CN109251526A - Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using alkyl phosphite - Google Patents
Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using alkyl phosphite Download PDFInfo
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- C08K5/16—Nitrogen-containing compounds
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- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C08K5/51—Phosphorus bound to oxygen
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- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
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Abstract
The invention discloses a kind of phosphorus nitrogen halogen-free flame-retardant compositions that thermal stability is improved using alkyl phosphite, and by weight percentage, raw material composition includes: 40~90wt% of diethyl hypo-aluminum orthophosphate；20~50wt% of melamine polyphosphate；0.1~10wt% of zinc compound；0.1~8wt% of alkyl phosphite；Shown in the structural formula such as following formula (I) or following formula (II) of the alkyl phosphite, in formula, R is selected from the linear fatty alkyl that aromatic radical or carbon number are 1~6, and Me is selected from zinc, calcium or magnesium.Flame-retardant system disclosed by the invention have the characteristics that high fire-retardance, high heat stability, it is non-migratory, do not corrode equipment.It can be applied in fiberglass reinforced thermoplastic engineering plastic, obtain halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic, the component or product of field of electronics can be prepared.
Description
Technical field
The present invention relates to the technical fields of fire retardant, and in particular to a kind of to improve thermal stability using alkyl phosphite
Phosphorus nitrogen halogen-free flame-retardant composition and the phosphorus nitrogen halogen-free flame-retardant composition are in preparing halogen-free flame-retardant glass fiber reinforced materials
Using.
Background technique
Fiberglass reinforced thermoplastic engineering plastic is steady because having good rigidity and impact resistance, low warpage properties, high size
Qualitative, good appearance, easy processing molding and the performance characteristics such as recyclable and be widely used in field of electronics.?
The application in these fields proposes fire-retardant requirement to material, and thermoplastic engineering plastic is combustible material, compound with glass
Afterwards, due to the wick effect of glass, so that fiberglass reinforced engineering plastics are easier to burn.Therefore fiberglass reinforced engineering plastics are at this
A little fields are in application, need to solve the problems, such as fire-retardant, and the presence of wick effect makes its fire-retardant difficulty bigger.Here heat
Plastic engineering plastics refer mainly to polyester and nylon.
Currently, including the basic flame-retardant system of two classes for the fire-retardant of fiberglass reinforced thermoplastic engineering plastic: halogen system resistance
Combustion system and non-halogen fire-retardant system.Halogen system flame-retardant system is usually brominated flame-retardant collaboration antimony oxide, a large number of studies show that,
Fiberglass reinforced thermoplastic engineering plastic added with bromide fire retardant can produce thick smoke and the harmful substances such as hydrogen bromide in burning,
Human body can be caused to suffocate, secondly, the electrical insulating property of halogenated flame retardant is poor, in some fields using also restrained.Therefore, it is
Fiberglass reinforced thermoplastic engineering plastic is developed safe and environment-friendly, high performance halogen-free flame-retardant system and is had become a hot topic of research, in recent years
There is the novel halogen-free flame retardants or flame-retardant system applied to fiberglass reinforced thermoplastic engineering plastic.
It according to the literature, mainly include that two major classes are basic applied to the halogen-free flame retardants of fiberglass reinforced thermoplastic engineering plastic
System: one kind is red phosphorus；Another kind of is phosphorus nitrogen system flame-retardant system.For red phosphorus, although its good flame retardation effect, it faces two
Problem: first is that the color of red phosphorus, limits its scope of application, it is generally only to apply in black products；Second is that in process
In be easy to produce the violents in toxicity such as hydrogen phosphide, bring environmental protection and safety problem, therefore red phosphorus is not fiberglass reinforced engineering thermoplastic
The optimal selection of plastics.For phosphorus nitrogen system flame-retardant system, this is a kind of efficient flame-retardant system, has high flame retarding efficiency,
The some defects for avoiding red phosphorus are the hot spots studied at present.
With the most use, the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate, for example, diethyl hypophosphorous acid is answered at present
Aluminium compounds melamine Quadrafos (MPP) system, can be with due to the synergistic effect of phosphorus content with higher and phosphorus nitrogen
It realizes the highly effective flame-retardant to fiberglass reinforced thermoplastic engineering plastic, product color problem is also not present, while there is very high de-agglomeration
Temperature will not generate the hypertoxic gas such as hydrogen phosphide in the high temperature working processes of fiberglass reinforced thermoplastic engineering plastic.But for
Phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate, however it remains some disadvantages are mainly manifested in: first is that two kinds of components are in height
Certain reaction is had when warm to decompose, and generates a small amount of acidic materials, these acidic materials can be to the metal parts of process equipment
The problem of generating corrosion, need replacing component after a certain time, bringing the increase of cost and reduce production efficiency；Second is that nitrogenous
Compound MPP is there are certain precipitation, and material is in injection molding process, after being molded the product of certain modulus, the meeting on mold
There are deposit, the presence of these deposits will affect the appearance of product, this is to need to stop work to clear up mold, can also reduce production
Efficiency, while this precipitation can also cause fire retardant to migrate to product surface, cause fire retardant to be unevenly distributed and be lost, finally make
The fire-retardant failure of material is obtained, there are security risks；Third is that the presence of MPP has degradation to thermoplastic polymer, it will be apparent that existing
As if the melting means of material becomes larger, and easy to change, the especially impact property decline of material larger to the Effect on Mechanical Properties of material
It is more.
As a whole, it is applied to the flame-retardant system of fiberglass reinforced thermoplastic engineering plastic at present, there are color, has
Poisonous gas is easily precipitated, has the problems such as burn into degradation, discoloration and material mechanical performance decline, some are that fatal problem cannot then make
With some are then to lead to increased costs, efficiency reduction etc..Therefore, it is necessary to develop novel halogen-free flame-retardant system.
Summary of the invention
The present invention is directed to the existing phosphorus based on diethyl hypo-aluminum orthophosphate applied to fiberglass reinforced thermoplastic engineering plastic
The defect of nitrogen compounding flame retardant provides a kind of phosphorus nitrogen halogen-free flame retardants group that thermal stability is improved using alkyl phosphite
Close object, the flame-retardant system have the characteristics that high fire-retardance, high heat stability, it is non-migratory, do not corrode equipment.It can be applied to fiberglass reinforced heat
In plastic engineering plastics, obtain halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic, can prepare field of electronics component or
Product.
Specific technical solution is as follows:
A kind of phosphorus nitrogen halogen-free flame-retardant composition improving thermal stability using alkyl phosphite, by weight percentage
Meter, raw material composition include:
Shown in the structural formula such as following formula (I) or following formula (II) of the alkyl phosphite:
In formula, R is selected from the linear fatty alkyl that aromatic radical or carbon number are 1~6, and Me is selected from zinc, calcium or magnesium.
Present invention application diethyl hypo-aluminum orthophosphate is formed by cooperateing with MPP, zinc compound and alkyl phosphite
By the heat-staple phosphorus nitrogen halogen-free flameproof compound system of alkyl phosphite, solve that existing flame-retardant system is perishable, precipitation easy to migrate
The defects of with destruction to basis material.The novel flame-retardant system can be well adapted for fiberglass reinforced thermoplastic engineering plastic,
The bittern-free flame-proof material being had excellent performance.
It will elaborate below to the present invention.
The present invention is to solve existing for the existing halogen-free flame-retardant system applied in fiberglass reinforced thermoplastic engineering plastic
For the purpose of various defects, inventor is had made extensive and intensive studies.For the existing compounding based on diethyl hypo-aluminum orthophosphate
Flame-retardant system has investigated new flame-retardant system, as a result, it has been found that in diethyl the flame-proof glass fibre enhancement engineering plastics the problem of
In base hypo-aluminum orthophosphate and MPP collaboration system, a small amount of zinc compound and alkyl phosphite are added, these is can be well solved and asks
Topic.
The chemical structure of diethyl hypo-aluminum orthophosphate is shown below:
Diethyl hypo-aluminum orthophosphate is characterized in phosphorus content height, good flame resistance, temperature of initial decomposition with higher, water solubility
Low, resistance to migration is nonhygroscopic, and more application is in the engineering plastics such as nylon, PBT at present, especially engineering plastics of fiberglass reinforced
In.Diethyl hypo-aluminum orthophosphate is used alone, there is no being precipitated, but its flame retardant property is insufficient, therefore also need with it is nitrogenous
MPP compounding, can be only achieved fire-retardant ask.It applies at present in the flame-retardant system of glass fiber enhanced nylon substantially with diethyl hypophosphorous acid
Aluminium cooperates with MPP system.
But diethyl hypophosphorous acid with MPP when being used in compounding, although its flame retardant property is preferable, its decomposition temperature can drop
It is low, sour gas and ammonia can be released in process, process equipment metal parts can be generated and be corroded, and the migration of MPP
Characteristic influences appearance so that there are deposits for die surface, needs periodic cleaning mold, production efficiency is reduced, in addition, MPP pairs
Matrix polymer has degradation, will lead to melting means increase, mechanical properties decrease and easy to change.It will be apparent that needing to eliminate
Other negative effects in addition to fire-retardant of MPP.
Inventors discovered through research that a small amount of alkane is added in the flame-retardant system that diethyl hypo-aluminum orthophosphate and MPP are cooperateed with
Base phosphite and special zinc compound, can play the role of it is heat-staple, solve MPP pyrolytic and to matrix polymerize
The degradation of object, avoid burn into be precipitated, discoloration and the problems such as mechanical properties decrease, while the flame retardant property of the system does not have
It is affected.
Alkyl phosphite compound with the structural formula as shown in above formula (I) or above formula (II) has very high thermal decomposition
Temperature can act synergistically with diethyl hypo-aluminum orthophosphate, keep higher anti-flammability, while water-soluble low, resistance to migration.
Preferably, the R is selected from methyl or ethyl；The molecular weight of R group is smaller, and phosphorus content is higher, to fire-retardant more advantageous.
The alkyl phosphorous acid metal salt the preparation method comprises the following steps:
(1) alkyl phosphite hydrolyzes in acid condition, and alkyl phosphorous acid is made；
(2) alkyl phosphorous acid and metal hydroxides are in acid condition, in an aqueous medium, anti-in 150~180 DEG C of high pressures
It answers；
(3) suspension is filtered, washed and is dry, pulverize at 200~240 DEG C to certain partial size.
The alkyl phosphorous acid metal salt being prepared has very high thermal decomposition temperature, can cooperate with diethyl hypophosphites
Effect, while water-soluble low, resistance to migration, white in appearance are powdered.
The zinc compound includes zinc borate, zinc stannate, zinc oxide etc..These special zinc compounds have height
Decomposition temperature, water-soluble low, not migration precipitation.It can be cooperateed with phosphorus constructed of aluminium, improve anti-flammability, and there is suppression cigarette to make
With reduction smoke density.
After study, to obtain the P-N type compositional flame-retardant applied to fiberglass reinforced engineering plastics of high thermostabilization
System, the raw material of the phosphorus nitrogen halogen-free flame-retardant composition, which forms, includes:
Preferably, the average grain diameter D50 of the diethyl hypo-aluminum orthophosphate is 20~50 μm；
The average grain diameter D50 of the melamine polyphosphate is 20~50 μm；
The average grain diameter D50 of the zinc compound is 20~50 μm；
The average grain diameter D50 of the alkyl phosphite is 20~50 μm.
After above-mentioned specific proportions, specific composition raw material is blended, that is, the phosphorus with high high-temp stability is prepared
Nitrogen halogen-free flame-retardant composition.
The application of the invention also discloses the described phosphorus nitrogen halogen-free flame-retardant composition with high high-temp stability, it is specific public
A kind of halogen-free flame-retardant glass fiber reinforced materials, including substrate, fiberglass reinforced body, fire retardant and other processing aids are opened；
The fire retardant includes the phosphorus nitrogen halogen-free flame-retardant composition with high high-temp stability；
The phosphorus nitrogen halogen-free flame-retardant composition of the high high-temp stability, is to confer to the function of high molecular material flame retardant property
Property auxiliary agent, to reach relevant standard requirements, account for entire material system weight percent be 10~30%.
Preferably, the halogen-free flame-retardant glass fiber reinforced materials, by weight percentage, raw material composition includes:
The substrate is selected from nylon or polyester；
Preferably, the substrate is selected from nylon or polyester.Nylon base includes fatty polyamide, semi-aromatic polyamides
Amine, such as nylon 6, nylon66 fiber, nylon MXD 6, nylon 12 and the high-temperature nylons such as nylon 46,4T, 6T, 9T, 10T, 12T；Polyester
Substrate includes PBT and PET.
Further preferably, when the substrate is nylon, the phosphorus nitrogen halogen-free flame-retardant composition, by weight percentage
Meter, raw material composition include:
The alkyl phosphite is selected from methylisothiouronium methylphosphite aluminium；
In terms of raw material gross weight, the additive amount of the fire retardant is 15~25%.
When the substrate is polyester, the phosphorus nitrogen halogen-free flame-retardant composition, by weight percentage, raw material composition packet
It includes:
The alkyl phosphite is selected from methylisothiouronium methylphosphite aluminium；
In terms of raw material gross weight, the additive amount of the fire retardant is 15~20%.
Using the above-mentioned halogen-free flameproof for preferably constituting and being prepared with the phosphorus nitrogen halogen-free flame-retardant composition of content as fire retardant
Glass fiber enhanced nylon or polyester, in the case where keeping excellent flame retardant properties, mechanical properties, polymeric matrix material does not occur
Apparent degradation.
Halogen-free flame-retardant glass fiber reinforced materials are prepared, flame-retardant system is also needed to be dispersed in material.Pass through band plus glass
Each component is completed melt blending in an extruder, and squeezes out and make by the double screw extruder of fine mouth and fire retardant powder feed inlet
Grain.
Compared with prior art, the present invention has the advantage that
The invention discloses it is a kind of using alkyl phosphite improve thermal stability phosphorus nitrogen halogen-free flame-retardant composition,
In diethyl hypo-aluminum orthophosphate and the flame-retardant system of MPP collaboration, the alkyl phosphite and zinc compound of specific proportions is added, then
After blended, the phosphorus nitrogen halogen-free flame-retardant composition with high thermal stability is prepared, which overcome existing flame-retardant systems
Defect may be used as the halogen-free flame-retardant system of fiberglass reinforced engineering plastics, can prepare and novel be applied to electric and electronic field
Halogen-free flame-retardant glass fiber enhance proprietary material.
Specific embodiment
Raw material:
(1) diethyl hypo-aluminum orthophosphate, 8003, Jiangsu Li Side new material Co., Ltd
(2) MPP, Melapur 200 is purchased from BASF
(3) zinc borate, Firebrake 500 are purchased from Borax
(4) nylon66 fiber, EPR27, table mountain mind horse
(5) glass, ECS301UW, Chongqing Polycomp International Co., Ltd
(6) antioxidant, 1098, BASF
(7) silicone, middle indigo plant morning twilight
(8) PBT, 211M, Changchun chemistry
(9) methylisothiouronium methylphosphite aluminium, Jiangsu Li Side new material Co., Ltd
Embodiment 1
Compounding flame retardant is applied in fiberglass reinforced engineering plastics, follows these steps and test method investigates fire retardant
Performance.
1, the mixture of halogen-free flame-retardant system
The compounding flame retardant each component and other auxiliary agents for being added in machine and weighing up in advance according to the ratio are stirred in height, starts high-speed stirring
It mixes, stirs 10min, complete the mixture of halogen-free flame-retardant system, discharge.
2, the extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature, after temperature stablizes 20min, it is added from hopper poly-
Object matrix is closed, by adding glass fiber opening to be added, fire retardant powder is fed glass by powder charging aperture, start host and feeder,
Complete the extruding pelletization of material.The material for having made grain is sent into feed bin by blast system, and dries.
3, the application and test of material
The material dried is molded by the standard sample of various testing standard defineds in injection molding machine, and carries out correlation
The test of material property.It is primarily upon following performance indicator:
A, fire-retardant
It is tested according to UL94V0 testing standard.
B, resistance to migration experiment
The plastic sample that will be prepared, is put into climatic chamber, is arranged 85 DEG C of temperature, relative humidity 85%, range estimation is seen
Examine the state of the specimen surface after 168 hours.
C, corrosion experiment
One metal block is set on die head, and high-temperature material passes through 25Kg material granulation in die head and metal block contact, test
The waste of metal afterwards, loss is higher, and corrosion resistance is poorer.Think that corrosion is acceptable if etching extent < 0.1%.
D, Mechanics Performance Testing
Impact strength is tested by ASTM D256, impact property is lower, and polymeric matrix degradation is more obvious.
E, melt index is tested
Test condition: 280 DEG C/2.16Kg, by melting means size come the palliating degradation degree of comparative polymers.
Each material and proportion are shown in Table 1 in embodiment 1, and obtained testing of materials the results are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, and in addition to the amount of adjustment methylisothiouronium methylphosphite aluminium, other materials and proportion are shown in Table 1, institute
Obtained material the results are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, and in addition to the amount of adjustment methylisothiouronium methylphosphite aluminium, other materials and proportion are shown in Table 1, institute
Obtained material the results are shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, and in addition to the amount of adjustment methylisothiouronium methylphosphite aluminium, other materials and proportion are shown in Table 1, institute
Obtained material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, other than without using methylisothiouronium methylphosphite aluminium.Other materials and proportion are shown in Table 1, institute
Obtained material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than without using MPP and zinc borate.Other materials and proportion are shown in Table 1, institute
Obtained material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than without using MPP.Other materials and proportion are shown in Table 1, obtained material
Material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, other than only using diethyl hypo-aluminum orthophosphate.Other materials and proportion are shown in Table 1,
Obtained material the results are shown in Table 1.
Comparative example 5
Implementation process is same as Example 1, in addition to methylisothiouronium methylphosphite aluminium account for fire retardant weight ratio be 10% other than.Other objects
Material and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Table 1
Embodiment 5
Implementation process is same as Example 1, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Embodiment 6
Implementation process is same as Example 2, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Embodiment 7
Implementation process is same as Example 3, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Embodiment 8
Implementation process is same as Example 4, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Comparative example 6
Implementation process is identical as comparative example 1, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Comparative example 7
Implementation process is identical as comparative example 2, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Comparative example 8
Implementation process is identical as comparative example 3, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Comparative example 9
Implementation process is identical as comparative example 4, and nylon66 fiber is used instead PBT.Other materials and proportion are shown in Table 2, obtained material
Material the results are shown in Table 2.
Comparative example 10
Implementation process is same as Example 5, is 11.8% in addition to the content of methylisothiouronium methylphosphite aluminium accounts for fire retardant weight ratio
Outside.Other materials and proportion are shown in Table 2, and obtained material the results are shown in Table 2.
Table 2
。
Claims (9)
1. a kind of phosphorus nitrogen halogen-free flame-retardant composition for improving thermal stability using alkyl phosphite, which is characterized in that by weight
Percentages are measured, raw material composition includes:
Shown in the structural formula such as following formula (I) or following formula (II) of the alkyl phosphite:
In formula, R is selected from the linear fatty alkyl that aromatic radical or carbon number are 1~6, and Me is selected from zinc, calcium or magnesium.
2. the phosphorus nitrogen halogen-free flame-retardant composition according to claim 1 that thermal stability is improved using alkyl phosphite,
It is characterized in that, the R is selected from methyl or ethyl.
3. the phosphorus nitrogen halogen-free flame-retardant composition according to claim 1 that thermal stability is improved using alkyl phosphite,
It is characterized in that, the zinc compound is selected from least one of zinc borate, zinc stannate, zinc oxide.
4. the phosphorus nitrogen halogen-free flame-retardant composition according to claim 1 that thermal stability is improved using alkyl phosphite,
It is characterized by:
The average grain diameter D50 of the diethyl hypo-aluminum orthophosphate is 20~50 μm；
The average grain diameter D50 of the melamine polyphosphate is 20~50 μm；
The average grain diameter D50 of the zinc compound is 20~50 μm；
The average grain diameter D50 of the alkyl phosphite is 20~50 μm.
5. a kind of halogen-free flame-retardant glass fiber reinforced materials, which is characterized in that raw material composition includes substrate, reinforcement, fire retardant and adds
Work auxiliary agent, which is characterized in that the fire retardant includes phosphorus nitrogen halogen-free flame retardants combination according to any one of claims 1 to 4
Object；
In terms of raw material gross weight, the additive amount of the fire retardant is 10~30%.
6. halogen-free flame-retardant glass fiber reinforced materials according to claim 5, which is characterized in that by weight percentage, raw material
Composition includes:
7. halogen-free flame-retardant glass fiber reinforced materials according to claim 5, which is characterized in that the substrate is selected from nylon or poly-
Ester.
8. halogen-free flame-retardant glass fiber reinforced materials according to claim 5 or 6, which is characterized in that the substrate is nylon, institute
Fire retardant is stated, by weight percentage, raw material composition includes:
The alkyl phosphite is selected from methylisothiouronium methylphosphite aluminium；
In terms of raw material gross weight, the additive amount of the fire retardant is 15~25%.
9. halogen-free flame-retardant glass fiber reinforced materials according to claim 5 or 6, which is characterized in that the substrate is polyester, institute
Fire retardant is stated, by weight percentage, raw material composition includes:
The alkyl phosphite is selected from methylisothiouronium methylphosphite aluminium；
In terms of raw material gross weight, the additive amount of the fire retardant is 15~20%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810902922.XA CN109251526A (en) | 2018-08-09 | 2018-08-09 | Phosphorus nitrogen halogen-free flame-retardant composition and its application of thermal stability are improved using alkyl phosphite |
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Application publication date: 20190122 |