CN106084371A - A kind of halogen-free polyolefin fire-retardant carbon forming agent compound and preparation method thereof - Google Patents
A kind of halogen-free polyolefin fire-retardant carbon forming agent compound and preparation method thereof Download PDFInfo
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- CN106084371A CN106084371A CN201610410754.3A CN201610410754A CN106084371A CN 106084371 A CN106084371 A CN 106084371A CN 201610410754 A CN201610410754 A CN 201610410754A CN 106084371 A CN106084371 A CN 106084371A
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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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- 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
- 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
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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
- 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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- 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 a kind of halogen-free polyolefin fire-retardant carbon forming agent compound and preparation method thereof, the structure of this compound is shown below:
Description
Technical field
The present invention relates to a kind of halogen-free polyolefin fire-retardant carbon forming agent compound and preparation method thereof, this compound can be used as gathering
The carbon forming agent of the materials such as ethylene (PE), polypropylene (PP), silicone rubber.
Background technology
Polypropylene (PP) developed general-purpose plastics faster in recent years, and because it has, odorless is nonpoisonous and tasteless, physical chemistry is stable
Property is good, density is little, electrical insulating property is excellent, the feature such as easy to process, at auto industry, household electrical appliance, electronics, electric wire, bag
The aspects such as dress and building materials are widely used.But PP is the material of a kind of burning easily, and charring rate is almost 0, meltable
Melt drippage, thus limit the application of PP.Nowadays applying most in PP is halogenated flame retardant, and its flame-retarded efficiency is high,
Comprehensive cost performance is high, but can discharge a large amount of smog, two harmful gass such as silent during general Halogen fire proofing breaking out of fire, special
Halogenated flame retardant is sent after ordering within a certain time by Bie Shi European Union, has coverd with one layer of shade to the prospect of halogenated flame retardant.Therefore nothing is developed
Halogen environmental protection, inexpensive, efficient, heat-resisting and good processability carbon forming agent are the directions of current PP fire retardant research.
The fire-retardant carbon forming agent of halogen-free polyolefin of the present invention is demonstrate,proved rich in tertiary carbon and polyhydroxy structure, the compound of tertiary carbon structure
Bright have preferably one-tenth charcoal effect, and polyhydroxy structure compound, in the presence of acid source, has and is dehydrated into charcoal effect, thus
The fire-retardant carbon forming agent of halogen-free polyolefin of the present invention be fire-retardant PP provide that one novel, Halogen, environmental protection, inexpensive, become charcoal excellent
Carbon forming agent；The synthetic method of the fire-retardant carbon forming agent of halogen-free polyolefin of the present invention belongs to additive reaction, atom utilization 100%, productivity
Higher, solvent can directly reclaim use, does not has " three wastes " to discharge, meets green synthesis process, has good environmental benefit；
Halogen-free polyolefin of the present invention fire-retardant one-tenth charcoal its cheaper starting materials of profit is easy to get, and technique is simple, it is easy to large-scale production, is applied to the materials such as PP
Material has good one-tenth charcoal usefulness, mechanical property, water resistance and processing characteristics, before there is the most wide development and application
Scape.
Summary of the invention
An object of the present invention is to propose a kind of halogen-free polyolefin fire-retardant carbon forming agent compound.Its physical and chemical performance
Stable, heat-resist, water-tolerant, become charcoal usefulness high, good with the macromolecular material compatibility, processing characteristics is excellent, can overcome existing
There is the deficiency in technology.
For achieving the above object, present invention employs following technical scheme:
A kind of halogen-free polyolefin fire-retardant carbon forming agent compound, it is characterised in that this compound structure is shown below:
N ＞ 1 in its formula ,-X are(n1=2～4) ,-NHNHCH2CH2OH、-Y-be
Another object of the present invention is to propose the preparation method of a kind of halogen-free polyolefin fire-retardant carbon forming agent compound, it is former
Expecting cheap and easy to get, technique is simple, it is easy to large-scale production, and technical scheme is as follows:
The preparation method of the fire-retardant carbon forming agent of halogen-free polyolefin as mentioned above, it is characterised in that the method is:
Under agitation, in the solution of isocyanuric acid three-glycidyl ester, add equimolar hydramine, be increased to 30 afterwards
～60 DEG C, insulation reaction 1～5h, make the pH of solution reach 7～8；Add two alkanamines of certain mole, be warming up to 80～120
DEG C, insulation reaction 8～22h, make the pH of solution reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and powder
The fire-retardant carbon forming agent of product halogen-free polyolefin is i.e. obtained after broken.
Solvent in the solution of isocyanuric acid three-glycidyl ester as above is: water, dioxane, toluene, diformazan
Benzene and diethylene glycol dimethyl ether.
Hydramine as above is ethanolamine, Propanolamine, butanolamine, 2-hydrazinoethanol, equal amido phenenyl alcohol, m-aminophenyl
Phenol or para-aminophenol.
Two alkanamines as above be piperazine, piperazine-2-ketone, 2-phenylpiperazine, 2-methyl piperazine, 2,6-dimethyl piperazine
Piperazine, 2-(4-xenyl) piperazine, homopiperazine, homopiperazine-5-ketone, ethylidene-urea, hydantoin or 2-(2-furyl) piperazine.
Certain mol proportion as above is isocyanuric acid three-glycidyl ester: the mol 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 its productivity is 93.0%～98.5%, 1%
Thermal weight loss decomposition temperature: 260.0～310.3 DEG C, it is adaptable in 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 in its formula, X are(n1=2～4), NH2NHCH2CH2OH、 Y is
Compared with prior art, the beneficial effects of the present invention is:
Halogen-free polyolefin the most of the present invention fire-retardant carbon forming agent compound, its physical and chemical performance is stable, and decomposition temperature is high, with height
The molecular material compatibility is good, adapts to the high temperature process in engineering plastics.
Rich in tertiary carbon structure and polyhydroxy structure in halogen-free polyolefin the most of the present invention fire-retardant carbon forming agent compound molecule, have
Good one-tenth charcoal effect, thus the second-time burning effectively preventing material melted by heating drippage and producing.
The synthesis mode of halogen-free polyolefin the most of the present invention fire-retardant carbon forming agent compound is additive reaction, atom utilization
100%, yield is high, meets green synthesis process.
Solvent in halogen-free polyolefin the most of the present invention fire-retardant carbon forming agent compou nd synthesis can directly recycle, building-up process
In do not have " three wastes " to discharge, there is good environmental benefit.
Halogen-free polyolefin the most of the present invention fire-retardant carbon forming agent its raw material of compound is cheap and easy to get, and production cost is low, equipment investment
Few, it is easy to large-scale production, it is applied in the materials such as PP have good one-tenth charcoal usefulness, mechanical property and processing characteristics, has very
Application well, DEVELOPMENT PROSPECT.
Accompanying drawing explanation
Structure and performance spy in order to further illustrate specific product provide drawings described below.
1, the infrared spectrogram of halogen-free polyolefin fire-retardant carbon forming agent CFA-1, refers to Figure of description Fig. 1；
Fig. 1 shows, 3012cm-1Place is-CH2CH(OH)NHCH2CH2OH upper-NH-key stretching vibration peak；1690-2020cm-1Place is C=O key stretching vibration peak；1280-1580cm-1Place is the stretching vibration peak of C-N key；1175cm-1Place is-CH2CH
(OH)NHCH2CH2The stretching vibration peak of the upper left side of OH-OH key；1155cm-1Place isUpper the flexible of-OH key shakes
Dynamic peak；1020cm-1Place is-CH2CH(OH)NHCH2CH2The stretching vibration peak of the upper the right of OH-OH key.
2, the nuclear magnetic spectrum figure of halogen-free polyolefin fire-retardant carbon forming agent CFA-1, refers to Figure of description Fig. 2；
Fig. 2 shows, δ 1.208-1.352 is-CH2CH(OH)NHCH2CH2H peak on the-OH of the upper left side of OH；δ1.422-
1.588 it isH peak on upper-OH；δ 3.460-3.608 is-CH2CH(OH)NHCH2CH2Methylene in the middle of OH is upper
H peak on base；δ 3.729-3.905 is-CH2CH(OH)NHCH2CH2H peak on the methylene on the upper the right of OH；δ 4.003-4.161 isH peak on upper 1 position methylene；δ 4.230-4.410 isH on upper 2 position methylene
Peak；δ 4.459-4.701 is-CH2CH(OH)NHCH2CH2H peak on the methylene of the OH upper left side；δ 4.798-4.887 isH peak on the methylene of the upper left side；δ 5.340-5.501 is-CH2CH(OH)NHCH2CH2On the upper methine of OH
H peak；δ 5.613-5.726 isH peak on upper methine；δ 6.407-6.502 is-CH2CH(OH)
NHCH2CH2H peak on the upper-NH-of OH；δ 7.580-7.701 is-CH2CH(OH)NHCH2CH2The H peak of the upper the right of OH-OH；δ7.265
Proton peak for solvent carbon deuterium chloride exchange.
3, the TG figure of halogen-free polyolefin fire-retardant carbon forming agent CFA-1, refers to Figure of description Fig. 3；
Fig. 3 shows, the 1% thermal weight loss decomposition temperature of CFA-1 is 301.5 DEG C.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described further.
Carbon forming agent structural formula described in embodiment 1 present embodiment 1 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Drip again
8.61g (0.1mol) Piperazine anhydrous, controls temperature and is less than 50 DEG C, after dripping off, be warming up to 80 DEG C, insulation reaction during dropping
8h, makes the pH of solution reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-
1；Its productivity is 98.5%, and the thermal weight loss decomposition temperature of 1% is 301.5 DEG C, by FTIR and NMR test analysis, determines this product
Product structure.
Carbon forming agent structural formula described in embodiment 2 present embodiment 2 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Drip again
10.01g (0.1mol) piperazine-2-ketone, controls temperature and is less than 50 DEG C, after dripping off, be warming up to 90 DEG C during dropping, insulation is anti-
Answer 10h, make the pH of solution reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain product
CFA-2；Its productivity is 98.0%, and the thermal weight loss decomposition temperature of 1% is 292.3 DEG C, by FTIR and NMR test analysis, determines
This product structure.
Carbon forming agent structural formula described in embodiment 3 present embodiment 3 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 270ml toluene and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Drip again
16.22g (0.1mol) 2-phenylpiperazine, controls temperature and is less than 50 DEG C, after dripping off, be warming up to 105 DEG C, insulation during dropping
Reaction 12h, make the pH of solution reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain product
Product CFA-3；Its productivity is 94.0%, and the thermal weight loss decomposition temperature of 1% is 308.0 DEG C, by FTIR and NMR test analysis, really
This product structure fixed.
Carbon forming agent structural formula described in embodiment 4 present embodiment 4 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Drip again
10.02g (0.1mol) 2-methyl piperazine, controls temperature and is less than 50 DEG C during dropping, after dripping off, and back flow reaction 9h, make molten
The pH of liquid reaches 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-4；It produces
Rate is 95.0%, and the thermal weight loss decomposition temperature of 1% is 273.5 DEG C, by FTIR and NMR test analysis, determines this product structure.
Carbon forming agent structural formula described in embodiment 5 present embodiment 5 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml dioxane and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, dropping
6.11g (0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Again
Add 11.42g (0.1mol) 2,6-dimethyl-piperizine, adition process controls temperature and is less than 50 DEG C, back flow reaction afterwards
8.5h, makes the pH of solution reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain product
CFA-5；Its productivity is 94.7%, and the thermal weight loss decomposition temperature of 1% is 278.4 DEG C, by FTIR and NMR test analysis, determines
This product structure.
Carbon forming agent structural formula described in embodiment 6 present embodiment 6 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 300ml toluene and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Add
23.83g (0.1mol) 2-(4-xenyl) piperazine, controls temperature and is less than 50 DEG C in adition process, back flow reaction 8h afterwards makes
The pH of solution reaches 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-6；Its
Productivity is 93.2%, and the thermal weight loss decomposition temperature of 1% is 310.0 DEG C, by FTIR and NMR test analysis, determines that this product is tied
Structure.
Carbon forming agent structural formula described in embodiment 7 present embodiment 7 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Add
10.01g (0.1mol) homopiperazine, controls temperature and is less than 50 DEG C in adition process, back flow reaction 10h afterwards makes the pH of solution
Reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-7；Its productivity is
96.0%, the thermal weight loss decomposition temperature of 1% is 292.4 DEG C, by FTIR and NMR test analysis, determines this product structure.
Carbon forming agent structural formula described in embodiment 8 present embodiment 8 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Add
11.41g (0.1mol) homopiperazine-5-ketone, controls temperature and is less than 50 DEG C in adition process, back flow reaction 11h afterwards makes solution
PH reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-8；Its productivity
Being 96.5%, the thermal weight loss decomposition temperature of 1% is 289.7 DEG C, by FTIR and NMR test analysis, determines this product structure.
Carbon forming agent structural formula described in embodiment 9 present embodiment 9 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 220ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Add
8.61g (0.1mol) ethylidene-urea, controls temperature and is less than 50 DEG C, be warming up to 85 DEG C afterwards in adition process, insulation reaction 9h,
The pH making solution reaches 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-9；
Its productivity is 97.3%, and the thermal weight loss decomposition temperature of 1% is 263.0 DEG C, by FTIR and NMR test analysis, determines this product
Structure.
Carbon forming agent structural formula described in embodiment 10 present embodiment 10 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 250ml water and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Add
10.01g (0.1mol) hydantoin, controls temperature and is less than 50 DEG C, be warming up to 80 DEG C afterwards, insulation reaction in adition process
10h, makes the pH of solution reach 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain product
CFA-10；Its productivity is 96.8%, and the thermal weight loss decomposition temperature of 1% is 260.0 DEG C, by FTIR and NMR test analysis, determines
This product structure.
Carbon forming agent structural formula described in embodiment 11 present embodiment 11 is:
Preparation method is: at the 500ml tetra-equipped with agitator, thermometer, constant temperature Dropping funnel and high performance reflux condenser
In mouth flask, add 270ml toluene and 29.72g (0.1mol) isocyanuric acid three-glycidyl ester, open stirring, drip 6.11g
(0.1mol) ethanolamine, after dripping off, is warming up to 30 DEG C, and insulation reaction 1.5h makes the pH value of reactant liquor reach 7～8；Add
15.22g (0.1mol) 2-(2-furyl) piperazine, controls temperature and is less than 50 DEG C in adition process, back flow reaction 16h afterwards,
The pH making solution reaches 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain products C FA-11；
Its productivity is 94.1%, and the thermal weight loss decomposition temperature of 1% is 288.6 DEG C, by FTIR and NMR test analysis, determines this product
Structure.
The concrete halogen-free polyolefin fire-retardant carbon forming agent compound of above-mentioned synthesis is also applied in PP by inventor, makes
Composite, tests its fire resistance, physical property and water resistance.
Method particularly includes: CFA1～CFA11, APP (APP II) and pure PP uniform particle are mixed into flame-retardant formulations
Note formula 1～11, wherein CFA1～CFA11 is 1: 3～8 with the weight ratio of APP (APP II), and APP II and CFA adds
Adding total amount is 20～27%, and result of the test is shown in Table 1.By flame-retardant formulations 1～11 at 35# double screw extruder extruding pelletization, obtain PP
Fire-retardant master granule, wherein double screw extruder each district temperature is provided that head 180 DEG C, 170 DEG C of 1st district, 175 DEG C of 2nd district, 3 districts 175
DEG C, 175 DEG C of 4th district, 175 DEG C of 5th district, 175 DEG C of 6th district, 180 DEG C of 7th district, 185 DEG C of 8th district, 185 DEG C of 9th district, 190 DEG C of 10th district, 190 DEG C of 11st district,
Melt temperature 185 DEG C；PP fire-retardant master granule is molded in injection machine, wherein injection temperature be provided that head 185 DEG C, 1
200 DEG C of district, 200 DEG C of 2nd district, 185 DEG C of 3rd district, stretched, impacted, the standard batten such as vertical combustion (UL-94), measures its stretching
Intensity, impact strength, limited oxygen index, the performance such as fire-retardant, result of the test is shown in Table 2 and table 3.By fire-retardant for vertical combustion batten through 70
DEG C hot-water soak 168h, takes out, and dries, surveys the fire resistance after its decocting in water, and result of the test is shown in Table 2 and table 3.
Table 1
Table 2
Table 3
Note: N represents no, Y represents and is.
From table 2 and table 3, halogen-free polyolefin fire-retardant carbon forming agent compound is applied in PP, to its Effect on Mechanical Properties
Little, show that it has the preferable compatibility in PP, processing characteristics is excellent；In general, the limited oxygen index of material is more than 27 just
Belonging to nonflammable material, vertical combustion UL-94V0 level is highest ranking, and PP flame-proof composite material not only limited oxygen index is more than 27,
And vertical combustion all can reach UL-94V0 level, and batten becomes charcoal not drip, and this shows its one-tenth charcoal excellent in PP applies
Property and and APPII compounding after the most excellent cooperative resistance combustion；Through 70 DEG C, the decocting in water of 168h, vertical combustion batten still can reach
To UL-94V0 level, this shows its resistance to water excellent in PP applies.
Claims (6)
1. a halogen-free polyolefin fire-retardant carbon forming agent compound, it is characterised in that the structure of this compound is shown below:
N ＞ 1 in its formula ,-X are(n1=2～4) ,-NHNHCH2CH2OH、-Y-be
A kind of halogen-free polyolefin fire-retardant carbon forming agent compound, its preparation method is: under agitation,
In the solution of isocyanuric acid three-glycidyl ester, add equimolar hydramine, be increased to 30～60 DEG C afterwards, insulation reaction 1～
5h, makes the pH of solution reach 7～8；Add two alkanamines of certain mole, be warming up to 80～120 DEG C, insulation reaction 8～22h,
The pH making solution reaches 7～8, after cooling, sucking filtration (recycled solvent), wash, dry and pulverize after i.e. obtain product Halogen gather
Flame retarding olefin carbon forming agent.
A kind of preparation method of halogen-free polyolefin fire-retardant carbon forming agent compound, it is characterised in that: institute
Solvent in the solution of the isocyanuric acid three-glycidyl ester stated is water, dioxane, toluene, dimethylbenzene or diethylene glycol diformazan
Base ether.
A kind of preparation method of halogen-free polyolefin fire-retardant carbon forming agent compound, it is characterised in that: institute
The hydramine stated is ethanolamine, Propanolamine, butanolamine, 2-hydrazinoethanol, equal amido phenenyl alcohol, m-aminophenol or p-aminophenyl
Phenol.
A kind of preparation method of halogen-free polyolefin fire-retardant carbon forming agent compound, it is characterised in that: institute
Two alkanamines stated are piperazine, piperazine-2-ketone, 2-phenylpiperazine, 2-methyl piperazine, 2,6-dimethyl-piperizine, 2-(4-xenyl)
Piperazine, homopiperazine, homopiperazine-5-ketone, ethylidene-urea, hydantoin or 2-(2-furyl) piperazine.
A kind of preparation method of halogen-free polyolefin fire-retardant carbon forming agent compound, it is characterised in that: institute
The certain mol proportion stated is isocyanuric acid three-glycidyl ester: the mol ratio of two alkanamines is 1: 1.
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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 |
| 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 |
| 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 |
| JP2005075924A (en) * | 2003-08-29 | 2005-03-24 | Neos Co Ltd | Silica scale remover |
| 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 |
| CN103333493A (en) * | 2013-06-25 | 2013-10-02 | 四川大学 | Phosphorus-containing macromolecule intumescent flame retardant char forming agent as well as preparation method thereof and intumescent flame retardant formed by char forming agent |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
| 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 |
| JP2005075924A (en) * | 2003-08-29 | 2005-03-24 | Neos Co Ltd | Silica scale remover |
| 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 |
| CN103333493A (en) * | 2013-06-25 | 2013-10-02 | 四川大学 | Phosphorus-containing macromolecule intumescent flame retardant char forming agent as well as preparation method thereof and intumescent flame retardant formed by char forming agent |
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| CN106084371B (en) | 2018-10-30 |
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Address after: No.166 Chenggong Road, Huimin street, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: Zhejiang xusen flame retardant Co.,Ltd. Address before: No.166 Chenggong Road, Huimin street, Jiashan County, Jiaxing City, Zhejiang Province Patentee before: ZHEJIANG XUSEN HALOGEN FREE SMOKE ABATEMENT FIRE RETARDANT CO.,LTD. |