CN109897357A - A kind of plastics high stability halogen-free environment-friendlyflame flame retardant and preparation method thereof - Google Patents
A kind of plastics high stability halogen-free environment-friendlyflame flame retardant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of plastics high stability halogen-free environment-friendlyflame flame retardant and preparation method thereof, the fire retardant is by including that the raw material of following components and parts by weight content is prepared: 45-80 parts of modified polyorganosiloxanes, 20-32 parts of gas-phase silica, 8-15 parts of modification infusorial earth, 2-5 parts of surface treating agent and 1-2 parts of polyethylene wax.Compared with prior art, fire retardant and smoke suppressing effect of the present invention are good, securely and reliably, raw material sources are wide, at low cost, are free of toxic additive, the machining and flame-proof heat-resistant performance of substrate can be improved, with good plasticity, it can effectively reduce smoke amount and carbon dioxide inhibited to generate, comply fully with the environmental requirement of new flame retardant non-halogen non-phosphate.
Description
Technical field
The invention belongs to field of fire-proof technology, it is related to a kind of plastics high stability halogen-free environment-friendlyflame flame retardant and its preparation side
Method.
Background technique
Many institutes are well-known, high molecular material of the plastics as synthesis, due to good mouldability, film forming, insulating properties
The features such as with resistance to acid and alkali and low-permeable, water penetration and easy coloring, has been widely used in the various aspects of people's life.
However, plastics and most of high molecular materials belong to combustible material, when burning, can generate a large amount of smog, toxic gas, not only
Pollute environment, can also seriously endanger the health of people, in addition make one poisoning and it is dead, this has become people's growing interest
Social concern.The fire hazard of plastics is reduced in order to try one's best, therefore how to improve the anti-flammability of plastic material,
A urgent problem as the research of current plastic material.
Fire retardant is widely used in general-purpose plastics, engineering plastics and plastics as one of most important chemical industry additive
In alloy, polyurethane etc..Halogen containing flame-retardant has many advantages, such as that flame retarding efficiency is high, additive amount is few, is still widely used at present,
But since smoke amount is big, burning release is a large amount of toxic and has in combustion for halogen containing flame-retardant, especially brominated flame retardant
Corrosive gas, to bring huge environmental protection pressure.And organic phosphorus flame retardant is most important nothing currently on the market
Halogen fire retardant type is typically used in engineering plastic alloy and polyurethane, has the advantages that small toxicity, smoke are low etc..But
Organic phosphorus flame retardant burning can release mordant acidic materials, have biggish corrosion to substrate and ambient enviroment
Property, and this based flame retardant will reach the flame retardant effect of UL V0, and additive amount will reach 10% or more, in turn result in plastic alloy
Heat resistance reduce, degraded toughness, mechanical strength decline, therefore its application range also receives certain restriction.It is inorganic fire-retarded
Agent has many advantages, such as cheap, fire-retardant, smoke elimination, is the fire retardant of a kind of environmental protection, is commonly used in the polyolefin of halogen-free flameproof.
But based flame retardant the shortcomings that overcoming whether there is or not method, that is, to reach preferable fire-retardant rank, it is necessary to a large amount of additions are usually big
In 50%, this results in plastics specific gravity and seriously increases, and then loses the small advantage of specific gravity, also results in poor processability, tough
Property reduce and then the field that limits its application.
Summary of the invention
It is good that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of economic and practicals,
Good with plastic compatible stability, the plastics that can effectively take into account plastic processing performance and mechanical performance are hindered with high stability halogen-free environmental
Fire agent.
Another object of the present invention is just to provide the preparation method of the plastics high stability halogen-free environment-friendlyflame flame retardant.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of plastics high stability halogen-free environment-friendlyflame flame retardant, the fire retardant is by the raw material including following components and parts by weight content
It is prepared: 45-80 parts of modified polyorganosiloxanes, 20-32 parts of gas-phase silica, 8-15 parts of modification infusorial earth, surface treatment
2-5 parts of agent and 1-2 parts of polyethylene wax.
The preparation methods of the modified polyorganosiloxanes the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 8-12:1 with polyester resin, it is transferred to batch mixer
In, it is heated to 120-140 DEG C, 30-50min is first stirred with 1000-2000r/min revolving speed, it is polyester resin that quality, which is then added,
The peroxide of the 1.5-2% of quality, then 60-75min is stirred with 4000-5000r/min revolving speed, cooled to room temperature is made
The blend of amber resin and polyester resin；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, 130-136 is then heated to
DEG C, catalyst is added, polysiloxane, coupling agent is then added, constant temperature is anti-under 30-40Mpa pressure, at 135 DEG C
2-4h is answered, then decompression, drying, obtain modified polyorganosiloxanes.
Polyester resin described in step (I) is polypropylene terephthalate, and the peroxide is peroxidating
One or more of t-butyl perbenzoate, benzoyl peroxide or dilauroyl peroxide.
The concentration of the blend of amber resin described in step (II) and polyester resin in organic solvent is 0.4-
The mass ratio of 0.6g/mL, the polysiloxane and coupling agent, amber resin is 100:0.8-1.2:10.
The polysiloxane is one in polydiethylsiloxane, dimethyl silicone polymer or polymethyl siloxane
Kind is several, and the coupling agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
The preparation method of the modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 50-60 DEG C, then fill
Point being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent described in step (i) and isopropanol is 3:8, propylene described in step (ii)
The mass ratio of acid resin and ethyl alcohol is 1:6, and the mass ratio of diatomite described in step (iii) and premixed liquid I are 1:3.
The surface treating agent is in amido silicon oil, hydroxy silicon oil, diphenyl silanediol or methylethoxy base silane
It is one or more of.
A kind of preparation method of plastics high stability halogen-free environment-friendlyflame flame retardant, method includes the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 60-80 DEG C
Uniformly, surface treating agent is then atomized using high-pressure atomization spray thrower by the gas-phase silica being added under stirring several times
In the mixture of modification infusorial earth, premix is made；
Step (2): at 120-160 DEG C, under stirring, modified polyorganosiloxanes are added dropwise to premix by weight
In, constant temperature stirs 1-3h, adds polyethylene wax, is uniformly mixed, it discharges, vacuum drying.
Surface treating agent is first heated to 90-110 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Plastics of the present invention high stability halogen-free environment-friendlyflame flame retardant is in practical application, additive amount in the plastic is 3-
10%。
Compared with prior art, the invention has the characteristics that:
1) active group can be introduced on molecule chain end or side chain come modified polyorganosiloxanes using kochenite, urged
Under the action of agent, the active group of polyester resin and active group and polysiloxane on kochenite strand is anti-
It answers, produces the copolymer of block, grafting or interpenetrating networks, not only there is excellent heat resistance, can also be effectively improved fire retardant
The compatibility of system and plastics, plays the role of activeness and quietness, and conventional flame retardant is overcome to influence the defect of plastic strength and toughness；
2) combined modified to diatomite progress using titanate coupling agent and polyvinyl alcohol, it can be grafted in diatomite microparticle surfaces
Organic group can make diatomite microparticle outer surface be coated with acrylic resin, can make to have between diatomite microparticle fine
Dispersibility, prevent microparticle from reuniting the phenomenon that settle, can not only play the role of surfactant, enhancing modified poly- has
Compatibility between organic siloxane and plastic basis material, is alternatively arranged as reinforced filling to improve the mechanical strength of plastic basis material, with
Gas-phase silica is used in combination, and the two is synergistic, can play the role of starvation and reduce material surface temperature, can be effective
Ground is fire-retardant and presses down cigarette, substantially improves the flame retardant effect of fire retardant systems；
3) modified polyorganosiloxanes are similar to interpenetrating polymer networks (IPN) partial cross-linked mechanism and tie in fire retardant of the present invention
It is incorporated into plastic basis material structure, can effectively limit the dispersibility and mobility of gas-phase silica, modification infusorial earth, prevent its migration
To by the surface of flame-retardant polymer, there is excellent fire-retardant stability；
4) fire retardant and smoke suppressing effect of the present invention are good, and securely and reliably, raw material sources are wide, at low cost, are free of toxic addition
Agent can improve the machining and flame-proof heat-resistant performance of substrate, have good plasticity, can effectively reduce smoke amount and suppression
Carbon dioxide processed generates, and complies fully with the environmental requirement of new flame retardant non-halogen non-phosphate.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 52 parts of modified polyorganosiloxanes, 21 parts of gas-phase silica, 10 parts of modification infusorial earth, 3 parts of surface treating agent and poly- second
1 part of alkene wax.
Wherein, modified polyorganosiloxanes preparation method the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 9:1 with polyester resin, it is transferred in batch mixer,
130 DEG C are heated to, 40min is first stirred with 2000r/min revolving speed, 1.6% peroxide that quality is polyester resin quality is then added
Compound, then 60min, cooled to room temperature are stirred with 4000r/min revolving speed, obtained amber resin is blended with polyester resin
Object；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, is then heated to 132 DEG C, then
Be added catalyst, then be added polysiloxane, coupling agent, under 32Mpa pressure, at 135 DEG C isothermal reaction 3h, then
Decompression, drying, obtain modified polyorganosiloxanes.
Polyester resin is polypropylene terephthalate in step (I), and peroxide is peroxidized t-butyl perbenzoate.
The concentration of the blend of amber resin and polyester resin in organic solvent is 0.5g/mL in step (II), poly- to have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:0.8:10.Polysiloxane is polydiethylsiloxane, even
Connection agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
The preparation method of modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 55 DEG C, then sufficiently
Being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent and isopropanol is 3:8, acrylic resin and ethyl alcohol in step (ii) in step (i)
Mass ratio be 1:6, the mass ratio of diatomite and premixed liquid I are 1:3 in step (iii).
In the present embodiment, surface treating agent is amido silicon oil.
The preparation method of the present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant, comprising the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 70 DEG C
It is even, then using high-pressure atomization spray thrower surface treating agent be atomized several times the gas-phase silica that is added under stirring and
In the mixture of modification infusorial earth, premix is made；
Modified polyorganosiloxanes: at 135 DEG C, under stirring, being added dropwise in premix by step (2) by weight,
Constant temperature stirs 2.5h, adds polyethylene wax, is uniformly mixed, and discharges, vacuum drying.
Surface treating agent is first heated to 95 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Embodiment 2:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 58 parts of modified polyorganosiloxanes, 22 parts of gas-phase silica, 9 parts of modification infusorial earth, 2 parts of surface treating agent and poly- second
1 part of alkene wax.
Wherein, modified polyorganosiloxanes preparation method the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 8:1 with polyester resin, it is transferred in batch mixer,
135 DEG C are heated to, 45min is first stirred with 1800r/min revolving speed, 1.7% peroxide that quality is polyester resin quality is then added
Compound, then 65min, cooled to room temperature are stirred with 4200r/min revolving speed, obtained amber resin is blended with polyester resin
Object；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, is then heated to 134 DEG C, then
Be added catalyst, then be added polysiloxane, coupling agent, under 35Mpa pressure, at 135 DEG C isothermal reaction 3.5h, with
It depressurizes afterwards, is dry, obtaining modified polyorganosiloxanes.
Polyester resin is polypropylene terephthalate in step (I), and peroxide is benzoyl peroxide.
The concentration of the blend of amber resin and polyester resin in organic solvent is 0.48g/mL in step (II), poly- to have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:1:10.Polysiloxane is dimethyl silicone polymer, coupling
Agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
The preparation method of modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 52 DEG C, then sufficiently
Being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent and isopropanol is 3:8, acrylic resin and ethyl alcohol in step (ii) in step (i)
Mass ratio be 1:6, the mass ratio of diatomite and premixed liquid I are 1:3 in step (iii).
In the present embodiment, surface treating agent is hydroxy silicon oil.
The preparation method of the present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant, comprising the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 72 DEG C
It is even, then using high-pressure atomization spray thrower surface treating agent be atomized several times the gas-phase silica that is added under stirring and
In the mixture of modification infusorial earth, premix is made；
Modified polyorganosiloxanes: at 140 DEG C, under stirring, being added dropwise in premix by step (2) by weight,
Constant temperature stirs 2h, adds polyethylene wax, is uniformly mixed, and discharges, vacuum drying.
Surface treating agent is first heated to 98 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Embodiment 3:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 64 parts of modified polyorganosiloxanes, 25 parts of gas-phase silica, 12 parts of modification infusorial earth, 4 parts of surface treating agent and poly- second
1.5 parts of alkene wax.
Wherein, modified polyorganosiloxanes preparation method the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 10:1 with polyester resin, it is transferred to batch mixer
In, 130 DEG C are heated to, 40min is first stirred with 1500r/min revolving speed, 1.8% that quality is polyester resin quality is then added
Peroxide, then 65min is stirred with 4500r/min revolving speed, being total to for amber resin and polyester resin is made in cooled to room temperature
Mixed object；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, is then heated to 135 DEG C, then
Be added catalyst, then be added polysiloxane, coupling agent, under 36Mpa pressure, at 135 DEG C isothermal reaction 4h, then
Decompression, drying, obtain modified polyorganosiloxanes.
Polyester resin is polypropylene terephthalate in step (I), and peroxide is dilauroyl peroxide.
The concentration of the blend of amber resin and polyester resin in organic solvent is 0.52g/mL in step (II), poly- to have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:1.1:10.Polysiloxane is polymethyl siloxane, coupling
Agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
The preparation method of modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 52 DEG C, then sufficiently
Being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent and isopropanol is 3:8, acrylic resin and ethyl alcohol in step (ii) in step (i)
Mass ratio be 1:6, the mass ratio of diatomite and premixed liquid I are 1:3 in step (iii).
In the present embodiment, surface treating agent is diphenyl silanediol.
The preparation method of the present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant, comprising the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 75 DEG C
It is even, then using high-pressure atomization spray thrower surface treating agent be atomized several times the gas-phase silica that is added under stirring and
In the mixture of modification infusorial earth, premix is made；
Modified polyorganosiloxanes: at 150 DEG C, under stirring, being added dropwise in premix by step (2) by weight,
Constant temperature stirs 2h, adds polyethylene wax, is uniformly mixed, and discharges, vacuum drying.
Surface treating agent is first heated to 100 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Embodiment 4:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 45 parts of modified polyorganosiloxanes, 20 parts of gas-phase silica, 8 parts of modification infusorial earth, 2.8 parts of surface treating agent and poly-
1.2 parts of ethylene waxes.
Wherein, modified polyorganosiloxanes preparation method the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 9:1 with polyester resin, it is transferred in batch mixer,
120 DEG C are heated to, 50min is first stirred with 1000r/min revolving speed, 1.5% peroxide that quality is polyester resin quality is then added
Compound, then 75min, cooled to room temperature are stirred with 4000r/min revolving speed, obtained amber resin is blended with polyester resin
Object；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, is then heated to 130 DEG C, then
Be added catalyst, then be added polysiloxane, coupling agent, under 30Mpa pressure, at 135 DEG C isothermal reaction 3.5h, with
It depressurizes afterwards, is dry, obtaining modified polyorganosiloxanes.
Polyester resin is polypropylene terephthalate in step (I), and peroxide is dilauroyl peroxide.
The concentration of the blend of amber resin and polyester resin in organic solvent is 0.4g/mL in step (II), poly- to have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:0.8:10.Polysiloxane is polydiethylsiloxane, even
Connection agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
The preparation method of modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 52 DEG C, then sufficiently
Being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent and isopropanol is 3:8, acrylic resin and ethyl alcohol in step (ii) in step (i)
Mass ratio be 1:6, the mass ratio of diatomite and premixed liquid I are 1:3 in step (iii).
In the present embodiment, surface treating agent is methylethoxy base silane.
The preparation method of the present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant, comprising the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 60 DEG C
It is even, then using high-pressure atomization spray thrower surface treating agent be atomized several times the gas-phase silica that is added under stirring and
In the mixture of modification infusorial earth, premix is made；
Modified polyorganosiloxanes: at 120 DEG C, under stirring, being added dropwise in premix by step (2) by weight,
Constant temperature stirs 3h, adds polyethylene wax, is uniformly mixed, and discharges, vacuum drying.
Surface treating agent is first heated to 90 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Embodiment 5:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 80 parts of modified polyorganosiloxanes, 32 parts of gas-phase silica, 15 parts of modification infusorial earth, 5 parts of surface treating agent and poly- second
2 parts of alkene wax.
Wherein, modified polyorganosiloxanes preparation method the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 12:1 with polyester resin, it is transferred to batch mixer
In, 140 DEG C are heated to, 30min is first stirred with 2000r/min revolving speed, 2% mistake that quality is polyester resin quality is then added
Oxide, then 60min, cooled to room temperature are stirred with 5000r/min revolving speed, obtained amber resin is blended with polyester resin
Object；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, is then heated to 136 DEG C, then
Be added catalyst, then be added polysiloxane, coupling agent, under 40Mpa pressure, at 135 DEG C isothermal reaction 2h, then
Decompression, drying, obtain modified polyorganosiloxanes.
Polyester resin is polypropylene terephthalate in step (I), and peroxide is peroxidized t-butyl perbenzoate.
The concentration of the blend of amber resin and polyester resin in organic solvent is 0.6g/mL in step (II), poly- to have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:1.2:10.Polysiloxane is polymethyl siloxane, coupling
Agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
The preparation method of modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 52 DEG C, then sufficiently
Being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent and isopropanol is 3:8, acrylic resin and ethyl alcohol in step (ii) in step (i)
Mass ratio be 1:6, the mass ratio of diatomite and premixed liquid I are 1:3 in step (iii).
In the present embodiment, surface treating agent is amido silicon oil.
The preparation method of the present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant, comprising the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 80 DEG C
It is even, then using high-pressure atomization spray thrower surface treating agent be atomized several times the gas-phase silica that is added under stirring and
In the mixture of modification infusorial earth, premix is made；
Modified polyorganosiloxanes: at 160 DEG C, under stirring, being added dropwise in premix by step (2) by weight,
Constant temperature stirs 1h, adds polyethylene wax, is uniformly mixed, and discharges, vacuum drying.
Surface treating agent is first heated to 110 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Embodiment 6:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 72.4 parts of modified polyorganosiloxanes, 26 parts of gas-phase silica, 10 parts of modification infusorial earth, 4 parts of surface treating agent and poly-
1.6 parts of ethylene waxes.
Wherein, modified polyorganosiloxanes preparation method the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 10:1 with polyester resin, it is transferred to batch mixer
In, 140 DEG C are heated to, 30min is first stirred with 2000r/min revolving speed, 1.8% that quality is polyester resin quality is then added
Peroxide, then 60min is stirred with 5000r/min revolving speed, being total to for amber resin and polyester resin is made in cooled to room temperature
Mixed object；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, is then heated to 135 DEG C, then
Be added catalyst, then be added polysiloxane, coupling agent, under 32Mpa pressure, at 135 DEG C isothermal reaction 3h, then
Decompression, drying, obtain modified polyorganosiloxanes.
Polyester resin is polypropylene terephthalate in step (I), and peroxide is peroxidized t-butyl perbenzoate
It is mixed in mass ratio for 6:1 with dilauroyl peroxide.
The concentration of the blend of amber resin and polyester resin in organic solvent is 0.5g/mL in step (II), poly- to have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:1:10.Polysiloxane is polydiethylsiloxane, poly- two
Methylsiloxane mixes in mass ratio for 3:5:2 with polymethyl siloxane, and coupling agent is Alpha-Methyl acryloyloxymethyl
Trimethoxy silane.
The preparation method of modification infusorial earth the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 60 DEG C, then sufficiently
Being ground to granularity was 800 meshes up to 95%.
The mass ratio of titanate coupling agent and isopropanol is 3:8, acrylic resin and ethyl alcohol in step (ii) in step (i)
Mass ratio be 1:6, the mass ratio of diatomite and premixed liquid I are 1:3 in step (iii).
In the present embodiment, it with diphenyl silanediol is that 3:4 is mixed that surface treating agent is amido silicon oil in mass ratio.
The preparation method of the present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant, comprising the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 75 DEG C
It is even, then using high-pressure atomization spray thrower surface treating agent be atomized several times the gas-phase silica that is added under stirring and
In the mixture of modification infusorial earth, premix is made；
Modified polyorganosiloxanes: at 140 DEG C, under stirring, being added dropwise in premix by step (2) by weight,
Constant temperature stirs 2.5h, adds polyethylene wax, is uniformly mixed, and discharges, vacuum drying.
Surface treating agent is first heated to 105 DEG C in (1) by step, is subsequently transferred in high-pressure atomization spray thrower.
Embodiment 7:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 68 parts of modified polyorganosiloxanes, 30 parts of gas-phase silica, 12 parts of modification infusorial earth, 3 parts of surface treating agent and poly- second
1 part of alkene wax.
Remaining is the same as embodiment 6.
Embodiment 8:
The present embodiment plastics high stability halogen-free environment-friendlyflame flame retardant is prepared by the raw material for including following components and parts by weight content
It forms: 74 parts of modified polyorganosiloxanes, 23 parts of gas-phase silica, 13 parts of modification infusorial earth, 5 parts of surface treating agent and poly- second
2 parts of alkene wax.
Remaining is the same as embodiment 6.
Comparative example 1:
In the formula of this comparative example, modified polyorganosiloxanes are replaced using common commercially available polysiloxane, remaining is the same as real
Apply example 6.
Comparative example 2:
In the formula of this comparative example, modification infusorial earth is replaced using common commercially available diatomite, remaining is the same as embodiment 6.
Comparative example 3:
This comparative example is commercially available halogen-free flame retardants.
Performance test:
Test formulations: 72 parts of PC, 23 parts of plasticizer DOP, 5 parts of fire retardant (embodiment 1-8 and comparative example 1-3).
PC, plasticizer are weighed by the mass ratio of above-mentioned test formulations, then is separately added into 5 parts of fire retardants to be tested, small
10min is mixed in type high-speed mixer, through extruding pelletization, injection molding batten then carries out flame retardant property and related mechanical property
It can test, test result is shown in Table 1.
Table 1: flame retardant property and related mechanical experimental results
As can be seen from Table 1, the flame retardant effect of fire retardant of the present invention is excellent, and the influence to the mechanical property of material compared with
It is small, while mechanical property can be taken into account, it is effectively improved the anti-flammability of material, is had a good application prospect.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant, which is characterized in that the fire retardant is by including following components and again
The raw material of amount part content is prepared: 45-80 parts of modified polyorganosiloxanes, 20-32 parts of gas-phase silica, modification infusorial earth 8-
15 parts, 2-5 parts of surface treating agent and 1-2 parts of polyethylene wax.
2. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 1, which is characterized in that described changes
The preparation method of property polysiloxane the following steps are included:
Step (I): amber resin is uniformly admixed together by the mass ratio of 8-12:1 with polyester resin, it is transferred to batch mixer
In, it is heated to 120-140 DEG C, 30-50min is first stirred with 1000-2000r/min revolving speed, it is polyester resin that quality, which is then added,
The peroxide of the 1.5-2% of quality, then 60-75min is stirred with 4000-5000r/min revolving speed, cooled to room temperature is made
The blend of amber resin and polyester resin；
Step (II): the blend of amber resin and polyester resin is dissolved in organic solvent, 130-136 is then heated to
DEG C, catalyst is added, polysiloxane, coupling agent is then added, constant temperature is anti-under 30-40Mpa pressure, at 135 DEG C
2-4h is answered, then decompression, drying, obtain modified polyorganosiloxanes.
3. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 2, which is characterized in that step (I)
Described in polyester resin be polypropylene terephthalate, the peroxide be peroxidized t-butyl perbenzoate, mistake
One or more of Benzoyl Oxide or dilauroyl peroxide.
4. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 2, which is characterized in that step (II)
Described in amber resin and the blend concentration in organic solvent of polyester resin be 0.4-0.6g/mL, described poly- have
The mass ratio of organic siloxane and coupling agent, amber resin is 100:0.8-1.2:10.
5. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 4, which is characterized in that described is poly-
Organosiloxane is one or more of polydiethylsiloxane, dimethyl silicone polymer or polymethyl siloxane, described
Coupling agent is Alpha-Methyl acryloyloxymethyl trimethoxy silane.
6. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 1, which is characterized in that described changes
The preparation method of property diatomite the following steps are included:
Step (i): titanate coupling agent being added into isopropanol, is uniformly mixed, and titanate coupling agent aqueous isopropanol is made, so
In mass ratio it is afterwards that 1:0.4 is mixed with polyvinyl alcohol by titanate coupling agent aqueous isopropanol, premixed liquid I is made；
Step (ii): acrylic resin being added into ethyl alcohol, is stirred to abundant dissolution, premixed liquid II is made；
Step (iii): diatomite is added in premixed liquid I, with 3000 r/min high-speed stirred 1h at 25 DEG C；Filtering retains solid
Body is added into premixed liquid II, stirs at low speed 2h at 35 DEG C with 800 r/min；Filtering, the sulphur for being 10% with mass fraction
Acid solution wash solid removes impurity, after be washed to solution system and be in neutrality, filter, and be dried in vacuo at 50-60 DEG C, then fill
Point being ground to granularity was 800 meshes up to 95%.
7. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 6, which is characterized in that step is (i)
Described in titanate coupling agent and the mass ratio of isopropanol be 3:8, acrylic resin described in step (ii) and ethyl alcohol
Mass ratio is 1:6, and the mass ratio of diatomite described in step (iii) and premixed liquid I are 1:3.
8. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 1, which is characterized in that the table
Surface treatment agent is one or more of amido silicon oil, hydroxy silicon oil, diphenyl silanediol or methylethoxy base silane.
9. a kind of preparation method of plastics high stability halogen-free environment-friendlyflame flame retardant as described in claim 1, which is characterized in that
Method includes the following steps:
Gas-phase silica, modification infusorial earth: being added in mixing machine by step (1) by weight, is stirred at 60-80 DEG C
Uniformly, surface treating agent is then atomized using high-pressure atomization spray thrower by the gas-phase silica being added under stirring several times
In the mixture of modification infusorial earth, premix is made；
Step (2): at 120-160 DEG C, under stirring, modified polyorganosiloxanes are added dropwise to premix by weight
In, constant temperature stirs 1-3h, adds polyethylene wax, is uniformly mixed, it discharges, vacuum drying.
10. a kind of plastics high stability halogen-free environment-friendlyflame flame retardant according to claim 1, which is characterized in that step (1)
It is middle that surface treating agent is first heated to 90-110 DEG C, it is subsequently transferred in high-pressure atomization spray thrower.
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| CN112920490A (en) * | 2021-01-29 | 2021-06-08 | 湖南省升阳新材料有限公司 | High-tinting-strength flame-retardant general color master batch and preparation method thereof |
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|---|---|---|---|---|
| JP2005320457A (en) * | 2004-05-10 | 2005-11-17 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded article using the same |
| CN106928721A (en) * | 2015-12-29 | 2017-07-07 | 宁波福天新材料科技有限公司 | A kind of halogen-free flame retardant for plastics and preparation method thereof |
| CN108842511A (en) * | 2018-05-25 | 2018-11-20 | 安徽银兔装饰材料有限公司 | Wallpaper fire-retardant filler and preparation method thereof |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005320457A (en) * | 2004-05-10 | 2005-11-17 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded article using the same |
| CN106928721A (en) * | 2015-12-29 | 2017-07-07 | 宁波福天新材料科技有限公司 | A kind of halogen-free flame retardant for plastics and preparation method thereof |
| CN108842511A (en) * | 2018-05-25 | 2018-11-20 | 安徽银兔装饰材料有限公司 | Wallpaper fire-retardant filler and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112920490A (en) * | 2021-01-29 | 2021-06-08 | 湖南省升阳新材料有限公司 | High-tinting-strength flame-retardant general color master batch and preparation method thereof |
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