CN108795038A - The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite - Google Patents
The halogen-free flame-retardant system and its application that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a kind of halogen-free flame-retardant system that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite, raw material composition includes：The thio hypophosphites 50~94% of dialkyl group list, inorganic phosphite 5~40% and zinc compound 1~10%；The thio hypophosphites of dialkyl group list, structural formula such as formula (I) or (II) are shown, 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 engineering plastics 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 thio hypophosphites of dialkyl group list and inorganic phosphorous
The halogen-free flame-retardant system of hydrochlorate collaboration and its application in preparing halogen-free flame-retardant glass fiber enhancing thermoplastic engineering plastic.
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 Halogen that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite resistance
Combustion system, the halogen-free flame-retardant system have many advantages, such as high fire-retardance, non-migratory, not etching apparatus, the Halogen prepared based on this
Flame-proof glass fibre enhances thermoplastic engineering plastic, can prepare the component or product of field of electronics.
Specific technical solution is as follows：
A kind of halogen-free flame-retardant system that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite, by weight percentage
Meter, raw material composition include：
The thio hypophosphites of dialkyl group list 50~94%；
Inorganic phosphite 5~40%；
Zinc compound 1~10%；
Shown in the thio hypophosphites of dialkyl group list, structural formula such as following formula (I) or following formula (II)：
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 the novel thio hypophosphite fire retardant of dialkyl group list, by containing with inorganic phosphite and on a small quantity
The collaboration of zinc compound forms and cooperates with compounding flame retardant based on the multielement of phosphorus sulphur and metal, solves existing based on diethyl
The precipitation perishable, easy to migrate etc. existing for flame-proof glass fibre enhancing thermoplastic engineering plastic of the compounding flame retardant of hypo-aluminum orthophosphate lacks
It falls into.The novel flame-retardant system can be well adapted for fiberglass reinforced thermoplastic engineering plastic material, the Halogen being had excellent performance
Fire proofing.
Preferably, in the general formula of the thio hypophosphites of dialkyl group list, 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.
The invention also discloses a kind of preparation processes of the thio hypophosphites of dialkyl group list, to prepare dialkyl group list sulphur
For generation aluminum phosphate, specially：
(1) the thio sodium hypophosphite solution of dialkyl group list is reacted in acid condition with aluminum sulfate solution, obtains dialkyl group
The suspension of single thio hypo-aluminum orthophosphate sediment；
(2) suspension will be filtered, washed and dry, pulverize to certain grain size at 120 DEG C, obtain dialkyl group list sulphur
For hypo-aluminum orthophosphate combustion inhibitor.
It wherein, can be by commercially available acquisition, or by the following method as the thio sodium hypophosphite of dialkyl group list of raw material
It prepares：
(a) the thio hypophosphorous acid of dialkyl group list can be generated by reacting Acidic phosphates in the presence of the concentrated sulfuric acid with phosphorus pentasulfide；
(b) the thio hypophosphorous acid of dialkyl group list is reacted with sodium hydroxide generates the thio hypophosphorous acid sodium salt of dialkyl group list soluble easily in water.
The characteristics of dialkyl group list thio 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.The thio hypophosphites of dialkyl group list 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 group list thio hypophosphites, it is added suitable inorganic
Phosphite, forms the non-nitrogen flame-retardant system based on phosphorus sulphur and metal structure, which has preferable flame-retarding characteristic.
Preferably, the inorganic phosphite is selected from aluminium phosphite and/or zinc phosphite.With higher thermal decomposition temperature
Degree, flame retarding efficiency is low when exclusive use, need to usually be cooperateed with other fire retardants.
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, the thio hypophosphites of dialkyl group list 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；Zinc compound is
Powdered, 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：
The thio hypophosphites of dialkyl group list 73~83%；
Inorganic phosphite 11~21%；
Zinc compound 2.5~6%.
Further preferably, the base material is selected from PA66, and the inorganic phosphite is selected from aluminium phosphite, and zinc compound is selected from boron
Sour zinc；The thio hypophosphites of dialkyl group list is selected from the thio hypo-aluminum orthophosphate of diethyl list.
When the base material is selected from polyester, preferably raw material composition includes：
Further preferably, the raw material composition of the halogen-free flame-retardant system includes：
The thio hypophosphites of dialkyl group list 56~80%；
Inorganic phosphite 13~37%；
Zinc compound 3~7%.
Further preferably, the base material is selected from PBT, and the inorganic phosphite is selected from aluminium phosphite, and zinc compound is selected from boron
Sour zinc；The thio hypophosphites of dialkyl group list is selected from the thio hypo-aluminum orthophosphate of diethyl list.
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 by the thio hypophosphites of dialkyl group list and inorganic phosphite phosphorus sulphur and metal multielement association
With the non-nitrogen flame-retardant system of compounding, has many advantages, such as high fire-retardance, non-migratory, not etching apparatus, may be used as fiberglass reinforced thermoplastic
Property engineering plastics halogen-free flame-retardant system, can prepare the novel halogen-free flame-retardant glass fiber applied to electric and electronic field enhances heat
Plastic engineering plastics proprietary material.
Specific implementation mode
Raw material：
(1) preparation of the thio hypo-aluminum orthophosphate of diethyl list
The sulphur of diethyl list thio the sodium hypophosphite aqueous solution 960g and a concentration of 30wt% of compound concentration 20wt% respectively
Desalted water 1000g is added into reactor, and the sulfuric acid solution 50g of a concentration of 25wt% is added by sour aluminum water solution 228g, heats up
To 80 DEG C, starts to synchronize the thio sodium hypophosphite aqueous solution of dropwise addition diethyl list and aluminum sulfate solution in proportion into reaction kettle, obtain
It to the thio hypo-aluminum orthophosphate sediment of diethyl list, is added dropwise to complete within 2 hours, keeps the temperature 1 hour, be then filtered, washed, dry, obtain
The thio hypo-aluminum orthophosphate combustion inhibitor 166g (yield 95%) of diethyl list.
After tested, 345 DEG C of the initial decomposition temperature of product, (20 DEG C) of solubility is 0.05% 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 the thio hypo-aluminum orthophosphate of diethyl list
With the ratio of aluminium phosphite.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 the thio hypo-aluminum orthophosphate of diethyl list
With the ratio of aluminium phosphite.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, and the thio hypo-aluminum orthophosphate accounting of diethyl list is protected
Hold constant, the ratio of other two components of adjustment.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 the thio hypo-aluminum orthophosphate of diethyl list
Outside.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 the thio hypo-aluminum orthophosphate of diethyl list and zinc borate, does not 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 the thio hypo-aluminum orthophosphate of diethyl list.Other materials and proportioning
It is 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 (9)
1. a kind of halogen-free flame-retardant system that the thio hypophosphites of dialkyl group list is cooperateed with inorganic phosphite, which is characterized in that press
Weight percent meter, raw material composition include：
The thio hypophosphites of dialkyl group list 50~94%；
Inorganic phosphite 5~40%；
Zinc compound 1~10%；
Shown in the thio hypophosphites of dialkyl group list, structural formula such as following formula (I) or following formula (II)：
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.
2. the halogen-free flameproof body that the thio hypophosphites of dialkyl group list according to claim 1 is cooperateed with inorganic phosphite
System, which is characterized in that the R1、R2Independently selected from methyl, ethyl, n-propyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl,
Isopentyl, n-hexyl or isohesyl；
The M is selected from Mg, Ca, Al, Sn, Ti or Zn.
3. the halogen-free flameproof that the thio hypophosphites of dialkyl group list according to claim 1 or 2 is cooperateed with inorganic phosphite
System, which is characterized in that the average grain diameter D50 of the thio hypophosphites of dialkyl group list is 20~50 μm.
4. the halogen-free flameproof body that the thio hypophosphites of dialkyl group list according to claim 1 is cooperateed with inorganic phosphite
System, which is characterized in that the inorganic phosphite is selected from aluminium phosphite and/or zinc phosphite, and average grain diameter D50 is 20~50 μ
m。
5. the halogen-free flameproof body that the thio hypophosphites of dialkyl group list according to claim 1 is cooperateed with inorganic phosphite
System, which is characterized in that the zinc compound is selected from zinc borate and/or zinc stannate, and average grain diameter D50 is 20~50 μm.
6. a kind of halogen-free flame-retardant glass fiber enhances thermoplastic engineering plastic, which is characterized in that including any according to Claims 1 to 5
The halogen-free flame-retardant system, by weight percentage, raw material composition includes：
The base material is selected from polyamide or polyester.
7. halogen-free flame-retardant glass fiber according to claim 6 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：
The thio hypophosphites of dialkyl group list 73~83%；
Inorganic phosphite 11~21%；
Zinc compound 2.5~6%.
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 polyester；
The raw material of the halogen-free flame-retardant system forms：
The thio hypophosphites of dialkyl group list 56~80%；
Inorganic phosphite 13~37%；
Zinc compound 3~7%.
9. enhancing thermoplastic engineering plastic according to any halogen-free flame-retardant glass fiber of claim 6~8, which is characterized in that institute
It states inorganic phosphite and is selected from aluminium phosphite, zinc compound is selected from zinc borate.
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| WO2009035881A2 (en) * | 2007-09-13 | 2009-03-19 | Dow Global Technologies, Inc. | Phosphorus-sulfur fr additives and polymer systems containing same |
| CN102939332A (en) * | 2010-02-05 | 2013-02-20 | 巴斯夫欧洲公司 | Flame retardant |
| CN107223149A (en) * | 2015-04-13 | 2017-09-29 | 科莱恩塑料和涂料有限公司 | The method for preparing fire-retardant, noncorrosive and stable polyamide moulding composition |
| CN107778527A (en) * | 2017-11-22 | 2018-03-09 | 江苏利思德新材料有限公司 | A kind of halogen-free flameproof compound system based on phosphorus aluminium compound and its application in fiberglass reinforced engineering plastics |
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