CN106084287B - A kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class and preparation method thereof - Google Patents

A kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class and preparation method thereof Download PDF

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CN106084287B
CN106084287B CN201610410718.7A CN201610410718A CN106084287B CN 106084287 B CN106084287 B CN 106084287B CN 201610410718 A CN201610410718 A CN 201610410718A CN 106084287 B CN106084287 B CN 106084287B
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fire
forming agent
carbon forming
sulfur
triazine class
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CN106084287A (en
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孟凡
孟凡一
李四新
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Zhejiang xusen flame retardant Co.,Ltd.
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Zhejiang Xusen Non-Halogen Smoke Suppressing Fire Retardants Co Ltd
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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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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

Abstract

The present invention relates to fire-retardant carbon forming agent compounds of a kind of sulfur-bearing macro molecular triazine class and preparation method thereof, and the structure of the compound is shown below：

Description

A kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class and preparation method thereof
Technical field
The present invention relates to fire-retardant carbon forming agent compounds of a kind of sulfur-bearing macro molecular triazine class and preparation method thereof, which can Carbon forming agent as materials such as polyethylene (PE), polypropylene (PP), silicon rubber.
Background technology
Expansion type flame retardant (IFR) is a kind of with nitrogen, the Green Flammability agent that phosphorus is the composite environmental-friendly mainly formed, not halogen Element does not use antimony oxide for synergist yet, and system itself has synergistic effect.Plastics containing expansion type flame retardant are in burning Surface can generate carbonaceous froth bed, play heat-insulated, oxygen barrier, suppression cigarette, antidrip and other effects, have an excellent flame retardant property, and low cigarette, Less toxic, non-corrosive gas generates, and meets the research and development direction of the following fire retardant, has become resistance the most active both at home and abroad Fire one of agent research field.IFR generally comprises charcoal source (being often polyol, such as pentaerythrite), acid source (such as polyphosphoric acid Ammonium, i.e. APP) and foaming agent (such as melamine).
In recent years, polypropylene (PP) because its with it is odorless it is non-toxic and tasteless, physical and chemical stability is good, density is small, electrical isolation The features such as property is excellent, easy to process, is widely used in auto industry, household electrical appliance, electronics, electric wire, packaging and building and builds Material etc..But PP is a kind of material of burning easily, and charring rate is almost 0, easily melting drippage, to limit PP Application field.In order to solve the problems, such as that PP's is inflammable, IFR is gradually applied in the polyolefine materials such as polypropylene (PP), wherein institute Charcoal source is pentaerythrite and its series mostly, but less desirable at charcoal effect in PP, and with the resistance to temperature difference, resistance to The shortcomings of aqueous poor, easy to migrate, to limit application ranges of the IFR in PP.Thus develop a kind of halogen-free environmental, it is inexpensive, Efficiently, the good polyolefin carbon forming agent of high temperature resistant, water-fast and processing performance is the research direction of current fire retardant.
The fire-retardant carbon forming agent of sulfur-bearing macro molecular triazine class 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, and two kinds of excellent ignition-proof elements of N, S have cooperative flame retardant effect, and thus the fire-retardant carbon forming agent of halogen-free polyolefin of the present invention is The materials such as fire-retardant PP provide one novel, Halogen, environmental protection, it is inexpensive, at the excellent carbon forming agent of charcoal；Halogen-free polyolefin of the present invention The synthetic method of fire-retardant carbon forming agent belongs to addition reaction, and atom utilization 100%, yield is higher, and solvent, which can be recycled directly, to be made With, do not have " three wastes " discharge, meet green synthesis process, have good environmental benefit；Sulfur-bearing macro molecular triazine class of the present invention Its raw material of fire-retardant carbon forming agent is cheap and easy to get, simple for process, is easy to large-scale production, good at charcoal applied to having in the materials such as PP Efficiency, mechanical property, water resistance, heat resistance and processing performance have very wide development and application foreground.
Invention content
It is an object of the present invention to propose a kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class.Its is physico It learns performance to stablize, heat-resist, water-tolerant, high at charcoal efficiency, good with high molecular material compatibility, processing performance is excellent, can Overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions：
A kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class, which is characterized in that the compound structure such as following formula institute Show：
N > 1 in its formula,-NHNHCH2CH2OH、
Another object of the present invention is to propose a kind of preparation side of the fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class 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 the fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class as described above, which is characterized in that this method For：
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, 6~15h 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 sulfur-bearing macro molecular triazine class after broken.
The solvent in the solution of isocyanuric acid three-glycidyl ester is as described above：Acetonitrile, water, dioxane, toluene Or dimethylbenzene.
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 be thiocarbamide, thiosemicarbazides, dithiobiuret, guanyl thiourea, 2- methylthiosemicarbazones, 2,5- bis- thioureas, beta-aminoethyl isothiourea, thiocarbonic acid hydrazine, dithiooxamide, 1,2- ethylene thioureas, the thio second of 2- Interior uride, 2,4- disulfide groups pyrimidine or 2- (2- thienyls) 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 sulfur-bearing macro molecular triazine class disclosed by the invention be white solid, yield be 94.0%~ 98.3%, 1% thermal weight loss decomposition temperature：265.0~308.3 DEG C, suitable for the materials such as PE, PP, silicon rubber.Sulfur-bearing macromolecular The synthesis technology principle of the fire-retardant carbon forming agent of triazines is shown below：
Wherein n > 1,NH2NHCH2CH2OH、
Compared with prior art, the beneficial effects of the present invention are：
1. the fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class of the present invention, physical and chemical performance is stablized, decomposition temperature Height, water-tolerant is good with high molecular material compatibility, adapts to the high temperature process in engineering plastics.
2. being rich in tertiary carbon structure and polyhydroxy base junction in the fire-retardant carbon forming agent compound molecule of sulfur-bearing macro molecular triazine class 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. containing two kinds of excellent fire-retardant members of N, S in the fire-retardant carbon forming agent compound molecule of sulfur-bearing macro molecular triazine class of the present invention Element, two kinds of element cooperative flame retardants make the flame-retarded efficiency of carbon forming agent improve.
4. containing element sulphur in the fire-retardant carbon forming agent compound molecule of sulfur-bearing macro molecular triazine class of the present invention, make the anti-of polymer Corrosive nature improves.
5. the synthesis mode of the fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class of the present invention is addition reaction, atom utilizes Rate 100%, high income meet green synthesis process.
6. the solvent in the fire-retardant carbon forming agent compound synthesis of sulfur-bearing macro molecular triazine class of the present invention can be recycled directly, close At not having " three wastes " discharge in the process, there is good environmental benefit.
7. fire-retardant its raw material of carbon forming agent compound of sulfur-bearing macro molecular triazine class 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 the fire-retardant carbon forming agent compound CFA-1 of sulfur-bearing macro molecular triazine class, refers to Figure of description figure 1；
Fig. 1 shows 3090cm-1Place is-CH2CH(OH)NHCH2CH2Upper-NH- keys the stretching vibration peaks of OH；2993cm-1Place For-CH2The upper left side-NH- keys the stretching vibration peaks of CH (OH) NHC (S) NH-；2923cm-1Place is-CH2On CH (OH) NHC (S) NH- The right-NH- key stretching vibration peaks；1730cm-1Place is the stretching vibration peak of C-S keys；1450-1590cm-1Place is that C=O keys are flexible Vibration peak；1220-1350cm-1Place is the stretching vibration peak of C-N keys；1160cm-1Place is-CH2CH(OH)NHCH2CH2OH is upper left The stretching vibration peak of side-OH keys；1040cm-1Place is-CH2The stretching vibration peak of the upper-OH keys of CH (OH) NHC (S) NH-；1008cm-1 Place 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 compound CFA-1 of sulfur-bearing macro molecular triazine class, refers to Figure of description figure 2；
Fig. 2 shows that δ 1.287-1.400 are-CH2CH(OH)NHCH2CH2The peaks H on the upper left side-OH of OH；δ1.443- 1.610 being-CH2The peaks H on the upper-OH of CH (OH) NHC (S) NH-；δ 3.261-3.401 are-CH2CH(OH)NHCH2CH2During OH is upper Between peaks H on methylene；δ 3.553-3.701 are-CH2CH(OH)NHCH2CH2The peaks H on the methylene on the upper the right OH；δ4.275- 4.376 being-CH2CH(OH)NHCH2CH2The peaks H on the upper left side methylene of OH；δ 4.441-4.608 are-CH2CH(OH)NHC(S) The peaks H on the upper left side methylene of NH-；δ 5.135-5.281 are-CH2CH(OH)NHCH2CH2The peaks H on the upper methines of OH；δ 5.368-5.442 being-CH2The peaks H on the upper methines of CH (OH) NHC (S) NH-；δ 6.235-6.341 are-CH2CH(OH)NHC(S) The peaks H on the upper the right-NH- of NH-；δ 6.356-6.501 are-CH2The peaks H on the upper left side-NH- of CH (OH) NHC (S) NH-；δ 6.602-6.720 being-CH2CH(OH)NHCH2CH2The peaks H on the upper-NH- of OH；δ 7.505-7.710 are-CH2CH(OH) NHCH2CH2The peaks H of the upper the right-OH of OH；δ 7.265 is the proton peak that solvent carbon deuterium chloride exchanges.
3, the TG figures of the fire-retardant carbon forming agent compound CFA-1 of sulfur-bearing macro molecular triazine class, refer to Figure of description Fig. 3；
Fig. 3 shows that the 1% thermal weight loss decomposition temperature of CFA-1 is 265.0 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, 200ml acetonitriles 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 7.60g (0.1mol) thiocarbamide, control temperature is no more than 50 DEG C in adition process, and back flow reaction 6h, makes the pH of solution reach 7 later ~8, after cooling, up to products C FA-1 after suction filtration (recycled solvent), washing, drying and crushing；Its yield is 98.3%, 1% thermal weight loss decomposition temperature is 265.0 DEG C, by 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 acetonitriles 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 9.11g (0.1mol) thiosemicarbazides, control temperature is no more than 50 DEG C in adition process, and back flow reaction 7h, makes the pH of solution later Reach 7~8, after cooling, up to products C FA-2 after suction filtration (recycled solvent), washing, drying and crushing；Its yield is 97.5%, 1% thermal weight loss decomposition temperature is 268.3 DEG C, by FTIR and NMR test analysis, determines 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, 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 13.52g (0.1mol) dithiobiuret, control temperature is no more than 50 DEG C in adition process, and back flow reaction 8h, makes solution later PH reach 7~8, after cooling, filter (recycled solvent), washing, drying and after crushing up to products C FA-3；Its yield It is 96.4%, 1% thermal weight loss decomposition temperature is 265.4 DEG C, by FTIR and NMR test analysis, determines the 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 adds 11.82g (0.1mol) guanyl thiourea, control temperature is no more than 50 DEG C in adition process, and back flow reaction 11h, makes solution later PH reaches 7~8, after cooling, up to products C FA-4 after suction filtration (recycled solvent), washing, drying and crushing；Its yield is 95.8%, 1% thermal weight loss decomposition temperature is 280.1 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, 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 10.52g (0.1mol) 2- methylthiosemicarbazones, control temperature is no more than 50 DEG C in adition process, and back flow reaction 14h, makes later The pH of solution reaches 7~8, after cooling, up to products C FA-5 after suction filtration (recycled solvent), washing, drying and crushing；Its Yield is 97.7%, and 1% thermal weight loss decomposition temperature is 278.5 DEG C, by FTIR and NMR test analysis, determines the product knot 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, 270ml 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 Bis- thioureas of 15.00g (0.1mol) 2,4-, control temperature is no more than 50 DEG C in adition process, and back flow reaction 8h, makes solution later PH reach 7~8, after cooling, filter (recycled solvent), washing, drying and after crushing up to products C FA-6；Its yield It is 95.2%, 1% thermal weight loss decomposition temperature is 267.3 DEG C, by FTIR and NMR test 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 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 11.92g (0.1mol) beta-aminoethyl isothiourea, control temperature is no more than 50 DEG C in adition process, and back flow reaction 9h, makes later The pH of solution reaches 7~8, after cooling, up to products C FA-7 after suction filtration (recycled solvent), washing, drying and crushing；Its Yield is 94.9%, and 1% thermal weight loss decomposition temperature is 270.2 DEG C, by FTIR and NMR test analysis, determines the product knot 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 10.62g (0.1mol) thiocarbonic acid hydrazine, control temperature is no more than 50 DEG C in adition process, and back flow reaction 7h, makes solution later PH reaches 7~8, after cooling, up to products C FA-8 after suction filtration (recycled solvent), washing, drying and crushing；Its yield is 98.0%, 1% thermal weight loss decomposition temperature is 268.4 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, 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 12.02g (0.1mol) dithiooxamide, control temperature is no more than 50 DEG C in adition process, and back flow reaction 8h, makes solution later PH reach 7~8, after cooling, filter (recycled solvent), washing, drying and after crushing up to products C FA-9；Its yield It is 96.7%, 1% thermal weight loss decomposition temperature is 270.1 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 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 10.22g (0.1mol) 1,2- ethylene thioureas are added, control temperature is no more than 50 DEG C in adition process, later back flow 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 94.9%, and 1% thermal weight loss decomposition temperature is 294.3 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 14.42g (0.1mol) 2,4- disulfide group pyrimidines, control temperature is no more than 50 DEG C in adition process, and back flow reaction 13h, makes later The pH of solution reaches 7~8, after cooling, up to products C FA-11 after suction filtration (recycled solvent), washing, drying and crushing；Its Yield is 94.3%, and 1% thermal weight loss decomposition temperature is 290.8 DEG C, by FTIR and NMR test analysis, determines the product knot Structure.
Carbon forming agent structural formula described in 12 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, 300ml 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 16.26g (0.1mol) 2- (2- thienyls) piperazine is added, control temperature is no more than 50 DEG C in adition process, is warming up to 120 later DEG C, insulation reaction 15h makes the pH of solution reach 7~8, after cooling, filters (recycled solvent), washes, after drying and crushing Up to products C FA-12；Its yield is 94.0%, and 1% thermal weight loss decomposition temperature is 308.3 DEG C, is tested by FTIR and NMR Analysis, determines the product structure.
The specific fire-retardant carbon forming agent of sulfur-bearing macro molecular triazine class 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~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: 4~7, APP II and CFA Total amount is 18~25%, 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.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 of sulfur-bearing macro molecular triazine class 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 with the excellent cooperative resistance combustion after APP II compounding；By 70 DEG C, the boiling of 168h, vertical combustion batten still can Reach UL-94V0 grades, this shows its excellent water resistance in PP applications.

Claims (4)

1. a kind of fire-retardant carbon forming agent compound of sulfur-bearing macro molecular triazine class, which is characterized in that the structure of the compound such as following formula institute Show：
N > 1 ,-X are in its formula-NHNHCH2CH2OH, n1=2~4,- Y- is
2. the preparation method of the fire-retardant carbon forming agent compound of a kind of sulfur-bearing macro molecular triazine class according to claim 1, feature It is, preparation method is：Under stiring, equimolar hydramine is added into the solution of isocyanuric acid three-glycidyl ester, it After be increased to 30~60 DEG C, 1~5h of insulation reaction makes the pH of solution reach 7~8；Add certain mole of thiocarbamide, amino sulphur Urea, dithiobiuret, guanyl thiourea, 2- methylthiosemicarbazones, 2,5-, bis- thioureas, beta-aminoethyl isothiourea, thio carbon Sour hydrazine, dithiooxamide, 1,2- ethylene thioureas, 2- thio-hydantoins, 2,4- disulfide groups pyrimidine or 2- (2- thienyls) Piperazine is warming up to 80~120 DEG C, 6~15h of insulation reaction, and the pH of solution is made to reach 7~8, after cooling, filters, washing, dries With after crushing up to the fire-retardant carbon forming agent of product sulfur-bearing macro molecular triazine class；
Certain mol proportion is isocyanuric acid three-glycidyl ester: thiocarbamide, thiosemicarbazides, dithiobiuret, guanyl thiourea, 2- first Base thiosemicarbazides, 2,5-, bis- thioureas, beta-aminoethyl isothiourea, thiocarbonic acid hydrazine, dithiooxamide, 1,2- ethylidene sulphur Urea, 2- thio-hydantoins, 2,4- disulfide groups pyrimidine or 2- (2- thienyls) piperazine molar ratio be 1: 1.
3. the preparation method of the fire-retardant carbon forming agent compound of a kind of sulfur-bearing macro molecular triazine class according to claim 2, feature It is：Solvent in the solution of the isocyanuric acid three-glycidyl ester is acetonitrile, water, dioxane, toluene or dimethylbenzene.
4. the preparation method of the fire-retardant carbon forming agent compound of a kind of sulfur-bearing macro molecular triazine class according to claim 2, feature It is：The hydramine is ethanol amine, Propanolamine, butanolamine, 2- hydrazinoethanols, equal amido phenenyl alcohol, m-aminophenol or right Amino-phenol.
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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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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

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