CN108794804B - The halogen-free flame-retardant system and its application of dialkyl dithio hypophosphites and nitrogenous compound collaboration - Google Patents
The halogen-free flame-retardant system and its application of dialkyl dithio hypophosphites and nitrogenous compound collaboration Download PDFInfo
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Abstract
The invention discloses the halogen-free flame-retardant systems that a kind of dialkyl dithio hypophosphites and nitrogenous compound cooperate with, by weight percentage, raw material composition includes: dialkyl dithio hypophosphites 50~90%, nitrogenous compound 9~40% and zinc compound 1~10%；The dialkyl dithio hypophosphites, shown in structural formula such as formula (I), in formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, carbon number is 1~6；M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m is 1~4.The halogen-free flame-retardant system have the characteristics that high fire-retardance, it is non-migratory, do not corrode equipment, be well adapted for fiberglass reinforced thermoplastic engineering plastic system, obtain excellent combination property halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic.
Description
Technical field
The present invention relates to the technical fields of fire retardant, and in particular to a kind of dialkyl dithio hypophosphites and nitrogenous chemical combination
The halogen-free flame-retardant system and its preparing the application in halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic that object cooperates with.
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.
Currently, with the most use, the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate is answered, for example, diethyl time phosphorus
Sour aluminium compounding melamine Quadrafos (MPP) system can due to the synergistic effect of phosphorus content with higher and phosphorus nitrogen
To realize the highly effective flame-retardant to fiberglass reinforced thermoplastic engineering plastic, product color problem is also not present, while there is very high score
Temperature is solved, in the high temperature working processes of fiberglass reinforced thermoplastic engineering plastic, the hypertoxic gas such as hydrogen phosphide will not be generated.But it is right
In the phosphorus nitrogen compound system based on diethyl hypo-aluminum orthophosphate, however it remains some disadvantages are mainly manifested in:
It is decomposed first is that two kinds of components have certain reaction at high temperature, generates a small amount of acidic materials, these acids
Matter can generate corrosion to the metal parts of process equipment, need replacing component after a certain time, bring the increase and drop of cost
The problem of low production efficiency；Second is that nitrogenous compound MPP, there are certain precipitation, material is in injection molding process, injection molding one
After the product of cover half number, there can be deposit on mold, the presence of these deposits will affect the appearance of product, this is desirable
It stops work and clears up mold, can also reduce production efficiency, while this precipitation can also cause fire retardant to migrate to product surface, cause to hinder
Combustion agent is unevenly distributed and is lost, and finally makes the fire-retardant failure of material, there are security risks；Third is that additive amount is big, to material
Effect on Mechanical Properties is larger.
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 corrosion and reduction material mechanical performance, some are that fatal problem cannot then use, some are then
It is 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 invention discloses a kind of halogen-free flame-retardant system applied to fiberglass reinforced thermoplastic engineering plastic, the halogen-free flameproofs
System have many advantages, such as high fire-retardance, it is non-migratory, do not corrode equipment, the halogen-free flame-retardant glass fiber for preparing based on this enhancing thermoplasticity
Engineering plastics can prepare the component or product of field of electronics.
Specific technical solution is as follows:
A kind of halogen-free flame-retardant system of dialkyl dithio hypophosphites and nitrogenous compound collaboration, by weight percentage
Meter, raw material composition include:
Dialkyl dithio hypophosphites 50~90%；
Nitrogenous compound 9~40%；
Zinc compound 1~10%；
The dialkyl dithio hypophosphites, shown in structural formula such as following formula (I):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1
~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H or NH4, m be 1~
4。
The present invention uses novel dialkyl dithio hypophosphite fire retardant, by being cooperateed with nitrogenous compound, shape
Compounding flame retardant is cooperateed at the multielement based on phosphorus sulphur nitrogen, solves the existing compounding flame retardant based on diethyl hypo-aluminum orthophosphate
The defects of perishable existing for the flame-proof glass fibre enhancing thermoplastic engineering plastic, precipitation easy to migrate.The novel flame-retardant system can be with
It is well adapted for fiberglass reinforced thermoplastic engineering plastic material, the bittern-free flame-proof material being had excellent performance.
Preferably, in the general formula of the dialkyl dithio hypophosphites, R1、R2Independently selected from methyl, ethyl, positive third
Base, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohesyl；M is selected from Mg, Ca, Al, Sn, Ti or Zn.
Further preferably, the dialkyl dithio hypophosphites is selected from diethyl-dithio hypo-aluminum orthophosphate or diisobutyl
Dithiophosphlic acid aluminium.
The invention also discloses a kind of preparation processes of the dialkyl dithio hypophosphites, to prepare dialkyl disulfides
For generation aluminum phosphate, specifically:
(1) dialkyl dithio sodium hypophosphite solution is reacted in acid condition with aluminum sulfate solution, obtains dialkyl group
The suspension of dithiophosphlic acid aluminum precipitation object；
(2) suspension will be filtered, washed and dry, pulverize at 120 DEG C to certain partial size, obtain dialkyl disulfides
For hypo-aluminum orthophosphate combustion inhibitor.
It wherein, can be by commercially available acquisition, or by the following method as the dialkyl dithio sodium hypophosphite of raw material
Preparation:
(a) linear alkene and hydrogen phosphide exist in initiator and free radical can occur under certain temperature and pressure
Addition reaction generates dialkyl group hydrogen phosphide；
(b) dialkyl group hydrogen phosphide and sulfur reaction are generated into dialkyl dithio hypophosphorous acid；
(c) dialkyl dithio hypophosphorous acid is reacted with sodium hydroxide and generates dialkyl dithio hypophosphorous acid soluble easily in water
Sodium salt.
The characteristics of dialkyl dithio hypophosphites is phosphorus content height, and there are also the collaboration of element sulphur, good flame resistance, tools
There is a higher temperature of initial decomposition, water-soluble extremely low, resistance to migration is nonhygroscopic, is that a kind of novel can be applied to nylon, polyester etc.
In engineering plastics, especially in the engineering plastics of fiberglass reinforced.Dialkyl dithio hypophosphites is used alone, in certain applications
Field, flame retardant property still are apparent not enough, therefore also need and component is cooperateed with to compound, and can be only achieved fire-retardant requirement.
Inventors discovered through research that being added suitable nitrogenous in the presence of dialkyl dithio hypophosphites
Compound, forms the halogen-free flame-retardant system based on phosphorus sulphur N structure, which has preferable flame-retarding characteristic.
The nitrogenous compound is usually melamine derivative, contains nitrogen in molecular structure, in halogen-free flameproof body
It is often gas source in system, thermal decomposition temperature with higher can be used alone as fire retardant, but its flame retarding efficiency is low, and additive amount is big,
It also needs to cooperate with other fire retardants.Studied through inventor, discovery introduce in the above system a small amount of high temperature resistant be not precipitated it is nitrogenous
Compound, not only can solve corrosion-resistant, and can provide anti-flammability, there is not yet the problem of precipitation.Preferably, the melamine
Amine derivative is selected from melamine cyanurate (MCA), melamine polyphosphate (MPP), melamine metal phosphinates
At least one of.The melamine metal phosphinates are selected from melamine calcium phosphite and/or melamine aluminium is sub-
Phosphate.
Moreover, it has been found that introducing the zinc compound that a small amount of high temperature resistant is not precipitated in the above system, can be further improved
Corrosion-resistant and thermal stability, and anti-flammability is provided, there is not yet the problem of precipitation.Preferably, the zinc compound is selected from boron
Both sour zinc and/or zinc stannate have high decomposition temperature, water-soluble low, not migration precipitation.It can be assisted with phosphorus aluminium sulphur structure
Together, anti-flammability is improved, and there is suppression cigarette effect, reduces smoke density.
To further increase cooperative flame retardant effect, in the compound system, dialkyl dithio hypophosphites be it is powdered,
Average grain diameter D50 is 20~50 μm；Nitrogenous compound be it is powdered, average grain diameter D50 be 20~50 μm；Zinc compound is powder
Last shape, average grain diameter D50 are 20~50 μm.
The invention also discloses the halogen-free flame-retardant glass fiber enhancing engineering thermoplastic modelings that the halogen-free flame-retardant system preparation is added
Material, by weight percentage, raw material composition includes:
The substrate is selected from polyamide or polyester.
The polyamide includes fatty polyamide, semiaromatic polyamide composition, such as nylon 6, nylon66 fiber, nylon MXD 6, Buddhist nun
Dragon 12 and the high-temperature nylons such as nylon 46,4T, 6T, 9T, 10T, 12T.
The polyester includes PBT or PET.
When the substrate is selected from polyamide, preferably raw material composition includes:
Further preferably, the raw material composition of the halogen-free flame-retardant system includes:
Dialkyl dithio hypophosphites 56~80%；
Nitrogenous compound 13~40%；
Zinc compound 3~7%.
Further preferably, the substrate is selected from PA66, and the nitrogenous compound is selected from melamine polyphosphate, zinc compound
Selected from zinc borate, dialkyl dithio hypophosphites is selected from diisobutyl dithiophosphlic acid aluminium.
When the substrate is selected from polyester, raw material composition includes:
Further preferably, the raw material composition of the halogen-free flame-retardant system includes:
Dialkyl dithio hypophosphites 50~80%；
Nitrogenous compound 15~45%；
Zinc compound 3~8%.
Further preferably, the substrate is selected from PBT, and the nitrogenous compound is selected from melamine polyphosphate, zinc compound
Selected from zinc borate, dialkyl dithio hypophosphites is selected from diisobutyl dithiophosphlic acid aluminium.
Thermoplastic engineering plastic is enhanced by the halogen-free flame-retardant glass fiber that above-mentioned formula is prepared, can reach UL94V0
(1.6mm) flame retardant rating, and have the advantages that not corrode equipment, without being precipitated.
The invention also discloses the preparation method of halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic, each raw material is blended
Afterwards, flame-retardant system is dispersed in substrate, then passes through band plus the twin-screw extrusion of glass fiber opening and fire retardant powder feed inlet
Machine, each component complete melt blending, and extruding pelletization in an extruder.
Compared with prior art, the present invention has the advantage that
The invention discloses the phosphorus sulphur nitrogen multielement being made of dialkyl dithio hypophosphites and nitrogenous compound collaborations
The halogen-free flame-retardant system of compounding, have many advantages, such as high fire-retardance, it is non-migratory, do not corrode equipment, may be used as fiberglass reinforced thermoplasticity
The halogen-free flame-retardant system of engineering plastics, can prepare the novel halogen-free flame-retardant glass fiber applied to electric and electronic field enhances thermoplastic
Property engineering plastics proprietary material.
Specific embodiment
Raw material:
(1) preparation of diisobutyl dithiophosphlic acid aluminium
The sulphur of diisobutyl the dithiophosphlic acid sodium water solution 1392g and concentration 30wt% of compound concentration 20wt% respectively
Desalted water 1500g is added into reactor, and the sulfuric acid solution 75g of concentration 25wt% is added by sour aluminum solutions 228g, is warming up to 80
DEG C, start to synchronize dropwise addition diisobutyl dithiophosphlic acid sodium water solution and aluminum sulfate solution in proportion into reaction kettle, obtain
Diisobutyl dithiophosphlic acid aluminum precipitation object, is added dropwise to complete for 2 hours, keeps the temperature 1 hour, is then filtered, washed, dries, obtain
Diisobutyl dithiophosphlic acid aluminium fire retardant 254g (yield 97%).
After tested, 350 DEG C of the initial decomposition temperature of product, solubility is 0.02% in water；
(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) diethyl hypo-aluminum orthophosphate, 8003, Jiangsu Li Side new material Co., Ltd；
(7) antioxidant, 1098, BASF；
(8) silicone, middle Lan Chenguang；
(9) PBT, 211M, Changchun chemistry.
Embodiment 1
Halogen-free flameproof compound system is applied in glass fiber enhanced nylon, follows these steps and test method investigates fire retardant
Performance.
(1) 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 powder, discharge.
(2) extruding pelletization of material
Buddhist nun is added after temperature stablizes 20min in predetermined temperature in each area's temperature setting of double screw extruder from hopper
Dragon, by adding glass fiber opening to be added, the powder of step (1) mixture is fed glass by powder charging aperture, starts 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) 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:
Fire-retardant experiment
It is tested according to UL94V0 testing standard.
Resistance to migration experiment
The halogen-free flame-retardant glass fiber prepared is enhanced into nylon sample, is put into climatic chamber, is arranged 85 DEG C of temperature, relatively
Humidity 85%, the state of specimen surface of the visual observations after 168 hours.
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%.
Mechanics Performance Testing
Tensile strength is tested by ASTM D638 and presses ASTM D256 impact strength.
Each material and proportion are shown in Table 1 in the present embodiment, and obtained testing of materials the results are shown in Table 1.
Embodiment 2
Implementation process is same as Example 1, keeps fire retardant systems total amount constant, adjusts diisobutyl dithiophosphlic acid
The ratio of aluminium and MPP.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 3
Implementation process is same as Example 1, keeps fire retardant systems total amount constant, adjusts diisobutyl dithiophosphlic acid
The ratio of aluminium and MPP.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Embodiment 4
Implementation process is same as Example 1, keeps flame-retardant system total amount constant, diisobutyl dithiophosphlic acid aluminium accounting
It remains unchanged, adjusts the ratio of other two components.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 1
Implementation process is same as Example 1, in addition to using diethyl hypo-aluminum orthophosphate to replace diisobutyl dithiophosphlic acid
Outside aluminium.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 2
Implementation process is same as Example 1, other than without using zinc borate.Other materials and proportion are shown in Table 1, obtained
Material the results are shown in Table 1.
Comparative example 3
Implementation process is same as Example 1, other than only using diisobutyl dithiophosphlic acid aluminium and zinc borate, does not make
Use MPP.Other materials and proportion are shown in Table 1, and obtained material the results are shown in Table 1.
Comparative example 4
Implementation process is same as Example 1, other than only using diisobutyl dithiophosphlic acid aluminium.Other materials and match
Than being 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 flame-retardant system uses the compound system of diethyl hypo-aluminum orthophosphate and MPP.
Other materials 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 replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Embodiment 6
Implementation process is same as Example 2, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Embodiment 7
Implementation process is same as Example 3, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Embodiment 8
Implementation process is same as Example 4, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 6
Implementation process is identical as comparative example 1, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 7
Implementation process is identical as comparative example 2, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 8
Implementation process is identical as comparative example 3, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 9
Implementation process is identical as comparative example 4, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Comparative example 10
Implementation process is identical as comparative example 5, and nylon66 fiber is replaced with PBT.Other materials and proportion are shown in Table 2, obtained
Material the results are shown in Table 2.
Table 2
Claims (10)
1. the halogen-free flame-retardant system of a kind of dialkyl dithio hypophosphites and nitrogenous compound collaboration, which is characterized in that by weight
Percentages are measured, raw material composition includes:
Dialkyl dithio hypophosphites 50~90%；
Nitrogenous compound 9~40%；
Zinc compound 1~10%；
The dialkyl dithio hypophosphites, shown in structural formula such as following formula (I):
In formula, R1、R2Independently selected from straight chained alkyl or branched alkyl, the carbon number of the straight chained alkyl or branched alkyl is 1~6；
M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K or NH4, m is 1~4.
2. the halogen-free flame-retardant system of dialkyl dithio hypophosphites according to claim 1 and nitrogenous compound collaboration,
It is characterized in that, the R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, different
Amyl, n-hexyl or isohesyl；
The M is selected from Mg, Ca, Al, Sn, Ti or Zn.
3. the halogen-free flameproof body of dialkyl dithio hypophosphites according to claim 1 or 2 and nitrogenous compound collaboration
System, which is characterized in that the average grain diameter D50 of the dialkyl dithio hypophosphites is 20~50 μm.
4. the halogen-free flame-retardant system of dialkyl dithio hypophosphites according to claim 1 and nitrogenous compound collaboration,
It is characterized in that, the nitrogenous compound is selected from melamine derivative, average grain diameter D50 is 20~50 μm.
5. the halogen-free flame-retardant system of dialkyl dithio hypophosphites according to claim 4 and nitrogenous compound collaboration,
It is characterized in that, the melamine derivative includes melamine cyanurate, melamine polyphosphate, melamine gold
Belong at least one of phosphite.
6. the halogen-free flame-retardant system of dialkyl dithio hypophosphites according to claim 1 and nitrogenous compound collaboration,
It is characterized in that, the zinc compound is selected from zinc borate and/or zinc stannate, average grain diameter D50 is 20~50 μm.
7. a kind of halogen-free flame-retardant glass fiber enhances thermoplastic engineering plastic, which is characterized in that including any according to claim 1~6
The halogen-free flame-retardant system, by weight percentage, raw material composition includes:
The substrate is selected from polyamide or polyester.
8. halogen-free flame-retardant glass fiber according to claim 7 enhances thermoplastic engineering plastic, which is characterized in that percentage by weight
Than meter, raw material composition includes:
The substrate is selected from polyamide；
The raw material of the halogen-free flame-retardant system forms
Dialkyl dithio hypophosphites 56~80%；
Nitrogenous compound 13~40%；
Zinc compound 3~7%.
9. halogen-free flame-retardant glass fiber according to claim 7 enhances thermoplastic engineering plastic, which is characterized in that percentage by weight
Than meter, raw material composition includes:
The substrate is selected from polyester；
The raw material of the halogen-free flame-retardant system forms
Dialkyl dithio hypophosphites 50~80%；
Nitrogenous compound 15~40%；
Zinc compound 3~8%.
10. enhancing thermoplastic engineering plastic according to any halogen-free flame-retardant glass fiber of claim 7~9, which is characterized in that institute
It states nitrogenous compound and is selected from melamine polyphosphate, zinc compound is selected from zinc borate.
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