CN107828055B - A kind of phosphorous nitrogen and tool at charcoal function cross-linked polymer fire retardant and its preparation method and application - Google Patents
A kind of phosphorous nitrogen and tool at charcoal function cross-linked polymer fire retardant and its preparation method and application Download PDFInfo
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- CN107828055B CN107828055B CN201711175851.XA CN201711175851A CN107828055B CN 107828055 B CN107828055 B CN 107828055B CN 201711175851 A CN201711175851 A CN 201711175851A CN 107828055 B CN107828055 B CN 107828055B
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
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- 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 a kind of phosphorous nitrogen and tools into the cross-linked polymer fire retardant of charcoal function, shown in Crosslink structure such as following formula (I)；The present invention develops a kind of phosphorous nitrogen and tool into the cross-linked polymer fire retardant of charcoal function.The cross-linked polymer fire retardant has the characteristics that good flame resistance, molecular weight height, resistance to migration, nonhygroscopic, high temperature resistant, the mechanical property for not influencing basis material.It can be used alone, can also be cooperateed with phosphorus-nitrogen containing flame retardant, is applied in the materials such as nylon, polyester, polyurethane.
Description
Technical field
The present invention relates to the technical fields of high molecular weight flame retardant, and in particular to a kind of phosphorous nitrogen and tool are at charcoal function
Cross-linked polymer fire retardant 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 defect of existing halogen-free flame retardants, develops a kind of phosphorous nitrogen and tool into the crosslinking of charcoal function
High molecular weight flame retardant.The cross-linked polymer fire retardant has good flame resistance, molecular weight high, resistance to migration, nonhygroscopic, high temperature resistant, no
The features such as influencing the mechanical property of basis material.Can be used alone, can also be cooperateed with phosphorus-nitrogen containing flame retardant, be applied to nylon,
In the materials such as polyester, polyurethane.
Specific technical solution is as follows:
A kind of phosphorous nitrogen and tool at charcoal function cross-linked polymer fire retardant, shown in Crosslink structure such as following formula (I):
The phosphorous nitrogen and tool at charcoal function cross-linked polymer fire retardant the preparation method comprises the following steps:
With the trihydroxyethyl isocyanuric ester of equivalent and [(the own ring-of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha
6- yl) methyl] succinic acid (DDP) be raw material, be prepared after polycondensation reaction.
The preparation of the cross-linked polymer fire retardant 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 is and to develop novel fire retardant for the purpose of the various defects for solving existing halogen-free flame-retardant system, is
The invention people has made extensive and intensive studies.Existing carbon forming agent is all polyol, and with small-molecule substance
Based on, although these substances have as carbon forming agent preferably at charcoal effect, but face water-soluble strong and low 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 solubility of substance simultaneously
Decomposition temperature is improved, naturally expects that hydroxy esterification is reduced the amount of hydroxyl with some carboxylated compounds, and to improve heat point
Temperature is solved, then needs to improve molecular weight, if it is thermoplastic high-molecular weight compounds are formed, then can be present in base in application
The consistency problem of body 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 that trihydroxyethyl isocyanuric ester and DPP are condensed, then
The thermosetting polyester condensation product with cross-linked structure can be obtained, not only contains phosphorus nitrogen in molecular structure, but also have into charcoal effect, water
Dissolubility is low, and thermal decomposition temperature is high.
The phosphorous nitrogen and tool at the cross-linked polymer fire retardant of charcoal function preparation method, specifically:
(1) trihydroxyethyl isocyanuric ester of equivalent and [(6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha oneself
Ring -6- base) methyl] succinic acid, under phase transfer catalyst effect, esterification pre-polymerization is made in 4~8h of reaction at 150~230 DEG C
Object；
(2) it vacuumizes and is warming up to 260~280 DEG C, the esterification prepolymer is obtained through condensation curing, then after crushed
The phosphorous nitrogen and tool at charcoal function cross-linked polymer fire retardant.
There are three hydroxyls for trihydroxyethyl isocyanuric ester tool, belong to trifunctional compound, DDP is binary acid, belongs to two
Functional compounds can form the thermosetting polyester condensation product with cross-linked structure under equivalent.2 steppings of condensation reaction point
Row first prepares polyester prepolyer at a lower temperature, then carries out condensation curing at high temperature, obtains the cross-linked polymer resistance
Fire agent.
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 obtained after condensation curing, in order to be added in basis material, it is also necessary to carry out powder
Broken processing controls average grain diameter D50 < 5 μm of fire retardant using mechanical crushing equipment.
Cross-linked polymer fire retardant prepared by the above method not only has good at charcoal effect, but also 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 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 cross-linked polymer fire retardant can also be compounded with phosphorus-nitrogen containing flame retardant, such as organic hypophosphites, altogether
With applying in the materials such as nylon, polyester, polyurethane, good flame retardant effect is realized.
It further preferably, is fire-retardant with the cross-linked polymer fire retardant and the alternative phosphorus-nitrogen containing flame retardant being added
The flame retarded polymeric material of system preparation, 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 weight flame retardant, nitrogen content 5.4%, phosphorus content 6.0%.Through into one
The application test of step finds that the high molecular weight flame retardant individually or after compounding with phosphorus-nitrogen containing flame retardant is applied to above-mentioned several bases
In material, splendid flame retardant effect can be obtained, the flame-retardant standard of UL94V0 (1.0mm) and VW-1 can be met respectively.
Compared with prior art, the present invention has the advantage that
The present invention provides a kind of phosphorous nitrogens and tool into the cross-linked polymer fire retardant of charcoal function, and flame retardant property is excellent
It is different；Hydroxyl, water-soluble very little are not present in molecular structure；There is cross-linked structure, decomposition temperature is high, and does not melt not in molecular structure
Molten, there is no the consistency problems with basis material when application, do not influence the mechanical property of material.It can be used alone, it can also be with
Phosphorus-nitrogen containing flame retardant collaboration, is 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, 3.5 grams of tetrabutylammonium bromide and 1041g (3 moles) DDP, strength is then added
Mixture is stirred, heating is raised to 220 DEG C from 150 DEG C within 6 hours, the water in reaction process is discharged, and condense metering, 220
DEG C heat preservation 1 hour, 150 DEG C are cooled to, melt is discharged to a metal tray, it is solid that a kind of faint yellow embrittlement is obtained after melt is cooling
Body object, for melting range from 100 to 120 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 40KPa, is heated to 270
DEG C, it is kept for 2 hours, completes solidification, cooling discharge.Crushing material is stand-by to average grain diameter D50 < 5 micron.
Through analyzing: cross-linked polymer fire retardant manufactured in the present embodiment, phosphorus content are as follows: 5.7%, nitrogen content are as follows: 5.2%
(phosphorus, nitrogen content are actual measured value, the slightly below calculated value in specification), solubility < 0.1%, 1% is weightless to decompose
330 DEG C of temperature.
Unless otherwise instructed, fire retardant as described below is the cross-linked polymer fire retardant that the present embodiment is prepared.
2 fire retardant 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 94 V2 of UL (1mm is thick).In constant temperature and humidity
Condition test migration precipitation, it is non-migratory as the result is shown.
Embodiment 3 and diethyl hypo-aluminum orthophosphate Application of composite are 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 94 V0 of UL (1mm is thick).With diethyl
Aluminum phosphate compounding, under less additive amount, can achieve better flame retardant rating, there is preferable concertedness.In constant temperature and humidity
Condition test migration precipitation, it is non-migratory as the result is shown.
Embodiment 5 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 94 V2 of UL (1mm is thick).In constant temperature and humidity
Condition test migration precipitation, it is non-migratory as the result is shown.
Embodiment 6 and diethyl hypo-aluminum orthophosphate Application of composite are 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 94 V0 of UL (1mm is thick).With diethyl
Aluminum phosphate compounding, under less additive amount, can achieve better flame retardant rating, there is preferable concertedness.In constant temperature and humidity
Condition test migration precipitation, it is non-migratory as the result is shown.
Embodiment 7 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.
Embodiment 8 and diethyl hypo-aluminum orthophosphate are 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.With diethyl
Base hypo-aluminum orthophosphate compounding, under less additive amount, can achieve identical flame retardant effect, shows preferable concertedness.In perseverance
Constant temperature and humidity condition test migration precipitation, it is non-migratory as the result is shown.
Table 1
Claims (9)
1. a kind of phosphorous nitrogen and tool at charcoal function cross-linked polymer fire retardant, which is characterized in that Crosslink structure is as follows
Shown in formula (I):
The phosphorous nitrogen and tool do not melt insoluble at the cross-linked polymer fire retardant of charcoal function, and preparation method is with equivalent
Trihydroxyethyl isocyanuric ester and [(the own ring -6- base of 6- oxo -6H- dibenzo [c, e] [1,2] oxygen phospha) methyl] succinic acid
For raw material, it is prepared after polycondensation reaction.
2. phosphorous nitrogen according to claim 1 and tool at charcoal function cross-linked polymer fire retardant, which is characterized in that
Nitrogen content is 5.2%, phosphorus content 5.7%.
3. phosphorous nitrogen according to claim 1 and tool at charcoal function cross-linked polymer fire retardant, which is characterized in that
The preparation method specifically:
(1) trihydroxyethyl isocyanuric ester of equivalent and [(6- oxo -6H- dibenzo [c, e] [1,2] own ring -6- of oxygen phospha
Base) methyl] succinic acid, under phase transfer catalyst effect, esterification prepolymer is made in 4~8h of reaction at 150~230 DEG C；
(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 and tool at charcoal function cross-linked polymer fire retardant.
4. phosphorous nitrogen according to claim 3 and tool at charcoal function cross-linked polymer fire retardant, which is characterized in that
In step (1), the phase transfer catalyst is selected from quaternary ammonium salt.
5. phosphorous nitrogen according to claim 3 and tool at charcoal function cross-linked polymer fire retardant, which is characterized in that
In step (2), vacuum degree is evacuated to lower than 50KPa.
6. phosphorous nitrogen according to claim 3 and tool at charcoal function cross-linked polymer fire retardant, which is characterized in that
In step (2), it is crushed to average grain diameter D50 < 5 μm.
7. a kind of phosphorous nitrogen according to claim 1 or 2 and tool are at the cross-linked polymer fire retardant of charcoal function in height
Molecular material it is fire-retardant in application.
8. application according to claim 7, which is characterized in that the high molecular material is selected from polyester, nylon, polyurethane
At least one of.
9. application according to claim 8, which is characterized in that the phosphorous nitrogen and tool is high at the crosslinking of charcoal function
Molecule fire retardant and diethyl hypo-aluminum orthophosphate composite usage are in the high molecular material.
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| CN113234324B (en) * | 2021-06-03 | 2022-06-10 | 山东弗克新材料有限公司 | Flame-retardant ceramizable organic silicon material and preparation method thereof |
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| CN101743266A (en) * | 2008-03-06 | 2010-06-16 | 席尔及赛拉赫股份公司 | Halogen-free flame retardant |
| CN103319748A (en) * | 2013-06-03 | 2013-09-25 | 公安部四川消防研究所 | Phosphorus-nitrogen compound fire retardant and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101743266A (en) * | 2008-03-06 | 2010-06-16 | 席尔及赛拉赫股份公司 | Halogen-free flame retardant |
| CN103319748A (en) * | 2013-06-03 | 2013-09-25 | 公安部四川消防研究所 | Phosphorus-nitrogen compound fire retardant and its preparation method |
Non-Patent Citations (1)
| Title |
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| Novel star-shaped and hyperbranched phosphorus-containing flame retardants in epoxy resins;Lin Zang等;《Polymers for Advanced Technologies》;20110526;第22卷(第7期);第1182-1191页 * |
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