CN107868237A - A kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen and its preparation method and application - Google Patents
A kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen and its preparation method and application Download PDFInfo
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention discloses the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen, Crosslink structure such as following formula (I) are shown.The defects of present invention is directed to the existing component into charcoal, develop a kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen.The high molecular fire retardant carbon forming agent have the characteristics that into charcoal is good, molecular weight is high, resistance to migration, nonhygroscopic, high temperature resistant, the mechanical property for not influenceing matrix material.It can be cooperateed with phosphorus-nitrogen containing flame retardant, applied in the materials such as nylon, polyester, polyurethane.
Description
Technical field
The present invention relates to the technical field of high molecular fire retardant carbon forming agent, and in particular to a kind of thermosetting of phosphorous nitrogen gathers
Ester high molecular fire retardant carbon forming agent and its preparation method and application.
Background technology
High polymer material has combustibility mostly, but in many application fields, fire-retardant requirement is proposed to material, such as
Electric appliance and electronic field, electric wire, furniture, building, automotive trim, textile etc., that is, require flammable inflammable high polymer material
Reach fire-retardant.Generally making flammable high polymer material fire-retardant is realized by adding fire retardant in the material.Traditionally, fire retardant with
Based on bromide fire retardant, but substantial amounts of research is found, after the flame retarded polymeric material added with bromide fire retardant meets fire burning,
Substantial amounts of dense smoke and noxious material can be produced, causes personnel to suffocate, causes secondary injury；In addition, the discarded object of these materials exists
When high temperature reclaims, the carcinogens such as bioxin are easily generated, cause environmental pollution.Therefore, for halogenated flame retardant the problem of, closely
Developing novel halogen-free flame-retardant agent over year turns into focus, a large amount of novel halogen-free flame-retardant agent occurs, and obtain in multiple application fields
Applications well.
Especially mostly important with phosphorus-nitrogen containing flame retardant in halogen-free flame retardants, this based flame retardant has high flame retarding efficiency, adds
Dosage is low, does not influence the mechanical property of base material.It is usual according to its fire retardant mechanism, phosphorus-nitrogen containing flame retardant in phosphorus-nitrogen containing flame retardant
Include three kinds of function ingredients：Acid source, carbon source and source of the gas.Acid source is typically used as the catalyst of high temperature dehydration, may be such that polymer
Fast dewatering is into charcoal, based on phosphorus-containing compound；Source of the gas compound is then that generation non-combustible gas, such as nitrogen can be decomposed in high temperature
Gas, ammonia, carbon dioxide etc., high-temperature decomposition reaction are typically the endothermic reaction, can reduce the temperature of comburant, are unfavorable for firing
Burn, secondly caused a large amount of non-combustible gas, can reduce oxygen concentration, while these gases can also allow matrix polymer to produce
Foaming effect, the foaming layer formed also have iris action, are unfavorable for the diffusion of burning, play fire-retardant effect, source of the gas
Compound is typically nitrogen-containing compound, melamine, MCA in such as compound in triazine class；Charcoal source is carbon forming agent, its act on be
Easy dehydration carbonization under high temperature, high temperature dehydration process are an endothermic processes, can lower the temperature of comburant, caused steam can
To dilute the concentration of oxygen, and the layer of charcoal formed is one layer of compacted zone, can play a part of heat-insulated oxygen barrier, avoids the hair of burning
Exhibition, typically polyol.These three components are typically that three kinds of materials mutually cooperate with, and according to flame retardant effect and matrix material
The difference of material, mutual ratio is adjusted, realizes highly effective flame-retardant.If the material for possessing these functions is separate, then should
When in high polymer material, it is desirable to which good is scattered, and these components are dispersed in matrix macromolecule material in proportion
In material, this proposes higher requirement to dispersing apparatus, based on this problem, also has substantial amounts of research to wish development set acid at present
The compound in source, source of the gas and carbon source one, realizes more efficient collaboration, avoids scattered inequality of the fire retardant in matrix material from drawing
The efficiency risen is low.
In phosphorous-nitrogen system bittern-free flame-retardant system, the gentle source compound development relative maturity of acid source, existing a large amount of commercial products
In the presence of, but the problem of more is still suffered from for carbon-source cpd, and it is little that leeway may be selected.Carbon-source cpd is typically
Polyol, such as pentaerythrite, bipentaerythrite etc., but the carbon-source cpd of these polyhydroxy exist one it is maximum
Problem is exactly water-soluble.Water solubility can cause the flame retardance element moisture absorption, reduce the insulating properties of material, can be limited in electric and electronic neck
The application in domain；Because most of macromolecule matrix materials are non-polar materials, the water solubility of flame retardance element can cause flame retardance element
On the one hand migration precipitation influences outward appearance, on the other hand causes flame retardance element in the skewness of material so that fire-retardant to surface
Effect is gradually reduced, and influences the lasting fire resistance of material；Some can be used as the high-molecular compound of carbon forming agent, such as thermoplasticity
Petchem, due to the problem of compatibility be present with matrix material so that the mechanical properties decrease of material is very big and loses and answers
With value；Polyol or low-molecular-weight polyhydroxylated compound also have that heat decomposition temperature is relatively low, therefore not
Being suitable for application in has in higher processing temperature base material, such as nylon, polyester.
Therefore, low aqueous solubility is resistant to elevated temperatures is even more important into charing compound, and is having phosphorus nitrogen into introducing in charing compound
Element so that fire retardant collects acid source, source of the gas and into charcoal function in a concertedness for knowing from experience raising phosphorus nitrogen halogen-free flame-retardant system, improves
Flame retarding efficiency, dosage is reduced, while the mechanical property of matrix material can not be influenceed again, reduced to material processing plant and technique
It is required that.
The content of the invention
The defects of present invention is directed to the existing component into charcoal, develop a kind of thermosetting polyester macromolecule resistance of phosphorous nitrogen
Fire carbon forming agent.The high molecular fire retardant carbon forming agent has into charcoal is good, molecular weight is high, resistance to migration, nonhygroscopic, high temperature resistant, does not influence
The features such as mechanical property of matrix material.It can be cooperateed with phosphorus-nitrogen containing flame retardant, applied in the materials such as nylon, polyester, polyurethane.
Concrete technical scheme is as follows：
The thermosetting polyester high molecular fire retardant carbon forming agent of a kind of phosphorous nitrogen, shown in Crosslink structure such as following formula (I)：
The preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of described phosphorous nitrogen is：
Using the trihydroxyethyl isocyanuric ester of equivalent and mixed dibasic acid as raw material, it is prepared after polycondensation reaction；
Described mixed dibasic acid include terephthalic acid (TPA) and [(6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha oneself
Ring -6- bases) methyl] succinic acid (DDP).
The preparation of described high molecular fire retardant carbon forming agent be using containing trihydric compounds and binary acid as monomer, in equivalent
Under the conditions of occur polycondensation reaction, form the petchem with cross-linked structure, have into charcoal function；And due in molecule knot
Hydroxyl is not present in structure, its water-soluble very little；Heat-curable compounds are used as simultaneously, there is the characteristics of not molten insoluble, in matrix material
It is a kind of filler in material, does not influence the mechanical property of matrix material；Simultaneously in molecule containing phosphorus, nitrogen, have concurrently acid source and
The function of source of the gas, further increases fire resistance.
The present invention will be elaborated below.
The present invention is for the purpose of solving the various defects of existing fire-retardant carbon forming agent, and is developed new fire-retardant into charcoal
Agent, for this, inventor has made extensive and intensive studies.Existing carbon forming agent is all polyol, and with small molecule
Based on material, although these materials have preferably into charcoal effect as carbon forming agent, but it is low to face water-soluble strong and decomposition temperature
Shortcoming, it is limited in many fields.But from charcoal forming machine reason, carbon forming agent be unable to do without hydroxy compounds, in order to reduce the water of material
Dissolubility simultaneously improves decomposition temperature, naturally expects hydroxy esterification is reduced the amount of hydroxyl, and to carry with some carboxylated compounds
High heat decomposition temperature, then need to improve molecular weight, if forming thermoplastic high-molecular weight compounds, then can be deposited in application
It is the consistency problem of matrix material, reduces mechanical property.
Based on Such analysis, inventor propose using existing carbon forming agent polyhydroxy characteristic, there is polyfunctionality, by with
Esterification condensation occurs for acid, forms the heat-curable compounds with cross-linked structure, and the compound, which still has into charcoal, to be acted on, while ester
Change and cause the hydroxyl in molecular structure due to being esterified without hydrophily, and the heat-curable compounds of cross-linked structure have height
Decomposition temperature, the 3rd, the thermosetting polymer has infusible characteristic, application when in the absence of compatible with matrix material
Sex chromosome mosaicism, the mechanical property of material is not influenceed.
Can meet above-mentioned analysis molecular structure scheme have it is a variety of, such as polyol may be selected contain tetratomic season
Penta tetrol, the bipentaerythrite of hexahydroxy, triatomic trihydroxyethyl isocyanuric ester and binary acid condensation reaction, but at these
In polyol, due to containing nitrogen-atoms in trihydroxyethyl isocyanuric ester molecular structure, anti-flammability can be improved, therefore
Select trihydroxyethyl isocyanuric ester；And binary acid can select a variety of, including aromatic carboxylic acids, aliphatic carboxylic acid and binary organophosphor
Acid etc..Inventor is had found by studying, and phosphorus nitrogen is introduced in the molecular structure of carbon forming agent, carbon forming agent into charcoal except acting on
Outside, its phosphorous nitrogen of institute can produce synergy to fire-retardant, be that can reduce the addition of acid source and source of the gas in fire-retardant application,
It can be considered to phosphorous binary acid.Further, inventor also found trihydroxyethyl isocyanuric ester and terephthalic acid (TPA)
It is condensed with DDP mixed dibasic acid, then can obtains the thermosetting polyester condensation product with cross-linked structure, both contain in molecular structure
Phosphorus nitrogen, there is into charcoal effect again, water-soluble low, heat decomposition temperature is high.
The preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of described phosphorous nitrogen, it is specially：
(1) trihydroxyethyl isocyanuric ester and mixed dibasic acid of equivalent, under phase transfer catalyst effect, 150
4~8h is reacted at~230 DEG C esterification prepolymer is made；
In described mixed dibasic acid, terephthalic acid (TPA) and DDP mol ratio are 1~5：1, contained so that different phosphate is prepared
The high molecular fire retardant carbon forming agent of amount；
(2) vacuumize and be warming up to 260~280 DEG C, described esterification prepolymer obtains through condensation curing, then after crushed
The high molecular fire retardant carbon forming agent of the tool cross-linked structure of described phosphorous nitrogen.
Trihydroxyethyl isocyanuric ester has three hydroxyls, belongs to trifunctional compound, terephthalic acid (TPA) and DDP belong to
In binary acid, belong to two functional compounds, under equivalent, the thermosetting polyester condensation product with cross-linked structure can be formed.
2 steps of condensation reaction point are carried out, and first prepare polyester prepolyer at a lower temperature, then carry out condensation curing at high temperature, obtain institute
The high molecular fire retardant carbon forming agent stated.
In the preparation process of step (1) prepolymer, in order to accelerate reaction speed, it is necessary to using phase transfer catalyst.Make
To be preferred, described phase transfer catalyst is selected from quaternary ammonium salt, such as TBAB.
Meanwhile also the water that esterification generates is drained in time.In order to prevent prepolymer from changing colour, reaction can be in nitrogen
Atmosphere is carried out.
In step (2), high-temperature polycondensation solidification is carried out to prepolymer, it is necessary to high vacuum, hot conditions.Preferably, take out true
Sky to vacuum is less than 50KPa.The reaction can be carried out in an oven, and can also using, there is the high-power of agitating function to pinch
Conjunction machine.
It is block by the fire-retardant carbon forming agent obtained after condensation curing, in order to be added in matrix material, it is also necessary to enter
Row pulverization process, using mechanical crushing equipment, control the average grain diameter D50 of fire-retardant carbon forming agent<5μm.
Not only acted on by the macromolecule that the above method is prepared into carbon flame-proof agent with good into charcoal, and molecule knot
Contain phosphorus nitrogen in structure, there is good flame retarding efficiency, simultaneously because have cross-linked structure, not hydroxyl in molecular structure, water
Dissolubility is low, and heat decomposition temperature is high, can be applied to the fire-retardant of high polymer material.Especially apply in the base with higher processing temperature
In body material, such as nylon, polyester, polyurethane.
Preferably, the high molecular fire retardant carbon forming agent can compound with phosphorus-nitrogen containing flame retardant, such as organic hypophosphites, jointly
Apply in the materials such as nylon, polyester, polyurethane, realize good flame retardant effect.
Further preferably, prepared using described high molecular fire retardant carbon forming agent and phosphorus-nitrogen containing flame retardant as flame-retardant system fire-retardant
High polymer material, in terms of 100%, raw material composition includes gross mass：
Described base material is selected from nylon, polyester or polyurethane；
Described phosphorus-nitrogen containing flame retardant is selected from diethyl hypo-aluminum orthophosphate.
Still further preferably, in described high molecular fire retardant carbon forming agent, nitrogen content is 7.6~8.5%, phosphorus content 1.4
~3.6%.Find, described phosphorus, the high molecular fire retardant carbon forming agent of nitrogen content, can further reduce through further application test
The dosage of the phosphorus-nitrogen containing flame retardant compounded with it.
Compared with prior art, the invention has the advantages that：
The invention provides a kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen, carbon-forming performance are excellent；
Hydroxyl, water-soluble very little are not present in molecular structure；There is cross-linked structure in molecular structure, decomposition temperature is high, and not molten insoluble,
Using when in the absence of the consistency problem with matrix material, do not influence the mechanical property of material.It can be cooperateed with phosphorus-nitrogen containing flame retardant,
Applied in the materials such as nylon, polyester, polyurethane.
Embodiment
Embodiment 1
In 1L flask, 522 grams of (2 moles) trihydroxyethyl isocyanuric esters are added, leads to nitrogen protection, is heated to 150
DEG C cause trihydroxyethyl isocyanuric ester fusing, then add 2.7 grams of TBABs and 332 grams of (2 moles) terephthaldehydes
Acid and 347g (1 mole) DDP, strong stirring mixture, heated within 6 hours from 150 DEG C and be raised to 230 DEG C, in course of reaction
Water is discharged, and condenses metering, and 230 DEG C are incubated 1 hour, are cooled to 150 DEG C, melt is discharged to a metal tray, melt cooling
After obtain a kind of white embrittlement solids, for melting range from 110 to 130 DEG C, residual acid value is 7 milligrams of KOH/g.
Prepolymer is placed into vacuum drying oven together with pallet, vacuumized, vacuum keeps 50KPa, is heated to 280
DEG C, kept for 3 hours, complete solidification, cooling discharge.Crushing material to average grain diameter D50<5 microns stand-by.
Through analysis：High molecular fire retardant carbon forming agent (being designated as char-1) manufactured in the present embodiment, phosphorus content are：2.3%, nitrogen contains
Measure and be：6.7% (phosphorus, nitrogen content are actual measured value, the slightly below calculated value in specification), solubility<0.1%,
1% weightless 340 DEG C of decomposition temperature.
Embodiment 2
Implementation process is same as Example 1, except terephthalic acid (TPA) and DDP mol ratio are changed to 4:1.
After tested, high molecular fire retardant carbon forming agent (being designated as char-2) manufactured in the present embodiment, phosphorus content are：1.3%, nitrogen contains
Measure and be：7.2%, solubility<0.1%, 1% weightless 330 DEG C of decomposition temperature.
The char-1 of embodiment 3 is applied in fiber glass reinforced PBT
By the formula table dispensing of table 1, each component is well mixed in high-speed mixer, well mixed material passed through double
Screw extruder extruding pelletization, standard batten is prepared, test fire resistance, can reach UL 94V0 (1mm is thick), no molten drop.In perseverance
Constant temperature and humidity condition test migration precipitation, as a result shows non-migratory.And use conventional diethyl hypo-aluminum orthophosphate and MPP compound ligand
System, it can be found that there is migration precipitation.
The char-2 of embodiment 4 is applied in fiber glass reinforced PBT
By the formula table dispensing of table 1, each component is well mixed in high-speed mixer, well mixed material passed through double
Screw extruder extruding pelletization, standard batten is prepared, test fire resistance, can reach UL 94V0 (1mm is thick), no molten drop.Use
Char-2, to reach identical flame retardant effect, it is necessary to more diethyl hypo-aluminum orthophosphates.Migrate and analyse in constant temperature and humidity condition test
Go out, as a result show non-migratory.And conventional diethyl hypo-aluminum orthophosphate and MPP compound system are used, it can be found that there is migration precipitation.
The char-1 of embodiment 5 is applied in fiberglass reinforced PA 6,6
By the formula table dispensing of table 1, each component is well mixed in high-speed mixer, well mixed material passed through double
Screw extruder extruding pelletization, standard batten is prepared, test fire resistance.It can reach UL 94V0 (1mm is thick), no molten drop.In perseverance
Constant temperature and humidity condition test migration precipitation, as a result shows non-migratory.And use conventional diethyl hypo-aluminum orthophosphate and MPP compound ligand
System, it can be found that there is migration precipitation.
The char-2 of embodiment 6 is applied in fiberglass reinforced PA 6,6
By the formula table dispensing of table 1, each component is well mixed in high-speed mixer, well mixed material passed through double
Screw extruder extruding pelletization, standard batten is prepared, test fire resistance.It can reach UL 94V0 (1mm is thick), no molten drop.Use
Char-2, to reach identical flame retardant effect, it is necessary to more diethyl hypo-aluminum orthophosphates.Migrate and analyse in constant temperature and humidity condition test
Go out, as a result show non-migratory.And conventional diethyl hypo-aluminum orthophosphate and MPP compound system are used, it can be found that there is migration precipitation.
The char-1 of embodiment 7 is applied in TPU cable materials
By the formula table dispensing of table 1, each component is well mixed in high-speed mixer, well mixed material passed through double
Screw extruder extruding pelletization, cable is prepared on cable apparatus, test fire resistance.It can reach VW-1, no molten drop.In constant temperature
Constant humidity condition test migration precipitation, as a result shows non-migratory.And conventional diethyl hypo-aluminum orthophosphate is used, it can be found that there is molten drop.
The char-2 of embodiment 8 is applied in TPU cable materials
By the formula table dispensing of table 1, each component is well mixed in high-speed mixer, well mixed material passed through double
Screw extruder extruding pelletization, cable is prepared on cable apparatus, test fire resistance.It can reach VW-1, no molten drop.Use
Char-2, to reach identical flame retardant effect, it is necessary to more diethyl hypo-aluminum orthophosphates.Migrate and analyse in constant temperature and humidity condition test
Go out, as a result show non-migratory.And conventional diethyl hypo-aluminum orthophosphate is used, it can be found that there is molten drop.Table 1
Claims (10)
- A kind of 1. thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen, it is characterised in that Crosslink structure such as following formula (I) shown in：
- 2. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 1, it is characterised in that nitrogen Content is 7.6~8.5%, and phosphorus content is 1.4~3.6%.
- A kind of 3. preparation of the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 1 or 2 Method, it is characterised in that using the trihydroxyethyl isocyanuric ester of equivalent and mixed dibasic acid as raw material, made after polycondensation reaction It is standby to obtain；Described mixed dibasic acid includes terephthalic acid (TPA) and [(6- oxo -6H- dibenzo [c, e] [1,2] own ring -6- of oxygen phospha Base) methyl] succinic acid.
- 4. the preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 3, its It is characterised by, is specially：(1) trihydroxyethyl isocyanuric ester and mixed dibasic acid of equivalent, under phase transfer catalyst effect, 150~230 4~8h is reacted at DEG C esterification prepolymer is made；In described mixed dibasic acid, terephthalic acid (TPA) and [(6- oxo -6H- dibenzo [c, e] [1,2] own ring -6- of oxygen phospha Base) methyl] succinic acid mol ratio be 1~5：1；(2) vacuumize and be warming up to 260~280 DEG C, described esterification prepolymer is through condensation curing, then obtains after crushed described Phosphorous nitrogen thermosetting polyester high molecular fire retardant carbon forming agent.
- 5. the preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 4, its It is characterised by, in step (1), described phase transfer catalyst is selected from quaternary ammonium salt.
- 6. the preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 4, its It is characterised by, in step (2), is evacuated to vacuum and is less than 50KPa.
- 7. the preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 4, its It is characterised by, in step (2), is crushed to average grain diameter D50<5μm.
- 8. a kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 1 or 2 is in high score Sub- material it is fire-retardant in application.
- 9. application according to claim 8, it is characterised in that described high polymer material is selected from polyester, nylon, polyurethane At least one of.
- 10. application according to claim 9, it is characterised in that the thermosetting polyester macromolecule of described phosphorous nitrogen Fire-retardant carbon forming agent is with phosphorus-nitrogen containing flame retardant composite usage in described high polymer material.
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| CN110845712A (en) * | 2019-11-23 | 2020-02-28 | 李丹丹 | Novel polyester and preparation method thereof |
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