CN106009037B - A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof - Google Patents
A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof Download PDFInfo
- Publication number
- CN106009037B CN106009037B CN201610410728.0A CN201610410728A CN106009037B CN 106009037 B CN106009037 B CN 106009037B CN 201610410728 A CN201610410728 A CN 201610410728A CN 106009037 B CN106009037 B CN 106009037B
- Authority
- CN
- China
- Prior art keywords
- forming agent
- carbon forming
- nhch
- triazine system
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CC*(CC)Nc1cccc(NC(CN(C(N(CC(*)O)C(N2C(C)(*)CC)O)=O)C2=O)O)c1 Chemical compound CC*(CC)Nc1cccc(NC(CN(C(N(CC(*)O)C(N2C(C)(*)CC)O)=O)C2=O)O)c1 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D251/32—Cyanuric acid; Isocyanuric acid
Abstract
The present invention relates to a kind of triazine system macromolecular halogen-free flameproof carbon forming agent compounds and preparation method thereof, and the structure of the compound is shown below：
Description
Technical field
The present invention relates to a kind of triazine system macromolecular halogen-free flameproof carbon forming agent compounds and preparation method thereof, which can
Carbon forming agent as materials such as polyethylene (PE), polypropylene (PP), silicon rubber.
Background technology
Polypropylene (PP) is most widely used, maximum two big general-purpose plastics of yield, because with odorless non-toxic and tasteless, physico
The features such as stability is good, density is small, electrical insulating property is excellent, easy to process is learned, in auto industry, household electrical appliance, electronics, electric wire electricity
Cable, packaging and building materials etc. are widely used.But PP is a kind of material of burning easily, and charring rate is almost 0,
Easily melting drippage, to limit the application field of PP.It is fire-retardant to bromine system in recent years since the environmental consciousness of people constantly enhances
Agent has also been proposed tightened up requirement, therefore develops the good carbon forming agent of halogen-free environmental, inexpensive, efficient, heat-resisting and processing performance and be
The direction of current PP fire retardants research.
Triazine system macromolecular halogen-free flameproof carbon forming agent of the present invention is rich in tertiary carbon and polyhydroxy structure, the compound of tertiary carbon structure
It has been demonstrated to have preferably at charcoal effect, polyhydroxy structure compound has in the presence of acid source and is dehydrated into charcoal effect
Fruit, thus triazine system macromolecular halogen-free flameproof carbon forming agent of the present invention for fire-retardant PP provide one novel, Halogen, environmental protection, it is inexpensive,
At the carbon forming agent that charcoal is excellent；The synthetic method of triazine system macromolecular halogen-free flameproof carbon forming agent of the present invention belongs to addition reaction, former
Sub- utilization rate 100%, yield is higher, and solvent can directly recycle use, does not have " three wastes " discharge, meets green synthesis process,
With good environmental benefit；Its raw material of triazine system macromolecular halogen-free flameproof carbon forming agent of the present invention is cheap and easy to get, simple for process, easily
It is good at charcoal efficiency, mechanical property and processing performance applied to having in the materials such as PP in large-scale production, have very wide
Development and application foreground.
Invention content
It is an object of the present invention to propose a kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound.Its is physico
It learns performance to stablize, heat-resist, high at charcoal efficiency, good with high molecular material compatibility, processing performance is excellent, can overcome existing skill
Deficiency in art.
For achieving the above object, present invention employs following technical solutions：
A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound, which is characterized in that the compound structure such as following formula institute
Show：
N > 1 in its formula,-NHNHCH2CH2OH、 -NHCH2CH2NHCH2CH2NH-、-NHCH2CH2NHCH2CH2NHCH2CH2NH-、-NHCH2CH2N(CH3)
CH2CH2NH-、
Another object of the present invention is to propose a kind of preparation side of triazine system macromolecular halogen-free flameproof carbon forming agent compound
Method, raw material is cheap and easy to get, simple for process, is easy to large-scale production, and technical solution is as follows：
The preparation method of triazine system macromolecular halogen-free flameproof carbon forming agent 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 70~120
DEG C, 6~20h 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 triazine system macromolecular after broken.
The solvent in the solution of isocyanuric acid three-glycidyl ester is as described above：Water, dioxane, toluene or diformazan
Benzene.
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 ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, diethylenetriamine, three second
Alkene tetramine, N- methyl diethylenetriamine, semicarbazides, biuret, m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, 4- ethoxybenzenes-
1,2- diamines, methyl ring pentanediamine or adjacent diamines methyl cyclopentane.
Certain mol proportion as described above is isocyanuric acid three-glycidyl ester: the molar ratio of two alkanamines is 1: 1.
Triazine system macromolecular halogen-free flameproof carbon forming agent disclosed by the invention be white solid, yield be 93.0%~
98.2%, 1% thermal weight loss decomposition temperature：260.3~310.5 DEG C, suitable for the materials such as PE, PP.Triazine system macromolecular Halogen
The synthesis technology principle of fire-retardant carbon forming agent is shown below：
N > 1 in its formula,NH2NHCH2CH2OH、
NH2CH2CH2NHCH2CH2NH2、NH2CH2CH2NHCH2CH2NHCH2CH2NH2、NH2CH2CH2N(CH3)CH2CH2NH2、
Compared with prior art, the beneficial effects of the present invention are：
1. triazine system macromolecular halogen-free flameproof carbon forming agent compound of the present invention, physical and chemical performance is stablized, decomposition temperature
Height, it is good with high molecular material compatibility, adapt to the high temperature process in engineering plastics.
2. being rich in tertiary carbon structure and polyhydroxy base junction in triazine system macromolecular halogen-free flameproof carbon forming agent compound molecule of the present invention
Structure has good at charcoal effect, the second-time burning generated to effectively prevent material melted by heating to drip.
3. the synthesis mode of triazine system macromolecular halogen-free flameproof carbon forming agent compound of the present invention is addition reaction, atom utilizes
Rate 100%, high income meet green synthesis process.
4. the solvent in triazine system macromolecular halogen-free flameproof carbon forming agent compound synthesis of the present invention can be recycled directly, close
At not having " three wastes " discharge in the process, there is good environmental benefit.
5. its raw material of triazine system macromolecular halogen-free flameproof carbon forming agent compound of the present invention is cheap and easy to get, production cost is low, if
Standby small investment, is easy to large-scale production, good at charcoal efficiency, mechanical property and processing performance applied to having in the materials such as PP,
With good application, 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 triazine macromolecular Halogen carbon forming agent CFA-1, refers to Figure of description Fig. 1；
Fig. 1 shows 3063cm-1Place is-CH2CH(OH)NHCH2CH2Upper-NH- keys the stretching vibration peaks of OH；2912cm-1Place
For-CH2CH(OH)NHCH2CH2The upper left side-NH- keys the stretching vibration peaks of NH-；2870cm-1Place is-CH2CH(OH)NHCH2CH2NH-
Upper the right-NH- key stretching vibration peaks；1710-1720cm-1Place is C=O key stretching vibration peaks；1340-1467cm-1Place is C-N
The stretching vibration peak of key；1255cm-1Place is-CH2CH(OH)NHCH2CH2The stretching vibration peak of the upper left side-OH keys of OH；1115cm-1
Place is-CH2CH(OH)NHCH2CH2The stretching vibration peak of the upper-OH keys of NH-；1050cm-1Place is-CH2CH(OH)NHCH2CH2On OH
The stretching vibration peak of the right-OH keys.
2, the nuclear magnetic spectrum figure of triazine macromolecular Halogen carbon forming agent CFA-1, refers to Figure of description Fig. 2；
Fig. 2 shows that δ 1.253-1.392 are-CH2CH(OH)NHCH2CH2The peaks H on the upper left side-OH of OH；δ1.466-
1.596 being-CH2CH(OH)NHCH2CH2The peaks the H upper upper left side-OH of NH-；δ 3.403-3.602 are-CH2CH(OH)
NHCH2CH2The peaks H on the upper mid methylenes of OH；δ 3.751-3.902 are-CH2CH(OH)NHCH2CH2The methylene on the upper the right OH
The upper peaks H；δ 4.006-4.193 are-CH2CH(OH)NHCH2CH2The peaks H on the upper mid methylenes of NH-；δ 4.208-4.422 be-
CH2CH(OH)NHCH2CH2The peaks H on the methylene on the upper the right NH-；δ 4.501-4.710 are-CH2CH(OH)NHCH2CH2On OH
The peaks H on the methylene of the left side；δ 4.778-4.901 are-CH2CH(OH)NHCH2CH2The peaks H on the upper left side methylene of NH-；δ
5.380-5.611 being-CH2CH(OH)NHCH2CH2The peaks H on the upper methines of OH；δ 5.633-5.786 are-CH2CH(OH)
NHCH2CH2The peaks H on the upper methines of NH-；δ 6.198-6.310 are-CH2CH(OH)NHCH2CH2H on the upper the right-NH- of NH-
Peak；δ 6.345-6.460 are-CH2CH(OH)NHCH2CH2The peaks H on the upper left side-NH- of NH-；δ 6.513-6.672 are-CH2CH
(OH)NHCH2CH2The peaks H on the upper-NH- of OH；δ 7.503-7.655 are-CH2CH(OH)NHCH2CH2The peaks H of the upper the right-OH of OH；δ
7.265 proton peaks exchanged for solvent carbon deuterium chloride.
3, the TG figures of triazine macromolecular Halogen carbon forming agent CFA-1, refer to Figure of description Fig. 3；
Fig. 3 shows that the 1% thermal weight loss decomposition temperature of CFA-1 is 267.3 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, 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 is added dropwise again
6.01g (0.1mol) ethylenediamine, control temperature is no more than 50 DEG C during being added dropwise, and after dripping off, is warming up to 70 DEG C, insulation reaction
6h makes the pH of solution reach 7~8, after cooling, up to product triazine after suction filtration (recycled solvent), washing, drying and crushing
It is macromolecular carbon forming agent CFA-1；Its yield is 98.0%, and 1% thermal weight loss decomposition temperature is 267.3 DEG C, passes through FTIR and NMR
Test analysis determines the 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
10.32g (0.1mol) diethylenetriamine, control temperature is no more than 50 DEG C, after dripping off during being added dropwise, and is warming up to 75 DEG C, heat preservation
Reaction 7h makes the pH of solution reach 7~8, after cooling, up to product after suction filtration (recycled solvent), washing, drying and crushing
Triazine system macromolecular carbon forming agent CFA-2；Its yield is 95.9%, and 1% thermal weight loss decomposition temperature is 274.1 DEG C, passes through FTIR
With NMR test analysis, the product structure is determined.
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, 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
14.62g (0.1mol) triethylene tetramine, control temperature is no more than 50 DEG C, after dripping off during being added dropwise, and is warming up to 80 DEG C, heat preservation
Reaction 8h makes the pH of solution reach 7~8, after cooling, up to product after suction filtration (recycled solvent), washing, drying and crushing
Triazine system macromolecular carbon forming agent CFA-3；Its yield is 96.7%, and 1% thermal weight loss decomposition temperature is 271.2 DEG C, passes through FTIR
With NMR test analysis, the product structure is determined.
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
11.72g (0.1mol) N- methyl diethylenetriamines, control temperature is no more than 50 DEG C during being added dropwise, and after dripping off, is warming up to 75
DEG C, insulation reaction 8h makes the pH of solution reach 7~8, after cooling, filters (recycled solvent), washes, after drying and crushing
Up to product triazine system macromolecular carbon forming agent CFA-4；Its yield is 95.8%, and 1% thermal weight loss decomposition temperature is 273.4 DEG C,
By FTIR and NMR test analysis, the product structure is determined.
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, 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
7.51g (0.1mol) semicarbazides, control temperature is no more than 50 DEG C in adition process, is warming up to 75 DEG C later, insulation reaction 7h makes
The pH of solution reaches 7~8, after cooling, filters (recycled solvent), washes, is big up to product triazine system after drying and crushing
Molecule carbon forming agent CFA-5；Its yield is 97.2%, and 1% thermal weight loss decomposition temperature is 267.3 DEG C, is tested by FTIR and NMR
Analysis, determines 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, 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
10.31g (0.1mol) contracting diamines, control temperature is no more than 50 DEG C in adition process, is warming up to 85 DEG C, insulation reaction 8h later,
The pH of solution is set to reach 7~8, after cooling, up to product triazine system after suction filtration (recycled solvent), washing, drying and crushing
Macromolecular carbon forming agent CFA-6；Its yield is 97.5%, and 1% thermal weight loss decomposition temperature is 264.2 DEG C, is surveyed by FTIR and NMR
Examination analysis, determines the product 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 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
10.81g (0.1mol) m-phenylene diamine (MPD) is added, control temperature is no more than 50 DEG C in adition process, and back flow reaction 10h, makes molten later
The pH of liquid reaches 7~8, after cooling, filters (recycled solvent), washing, dries and divide greatly up to product triazine system after crushing
Sub- carbon forming agent CFA-7；Its yield is 94.2%, and 1% thermal weight loss decomposition temperature is 301.8 DEG C, passes through FTIR and NMR tests point
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 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；Add
Enter 10.81g (0.1mol) p-phenylenediamine, 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 product triazine system macromolecular
Carbon forming agent CFA-8；Its yield is 94.0%, and 1% thermal weight loss decomposition temperature is 302.2 DEG C, passes through FTIR and NMR tests point
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, 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
10.81g (0.1mol) o-phenylenediamine is added, control temperature is no more than 50 DEG C in adition process, and back flow reaction 9h, makes solution later
PH reach 7~8, after cooling, filter (recycled solvent), washing, drying and after crushing up to product triazine system macromolecular
Carbon forming agent CFA-9；Its yield is 94.8%, and 1% thermal weight loss decomposition temperature is 301.7 DEG C, passes through FTIR and NMR tests point
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 dimethylbenzene 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
15.21g (0.1mol) 4- ethoxybenzene -1,2- diamines is added, control temperature is no more than 50 DEG C in adition process, is warming up to later
115 DEG C, insulation reaction 12h, the pH of solution is made to reach 7~8, after cooling, filters (recycled solvent), washing, drying and powder
Up to product triazine system macromolecular carbon forming agent CFA-10 after broken；Its yield is 95.0%, and 1% thermal weight loss decomposition temperature is
307.5 DEG C, by FTIR and NMR test analysis, determine 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, 250ml 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
11.40g (0.1mol) methyl ring pentanediamine, control temperature is no more than 50 DEG C in adition process, and back flow reaction 8.5h, makes molten later
The pH of liquid reaches 7~8, after cooling, filters (recycled solvent), washing, dries and divide greatly up to product triazine system after crushing
Sub- carbon forming agent CFA-11；Its yield is 95.3%, and 1% thermal weight loss decomposition temperature is 290.4 DEG C, is tested by FTIR and NMR
Analysis, determines the product structure.
Carbon forming agent structural formula described in 12 present embodiment 12 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 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
11.40g (0.1mol) neighbour's diamines methyl cyclopentanes, control temperature is no more than 50 DEG C in adition process, later back flow reaction 7.5h,
The pH of solution is set to reach 7~8, after cooling, up to product triazine system after suction filtration (recycled solvent), washing, drying and crushing
Macromolecular carbon forming agent CFA-12；Its yield is 96.1%, and 1% thermal weight loss decomposition temperature is 294.8 DEG C, passes through FTIR and NMR
Test analysis determines the product structure.
The specific triazine system macromolecular carbon forming agent of above-mentioned synthesis is also applied in PP by inventor, makes composite wood
Material, tests its flame retardant property and physical property.
Specific method is：CFA1~CFA12, ammonium polyphosphate (APP II) and pure PP particles are mixed into flame-retardant formulations and be denoted as
The weight ratio of formula 1~12, wherein CFA1~CFA12 and ammonium polyphosphate (APP II) is the addition of 1: 2~7, APP II and CFA
Total amount is 20~28%, and test result is shown in Table 1.By flame-retardant formulations 1~12 in 35# double screw extruder extruding pelletizations, PP resistances are obtained
Master batch is fired, wherein each area's temperature setting of double screw extruder is as follows：180 DEG C of head, 170 DEG C of 1st area, 175 DEG C of 2nd area, 175 DEG C of 3rd area,
4 175 DEG C of areas, 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, are melted at 175 DEG C of 5th area
185 DEG C of temperature；PP fire-retardant master granules are molded in injection molding machine, wherein injection temperature setting is as follows：185 DEG C of head, 1st area
200 DEG C, 200 DEG C of 2nd area, 185 DEG C of 3rd area, stretched, impacted, the standards batten such as vertical combustion (UL-94), measure its stretch it is strong
The performances such as degree, impact strength, limit oxygen index, fire-retardant, test result are shown in Table 2 and table 3.
Table 1
Table 2
Table 3
Note：N represent it is no, Y representative is.
It is small to its Effect on Mechanical Properties by table 2 and table 3 it is found that triazine system macromolecular carbon forming agent is applied in PP, show it
There are preferable compatibility, processing performance excellent in PP；In general, the limit oxygen index of material just belongs to incombustibe material more than 27
Material, UL-94V0 grades of vertical combustion are highest levels, and not only limit oxygen index is more than 27 to PP flame retardant composite materials, but also vertically fires
Burning can all reach V0 grade, and batten is not dripped at charcoal, this show its in PP it is excellent at charcoal and with APP II compoundings
Excellent flame retardancy afterwards.
Claims (3)
1. a kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound, which is characterized in that the structure of the compound such as following formula institute
Show：
N > 1 ,-X are in its formulan1=2~4 ,-NHNHCH2CH2OH、- Y- isn2
=2~6 ,-NHCH2CH2NHCH2CH2NH-、-NHCH2CH2NHCH2CH2NHCH2CH2NH-、-NHCH2CH2N(CH3)CH2CH2NH-、
2. the preparation method of triazine system macromolecular halogen-free flameproof carbon forming agent compound according to claim 1, which is characterized in that
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 ethylenediamine, propane diamine, butanediamine, pentanediamine,
Hexamethylene diamine, diethylenetriamine, triethylene tetramine, N- methyl diethylenetriamine, semicarbazides, biuret, m-phenylene diamine (MPD), to benzene two
Amine, o-phenylenediamine, 4- ethoxybenzenes -1,2- diamines, methyl ring pentanediamine or adjacent diamines methyl cyclopentane, are warming up to 70~120
DEG C, 6~20h of insulation reaction makes the pH of solution reach 7~8, after cooling, up to product three after filtering, wash, dry and crushing
The fire-retardant carbon forming agent of piperazine system macromolecular；Certain mol proportion is isocyanuric acid three-glycidyl ester: ethylenediamine, propane diamine, butanediamine, penta
It is diamines, hexamethylene diamine, diethylenetriamine, triethylene tetramine, N- methyl diethylenetriamine, semicarbazides, biuret, m-phenylene diamine (MPD), right
Phenylenediamine, o-phenylenediamine, 4- ethoxybenzenes -1,2- diamines, methyl ring pentanediamine or adjacent diamines methyl cyclopentane molar ratio be 1
∶1。
3. the preparation method of triazine system macromolecular halogen-free flameproof carbon forming agent compound according to claim 2, it is characterised in that：
Solvent in the solution of the isocyanuric acid three-glycidyl ester is water, dioxane, toluene or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610410728.0A CN106009037B (en) | 2016-06-08 | 2016-06-08 | A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610410728.0A CN106009037B (en) | 2016-06-08 | 2016-06-08 | A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106009037A CN106009037A (en) | 2016-10-12 |
| CN106009037B true CN106009037B (en) | 2018-10-30 |
Family
ID=57090285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610410728.0A Active CN106009037B (en) | 2016-06-08 | 2016-06-08 | A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106009037B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054840B (en) * | 2019-05-24 | 2021-10-29 | 华北理工大学 | Hyperbranched triazine charring agent with high nitrogen content, preparation method thereof and flame-retardant composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573901A (en) * | 1991-04-11 | 1996-11-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic material and silver halide photographic emulsion used therefor |
| CN101362819A (en) * | 2008-09-10 | 2009-02-11 | 华南理工大学 | Triazines cross-linking compounds, preparation method and application thereof |
| CN102161763A (en) * | 2011-02-25 | 2011-08-24 | 中山大学 | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof |
| CN102977144A (en) * | 2012-12-25 | 2013-03-20 | 湖南美莱珀科技发展有限公司 | Organic hypophosphite containing triazine ring structure and method for preparing same |
| CN103030836A (en) * | 2012-12-25 | 2013-04-10 | 湖南美莱珀科技发展有限公司 | Halogen-free flame retardant and preparation method thereof |
-
2016
- 2016-06-08 CN CN201610410728.0A patent/CN106009037B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573901A (en) * | 1991-04-11 | 1996-11-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic material and silver halide photographic emulsion used therefor |
| CN101362819A (en) * | 2008-09-10 | 2009-02-11 | 华南理工大学 | Triazines cross-linking compounds, preparation method and application thereof |
| CN102161763A (en) * | 2011-02-25 | 2011-08-24 | 中山大学 | Novel expansion-type charring agent for flame-retardant polyolefine material and synthesis method thereof |
| CN102977144A (en) * | 2012-12-25 | 2013-03-20 | 湖南美莱珀科技发展有限公司 | Organic hypophosphite containing triazine ring structure and method for preparing same |
| CN103030836A (en) * | 2012-12-25 | 2013-04-10 | 湖南美莱珀科技发展有限公司 | Halogen-free flame retardant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106009037A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102352041B (en) | Nitrogen-phosphorus intumescent flame retardant oligopolymer and its preparation method | |
| CN104231266A (en) | Macromolecular expansion type flame retardant containing hindered amine structure and preparation method and application of macromolecular expansion type flame retardant | |
| CN104558683A (en) | DOPO-containing cyclic phosphate flame retardant as well as preparation method and application thereof | |
| CN103992351A (en) | Preparation method of dimethylsilyl dioxyl bi-cage ring phosphate | |
| CN103214691B (en) | Phosphorus-nitrogen expanding type flame retardant and preparation method thereof | |
| CN106009037B (en) | A kind of triazine system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof | |
| CN104017025A (en) | Flame retardant charring agent-tetra-{1-oxyphospha-2,6,7-trioxabicyclo-[2.2.2]-octane-(4)-methyl} silicate compound and preparation method thereof | |
| CN105860067B (en) | A kind of nitrogen system macromolecular halogen-free flameproof carbon forming agent compound and preparation method thereof | |
| CN106084289B (en) | One kind macromolecular fire retardant compound of triazines containing selenium and preparation method thereof | |
| CN106084371B (en) | A kind of fire-retardant carbon forming agent compound of halogen-free polyolefin and preparation method thereof | |
| CN104725426A (en) | Tri(2-dimethyl PEPA oxy-silicon acyloxy ethyl) isocyanurate compound and preparation method thereof | |
| CN106084287B (en) | A kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class and preparation method thereof | |
| CN102174057B (en) | Organic silicon flame-retardant carbon-forming agent and preparation method thereof | |
| CN106084286B (en) | A kind of halogen-free expansion type flame-proof carbon forming agent compound and preparation method thereof | |
| CN103333194B (en) | A kind of fire retardant silicic acid three (tribromo phenyl) (chloroethyl) compound and preparation method thereof | |
| CN104650146A (en) | Isocyanuric acid tris (2-(dimethylthioto-PEPA oxyl silicon acyloxy) ethyl) ester compound and preparation method thereof | |
| CN104672267B (en) | The preparation method of fire retardant match gram dimethyl halo ethyoxyl silicate ester compound | |
| CN105968351B (en) | A kind of sulfur-bearing macro molecular triazine quasi polymer and preparation method thereof | |
| CN103333192A (en) | Flame retardant tri-(tribromophenoxy) halogen propoxy silane compound and preparation method thereof | |
| CN103554152B (en) | Fire retardant three [2-tri-(3-chlorine propoxy-) silicon trimethylammonium] isocyanurate compounds and preparation method thereof | |
| CN103319514B (en) | A kind of fire retardant two (dibromo propoxy) two (tribromophenoxy) silane compound and preparation method thereof | |
| CN105566385A (en) | Method for preparing tetrabromobisphenol-A organic-phosphonate compound | |
| CN104004020A (en) | Cage-shaped flame-retardant charring agent trimethyl silicic acid PEPA ester compound and preparation method thereof | |
| CN103319517B (en) | A kind of fire retardant tribromophenoxy three halogen Ethoxysilane compound and preparation method thereof | |
| CN103360419B (en) | A kind of fire retardant three (tribromophenoxy) halogen Ethoxysilane compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
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. |
|
| CP01 | Change in the name or title of a patent holder |