CN107163375A - A kind of agent of halogen-free expanded flame-retardant containing halloysite nanotubes and its preparation method and application - Google Patents
A kind of agent of halogen-free expanded flame-retardant containing halloysite nanotubes and its preparation method and application Download PDFInfo
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- 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
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- 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
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention belongs to technical field of flame retardant, and in particular to a kind of agent of halogen-free expanded flame-retardant containing halloysite nanotubes and its preparation method and application.The agent of halogen-free expanded flame-retardant containing halloysite nanotubes includes triazine series carbon forming foaming agent, phosphorus compound and halloysite nanotubes, and wherein halloysite nanotubes account for the 1~30% of the agent gross weight of halogen-free expanded flame-retardant containing halloysite nanotubes；The mass ratio of triazine series carbon forming foaming agent and phosphorus compound is 1:1~5.The agent of halogen-free expanded flame-retardant containing halloysite nanotubes of the invention has flame retarding efficiency high, and addition is small, the characteristics of small on the physical and mechanical properties influence of composite, can be widely used for the fields such as automobile, household electrical appliance, building materials.
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of agent of halogen-free expanded flame-retardant containing halloysite nanotubes and its
Preparation method and application.
Background technology
Expansion type flame retardant is one of wide variety of fire retardant types in recent years, and the fire retardant overcomes halogenated flame retardant
Excitant and corrosive gas and smog are easily released in burning, environment is polluted, human health is endangered, while etching apparatus etc.
Shortcoming, is that a kind of very promising environmental type fire retardant expansion type flame retardant is made up of acid source, charcoal source and source of the gas：(1)
Acid source：The compound that inorganic acid can be discharged in a heated condition promotes polyol dehydration carbonization；(2) charcoal source：Rich in carbon
The polyol of atom, under the action of an acid dehydration forms charcoal；(3) source of the gas：Volatile products can be discharged when heated
Amine or phthalein amines.In PP expansion type flame retardants, charcoal source be it is crucial, traditional expanding fire retardant with pentaerythrite,
Starch etc. is carbon forming agent, big with addition, is easily separated out, and mechanical property damages big shortcoming.
A kind of triazine carbon forming foaming agent, ammonium polyphosphate and synergistic are disclosed in Chinese patent application CN101225187A
The Non-Halogen Flame Retardant of Polypropylene of agent composition, though the fire retardant good flame retardation effect being made up of triazine carbon forming foaming agent, polypropylene is answered
Condensation material mechanical property is still damaged greatly.
Halogen-free expansion fire retardant and PP poor compatibilities, can reduce mechanical property (the especially impact of PP composites
Can), so as to limit applications of the PP in the occasion for requiring higher.Document report, montmorillonite, stratiform hydrotalcite, POSS, graphite
The fire retarding synergists such as alkene, CNT can improve IFR flame retardant effect, but they are expensive, be not suitable for commercial Application.
The content of the invention
In place of shortcoming and defect to solve prior art, primary and foremost purpose of the invention is that provide one kind receives containing galapectite
Mitron halogen-free expanded flame-retardant agent.
Another object of the present invention is to provide the preparation method of the above-mentioned agent of halogen-free expanded flame-retardant containing halloysite nanotubes.
It is still another object of the present invention to provide the application of the above-mentioned agent of halogen-free expanded flame-retardant containing halloysite nanotubes.
A kind of main Halogen being made up of triazine series carbon forming foaming agent, phosphorus compound and halloysite nanotubes of the present invention is swollen
There is swollen fire retardant, halloysite nanotubes synergistic fire retardation can improve flame retardant effect of the fire retardant to PP, while galapectite is received
Mitron has humidification to PP, and to improve HNTs and triazine series carbon forming foaming agent compatibility, flame-retardant system can add phase
Hold agent or in HNTs surface grafting maleic anhydrides, make fire retardant efficiency high, addition is small, strengthen the physics of PP composites
Mechanical performance, expands application of the fire-retardant PP composites in fields such as automobile, household electrical appliance, building materials.
The object of the invention is achieved through the following technical solutions：
A kind of agent of halogen-free expanded flame-retardant containing halloysite nanotubes, including triazine series carbon forming foaming agent, phosphorus compound and Ai Luo
Stone nanotube, wherein halloysite nanotubes account for the 1~30% of the agent gross weight of halogen-free expanded flame-retardant containing halloysite nanotubes, institute
The mass ratio for stating triazine series carbon forming foaming agent and phosphorus compound is 1:1~5.To improve HNTs and triazine series carbon forming foaming agent
Compatibility, flame-retardant system can also add compatilizer or maleic anhydride modified in HNTs surface graftings.
It is preferred that, the triazine series carbon forming foaming agent replaces by raw material of Cyanuric Chloride through alkylamine, then with diamine
Condensation is formed, with the structure shown in formula (1)：
Wherein, R1ForNH-CH2CH2OH and NH2One in
Kind；
R2ForCH2CH2And CH2CH2NHCH2CH2In
It is a kind of；N=1~10000.
The triazine series carbon forming foaming agent is synthesized by following steps：
1. Cyanuric Chloride and acetone are added in a kettle., Cyanuric Chloride is uniformly dispersed, alkane is added dropwise at -5 DEG C~5 DEG C
Base amine and triethylamine, are 5~7 to solution ph, are reacted 1~3 hour after being added dropwise to complete；
2. rise temperature is added dropwise diamines and triethylamine, keeps solution to room temperature (room temperature of the present invention is 10-30 DEG C)
PH value is 5~7, and reaction temperature is raised after being added dropwise to complete to 40 DEG C~65 DEG C, is reacted 4~6 hours；
3. reaction temperature is raised, under the conditions of 80 DEG C~110 DEG C, diamines and triethylamine are added drop-wise in reactor, made molten
The pH value of liquid is 5~7, and reaction steams acetone after 5~7 hours, product is again through washing, and suction filtration obtains triazine after drying and is tied to form
Charcoal-foaming agent.
Polymerization degree n=1~10000 of synthesized triazine series carbon forming foaming agent.
It is preferred that, the phosphorus compound can be high polymerization degree crystallization II-type polyphosphoric acid, its polymerization degree n >=1500；Also may be used
To be trbasic zinc phosphate, phenyl hypo-aluminum orthophosphate or alkyl hypo-aluminum orthophosphate etc..
It is preferred that, the halloysite nanotubes (HNTs) are a kind of cheap natural nano pipe of well-crystallized, its point
Minor is Al2Si2O5(OH)4·nH2O, wherein n=0 or 2, are often multi-walled pipes shape structure, by alumina octahedral and silicon-oxy tetrahedron
Lattice mismatch curling is formed.
It is preferred that, to improve HNTs and triazine series carbon forming foaming agent compatibility, compatilizer is added in flame-retardant system,
Or carry out surface modification in HNTs surface graftings maleic anhydride；Wherein the addition of compatilizer is the gross weight of flame-retardant system
3-5%.
Wherein, the step of HNTs surface graftings maleic anhydride is：HNTs surfaces are first through coupling processing, then grafted maleic
Acid anhydride, shown in reaction equation such as formula (2)：
It is preferred that, the compatilizer be polymer grafted maleic anhydride, such as PP-g-MAH (maleic anhydride inoculated polypropylene),
PE-g-MAH (maleic anhydride grafted polyethylene), or EPDM-g-MAH (maleic anhydride grafting ethylene propylene diene rubber) etc..
It is preferred that, the preparation method of the above-mentioned agent of halogen-free expanded flame-retardant containing halloysite nanotubes comprises the following steps：By triazine
Series carbon forming foaming agent, phosphorus compound and halloysite nanotubes are mixed 5~10 minutes, obtain the Halogen containing halloysite nanotubes
Expanding fire retardant.
It is preferred that, the above-mentioned agent of halogen-free expanded flame-retardant containing halloysite nanotubes can be applied to automobile, household electrical appliance or building materials etc.
Field.
Specifically, the agent of halogen-free expanded flame-retardant containing halloysite nanotubes can be used for preparing flame-retardant polypropylene composite material；
Wherein described flame-retardant polypropylene composite material is received comprising 70-82 parts of thermoplastic resins and 18-30 parts containing galapectite by weight
Mitron halogen-free expanded flame-retardant agent；The thermoplastic resin is HOPP or acrylic resin copolymer.
Compared with prior art, the present invention has advantages below and beneficial effect：
The agent of halogen-free expanded flame-retardant containing halloysite nanotubes of the invention have flame retarding efficiency height, addition it is small, to composite
Physical and mechanical properties influence it is small the characteristics of, can be widely used for the fields such as automobile, household electrical appliance, building materials.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) synthesis step of triazine series carbon forming foaming agent：
1. 350 grams of Cyanuric Chlorides and 500 grams of acetone are added in a kettle., Cyanuric Chloride is uniformly dispersed, -5 DEG C~5
50 grams of monoethanolamines and 30 grams of triethylamines are added dropwise at DEG C, are 5~7 to solution ph, are reacted 1~3 hour after being added dropwise to complete；
2. 60 grams of ethylenediamines and 15 grams of triethylamines are added dropwise to room temperature in rise temperature, and it is 5~7 to keep solution ph, is dripped
Into rear rise reaction temperature to 40 DEG C~65 DEG C, react 4~6 hours；
3. reaction temperature is raised, under the conditions of 80 DEG C~110 DEG C, 60 grams of ethylenediamines and 15 grams of triethylamines are added drop-wise to reaction
In kettle, the pH value for making solution is 5~7, and reaction steams acetone after 5~7 hours, product is again through washing, and suction filtration is obtained after drying
300 grams of triazine series carbon forming foaming agents.
(2) 10 grams of triazine series carbon forming foaming agents, 10 grams of trbasic zinc phosphates are mixed 5~10 with 1 gram of halloysite nanotubes (HNTs)
Minute, obtain the agent of halogen-free expanded flame-retardant containing halloysite nanotubes.
Embodiment 2
(1) synthesis step of triazine series carbon forming foaming agent：
1. 50 grams of Cyanuric Chlorides and 150 grams of acetone are added in a kettle., Cyanuric Chloride is uniformly dispersed, -5 DEG C~5
10 grams of aniline and 8 grams of triethylamines are added dropwise at DEG C, are 5~7 to solution ph, are reacted 1~3 hour after being added dropwise to complete；
2. 20 grams of diethylenetriamines and 4 grams of triethylamines are added dropwise to room temperature in rise temperature, and holding solution ph is 5-7, is added dropwise
After the completion of rise reaction temperature to 40 DEG C~65 DEG C, react 4~6 hours；
3. reaction temperature is raised, under the conditions of 80 DEG C~110 DEG C, 20 grams of diethylenetriamines and 4 grams of triethylamines are added drop-wise to
In reactor, the pH value for making solution is 5~7, and reaction steams acetone after 5~7 hours, product is again through washing, and suction filtration is after drying
Obtain 60 grams of triazine series carbon forming foaming agents.
(2) halloysite nanotubes (HNTs) are modified
The ethanol solution for taking 100 grams of halloysite nanotubes to add 1.5 grams of KH-550 (refers to contain 1.5g KH- in solution
550), high-speed stirred, then 120 DEG C of oven for drying；To amidized halloysite nanotubes, 5 grams of maleic anhydride DMF solutions are added
(referring to contain 5g maleic anhydrides in solution), 120 DEG C of backflow 24h are filtered, are dried, obtain modified halloysite nanotubes.
(2) by 10 grams of triazine series carbon forming foaming agents, 30 grams of ammonium polyphosphates and the modified galapectite nanometer of 3 grams of steps (2)
Manage (HNTs) to mix 5~10 minutes, obtain the agent of halogen-free expanded flame-retardant containing halloysite nanotubes.
Embodiment 3
(1) synthesis step of triazine series carbon forming foaming agent：
1. 350 grams of Cyanuric Chlorides and 500 grams of acetone are added in a kettle., Cyanuric Chloride is uniformly dispersed, -5 DEG C~5
50 grams of monoethanolamines and 30 grams of triethylamines are added dropwise at DEG C, are 5~7 to solution ph, are reacted 1~3 hour after being added dropwise to complete；
2. 60 grams of ethylenediamines and 15 grams of triethylamines are added dropwise to room temperature in rise temperature, and it is 5~7 to keep solution ph, is dripped
Into rear rise reaction temperature to 40 DEG C~65 DEG C, react 4~6 hours；
3. reaction temperature is raised, under the conditions of 80 DEG C~110 DEG C, 60 grams of ethylenediamines and 15 grams of triethylamines are added drop-wise to reaction
In kettle, the pH value for making solution is 5~7, and reaction steams acetone after 5~7 hours, product is again through washing, and suction filtration is obtained after drying
300 grams of triazine series carbon forming foaming agents.
(2) halloysite nanotubes (HNTs) are modified
The ethanol solution for taking 100 grams of halloysite nanotubes to add 1.5 grams of KH-550 (refers to contain 1.5g KH- in solution
550), high-speed stirred, then 120 DEG C of oven for drying；To amidized halloysite nanotubes, 5 grams of maleic anhydride dimethylbenzene are added
Solution (refers to contain 5g maleic anhydrides in solution) that 120 DEG C of backflow 24h are filtered, dried, obtain modified halloysite nanotubes.
(2) by 30 grams of triazine series carbon forming foaming agents, 90 grams of hypo-aluminum orthophosphates and the modified galapectite nanometer of 18 grams of steps (2)
Manage (HNTs) to mix 5~10 minutes, obtain the agent of halogen-free expanded flame-retardant containing halloysite nanotubes.
Embodiment 4
The agent of halogen-free expanded flame-retardant containing halloysite nanotubes prepared by above-described embodiment 1-3 is used to make according to the proportioning of table 1
Standby flame-retardant polypropylene composite material：Thermoplastic resin and the agent of halogen-free expanded flame-retardant containing halloysite nanotubes are made by twin-screw extrusion
Grain, injection machine injection molding obtains flame-retardant polypropylene composite material, and thermoplastic resin therein is that HOPP or copolymerization are poly-
Allyl resin.
The flame-retardant polypropylene composite material constituent content of table 1
The flame-retardant polypropylene composite material performance of above-mentioned preparation such as table 2：
The flame-retardant polypropylene composite material performance test of table 2
| Experiment numbers | Fire resistance | With PP compatibilities | Impact strength | Tensile strength | Bending strength |
| 1 | 1.6mm, UL-94V0 | Surface is separated out without white point | ≥15MPa | ≥20MPa | ≥40MPa |
| 2 | 3.2mm, UL-94V0 | Surface is separated out without white point | ≥15MPa | ≥20MPa | ≥40MPa |
| 3 | 1.6mm, UL-94V00 | Surface is separated out without white point | ≥15MPa | ≥20MPa | ≥40MPa |
| 4 | 3.2mm, UL-94V00 | Surface is separated out without white point | ≥15MPa | ≥20MPa | ≥40MPa |
In table 2, it is with PP compatibility test methods：Flame-retardant polypropylene composite material is boiled 168 hours through 70 DEG C of water, estimates table
Face whether there is white point；
Impact strength presses GB/T 9341- by GB/T 1843-2008, tensile strength by GBT 1040-2006, bending strength
2008 standard methods are tested.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of agent of halogen-free expanded flame-retardant containing halloysite nanotubes, it is characterised in that the halogen-free expandable containing halloysite nanotubes
Fire retardant includes triazine series carbon forming foaming agent, phosphorus compound and halloysite nanotubes, wherein halloysite nanotubes account for it is described containing angstrom
The 1~30% of Lip river stone nanotube halogen-free expanded flame-retardant agent gross weight, the quality of the triazine series carbon forming foaming agent and phosphorus compound
Than for 1:1~5.
2. one kind agent of halogen-free expanded flame-retardant containing halloysite nanotubes according to claim 1, it is characterised in that the triazine is tied to form
Charcoal-foaming agent replaces by raw material of Cyanuric Chloride through alkylamine, is then formed with diamine condensation, with the knot shown in formula (1)
Structure：
Wherein, R1ForNH-CH2CH2OH and NH2In one kind；
R2ForCH2CH2And CH2CH2NHCH2CH2In one kind；n
=1~10000.
3. one kind agent of halogen-free expanded flame-retardant containing halloysite nanotubes according to claim 1, it is characterised in that the triazine
Series carbon forming foaming agent is synthesized by following steps：
1. Cyanuric Chloride and acetone are added in a kettle., Cyanuric Chloride is uniformly dispersed, alkylamine is added dropwise at -5 DEG C~5 DEG C
And triethylamine, it is 5~7 to solution ph, is reacted 1~3 hour after being added dropwise to complete；
2. diamines and triethylamine is added dropwise to room temperature in rise temperature, and it is 5~7 to keep solution ph, rise reaction temperature after being added dropwise to complete
Spend to 40 DEG C~65 DEG C, react 4~6 hours；
3. reaction temperature is raised, under the conditions of 80 DEG C~110 DEG C, diamines and triethylamine is added drop-wise in reactor, make solution
PH value is 5~7, and reaction steams acetone after 5~7 hours, product is again through washing, and suction filtration obtains triazine series carbon forming-hair after drying
Infusion.
4. one kind agent of halogen-free expanded flame-retardant containing halloysite nanotubes according to claim 1, it is characterised in that the phosphatization
Compound is one kind in high polymerization degree crystallization II-type polyphosphoric acid, trbasic zinc phosphate, phenyl hypo-aluminum orthophosphate and alkyl hypo-aluminum orthophosphate, the height
Degree of polymerization crystallization II-type polyphosphoric acid polymerization degree n >=1500.
5. one kind halogen-free expanded flame-retardant containing halloysite nanotubes agent according to claim 1, it is characterised in that described to contain angstrom
Lip river stone nanotube halogen-free expanded flame-retardant agent also includes compatilizer, and the compatilizer is maleic anhydride grafted polymer.
6. one kind agent of halogen-free expanded flame-retardant containing halloysite nanotubes according to claim 5, it is characterised in that described compatible
Agent is PP-g-MAH, PE-g-MAH, or EPDM-g-MAH.
7. one kind agent of halogen-free expanded flame-retardant containing halloysite nanotubes according to claim 1, it is characterised in that described angstrom of Lip river
Stone nanotube is the maleic anhydride modified halloysite nanotubes of surface grafting.
8. the preparation method of the agent of halogen-free expanded flame-retardant containing halloysite nanotubes described in any one of claim 1 to 7, its feature exists
In comprising the following steps：Triazine series carbon forming foaming agent, phosphorus compound and halloysite nanotubes are mixed 5~10 minutes, obtained
The agent of halogen-free expanded flame-retardant containing halloysite nanotubes.
9. described in any one of claim 1 to 7 the agent of halogen-free expanded flame-retardant containing halloysite nanotubes is in automobile, household electrical appliance or builds
Application in material field.
10. application according to claim 9, it is characterised in that the agent of halogen-free expanded flame-retardant containing halloysite nanotubes is used
In preparing flame-retardant polypropylene composite material, the flame-retardant polypropylene composite material is by weight comprising 70-82 parts of thermoplastics type trees
Fat and the 18-30 parts of agent of halogen-free expanded flame-retardant containing halloysite nanotubes；The thermoplastic resin is HOPP or copolymerization poly- third
Olefine resin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395626A (en) * | 2018-04-03 | 2018-08-14 | 广州大学 | One kind containing SiO2The halogen-free expanded flame-retardant agent of microballoon |
| CN109971037A (en) * | 2019-04-18 | 2019-07-05 | 宁波工程学院 | Phosphorous nano-meter flame retardants and preparation method thereof |
| CN113861433A (en) * | 2021-09-06 | 2021-12-31 | 浙大宁波理工学院 | Synergistic flame retardant and preparation method and application thereof |
| CN115433439A (en) * | 2022-08-19 | 2022-12-06 | 湖北合聚新材料有限公司 | PET flame-retardant reinforced material and preparation method and application thereof |
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| CN113861433A (en) * | 2021-09-06 | 2021-12-31 | 浙大宁波理工学院 | Synergistic flame retardant and preparation method and application thereof |
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| CN115433439B (en) * | 2022-08-19 | 2023-10-27 | 湖北合聚高分子材料有限公司 | PET flame-retardant reinforcing material, and preparation method and application thereof |
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