CN106084371B - A kind of fire-retardant carbon forming agent compound of halogen-free polyolefin and preparation method thereof - Google Patents
A kind of fire-retardant carbon forming agent compound of halogen-free polyolefin and preparation method thereof Download PDFInfo
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- CN106084371B CN106084371B CN201610410754.3A CN201610410754A CN106084371B CN 106084371 B CN106084371 B CN 106084371B CN 201610410754 A CN201610410754 A CN 201610410754A CN 106084371 B CN106084371 B CN 106084371B
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- 0 CCC(C)(*)N(C=O)C(N(CC(*C(C)(*)*)O)C(N(C)CC(*)*)=O)=[U] Chemical compound CCC(C)(*)N(C=O)C(N(CC(*C(C)(*)*)O)C(N(C)CC(*)*)=O)=[U] 0.000 description 2
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- 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
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The present invention relates to fire-retardant carbon forming agent compounds of a kind of halogen-free polyolefin and preparation method thereof, and the structure of the compound is shown below：N > 1 in its formula, X are hydramine, and Y is two alkanamines.Preparation method is：Under stiring, equimolar hydramine is added into the solution of isocyanuric acid three-glycidyl ester, is increased to certain temperature later, insulation reaction for a period of time, makes the pH of solution reach 7~8；Two alkanamines for adding certain mole, are warming up to certain temperature, and insulation reaction for a period of time, makes the pH of solution reach 7~8, after cooling, up to the fire-retardant carbon forming agent of product halogen-free polyolefin after suction filtration (recycled solvent), washing, drying and crushing.The fire-retardant carbon forming agent of halogen-free polyolefin of the present invention is excellent fire-retardant carbon forming agent, with at charcoal anti-drip effect, heat-resisting and water-tolerant good with high molecular material compatibility, processing performance is excellent, can be used as the fire-retardant carbon forming agent of the materials such as polyethylene (PE), polypropylene (PP)；Its raw material is cheap and easy to get, and production cost is low, and equipment investment is few, and simple production process is easy to large-scale production.
Description
Technical field
The present invention relates to fire-retardant carbon forming agent compounds of a kind of halogen-free polyolefin and preparation method thereof, which can be used as gathering
The carbon forming agent of the materials such as ethylene (PE), polypropylene (PP), silicon rubber.
Background technology
Polypropylene (PP) developed faster general-purpose plastics in recent years, because it stablizes with odorless non-toxic and tasteless, physical chemistry
The features such as property is good, density is small, electrical insulating property is excellent, easy to process, in auto industry, household electrical appliance, electronics, electric wire, packet
Dress and building materials etc. are widely used.But PP is a kind of material of burning easily, and charring rate is almost 0, meltable
Melt drippage, to limit the application field of PP.Nowadays it is halogenated flame retardant to be applied in PP at most, and flame-retarded efficiency is high,
Synthesis is cost-effective, but the pernicious gases such as a large amount of smog, two Evil are silent occur to release when fire for general halogen fire proofing, special
It is not that after European Union sends out halogenated flame retardant and orders within a certain time, one layer of shade has been coverd with to the foreground of halogenated flame retardant.Therefore exploitation nothing
The carbon forming agent that halogen is environmentally friendly, inexpensive, efficient, heat-resisting and processing performance is good is the direction of current PP fire retardants research.
The fire-retardant carbon forming agent of halogen-free polyolefin of the present invention is rich in tertiary carbon and polyhydroxy structure, and the compound of tertiary carbon structure is demonstrate,proved
Bright to have preferably at charcoal effect, polyhydroxy structure compound has in the presence of acid source and is dehydrated into charcoal effect, thus
The fire-retardant carbon forming agent of halogen-free polyolefin of the present invention provides that one novel, Halogen, environmental protection, inexpensive, excellent at charcoal for fire-retardant PP
Carbon forming agent；The synthetic method of the fire-retardant carbon forming agent of halogen-free polyolefin of the present invention belongs to addition reaction, atom utilization 100%, yield
Higher, solvent can directly recycle use, do not have " three wastes " discharge, meet green synthesis process, have good environmental benefit；
Halogen-free polyolefin of the present invention is fire-retardant cheap and easy to get at its sharp raw material of charcoal, simple for process, is easy to large-scale production, is applied to the materials such as PP
Have in material it is good at charcoal efficiency, mechanical property, water resistance and processing performance, before there is very wide development and application
Scape.
Invention content
It is an object of the present invention to propose a kind of fire-retardant carbon forming agent compound of halogen-free polyolefin.Its physical and chemical performance
Stablize, heat-resist, water-tolerant, high at charcoal efficiency, good with high molecular material compatibility, processing performance is excellent, can overcome existing
There is the deficiency in technology.
For achieving the above object, present invention employs following technical solutions：
A kind of fire-retardant carbon forming agent compound of halogen-free polyolefin, which is characterized in that the compound structure is shown below：
N > 1 ,-X are in its formula(n1=2~4) ,-NHNHCH2CH2OH、- Y- is
It is former another object of the present invention is to propose a kind of preparation method of the fire-retardant carbon forming agent compound of halogen-free polyolefin
Expect it is cheap and easy to get, it is simple for process, be easy to large-scale production, technical solution is as follows：
The preparation method of the fire-retardant carbon forming agent of halogen-free polyolefin as described above, which is characterized in that this method is：
Under stiring, equimolar hydramine is added into the solution of isocyanuric acid three-glycidyl ester, is increased to 30 later
~60 DEG C, 1~5h of insulation reaction makes the pH of solution reach 7~8；Two alkanamines for adding certain mole, are warming up to 80~120
DEG C, 8~22h of insulation reaction makes the pH of solution reach 7~8, after cooling, filters (recycled solvent), washing, drying and powder
Up to the fire-retardant carbon forming agent of product halogen-free polyolefin after broken.
The solvent in the solution of isocyanuric acid three-glycidyl ester is as described above：Water, dioxane, toluene, diformazan
Benzene and diethylene glycol dimethyl ether.
Hydramine as described above is ethanol amine, Propanolamine, butanolamine, 2- hydrazinoethanols, equal amido phenenyl alcohol, m-aminophenyl
Phenol or para-aminophenol.
Two alkanamine as described above is piperazine, piperazine -2- ketone, 2- phenylpiperazines, 2- methyl piperazines, 2,6- dimethyl piperazines
Piperazine, 2- (4- xenyls) piperazine, homopiperazine, homopiperazine -5- ketone, ethylidene-urea, hydantoins or 2- (2- furyls) piperazine.
Certain mol proportion as described above is isocyanuric acid three-glycidyl ester: the molar ratio of two alkanamines is 1: 1.
The fire-retardant carbon forming agent of halogen-free polyolefin disclosed by the invention is white solid, and yield is 93.0%~98.5%, 1%
Thermal weight loss decomposition temperature：260.0~310.3 DEG C, suitable for the materials such as PE, PP.The synthesis of the fire-retardant carbon forming agent of halogen-free polyolefin
Technological principle is shown below：
N > 1, X are in its formula(n1=2~4), NH2NHCH2CH2OH、
Y is
Compared with prior art, the beneficial effects of the present invention are：
1. the fire-retardant carbon forming agent compound of halogen-free polyolefin of the present invention, physical and chemical performance is stablized, and decomposition temperature is high, with height
Molecular material compatibility is good, adapts to the high temperature process in engineering plastics.
2. being rich in tertiary carbon structure and polyhydroxy structure in the fire-retardant carbon forming agent compound molecule of halogen-free polyolefin of the present invention, have
The good second-time burning at charcoal effect, generated to effectively prevent material melted by heating to drip.
3. the synthesis mode of the fire-retardant carbon forming agent compound of halogen-free polyolefin of the present invention is addition reaction, atom utilization
100%, high income meets green synthesis process.
4. the solvent in the fire-retardant carbon forming agent compound synthesis of halogen-free polyolefin of the present invention can be recycled directly, building-up process
In do not have " three wastes " discharge, have good environmental benefit.
5. fire-retardant its raw material of carbon forming agent compound of halogen-free polyolefin of the present invention is cheap and easy to get, production cost is low, equipment investment
It is few, it is easy to large-scale production, it is good at charcoal efficiency, mechanical property and processing performance applied to having in the materials such as PP, have very
Application well, development prospect.
Description of the drawings
Following attached drawing is provided in order to further illustrate the structure and performance spy of specific product.
1, the infrared spectrogram of the fire-retardant carbon forming agent CFA-1 of halogen-free polyolefin, refers to Figure of description Fig. 1；
Fig. 1 shows 3012cm-1Place is-CH2CH(OH)NHCH2CH2Upper-NH- keys the stretching vibration peaks of OH；1690-2020cm-1Place is C=O key stretching vibration peaks；1280-1580cm-1Place is the stretching vibration peak of C-N keys；1175cm-1Place is-CH2CH
(OH)NHCH2CH2The stretching vibration peak of the upper left side-OH keys of OH；1155cm-1Place isFlexible the shaking of upper-OH keys
Dynamic peak；1020cm-1Place is-CH2CH(OH)NHCH2CH2The stretching vibration peak of the upper the right-OH keys of OH.
2, the nuclear magnetic spectrum figure of the fire-retardant carbon forming agent CFA-1 of halogen-free polyolefin, refers to Figure of description Fig. 2；
Fig. 2 shows that δ 1.208-1.352 are-CH2CH(OH)NHCH2CH2The peaks H on the upper left side-OH of OH；δ1.422-
1.588 beingThe peaks H on upper-OH；δ 3.460-3.608 are-CH2CH(OH)NHCH2CH2The upper intermediate methylenes of OH
The peaks H on base；δ 3.729-3.905 are-CH2CH(OH)NHCH2CH2The peaks H on the methylene on the upper the right OH；δ 4.003-4.161 areThe peaks H on the methylene of upper 1 position；δ 4.230-4.410 areH on the methylene of upper 2 position
Peak；δ 4.459-4.701 are-CH2CH(OH)NHCH2CH2The peaks H on the upper left side methylene of OH；δ 4.798-4.887 areThe peaks H on upper left side methylene；δ 5.340-5.501 are-CH2CH(OH)NHCH2CH2On the upper methines of OH
The peaks H；δ 5.613-5.726 areThe peaks H on upper methine；δ 6.407-6.502 are-CH2CH(OH)
NHCH2CH2The peaks H on the upper-NH- of OH；δ 7.580-7.701 are-CH2CH(OH)NHCH2CH2The peaks H of the upper the right-OH of OH；δ7.265
The proton peak exchanged for solvent carbon deuterium chloride.
3, the TG figures of the fire-retardant carbon forming agent CFA-1 of halogen-free polyolefin, refer to Figure of description Fig. 3；
Fig. 3 shows that the 1% thermal weight loss decomposition temperature of CFA-1 is 301.5 DEG C.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with specific embodiment.
Carbon forming agent structural formula described in 1 present embodiment 1 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It is added dropwise again
8.61g (0.1mol) Piperazine anhydrous, control temperature is no more than 50 DEG C during being added dropwise, and after dripping off, is warming up to 80 DEG C, insulation reaction
8h makes the pH of solution reach 7~8, after cooling, up to products C FA- after suction filtration (recycled solvent), washing, drying and crushing
1；Its yield is 98.5%, and 1% thermal weight loss decomposition temperature is 301.5 DEG C, by FTIR and NMR test analysis, determines the production
Product structure.
Carbon forming agent structural formula described in 2 present embodiment 2 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It is added dropwise again
10.01g (0.1mol) piperazine -2- ketone, control temperature is no more than 50 DEG C, after dripping off during being added dropwise, and is warming up to 90 DEG C, heat preservation is anti-
10h is answered, so that the pH of solution is reached 7~8, after cooling, up to product after suction filtration (recycled solvent), washing, drying and crushing
CFA-2；Its yield is 98.0%, and 1% thermal weight loss decomposition temperature is 292.3 DEG C, by FTIR and NMR test analysis, is determined
The product structure.
Carbon forming agent structural formula described in 3 present embodiment 3 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 270ml toluene and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It is added dropwise again
16.22g (0.1mol) 2- phenylpiperazines, control temperature is no more than 50 DEG C, after dripping off during being added dropwise, and is warming up to 105 DEG C, heat preservation
12h is reacted, the pH of solution is made to reach 7~8, after cooling, (recycled solvent) is filtered, washing, dries and produced to obtain the final product after crushing
Product CFA-3；Its yield is 94.0%, and 1% thermal weight loss decomposition temperature is 308.0 DEG C, by FTIR and NMR test analysis, really
The fixed product structure.
Carbon forming agent structural formula described in 4 present embodiment 4 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It is added dropwise again
10.02g (0.1mol) 2- methyl piperazines, control temperature is no more than 50 DEG C during being added dropwise, and after dripping off, back flow reaction 9h makes molten
The pH of liquid reaches 7~8, after cooling, up to products C FA-4 after suction filtration (recycled solvent), washing, drying and crushing；It is produced
Rate is 95.0%, and 1% thermal weight loss decomposition temperature is 273.5 DEG C, by FTIR and NMR test analysis, determines the product structure.
Carbon forming agent structural formula described in 5 present embodiment 5 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml dioxane and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, is added dropwise
6.11g (0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；Again
11.42g (0.1mol) 2,6-dimethyl-piperizine is added, control temperature is no more than 50 DEG C in adition process, later back flow reaction
8.5h makes the pH of solution reach 7~8, after cooling, up to product after suction filtration (recycled solvent), washing, drying and crushing
CFA-5；Its yield is 94.7%, and 1% thermal weight loss decomposition temperature is 278.4 DEG C, by FTIR and NMR test analysis, is determined
The product structure.
Carbon forming agent structural formula described in 6 present embodiment 6 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 300ml toluene and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It adds
23.83g (0.1mol) 2- (4- xenyls) piperazine, control temperature is no more than 50 DEG C in adition process, and back flow reaction 8h, makes later
The pH of solution reaches 7~8, after cooling, up to products C FA-6 after suction filtration (recycled solvent), washing, drying and crushing；Its
Yield is 93.2%, and 1% thermal weight loss decomposition temperature is 310.0 DEG C, by FTIR and NMR test analysis, determines the product knot
Structure.
Carbon forming agent structural formula described in 7 present embodiment 7 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It adds
10.01g (0.1mol) homopiperazine, control temperature is no more than 50 DEG C in adition process, and back flow reaction 10h, makes the pH of solution later
Reach 7~8, after cooling, up to products C FA-7 after suction filtration (recycled solvent), washing, drying and crushing；Its yield is
96.0%, 1% thermal weight loss decomposition temperature is 292.4 DEG C, by FTIR and NMR test analysis, determines the product structure.
Carbon forming agent structural formula described in 8 present embodiment 8 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It is added
11.41g (0.1mol) homopiperazine -5- ketone, control temperature is no more than 50 DEG C in adition process, and back flow reaction 11h, makes solution later
PH reach 7~8, after cooling, filter (recycled solvent), washing, drying and after crushing up to products C FA-8；Its yield
It is 96.5%, 1% thermal weight loss decomposition temperature is 289.7 DEG C, by FTIR and NMR test analysis, determines the product structure.
Carbon forming agent structural formula described in 9 present embodiment 9 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 220ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It adds
8.61g (0.1mol) ethylidene-urea, control temperature is no more than 50 DEG C in adition process, is warming up to 85 DEG C, insulation reaction 9h later,
The pH of solution is set to reach 7~8, after cooling, up to products C FA-9 after suction filtration (recycled solvent), washing, drying and crushing；
Its yield is 97.3%, and 1% thermal weight loss decomposition temperature is 263.0 DEG C, by FTIR and NMR test analysis, determines the product
Structure.
Carbon forming agent structural formula described in 10 present embodiment 10 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It adds
10.01g (0.1mol) hydantoins, control temperature is no more than 50 DEG C in adition process, is warming up to 80 DEG C later, insulation reaction
10h makes the pH of solution reach 7~8, after cooling, up to product after suction filtration (recycled solvent), washing, drying and crushing
CFA-10；Its yield is 96.8%, and 1% thermal weight loss decomposition temperature is 260.0 DEG C, by FTIR and NMR test analysis, is determined
The product structure.
Carbon forming agent structural formula described in 11 present embodiment 11 of embodiment is：
Preparation method is：In the 500ml tetra- equipped with blender, thermometer, constant temperature dropping funel and high performance reflux condenser
In mouth flask, 270ml toluene and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester is added, opens stirring, 6.11g is added dropwise
(0.1mol) ethanol amine after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reaction solution reach 7~8；It adds
15.22g (0.1mol) 2- (2- furyls) piperazine, control temperature is no more than 50 DEG C in adition process, later back flow reaction 16h,
The pH of solution is set to reach 7~8, after cooling, up to products C FA-11 after suction filtration (recycled solvent), washing, drying and crushing；
Its yield is 94.1%, and 1% thermal weight loss decomposition temperature is 288.6 DEG C, by FTIR and NMR test analysis, determines the product
Structure.
The fire-retardant carbon forming agent compound of the specific halogen-free polyolefin of above-mentioned synthesis is also applied in PP by inventor, makes
Composite material tests its flame retardant property, physical property and water resistance.
Specific method is：CFA1~CFA11, ammonium polyphosphate (APP II) and pure PP uniform particles are mixed into flame-retardant formulations
The weight ratio of note formula 1~11, wherein CFA1~CFA11 and ammonium polyphosphate (APP II) is adding for 1: 3~8, APP II and CFA
Totalling amount is 20~27%, and test result is shown in Table 1.By flame-retardant formulations 1~11 in 35# double screw extruder extruding pelletizations, PP is obtained
Each area's temperature setting of fire-retardant master granule, wherein double screw extruder is as follows：180 DEG C of head, 170 DEG C of 1st area, 175 DEG C of 2nd area, 3 areas 175
DEG C, 175 DEG C of 4th area, 175 DEG C of 5th area, 175 DEG C of 6th area, 180 DEG C of 7th area, 185 DEG C of 8th area, 185 DEG C of 9th area, 190 DEG C of 10th area, 190 DEG C of 11st area,
185 DEG C of melt temperature；PP fire-retardant master granules are molded in injection molding machine, wherein injection temperature setting is as follows：185 DEG C of head, 1
200 DEG C of area, 200 DEG C of 2nd area, 185 DEG C of 3rd area are stretched, are impacted, the standards batten such as vertical combustion (UL-94), measuring its stretching
The performances such as intensity, impact strength, limit oxygen index, fire-retardant, test result are shown in Table 2 and table 3.By the fire-retardant batten of vertical combustion through 70
DEG C hot-water soak 168h takes out, and drying surveys the flame retardant property after its boiling, test result is shown in Table 2 and table 3.
Table 1
Table 2
Table 3
Note：N represent it is no, Y representative is.
By table 2 and table 3 it is found that the fire-retardant carbon forming agent compound of halogen-free polyolefin is applied in PP, to its Effect on Mechanical Properties
It is small, show that it has preferable compatibility, processing performance excellent in PP；In general, the limit oxygen index of material is more than 27 just
Belonging to nonflammable material, UL-94V0 grades of vertical combustion is highest level, and not only limit oxygen index is more than 27 to PP flame retardant composite materials,
And vertical combustion can all reach UL-94V0 grades, and batten is not dripped at charcoal, and this shows that it is excellent at charcoal in PP applications
Property and excellent cooperative resistance combustion after being compounded with APPII；By 70 DEG C, the boiling of 168h, vertical combustion batten can still reach
To UL-94V0 grades, this shows its excellent water resistance in PP applications.
Claims (3)
1. a kind of fire-retardant carbon forming agent compound of halogen-free polyolefin, which is characterized in that the structure of the compound is shown below：
2. the preparation method of the fire-retardant carbon forming agent compound of a kind of halogen-free polyolefin according to claim 1, which is characterized in that its
Preparation method is：Under stiring, equimolar ethanol amine, propyl alcohol are added into the solution of isocyanuric acid three-glycidyl ester
Amine, butanolamine, 2- hydrazinoethanols, equal amido phenenyl alcohol, m-aminophenol or para-aminophenol, are increased to 30~60 DEG C later,
1~5h of insulation reaction makes the pH of solution reach 7~8；Add certain mole piperazine, piperazine -2- ketone, 2- phenylpiperazines,
2- methyl piperazines, 2,6-dimethyl-piperizine, 2- (4- xenyls) piperazine, homopiperazine, homopiperazine -5- ketone, ethylidene-urea, acyl in second
Urea or 2- (2- furyls) piperazine, are warming up to 80~120 DEG C, 8~22h of insulation reaction, so that the pH of solution is reached 7~8, cooling
Afterwards, up to the fire-retardant carbon forming agent of product halogen-free polyolefin after filtering, wash, dry and crushing；
The isocyanuric acid three-glycidyl ester: piperazine, piperazine -2- ketone, 2- phenylpiperazines, 2- methyl piperazines, 2,6- dimethyl
Piperazine, 2- (4- xenyls) piperazine, homopiperazine, homopiperazine -5- ketone, ethylidene-urea, hydantoins or 2- (2- furyls) piperazine
Molar ratio be 1: 1.
3. the preparation method of the fire-retardant carbon forming agent compound of a kind of halogen-free polyolefin according to claim 2, it is characterised in that：Institute
Solvent in the solution for the isocyanuric acid three-glycidyl ester stated is water, dioxane, toluene, dimethylbenzene or diethylene glycol two
Methyl ether.
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| JPS5927259A (en) * | 1982-08-06 | 1984-02-13 | Sumitomo Chem Co Ltd | Assay by liquid chromatography for optical isomer of alcohol and secondary amine having asymmetric carbon |
| JP2005075924A (en) * | 2003-08-29 | 2005-03-24 | Neos Co Ltd | Silica scale remover |
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| US4059640A (en) * | 1975-10-28 | 1977-11-22 | National Distillers And Chemical Corp. | Transalkylation of tertiary amines and alcohols, to produce ethylene glycol |
| US6444779B1 (en) * | 2001-06-21 | 2002-09-03 | General Electric Company | Method of preparing a poly(arylene ether), and a poly(arylene ether) prepared thereby |
| CN101024632A (en) * | 2007-03-23 | 2007-08-29 | 东北林业大学 | Triazine series oligomer and its synthesizing method |
| CN103073788A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Weather-resistant moisture-resistant halogen-free flame-retardant polypropylene mixture and preparation method thereof |
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