CN108727633A - Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of inorganic phosphite and nitrogenous compound collaboration and its application - Google Patents
Dialkyl dithio hypophosphites, the halogen-free flame-retardant system of inorganic phosphite and nitrogenous compound collaboration and its application Download PDFInfo
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- 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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention discloses a kind of halogen-free flame-retardant system based on the collaboration of dialkyl dithio hypophosphites, inorganic phosphite and nitrogenous compound, raw material composition includes：Dialkyl dithio hypophosphites 30~90%, inorganic phosphite 8~30%, nitrogenous compound 1~30% and 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, 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 has the characteristics that high fire-retardance, non-migratory, not etching apparatus, is well adapted for fiberglass reinforced thermoplastic engineering plastic system, obtains the halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic of excellent combination property.
Description
Technical field
The present invention relates to the technical fields of fire retardant, and in particular to a kind of dialkyl dithio hypophosphites, inorganic phosphorous
Hydrochlorate and nitrogenous compound collaboration halogen-free flame-retardant system and its prepare halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic in
Application.
Background technology
Fiberglass reinforced thermoplastic engineering plastic is because steady with 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 material fire-retardant requirement, 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.
Include the basic flame-retardant system of two classes currently, for the fire-retardant of fiberglass reinforced thermoplastic engineering plastic：Halogen system hinders
Combustion system and non-halogen fire-retardant system.Halogen system flame-retardant system is typically brominated flame-retardant collaboration antimony oxide, and numerous studies show
Fiberglass reinforced thermoplastic engineering plastic added with bromide fire retardant will produce the harmful substances such as dense smoke and hydrogen bromide in burning,
Human body can be caused to suffocate, secondly, the electrical insulating property of halogenated flame retardant is poor, and the application in some fields is also restrained.Therefore, it is
Fiberglass reinforced thermoplastic engineering plastic, which develops safe and environment-friendly, high performance halogen-free flame-retardant system, becomes the hot spot of research, in recent years
There is the novel halogen-free flame retardants or flame-retardant system applied to fiberglass reinforced thermoplastic engineering plastic.
According to the literature, the halogen-free flame retardants for being applied to fiberglass reinforced thermoplastic engineering plastic includes mainly that two major classes are basic
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, 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 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,
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 with higher phosphorus content 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, not will produce the hypertoxic gas such as hydrogen phosphide.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, 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 increase and the 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 can influence 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 be migrated to product surface, cause to hinder
Combustion agent is unevenly distributed and is lost in, and the final fire-retardant failure for making material, there are security risks；Third, 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, which are fatal problems, cannot then use, some are then
It is to lead to cost increase, efficiency reduction etc..Therefore, it is necessary to develop novel halogen-free flame-retardant system.
Invention content
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 discloses a kind of dialkyl dithio hypophosphites, inorganic phosphite and nitrogenous compound
The halogen-free flame-retardant system of collaboration, which has many advantages, such as high fire-retardance, non-migratory, not etching apparatus, with this
Based on prepare halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic, the component or product of field of electronics can be prepared.
Specific technical solution is as follows：
A kind of halogen-free flame-retardant system of dialkyl dithio hypophosphites, inorganic phosphite and nitrogenous compound collaboration,
By weight percentage, raw material composition includes：
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 use novel dialkyl dithio hypophosphite fire retardant, by with inorganic phosphite, nitrogen
The collaboration of object is closed, the multielement based on phosphorus sulphur nitrogen is formed and cooperates with compounding flame retardant, is solved existing based on diethyl hypo-aluminum orthophosphate
The defects of compounding flame retardant is perishable existing for flame-proof glass fibre enhancing thermoplastic engineering plastic, precipitation easy to migrate.This is new
Type flame-retardant system can be well adapted for fiberglass reinforced thermoplastic engineering plastic material, the halogen-free flameproof material being had excellent performance
Material.
Preferably, in the general formula of the dialkyl dithio hypophosphites, R1、R2Independently selected from methyl, ethyl, positive third
Base, normal-butyl, isobutyl group, tertiary 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, specially：
(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 to certain grain size at 120 DEG C, 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
It prepares：
(a) linear alkene exists in initiator with hydrogen phosphide 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, the also collaboration of element sulphur, good flame resistance, tool
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 to and cooperate with component to compound, and can be only achieved fire-retardant requirement.
Inventors discovered through research that in the presence of dialkyl dithio hypophosphites, it is added suitable inorganic
Phosphite and nitrogenous compound, form the halogen-free flame-retardant system based on phosphorus sulphur N structure, which has preferable fire-retardant
Characteristic.
Preferably, the inorganic phosphite is selected from aluminium phosphite and/or zinc phosphite.Preferred aluminium phosphite and/or
Zinc phosphite has very high heat decomposition temperature, can act synergistically with dialkyl dithio hypophosphites, while water-soluble low, resistance to
Migration.
The nitrogenous compound is usually melamine derivative, contains nitrogen in molecular structure, in halogen-free flameproof body
It is often air source in system, there is higher heat decomposition temperature, fire retardant can be used alone as, but its flame retarding efficiency is low, additive amount is big,
It also needs to cooperate with other fire retardants.Studied through inventor, discovery introduced in above-mentioned system a small amount of high temperature resistant be not precipitated it is nitrogenous
Compound, can not only 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 above-mentioned system, can further increase
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 sulphur structure
Together, anti-flammability is improved, and with 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；Inorganic phosphite is powdered, and average grain diameter D50 is 20~50 μm；Nitrogenous compound is
Powdered, average grain diameter D50 is 20~50 μm；Zinc compound is powdered, and average grain diameter D50 is 20~50 μm.
The invention also discloses halogen-free flame-retardant glass fiber enhancing engineering thermoplastic prepared by the halogen-free flame-retardant system is added to mould
Material, by weight percentage, raw material composition includes：
The base material 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 base material is selected from polyamide, preferably raw material composition includes：
Further preferably, the raw material composition of the halogen-free flame-retardant system includes：
Further preferably, the base material is selected from PA66, and the inorganic phosphite is selected from aluminium phosphite, and nitrogenous compound is selected from three
Poly cyanamid Quadrafos, zinc compound are selected from zinc borate, and dialkyl dithio hypophosphites is selected from diisobutyl two thio times
Aluminum phosphate.
When the base material is selected from polyester, raw material composition includes：
Further preferably, the raw material composition of the halogen-free flame-retardant system includes：
Further preferably, the base material is selected from PBT, and the inorganic phosphite is selected from aluminium phosphite, and nitrogenous compound is selected from three
Poly cyanamid Quadrafos, zinc compound are selected from zinc borate, and dialkyl dithio hypophosphites is selected from diisobutyl two thio times
Aluminum phosphate.
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 etching apparatus, without be precipitated.
The invention also discloses the preparation method that the halogen-free flame-retardant glass fiber enhances thermoplastic engineering plastic, each raw material is blended
Afterwards, flame-retardant system is dispersed in base material, 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 invention has the advantages that：
The invention discloses more by the phosphorus sulphur nitrogen of dialkyl dithio hypophosphites, inorganic phosphite and nitrogenous compound
The halogen-free flame-retardant system of element collaboration compounding, has many advantages, such as high fire-retardance, non-migratory, not etching apparatus, may be used as glass and increases
The halogen-free flame-retardant system of strong thermoplastic engineering plastic, can prepare the novel halogen-free flame-retardant glass fiber applied to electric and electronic field
Enhance thermoplastic engineering plastic proprietary material.
Specific implementation mode
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 god horse；
(5) glass, ECS301UW, Chongqing Polycomp International Co., Ltd；
(6) diethyl hypo-aluminum orthophosphate, 8003, Jiangsu Li Side new materials Co., Ltd；
(7) antioxidant, 1098, BASF；
(8) silicone, middle indigo plant morning twilight；
(9) PBT, 211M, Changchun chemistry；
(10) aluminium phosphite, Jiangsu Li Side new materials Co., Ltd.
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
It is stirred in height and the compounding flame retardant each component weighed up in advance according to the ratio and other auxiliary agents is added in machine, start high-speed stirring
It mixes, stirs 10min, complete the mixture of powder, discharge.
(2) extruding pelletization of material
Each area's temperature setting of double screw extruder in predetermined temperature, after temperature stablizes 20min, Buddhist nun is added 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 with 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 standards.
Resistance to migration experiment
The halogen-free flame-retardant glass fiber prepared is enhanced into nylon sample, is put into climatic chamber, 85 DEG C of temperature is set, relatively
Humidity 85%, the state of specimen surface of the visual observations after 168 hours.
Corrosion experiment
One metal derby is set on die head, and high-temperature material passes through 25Kg material granulations in die head and metal block contact, test
The waste of metal afterwards, loss is higher, and corrosion resistance is poorer.If etching extent<0.1% is thought that corrosion is acceptable.
Mechanics Performance Testing
By ASTM D638 test tensile strengths and press ASTM D256 impact strengths.
Each material and proportioning 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, aluminium phosphite and MPP.Other materials and proportioning 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, aluminium phosphite and MPP.Other materials and proportioning 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 three components.Other materials and proportioning 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 proportioning 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 not using zinc borate.Other materials and proportioning 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 aluminium phosphite.Other materials and proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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 proportioning 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, inorganic phosphite and nitrogenous compound collaboration,
It is characterized in that, by weight percentage, raw material composition includes：
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 is 1~4.
What 2. dialkyl dithio hypophosphites according to claim 1, inorganic phosphite and nitrogenous compound cooperateed with
Halogen-free flame-retardant system, which is characterized in that the R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, n-hexyl or isohesyl；
The M is selected from Mg, Ca, Al, Sn, Ti or Zn.
3. dialkyl dithio hypophosphites according to claim 1 or 2, inorganic phosphite and nitrogenous compound collaboration
Halogen-free flame-retardant system, which is characterized in that the average grain diameter D50 of the dialkyl dithio hypophosphites be 20~50 μm.
What 4. dialkyl dithio hypophosphites according to claim 1, inorganic phosphite and nitrogenous compound cooperateed with
Halogen-free flame-retardant system, which is characterized in that the inorganic phosphite is selected from aluminium phosphite and/or zinc phosphite, average grain diameter D50
It is 20~50 μm.
What 5. dialkyl dithio hypophosphites according to claim 1, inorganic phosphite and nitrogenous compound cooperateed with
Halogen-free flame-retardant system, which is characterized in that the nitrogenous compound is selected from melamine derivative, and average grain diameter D50 is 20~50 μ
m。
What 6. dialkyl dithio hypophosphites according to claim 1, inorganic phosphite and nitrogenous compound cooperateed with
Halogen-free flame-retardant system, which is characterized in that the zinc compound be selected from zinc borate and/or zinc stannate, average grain diameter D50 be 20~
50μm。
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 base material 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 base material is selected from polyamide；
The raw material of the halogen-free flame-retardant system forms：
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 base material is selected from polyester；
The raw material of the halogen-free flame-retardant system forms：
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 inorganic phosphite and is selected from aluminium phosphite, nitrogenous compound is selected from melamine polyphosphate, and zinc compound is selected from boric acid
Zinc.
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|---|---|---|---|---|
| CN101343287A (en) * | 2008-08-29 | 2009-01-14 | 清华大学 | Synthesis of sicycle-ring hexyl di-thiophosphinic acid |
| WO2009035881A2 (en) * | 2007-09-13 | 2009-03-19 | Dow Global Technologies, Inc. | Phosphorus-sulfur fr additives and polymer systems containing same |
| CN107936297A (en) * | 2017-11-22 | 2018-04-20 | 江苏利思德新材料有限公司 | Glass fiber enhanced nylon halogen-free flameproof compound system and its application in halogen-free flame-retardant glass fiber strengthens nylon material |
-
2018
- 2018-06-28 CN CN201810684899.1A patent/CN108727633A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009035881A2 (en) * | 2007-09-13 | 2009-03-19 | Dow Global Technologies, Inc. | Phosphorus-sulfur fr additives and polymer systems containing same |
| CN101343287A (en) * | 2008-08-29 | 2009-01-14 | 清华大学 | Synthesis of sicycle-ring hexyl di-thiophosphinic acid |
| CN107936297A (en) * | 2017-11-22 | 2018-04-20 | 江苏利思德新材料有限公司 | Glass fiber enhanced nylon halogen-free flameproof compound system and its application in halogen-free flame-retardant glass fiber strengthens nylon material |
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Application publication date: 20181102 |