CN109957245A - Charging pile no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon and preparation method thereof - Google Patents
Charging pile no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon and preparation method thereof Download PDFInfo
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- CN109957245A CN109957245A CN201711413035.8A CN201711413035A CN109957245A CN 109957245 A CN109957245 A CN 109957245A CN 201711413035 A CN201711413035 A CN 201711413035A CN 109957245 A CN109957245 A CN 109957245A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
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Abstract
The invention discloses a kind of charging pile no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon and preparation method thereof, the charging pile includes the following ingredient calculated according to the mass fraction with no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon: 50-60 parts of PA66 resin slicer；8-15 parts of organic phosphonate fire retardant；1-6 parts of melamine class synergistic flame retardant；0.1-3 parts of acid binding agent；Glass grows 25-35 parts of fibre；0.5-1 parts of antioxidant；0.5-1 parts of lubricant.Charging pile of the present invention is with no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon PH3 burst size up to N.D, flame retardant property reaches V-0 grades of 1.5mm, creepage trace index up to 600V, GWIT/1.5mm up to 770 DEG C, good mechanical performance, processing performance is good and is suitable for flame-resistant electronic product, especially suitable for pipette tips and the socket use of charging on charging pile.
Description
Technical field
The invention belongs to technical field of polymer materials, in particular to a kind of charging pile is hindered with no hydrogen phosphide organic phosphonate
Combustion enhancing nylon.
Background technique
Under global energy crisis and the serious overall background of environmental crisis, the Chinese government actively pushes forward making for new-energy automobile
With with development, electric charging station has very important society as important mating infrastructure necessary to Development of EV
Benefit and economic benefit, charging pile play the role of the development and popularization of new-energy automobile extremely important.It is important as charging pile
Component-charging pipette tips and socket, the overwhelming majority are made by halogen-free flame-retardant reinforced nylon 66.PA66 is answered electric equal fields
With increasingly wider, with the continuous expansion of high molecular fire retardant Materials and application field with demand of the mankind to living environment not
Disconnected to improve, the bittern-free flame-proof material with low cigarette, low toxicity gradually occupies market, and the use of halogen-free flame retardants has become current resistance
The Hot spots for development and important directions of combustible material.Single fire retardant is no longer satisfied at present to PA66 Compound Material Engineering
Can, flame retardant property and the comprehensive demand of electrical property, a variety of environmental protection fire retarding agents by different modes are compounded to obtain excellent
There is the novel built type fire retardant of synergistic effect can effectively reduce fire retardant additive amount for gesture complementation, be conducive to PA66 composite wood
Expect the raising of mechanical property, flame retardant property and electrical property.The fire-retardant reinforced plastic PA66 composite material developed both at home and abroad at present is difficult
Meet that excellent in mechanical performance, flame retardant property be good and the requirement of excellent machinability simultaneously.
Phosphorus flame retardant is mainly inorganic phosphorus flame retardant on the market, and chemical structure is unstable.In twin screw extrusion
In, the Strong shear by twin-screw acts on, and goes out phosphine gas to Environment release.Material is heated and adds after secondary operation injection molding
The acute unstability of phosphorus flame retardant ingredient, injection-molded item release hydrogen phosphide.Hydrogen phosphide is a kind of colourless, inflammable, hypertoxic
Gas is chronically exposed under phosphine, seriously endangers human health.Therefore, no phosphatization hydrogenation is non-halogen and fire-retardant reinforced Nylon
A kind of development trend of dragon, is especially more important trend in new energy industry.
Summary of the invention
The defect that mesh of the present invention is discharged for the hydrogen phosphide of existing halogen-free flame-retardant reinforced nylon material, provides a kind of mechanicalness
Can good, good flame-retardance and without the environmental protection flame retardant engineering plastics that phosphatization hydrogen release is put, can satisfy general electronic apparatus cooling requirements,
It is cheap, have very high use value.
Another object of the present invention is to provide the no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of the charging pile and
Preparation method.
The technical solution used in the present invention is as follows:
50-60 parts of PA66 resin slicer；
8-15 parts of organic phosphonate fire retardant；
1-6 parts of melamine class synergistic flame retardant；
0.1-3 parts of acid binding agent；
Glass grows 25-35 parts of fibre；
0.5-1 parts of antioxidant；
0.5-1 parts of lubricant.
In 70Mpa or more, melt index is not less than the tensile strength of the PA66 slice in one of the embodiments,
10g/10min。
The organic phosphonate is aluminum diethylphosphinate fire retardant in one of the embodiments, and partial size is in 15-
50um, diethyl content >=92%.
The acid binding agent is borate fire retardant in one of the embodiments,.
The melamine class synergistic flame retardant is melamine cyanurate or melamine in one of the embodiments,
One kind or mixed thing of amine ammonium pyrophosphate.
The preparation method of the no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of the charging pile, comprising the following steps:
1) various raw materials are weighed by formula；
2) by height flowing PA66 resin slicer dry small inch of 2-3 at a temperature of 80-90 DEG C, then with other all raw materials
It is uniformly mixed；
3) mixed raw material is placed in the lower hopper of extruder, is granulated through double screw extruder melting extrusion, can obtained
It obtains without hydrogen phosphide organic phosphonate flame-retardant reinforced nylon.
The technological parameter that the double screw extruder melting extrusion is granulated in one of the embodiments, an are as follows: Qu Wendu
200-210 DEG C, two 245-250 DEG C of area's temperature, three 250-255 DEG C of area's temperature, four 240-245 DEG C of area's temperature, five area temperature 240-
245 DEG C, six 235-240 DEG C of area's temperature, seven 230-235 DEG C of area's temperature, eight 230-235 DEG C of area's temperature, nine area temperature 230-235
DEG C, 240-245 DEG C of die head temperature；The revolving speed of host is 240-260r/min, and the revolving speed of feeding is 60-70r/min.
The beneficial effects of the present invention are: the present invention is fire-retardant by compounding organic phosphonate fire retardant, melamine synergistic
Agent and acid binding agent etc. improve the flame retardant property of nylon and control the release of hydrogen phosphide, prepare the Halogen enhancing of environmental protection flame retardant rank
Nylon meets use and environmental requirement in electric appliances such as electrical and electronic components；No hydrogen phosphide organic phosphonate prepared by the present invention
N.D is put in flame-retardant reinforced nylon hydrogen release, flame retardant property reach V-0 grades, creepage trace index it is also reachable up to 600V, GWIT glowing filament
770 DEG C, satisfactory mechanical property, processing performance is excellent, is suitable for flame-resistant electronic component product, especially suitable for inserting on charging pile
Seat pipette tips.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, below in conjunction with specific embodiment, to this
Invention is described in further detail.It should be understood that the specific embodiments described herein are only to explain this hair
It is bright, and the scope of protection of the present invention is not limited.
Following embodiment is raw materials used as follows:
PA66 resin slicer: Henan mind horse EPR24；
Organic phosphonate fire retardant: aluminum diethylphosphinate, partial size is in 15-50um, diethyl content >=92%, Clariant
OP1230；
Melamine class synergistic flame retardant: melamine cyanurate, partial size 25um, Pu Saifu MCA-25；
Acid binding agent: zinc borate flame retardant, white powder are common domestic；
Glass is long fine: filament diameter 13um, megalith group ER13-2000-988A；
Antioxidant: 1098, N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, it is domestic；
Lubricant: modified EBS, it is common domestic.
Embodiment 1
A kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, preparation method are as follows:
1) raw material of following mass fraction is weighed: 55.6 parts of PA66 resin；10 parts of organophosphinic acids aluminium；Melamine cyanurea
3 parts of hydrochlorate；3.5 0.4 part of hydrate zinc borates；Glass is long 30 parts fine；1,098 0.5 parts of antioxidant；0.5 part of lubricant.
2) PA66 resin is placed in blast drier at a temperature of 80-90 DEG C the dry small inch of 2-3, then with other institutes
There is raw material to be put into togerther high-speed mixer and mixing 3 minutes, is uniformly mixed.
3) mixed raw material is placed in the lower hopper of extruder, through double screw extruder melting extrusion, makes material to get nothing
Hydrogen phosphide organic phosphonate flame-retardant reinforced nylon；
Wherein the technological parameter of material is made in double screw extruder melting extrusion are as follows: 200-210 DEG C of area's temperature, two area's temperature
245-250 DEG C, three 250-255 DEG C of area's temperature, four 240-245 DEG C of area's temperature, five 240-245 DEG C of area's temperature, six area temperature 235-
240 DEG C, seven 230-235 DEG C of area's temperature, eight 230-235 DEG C of area's temperature, nine 230-235 DEG C of area's temperature, die head temperature 240-245
℃.The revolving speed of host is 240-260r/min, and the revolving speed of feeding is 60-70r/min.Open lower hopper agitating device.
Embodiment 2
A kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, not in addition to raw materials used mass fraction
Together, preparation method is identical as the method for embodiment 1, and the mass fraction of each raw material in the present embodiment is as follows:
55.5 parts of PA66 resin；9.5 parts of organophosphinic acids aluminium；3.5 parts of melamine cyanurate；3.5 hydrate zinc borates 0.5
Part；Glass is long 30 parts fine；1,098 0.5 parts of antioxidant；0.5 part of lubricant.
Embodiment 3
A kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, not in addition to raw materials used mass fraction
Together, preparation method is identical as the method for embodiment 1, and the mass fraction of each raw material in the present embodiment is as follows: PA66 resin
55.5 parts；9 parts of organophosphinic acids aluminium；4 parts of melamine cyanurate；3.5 0.5 part of hydrate zinc borates；Glass is long 30 parts fine；Antioxygen
1,098 0.5 parts of agent；0.5 part of lubricant.
Embodiment 4
A kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, not in addition to raw materials used mass fraction
Together, preparation method is identical as the method for embodiment 1, and the mass fraction of each raw material in the present embodiment is as follows: PA66 resin 56
Part；10 parts of organophosphinic acids aluminium；3 parts of melamine cyanurate；Glass is long 30 parts fine；1,098 0.5 parts of antioxidant；Lubricant
0.5 part.
Embodiment 5
A kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, not in addition to raw materials used mass fraction
Together, preparation method is identical as the method for embodiment 1, and the mass fraction of each raw material in the present embodiment is as follows:
56 parts of PA66 resin；9.5 parts of organophosphinic acids aluminium；3.5 parts of parts of melamine cyanurate；Glass is long 30 parts fine；
1,098 0.5 parts of antioxidant；0.5 part of lubricant.
Embodiment 6
A kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, not in addition to raw materials used mass fraction
Together, preparation method is identical as the method for embodiment 1, and the mass fraction of each raw material in the present embodiment is as follows:
56 parts of PA66 resin；9 parts of organophosphinic acids aluminium；4 parts of melamine cyanurate；Glass is long 30 parts fine；Antioxidant
1098 0.5 parts；0.5 part of lubricant.
Performance detection is carried out to no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon prepared in the above embodiments below.
As follows or standard surveys material mechanical performance:
The resin that Examples 1 to 6 has been granulated is placed in drying 2-3 hours in the air dry oven that temperature is 120-130 DEG C,
The sample preparation on 80T injection molding machine.Cooling placement is tested after 24 hours.Testing standard is Unite States Standard, and test temperature is room temperature.It stretches
Strength criterion ASTM D638, batten is having a size of 57mm*127mm*3.2mm (effective dimensions), tensile speed 50mm/min；It is curved
Bent strength criterion: ASTM D790, batten is having a size of 127mm*13mm*3.2mm, rate of bending 2mm/min；Chalpy impact
Standard: ASTM D256, for batten having a size of 64mm*12.7mm*3.2mm, notch residue width is 10.12mm；Melt index mark
Quasi-: ASTMD1238, test condition are 275 DEG C/2.16kg；Flame retardant property is tested according to 94 standard of UL；PH3 content according to
7LA standard is tested；Glowing filament performance is tested according to IEC60695 standard.
The comparison of table 1 embodiment 1-6 and halogen-free flame-proof nylon 66 properties of product
By the test data in table 1 it is found that no hydrogen phosphide organic phosphonate fire-retardant nylon material phosphatization prepared by the present invention
N.D is put in hydrogen release, 1.5mm is fire-retardant can reach V-0 grades, creepage trace index up to 600V, GWIT glowing filament can also up to 770 DEG C,
Good mechanical performance, processing performance are excellent, especially suitable for pipette tips and the socket use of charging on charging pile.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile, which is characterized in that including pressing mass parts below
The ingredient that number calculates:
50-60 parts of PA66 resin slicer；
8-15 parts of organic phosphonate fire retardant；
1-6 parts of melamine class synergistic flame retardant；
0.1-3 parts of acid binding agent；
Glass grows 25-35 parts of fibre；
0.5-1 parts of antioxidant；
0.5-1 parts of lubricant.
2. the no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile according to claim 1, which is characterized in that institute
The tensile strength of PA66 slice is stated in 70Mpa or more, melt index is not less than 10g/10min.
3. the no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile according to claim 1, which is characterized in that institute
Stating organic phosphonate is aluminum diethylphosphinate fire retardant, and partial size is in 15-50um, diethyl content >=92%.
4. material according to claim 1, which is characterized in that the acid binding agent is borate fire retardant.
5. material according to claim 1, which is characterized in that the melamine class synergistic flame retardant is melamine cyanogen
One kind or mixed thing of lithate or melamine ammonium pyrophosphate.
6. the preparation of no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile described in claim 1-5 any claim
Method, which comprises the following steps:
1) various raw materials are weighed by formula；
2) PA66 resin slicer is dried to the small inch of 2-3 at a temperature of 80-90 DEG C, is then uniformly mixed with other all raw materials；
3) mixed raw material is placed in the lower hopper of extruder, is granulated through double screw extruder melting extrusion, can be obtained nothing
Hydrogen phosphide organic phosphonate flame-retardant reinforced nylon.
7. the preparation method of the no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon of charging pile according to claim 6, special
Sign is, the technological parameter that double screw extruder melting extrusion is granulated are as follows: 200-210 DEG C of area's temperature, two area temperature 245-250
DEG C, three 250-255 DEG C of area's temperature, four 240-245 DEG C of area's temperature, five 240-245 DEG C of area's temperature, six 235-240 DEG C of area's temperature, seven
230-235 DEG C of area's temperature, eight 230-235 DEG C of area's temperature, nine 230-235 DEG C of area's temperature, 240-245 DEG C of die head temperature；Host
Revolving speed is 240-260 r/min, and the revolving speed of feeding is 60-70 r/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711413035.8A CN109957245A (en) | 2017-12-24 | 2017-12-24 | Charging pile no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711413035.8A CN109957245A (en) | 2017-12-24 | 2017-12-24 | Charging pile no hydrogen phosphide organic phosphonate flame-retardant reinforced nylon and preparation method thereof |
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| Publication Number | Publication Date |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819958A (en) * | 2022-11-07 | 2023-03-21 | 河南天海电器有限公司 | Halogen-free flame-retardant nylon material for high-voltage connector or fuse box and preparation method and application thereof |
-
2017
- 2017-12-24 CN CN201711413035.8A patent/CN109957245A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819958A (en) * | 2022-11-07 | 2023-03-21 | 河南天海电器有限公司 | Halogen-free flame-retardant nylon material for high-voltage connector or fuse box and preparation method and application thereof |
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Application publication date: 20190702 |