CN107868237B - 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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- 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
- 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 agents of phosphorous nitrogen, shown in Crosslink structure such as following formula (I).The present invention is directed to the existing defect at charcoal component, develops a kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen.The high molecular fire retardant carbon forming agent has the characteristics that into that charcoal is good, molecular weight is high, resistance to migration, nonhygroscopic, high temperature resistant, the mechanical property for not influencing basis material.It can cooperate with, be applied in the materials such as nylon, polyester, polyurethane with phosphorus-nitrogen containing flame retardant.
Description
Technical field
The present invention relates to the technical fields of high molecular fire retardant carbon forming agent, and in particular to a kind of thermosetting property of phosphorous nitrogen is poly-
Ester high molecular fire retardant carbon forming agent and its preparation method and application.
Background technique
High molecular material has combustibility mostly, but in many application fields, fire-retardant requirement is proposed to material, such as
Electric appliance and electronic field, wire and cable, furniture, building, automobile interior decoration, textile etc. require flammable inflammable high molecular material
Reach fire-retardant.Usually making flammable high molecular material fire-retardant is realized by the way that fire retardant is added in the material.Traditionally, fire retardant with
Based on bromide fire retardant, but it is a large amount of the study found that the flame retarded polymeric material added with bromide fire retardant meets fire burning after,
A large amount of dense smoke and noxious material can be generated, personnel is caused to suffocate, causes secondary injury；In addition, the waste of these materials exists
When high temperature recycles, it is easy to generate the carcinogens such as dioxin, causes environmental pollution.Therefore, aiming at the problem that halogenated flame retardant, closely
Novel halogen-free flame-retardant agent is developed over year as hot spot, 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 substrate.In phosphorus-nitrogen containing flame retardant, according to its fire retardant mechanism, phosphorus-nitrogen containing flame retardant is usual
It include three kinds of function ingredients: acid source, carbon source and gas source.Acid source is typically used as the catalyst of high temperature dehydration, may make polymer
Fast dewatering is at charcoal, based on phosphorus-containing compound；Gas source compound is then that can decompose generation non-combustible gas, such as nitrogen at high temperature
Gas, ammonia, carbon dioxide etc., high-temperature decomposition reaction are usually the endothermic reaction, can reduce the temperature of comburant, are unfavorable for firing
It burns, a large amount of non-combustible gas secondly generated can reduce oxygen concentration, while these gases can also allow matrix polymer to generate
Foaming effect, being formed by foaming layer also has barrier action, is unfavorable for the diffusion of burning, plays fire-retardant effect, gas source
Closing object is usually melamine in nitrogenous compound, such as compound in triazine class, MCA；Charcoal source is carbon forming agent, effect be
Easy dehydration carbonization under high temperature, high temperature dehydration process are an endothermic processes, can lower the temperature of comburant, the steam of generation can
To dilute the concentration of oxygen, and the layer of charcoal formed is one layer of compacted zone, can play the role of heat-insulated oxygen-impermeable, avoids the hair of burning
Exhibition, usually polyol.These three components are usually that three kinds of substances mutually cooperate with, and according to flame retardant effect and matrix material
The difference of material adjusts mutual ratio, realizes highly effective flame-retardant.If the substance for having these functions is mutually indepedent, answer
When in high molecular material, it is desirable to which these components are dispersed in matrix macromolecule material by good dispersion in proportion
In material, this proposes higher requirement to dispersing apparatus, is based on this problem, also has a large amount of research to wish development set acid at present
Source, gas source and carbon source one compound, realize more efficient collaboration, dispersion unevenness of the fire retardant in basis material avoided to draw
The inefficiency risen.
In phosphorous-nitrogen system bittern-free flame-retardant system, the gentle source compound of acid source develops relative maturity, has a large amount of commercial products
In the presence of, but for carbon-source cpd, there are still many problems, and it is little that leeway may be selected.Carbon-source cpd is more usually
Polyol, such as pentaerythrite, dipentaerythritol etc., but the carbon-source cpd of these polyhydroxy is maximum there are one
Problem is exactly water-soluble.Water-soluble meeting can be limited in electric and electronic and lead so that the flame retardance element moisture absorption, reduces the insulating properties of material
The application in domain；Since most of macromolecule matrix materials are non-polar materials, the water-soluble meeting of flame retardance element is so that flame retardance element
On the one hand migration precipitation influences appearance, on the other hand leads to flame retardance element being unevenly distributed in material, so that fire-retardant to surface
Effect is gradually reduced, and influences the lasting flame retardant property of material；Some can be used as the high-molecular compound of carbon forming agent, such as thermoplasticity
Petchem, due to there is compatibility with basis material, so that the mechanical properties decrease of material is very big and loses and answers
With value；Polyol or the low-molecular-weight polyhydroxylated compound situation lower there is also thermal decomposition temperature, therefore not
Being suitable for application in has in higher processing temperature substrate, such as nylon, polyester.
Therefore, low aqueous solubility is resistant to high temperature is even more important at charcoal compound, and introducing has phosphorus nitrogen at charcoal compound
Element improves so that fire retardant collects acid source, gas source and the concertedness for knowing from experience raising phosphorus nitrogen halogen-free flame-retardant system in one at charcoal function
Flame retarding efficiency reduces dosage, while cannot influence the mechanical property of basis material again, reduces to material processing plant and technique
It is required that.
Summary of the invention
The present invention is directed to the existing defect at charcoal component, develops a kind of thermosetting polyester macromolecule resistance of phosphorous nitrogen
Fire carbon forming agent.The high molecular fire retardant carbon forming agent has at charcoal is good, molecular weight is high, resistance to migration, nonhygroscopic, high temperature resistant, does not influence
The features such as mechanical property of basis material.It can cooperate with, be applied in the materials such as nylon, polyester, polyurethane with phosphorus-nitrogen containing flame retardant.
Specific technical solution is as follows:
A kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen, shown in Crosslink structure such as following formula (I):
The thermosetting polyester high molecular fire retardant carbon forming agent of the phosphorous nitrogen the preparation method comprises the following steps:
Using the trihydroxyethyl isocyanuric ester of equivalent and mixed dibasic acid as raw material, it is prepared after polycondensation reaction；
The mixed dibasic acid include terephthalic acid (TPA) and [(6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha oneself
Ring -6- base) methyl] succinic acid (DDP).
The preparation of the high molecular fire retardant carbon forming agent is to contain trihydric compounds and binary acid as monomer, in equivalent
Under the conditions of occur polycondensation reaction, form the petchem with cross-linked structure, have the function of into charcoal；And due in molecule knot
Hydroxyl, water-soluble very little are not present in structure；Simultaneously be used as heat-curable compounds, have the characteristics that not melt it is insoluble, in matrix material
It is a kind of filler in material, does not influence the mechanical property of basis material；Contain phosphorus, nitrogen in molecule simultaneously, have both acid source and
The function of gas source, further improves flame retardant property.
It will elaborate below to the present invention.
The present invention and is developed novel fire-retardant at charcoal for the purpose of the various defects for solving existing fire-retardant carbon forming agent
Agent, inventor has made extensive and intensive studies thus.Existing carbon forming agent is all polyol, and with small molecule
Based on substance, although these substances have as carbon forming agent preferably at charcoal effect, but it is low to face water-soluble strong and decomposition temperature
Disadvantage, 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 substance
Dissolubility simultaneously improves decomposition temperature, naturally expects that hydroxy esterification is reduced the amount of hydroxyl with some carboxylated compounds, and to mention
High thermal decomposition temperature then needs to improve molecular weight, if it is thermoplastic high-molecular weight compounds are formed, is then applying Shi Huicun
It is the consistency problem of basis material, reduces mechanical property.
Based on Such analysis, inventor propose using existing carbon forming agent polyhydroxy characteristic, have polyfunctionality, by with
Esterification condensation occurs for acid, forms the heat-curable compounds with cross-linked structure, which still has into charcoal and act on, while ester
Change so that the hydroxyl in molecular structure is due to being esterified without hydrophily, and the heat-curable compounds of cross-linked structure have height
Decomposition temperature, third, the thermosetting polymer have infusible characteristic, application when there is no compatible with basis material
Property problem, does not influence the mechanical property of material.
There are many molecular structure schemes for being able to satisfy above-mentioned analysis, for example polyol may be selected to contain tetratomic season
Penta tetrol, the dipentaerythritol 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 choose a variety of, including aromatic carboxylic acids, aliphatic carboxylic acid and binary be organic phosphorus
Acid etc..Inventors discovered through research that introducing phosphorus nitrogen in the molecular structure of carbon forming agent, carbon forming agent at charcoal in addition to acting on
Outside, the phosphorous nitrogen of institute can act synergistically to fire-retardant generation, be the additive amount that can reduce acid source and gas source 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 the mixed dibasic acid of DDP, then can obtain the thermosetting polyester condensation product with cross-linked structure, both contain in molecular structure
Phosphorus nitrogen, and have into charcoal effect, water-soluble low, thermal decomposition temperature is high.
The preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of the phosphorous nitrogen, specifically:
(1) trihydroxyethyl isocyanuric ester and mixed dibasic acid of equivalent, under phase transfer catalyst effect, 150
4~8h is reacted at~230 DEG C, and esterification prepolymer is made；
In the mixed dibasic acid, the molar ratio of terephthalic acid (TPA) and DDP are 1~5:1, are contained so that different phosphate is prepared
The high molecular fire retardant carbon forming agent of amount；
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed
The high molecular fire retardant carbon forming agent of the tool cross-linked structure of the phosphorous nitrogen.
There are three hydroxyls for trihydroxyethyl isocyanuric ester tool, belong 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 carry 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, need using phase transfer catalyst.Make
To be preferred, the phase transfer catalyst is selected from quaternary ammonium salt, such as tetrabutylammonium bromide.
Meanwhile also the water that esterification generates is drained in time.Prepolymer changes colour in order to prevent, and reaction can be in nitrogen
Atmosphere carries out.
In step (2), high-temperature polycondensation solidification is carried out to prepolymer, needs high vacuum, hot conditions.Preferably, taking out true
Sky to vacuum degree is lower than 50KPa.The reaction can carry out in an oven, and also can be used with agitating function high-power pinches
Conjunction machine.
It is block by the fire-retardant carbon forming agent obtained after condensation curing, in order to be added in basis material, it is also necessary into
Row pulverization process controls average grain diameter D50 < 5 μm of fire-retardant carbon forming agent using mechanical crushing equipment.
Macromolecule prepared by the above method not only has good at charcoal effect, but also molecule knot at carbon flame-proof agent
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 thermal decomposition temperature is high, can be applied to the fire-retardant of high molecular material.It especially applies 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 be compounded with phosphorus-nitrogen containing flame retardant, such as organic hypophosphites, jointly
It applies in the materials such as nylon, polyester, polyurethane, realizes good flame retardant effect.
Further preferably, it is prepared using the high molecular fire retardant carbon forming agent and phosphorus-nitrogen containing flame retardant as flame-retardant system fire-retardant
High molecular material, in terms of 100%, raw material composition includes: gross mass
The substrate is selected from nylon, polyester or polyurethane；
The phosphorus-nitrogen containing flame retardant is selected from diethyl hypo-aluminum orthophosphate.
Still further preferably, in the high molecular fire retardant carbon forming agent, nitrogen content is 7.6~8.5%, phosphorus content 1.4
~3.6%.It is found through further application test, the high molecular fire retardant carbon forming agent of the phosphorus, nitrogen content can be further reduced
The dosage of the phosphorus-nitrogen containing flame retardant compounded with it.
Compared with prior art, the present invention has the advantage that
The present invention provides a kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen, carbon-forming performance is 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 do not melt it is insoluble,
Using when there is no the consistency problems with basis 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.
Specific embodiment
Embodiment 1
In the flask of 1L, 522 grams of (2 moles) trihydroxyethyl isocyanuric esters are added, leads to nitrogen protection, is heated to 150
DEG C trihydroxyethyl isocyanuric ester is melted, 2.7 grams of tetrabutylammonium bromide and 332 grams of (2 moles) terephthaldehydes are then added
Acid and 347g (1 mole) DDP, strong stirring mixture, heating is raised to 230 DEG C, in reaction process from 150 DEG C within 6 hours
Water discharge, and metering is condensed, 230 DEG C keep the temperature 1 hour, are cooled to 150 DEG C, melt are discharged to a metal tray, melt is 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, is vacuumized, vacuum degree keeps 50KPa, is heated to 280
DEG C, it is kept for 3 hours, completes solidification, cooling discharge.Crushing material is stand-by to average grain diameter D50 < 5 micron.
Through analyzing: high molecular fire retardant carbon forming agent (being denoted as char-1) manufactured in the present embodiment, phosphorus content are as follows: 2.3%, nitrogen contains
Amount are as follows: 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, in addition to the molar ratio of terephthalic acid (TPA) and DDP are changed to 4:1.
After tested, high molecular fire retardant carbon forming agent (being denoted as char-2) manufactured in the present embodiment, phosphorus content are as follows: 1.3%, nitrogen contains
Amount are as follows: 7.2%, solubility < 0.1%, 1% 330 DEG C of decomposition temperature of weightlessness.
3 char-1 of embodiment is applied in fiber glass reinforced PBT
By 1 formula table ingredient of table, each component is uniformly mixed in a high speed mixer, uniformly mixed material is passed through double
Screw extruder extruding pelletization prepares standard batten, tests flame retardant property, can reach UL 94V0 (1mm is thick), no molten drop.In perseverance
Constant temperature and humidity condition test migration precipitation, it is non-migratory as the result is shown.And use the compound ligand of conventional diethyl hypo-aluminum orthophosphate and MPP
System, it can be found that there is migration precipitation.
4 char-2 of embodiment is applied in fiber glass reinforced PBT
By 1 formula table ingredient of table, each component is uniformly mixed in a high speed mixer, uniformly mixed material is passed through double
Screw extruder extruding pelletization prepares standard batten, tests flame retardant property, can reach UL 94V0 (1mm is thick), no molten drop.It uses
Char-2 will reach identical flame retardant effect, need more diethyl hypo-aluminum orthophosphates.It migrates and analyses in constant temperature and humidity condition test
Out, non-migratory as the result is shown.And the compound system of conventional diethyl hypo-aluminum orthophosphate and MPP is used, it can be found that there is migration precipitation.
5 char-1 of embodiment is applied in fiberglass reinforced PA 6,6
By 1 formula table ingredient of table, each component is uniformly mixed in a high speed mixer, uniformly mixed material is passed through double
Screw extruder extruding pelletization prepares standard batten, tests flame retardant property.It can reach UL 94V0 (1mm is thick), no molten drop.In perseverance
Constant temperature and humidity condition test migration precipitation, it is non-migratory as the result is shown.And use the compound ligand of conventional diethyl hypo-aluminum orthophosphate and MPP
System, it can be found that there is migration precipitation.
6 char-2 of embodiment is applied in fiberglass reinforced PA 6,6
By 1 formula table ingredient of table, each component is uniformly mixed in a high speed mixer, uniformly mixed material is passed through double
Screw extruder extruding pelletization prepares standard batten, tests flame retardant property.It can reach UL 94V0 (1mm is thick), no molten drop.It uses
Char-2 will reach identical flame retardant effect, need more diethyl hypo-aluminum orthophosphates.It migrates and analyses in constant temperature and humidity condition test
Out, non-migratory as the result is shown.And the compound system of conventional diethyl hypo-aluminum orthophosphate and MPP is used, it can be found that there is migration precipitation.
7 char-1 of embodiment is applied in TPU cable material
By 1 formula table ingredient of table, each component is uniformly mixed in a high speed mixer, uniformly mixed material is passed through double
Screw extruder extruding pelletization prepares cable on cable apparatus, tests flame retardant property.It can reach VW-1, no molten drop.In constant temperature
Constant humidity condition test migration precipitation, it is non-migratory as the result is shown.And conventional diethyl hypo-aluminum orthophosphate is used, it can be found that there is molten drop.
8 char-2 of embodiment is applied in TPU cable material
By 1 formula table ingredient of table, each component is uniformly mixed in a high speed mixer, uniformly mixed material is passed through double
Screw extruder extruding pelletization prepares cable on cable apparatus, tests flame retardant property.It can reach VW-1, no molten drop.It uses
Char-2 will reach identical flame retardant effect, need more diethyl hypo-aluminum orthophosphates.It migrates and analyses in constant temperature and humidity condition test
Out, non-migratory as the result is shown.And conventional diethyl hypo-aluminum orthophosphate is used, it can be found that there is molten drop.Table 1
Claims (7)
1. a kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen high molecular material it is fire-retardant in application,
It is characterized in that, the thermosetting polyester high molecular fire retardant carbon forming agent and diethyl hypo-aluminum orthophosphate composite usage of the phosphorous nitrogen
In the high molecular material；
Shown in the Crosslink structure such as following formula (I) of the thermosetting polyester high molecular fire retardant carbon forming agent of the phosphorous nitrogen:
The thermosetting polyester high molecular fire retardant carbon forming agent of the phosphorous nitrogen the preparation method comprises the following steps: with three hydroxyl second of equivalent
Base chlorinated isocyanurates and mixed dibasic acid are raw material, are prepared after polycondensation reaction；
The 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.
2. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 1 is in high molecular material
Application in fire-retardant, which is characterized in that the nitrogen content of the thermosetting polyester high molecular fire retardant carbon forming agent of the phosphorous nitrogen is
6.7%, phosphorus content 2.3% or nitrogen content are 7.2%, phosphorus content 1.3%.
3. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 1 is in high molecular material
Application in fire-retardant, which is characterized in that the preparation method of the thermosetting polyester high molecular fire retardant carbon forming agent of the phosphorous nitrogen
Specifically:
(1) trihydroxyethyl isocyanuric ester and mixed dibasic acid of equivalent, under phase transfer catalyst effect, 150~230
4~8h is reacted at DEG C, and esterification prepolymer is made；
In the 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 molar ratio be 1~5:1；
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is through condensation curing, then obtains after crushed described
Phosphorous nitrogen thermosetting polyester high molecular fire retardant carbon forming agent.
4. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 3 is in high molecular material
Application in fire-retardant, which is characterized in that in step (1), the phase transfer catalyst is selected from quaternary ammonium salt.
5. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 3 is in high molecular material
Application in fire-retardant, which is characterized in that in step (2), be evacuated to vacuum degree lower than 50KPa.
6. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 3 is in high molecular material
Application in fire-retardant, which is characterized in that in step (2), be crushed to average grain diameter D50 < 5 μm.
7. the thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen according to claim 1 is in high molecular material
Application in fire-retardant, which is characterized in that the high molecular material is selected from least one of polyester, nylon, polyurethane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711174890.8A CN107868237B (en) | 2017-11-22 | 2017-11-22 | A kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711174890.8A CN107868237B (en) | 2017-11-22 | 2017-11-22 | A kind of thermosetting polyester high molecular fire retardant carbon forming agent of phosphorous nitrogen and its preparation method and application |
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| Publication Number | Publication Date |
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| CN107868237A CN107868237A (en) | 2018-04-03 |
| CN107868237B true CN107868237B (en) | 2019-11-26 |
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| JP2005272672A (en) * | 2004-03-25 | 2005-10-06 | Toray Ind Inc | Flame-retardant master batch, thermosetting resin composition, prepreg and fiber-reinforced composite material |
| CN103387733A (en) * | 2012-05-08 | 2013-11-13 | 财团法人工业技术研究院 | Polymer for flame retardant material, polymer blend, and flame retardant material comprising same |
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| CN104710604B (en) * | 2015-03-13 | 2017-05-31 | 四川大学 | Branched crosslinking expansion melt-drip resistant inflaming retarding copolyesters based on triazine ring structure and preparation method thereof |
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| CN103387733A (en) * | 2012-05-08 | 2013-11-13 | 财团法人工业技术研究院 | Polymer for flame retardant material, polymer blend, and flame retardant material comprising same |
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