of flame retardant plastics according to claim 1, it is characterised in that the composite flame-retardant agent also includes TiO2@Mg (OH)2The alcohol phase colloidal sol of nano-particle；Wherein, TiO2@Mg(OH)2The particle diameter of nano-particle is 100-700nm；TiO2@Mg(OH)2 The alcohol phase colloidal sol addition of nano-particle is 2-4 parts；TiO2@Mg(OH)2The solid content of the alcohol phase colloidal sol of nano-particle is 40- 60%。
3. a kind of flame retardant plastics according to claim 1, it is characterised in that the liquid halogenated phosphate is tricresyl phosphate One in (2- chloropropyls) ester, tricresyl phosphate (2- chloroethyls) ester, tricresyl phosphate (two chloropropyls) ester or tricresyl phosphate (propylene bromide) ester Kind.
4. a kind of flame retardant plastics according to claim 1, it is characterised in that the coupling agent is monoalkoxytitanates；
The dispersant is one kind in ethylene group bis-stearamides, glyceryl monostearate or glyceryl tristearate.
5. according to the preparation method of any described flame retardant plastics of claim 1-4, it is characterized in that, comprise the following steps：
（1）High density polyethylene (HDPE) and composite flame-retardant agent are mixed as at the beginning of ormal weight adds high-speed mixer；
（2）Coupling agent, dispersant and haloflex are added in high-speed mixer by ormal weight, add high-speed mixer heating Heat, temperature range is 55-105 DEG C；
（3）After heating 10-25 minutes, high-speed mixer is shut down and is cooled to after room temperature, adds double screw extruder extrusion, granulation, Flame retardant plastics is made.
6. the preparation method of flame retardant plastics according to claim 5, it is characterised in that the preparation side of the composite flame-retardant agent Method is：TiO will be contained2@Al(OH)3After the alcohol phase colloidal sol of nano-particle is added in liquid halogenated phosphate, stirred under ultrasonication Mix 5-10 minutes, composite flame-retardant agent is made；
Or TiO will be contained2@Al(OH)3After the alcohol phase colloidal sol of nano-particle is added in liquid halogenated phosphate, in ultrasonication Lower stirring 5-10 minutes, then adds TiO2@Mg(OH)2The alcohol phase colloidal sol of nano-particle, stirs 3-5 points under ultrasonication Clock, is made composite flame-retardant agent.
7. the preparation method of flame retardant plastics according to claim 6, it is characterised in that TiO2@Al(OH)3Nano-particle The preparation method of alcohol phase colloidal sol is：By 0.5-0.8mol/L AlCl3The aqueous solution is added to 40-60mmol/L TiCl4The aqueous solution Above-mentioned mixed solution, is then placed in after being incubated 1 hour under 80 degree, obtains TiO by middle mixing 2-4 minutes2@Al(OH)3Nanometer Above-mentioned aqueous phase colloidal sol, is then placed in ethanol after commutation by the aqueous phase colloidal sol of particle, concentration, and TiO is made2@Al(OH)3Nanoparticle The alcohol phase colloidal sol of son.
8. the preparation method of flame retardant plastics according to claim 7, it is characterised in that the TiCl4The preparation side of the aqueous solution Method is：According to the speed of 1-3 seconds/drop by TiCl4Slowly drop in mixture of ice and water, then stand 15-30 minutes, TiCl is made4 The aqueous solution.
9. the preparation method of flame retardant plastics according to claim 6, it is characterised in that TiO2@Mg(OH)2Nano-particle The preparation method of alcohol phase colloidal sol is：By 0.4-0.7mol/L MgCl2Alcoholic solution is added to 50-70mmol/L TiCl4The aqueous solution Above-mentioned mixed solution, is then placed in after standing 5-10 minutes under normal temperature, obtains TiO by middle mixing 1-2 minutes2@Mg(OH)2 Above-mentioned colloidal sol, is then placed in ethanol after commutation by the colloidal sol of nano-particle, concentration, and TiO is made2@Mg(OH)2Nano-particle Alcohol phase colloidal sol.
10. the preparation method of flame retardant plastics according to claim 9, it is characterised in that the MgCl2The preparation of alcoholic solution Method is：By MgCl2Add in ethanol, under the heating-up temperature of 30-40 degree, stir 30-40 minutes, MgCl is made2Alcoholic solution.
CN201710512895.0A 2017-06-29 2017-06-29 A kind of flame retardant plastics and preparation method thereof Pending CN107325367A (en)

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