CN108070198A - A kind of flame-retardant and anti-static polyformaldehyde composite material and preparation method thereof - Google Patents
A kind of flame-retardant and anti-static polyformaldehyde composite material and preparation method thereof Download PDFInfo
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- CN108070198A CN108070198A CN201711062548.9A CN201711062548A CN108070198A CN 108070198 A CN108070198 A CN 108070198A CN 201711062548 A CN201711062548 A CN 201711062548A CN 108070198 A CN108070198 A CN 108070198A
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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
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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
- C08K2201/001—Conductive additives
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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Abstract
The invention discloses a kind of flame-retardant and anti-static polyformaldehyde composite materials and preparation method thereof, and ingredient includes：65 ~ 79.9 parts of polyformaldehyde, 12 ~ 20 parts of nitrogen phosphorus fire retardant, 3 ~ 8 parts of antistatic agent, 0.1 ~ 0.5 part of antioxidant, 1 ~ 3 part of melamine, 4 ~ 8 parts of bulking agent.Using thermoplastic polyurethane elastomer as bulking agent, fire retardant, antistatic agent are coated respectively, covering material is prepared into, then flame-retardant and anti-static polyformaldehyde composite material is prepared after double screw extruder is blended with polyformaldehyde and other auxiliary agents.The present invention chooses the high nitrogen phosphorus fire retardant of phosphorus content and is compounded with other fire retardants, by enhancing flame retardant effect into charcoal；The carbon material of high conductivity and carbon fiber compounding use are selected, the usage amount of antistatic agent is reduced under same resistivity；Using thermoplastic polyurethane elastomer as the bulking agent between anti-electrostatic fire retardant auxiliary agent and polyformaldehyde, boundary caking property is effectively increased, flame-retardant and anti-static polyformaldehyde composite material obtained is made to maintain excellent mechanical strength.
Description
Technical field
The present invention relates to a kind of flame-retardant and anti-static polyformaldehyde composite materials and preparation method thereof, belong to plastics modification technology neck
Domain.
Background technology
Polyformaldehyde as a kind of highly crystalline engineering plastics, have excellent mechanical performance, wear resistance, dimensional stability,
The characteristics such as chemical resistance, fatigue durability, self lubricity make it metal can be replaced to use in various fields, such as in automobile, machine
The fields such as tool manufacture, electronic apparatus, chemical industry, building materials suffer from extensive use.But the limit oxygen index of polyformaldehyde is only 15%, is
Easily incendiary material, and resistivity great Rong is easy to produce static electricity, these defects hinder it in mine, chemical industry, electronic apparatus etc. pair
Fire-retardant, antistatic rank has the application in particular/special requirement field, such as plastic conveyer roller, equipment part.Polyformaldehyde is hindered
Combustion, it is antistatic modified be the main means for making up performance deficiency.But since polyformaldehyde is sensitive to acid or alkaline matter, to resistance
It is harsh to fire agent requirement, limits the application of halogen efficient flame-retarding agent.Therefore, existing flame-retardant and anti-static polyformaldehyde technology of preparing
Mostly using the Application of composite such as halogen-free flame retardants and conductive metal powder, fiber or conductive black, come improve the flame retardant property of material,
Reduce resistivity.Patent CN103740043A discloses a kind of Flame-retardant anti-static difunctional polyoxymethylene resin and preparation method thereof,
It mixes red phosphorus microcapsule fire retardant, carbon forming agent, the agent of suction aldehyde, antistatic agent, antioxidant with polyformaldehyde matrix by a certain percentage,
The difunctional polyformaldehyde of flame-retardant and anti-static is prepared for, antistatic agent is metallic fibers, metal powder or the particles such as copper, nickel, stainless steel.
Patent CN103435963B discloses a kind of flame-retardant and anti-static polyformaldehyde special color master batch and preparation method thereof, and the technology is by poly- first
Aldehyde, nano imvite, tourmaline powder, toner, zinc stearate, ethoxylated dodecyl base amine, dimethyl dimercapto acetic acid are different pungent
Ester tin, melamine cyanurate and superfine powder of polytetrafluoroethylene are added in high-speed mixer, are put into extruder after mixing
Then middle carry out melt blending prepares flame-retardant and anti-static polyformaldehyde special color by granulation after the shearing of screw rod or rotor, mixing
Master batch.Patent CN102807729A discloses a kind of formula of flame-proof antistatic modified polyformaldehyde, and the formula is with phosphate trimethylbenzene
Ester is light as antistatic agent, titanium dioxide as antioxidant, glycerin monostearate as fire retardant, N- phenyl-α-naphthylamines
Stabilizer, boron nitride are heat-resistant agent.Patent CN103694623A discloses a kind of fire-retardant anti-based on composite halogen-free flame-retardant system
Electrostatic acetal resin, material composition include polyformaldehyde, composite halogen-free fire retardant, carbon forming agent, inhale aldehyde agent, fire retarding synergist,
Antistatic agent, processing aid and antioxidant are prepared through double screw extruder melting extrusion.
However, the fire retardant and antistatic agent additive amount in the existing polyoxymethylene modified technology of flame-retardant and anti-static are big, and it is inorganic
Powder and polyformaldehyde compatibility are very poor, and the addition of substantial amounts of powder auxiliary agent makes the mechanical property of polyformaldehyde material deteriorate seriously, especially
It is that the defects of reunion of powder auxiliary agent causes is decreased obviously the impact resistance of material, and material embrittlement is fire-retardant, anti-quiet obtaining
While electrical property, use value is also lost.The nitrogen phosphorus fire retardant and there is high conductivity that the present invention has selected phosphorus content high
Carbon material as antistatic agent, then impregnated, coated using thermoplastic polyurethane elastomer as bulking agent respectively, it is final logical
It crosses double screw extruder melt blending and prepares flame-retardant and anti-static polyformaldehyde composite material, improve fire retardant, antistatic agent etc. and help
The dispersiveness of agent, reduces auxiliary dosage, while fire-retardant, the antistatic property of polyformaldehyde is made to be greatly improved, maintains
Excellent mechanical property can meet the application requirement in the fields such as mine, chemical industry, electronic apparatus.
The content of the invention
It is an object of the present invention to provide a kind of flame-retardant and anti-static polyformaldehyde composite materials and preparation method thereof, solve existing product
And deficiency existing in terms of technology of preparing.
To realize goal of the invention, technical solution of the present invention is as follows：
Ingredient includes in parts by weight：It is 65 ~ 79.9 parts of polyformaldehyde, 12 ~ 20 parts of nitrogen phosphorus fire retardant, 3 ~ 8 parts of antistatic agent, anti-
0.1 ~ 0.5 part of oxygen agent, 1 ~ 3 part of melamine, 4 ~ 8 parts of bulking agent.
The nitrogen phosphorus fire retardant is ammonium polyphosphate, the contracting of melamine condensed phosphoric esters, melamine borate salt, melamine
The compound of one or more of pyrophosphate and pentaerythritol bisphosphorate melamine salt.
The antistatic agent is the compound of one or more of conductive black, carbon nanotubes, graphene with carbon fiber.
The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic ester] pentaerythritol esters, three ［ 2,4-
Di-tert-butyl-phenyl ］ phosphite ester, in triethylene-glycol double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester]
One or more.
The bulking agent is polyether-type or polyester-type thermoplastic polyurethane elastomer.
Step of preparation process is as follows：
(1) a certain amount of bulking agent is taken to be put into kneading machine in proportion, be added to the nitrogen phosphorus fire retardant of compounding after melting mixed
It in mill, is taken out after bulking agent is sufficiently mixed with fire retardant, forms fire retardant coating.
(2) a certain amount of bulking agent is taken to be put into kneading machine in proportion, by conductive black, carbon nanotubes, stone after melting
One or more of black alkene is added in kneading machine, is taken out after bulking agent is sufficiently mixed with antistatic agent, is formed antistatic
Agent coating.
(3) it is dried fire retardant coating, antistatic agent coating, polyformaldehyde and melamine, antioxidant is abundant
Twin-screw extruder barrel is added to after mixing, carbon fiber is added in from side feeding, after double screw extruder melt blending, is drawn
Flame-retardant and anti-static polyformaldehyde composite material is prepared after item, pelletizing, drying.
Technological parameter：Technological parameter in step (1)：The preceding roll temperature of kneading machine is 168 ~ 175 DEG C, rear roll temperature is 175
~ 185 DEG C, roller speed be 20 ~ 30 rpm, mixing time is 30 min；Step（2）In technological parameter：Roll temperature is before kneading machine
168 ~ 175 DEG C, rear roll temperature be 175 ~ 185 DEG C, roller speed is 25 ~ 35 rpm, mixing time is 45 min；In step (3)
Technological parameter：Double screw extruder barrel zone temperature is 170 DEG C ~ 185 DEG C, head temperature is 180 DEG C, screw speed is 150 ~ 200
Rpm, feeding rotating speed are 12 ~ 15 rpm.
Implementation result：
The nitrogen phosphorus fire retardant for selecting phosphorus content high while being used as fire retardant, and plays the role of carbon forming agent, flame retarding efficiency
Height reduces fire retardant additive amount.
Using electric conductivity is excellent, surface area is big or draw ratio is big carbon material as antistatic agent, critical content is low, and adds
Enter carbon fiber, the fiber after blending shearing uniformly disperses in the base, since carbon fiber is conductive and maintains certain
Length, it is easier to form conductive network, significantly reduce the additive amount of antistatic agent, and appropriate addition may also function as the work of enhancing
With.
Polyformaldehyde is non-polar polymer, very poor with inorganic particle compatibility, and thermoplastic polyurethane elastomer is and poly- first
One of best polymer of aldehyde compatibility is prepared into cladding using thermoplastic polyurethane elastomer cladding fire retardant, antistatic agent
Object can effectively improve the interface adhesion between auxiliary agent and polyformaldehyde, so as to reduce the damage to mechanical property；And it solves anti-
Carbon nanotubes, graphene in electrostatic agent, conductive black is light, volume is big, it is difficult to uniform directly with polyformaldehyde by twin-screw
The problem of mixing；And thermoplastic polyurethane elastomer has toughening effect, can alleviate material embrittlement phenomenon.
Specific embodiment
Embodiment 1
Ingredient includes in parts by weight：76.5 parts of polyformaldehyde, 8 parts of ammonium polyphosphate, pentaerythritol bisphosphorate melamine salt 4
Part, 2 parts of carbon nanotubes, 2 parts of carbon fiber, triethylene-glycol are double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester]
0.5 part, 3 parts of melamine, 4 parts of polyester-type thermoplastic polyurethane elastomer.
Step of preparation process is as follows：
（1）Polyester-type thermoplastic polyurethane elastomer is put into kneading machine, by ammonium polyphosphate, the double phosphorus of pentaerythrite after melting
Acid esters melamine salt is added in kneading machine, is taken out after thermoplastic polyurethane elastomer is sufficiently mixed with fire retardant, is formed fire-retardant
Agent coating.Technological parameter：The preceding roll temperature of kneading machine is 168 DEG C, rear roll temperature is 175 DEG C, roller speed be 20 rpm, be kneaded when
Between be 30 min.
（2）Polyester-type thermoplastic polyurethane elastomer is put into kneading machine, is added to carbon nanotubes after melting mixed
It in mill, is taken out after polyester-type thermoplastic polyurethane elastomer is sufficiently mixed with carbon nanotubes, forms antistatic agent coating.
Technological parameter：Preceding roll temperature is 168 DEG C, rear roll temperature is 175 DEG C, roller speed is 25 rpm, mixing time is 45 min.
（3）Dried fire retardant coating, antistatic agent coating, polyformaldehyde and melamine, antioxidant is abundant
Twin-screw extruder barrel is added to after mixing, carbon fiber is added in from side feeding, after double screw extruder melt blending, is drawn
Flame-retardant and anti-static polyformaldehyde composite material is prepared after item, pelletizing, drying.Technological parameter：Double screw extruder barrel zone temperature is
170 DEG C ~ 185 DEG C, head temperature be 180 DEG C, screw speed is 150 rpm, feeding rotating speed is 12rpm.
Embodiment 2
Ingredient includes in parts by weight：68.5 parts of polyformaldehyde, 8 parts of melamine condensed phosphoric esters, pentaerythrite diphosphate
6 parts of ester melamine salt, 4 parts of carbon nanotubes, 1 part of conductive black, 3 parts of carbon fiber, three ［ 2,4- di-tert-butyl-phenyls ］ phosphite esters
0.5 part, 1 part of melamine, 8 parts of Polyether-type thermoplastic polyurethane elastomer.
Step of preparation process is as follows：
（1）Polyether-type thermoplastic polyurethane elastomer is put into kneading machine, by melamine condensed phosphoric esters, season after melting
Penta tetrol biphosphonate melamine salt is added in kneading machine, is taken after thermoplastic polyurethane elastomer is sufficiently mixed with fire retardant
Go out, form fire retardant coating.Technological parameter：The preceding roll temperature of kneading machine is 170 DEG C, rear roll temperature is 180 DEG C, roller speed is 25
Rpm, mixing time are 30 min.
（2）Polyether-type thermoplastic polyurethane elastomer is put into kneading machine, by carbon nanotubes and conductive charcoal after melting
It is black to be added in kneading machine, it takes out, is formed anti-quiet after Polyether-type thermoplastic polyurethane elastomer is sufficiently mixed with antistatic agent
Electric agent coating.Technological parameter：Preceding roll temperature is 170 DEG C, rear roll temperature is 178 DEG C, roller speed is 30 rpm, mixing time is
45 min。
（3）Dried fire retardant coating, antistatic agent coating, polyformaldehyde and melamine, antioxidant is abundant
Twin-screw extruder barrel is added to after mixing, carbon fiber is added in from side feeding, after double screw extruder melt blending, is drawn
Flame-retardant and anti-static polyformaldehyde composite material is prepared after item, pelletizing, drying.Technological parameter：Double screw extruder barrel zone temperature is
170 DEG C ~ 185 DEG C, head temperature be 180 DEG C, screw speed is 200 rpm, feeding rotating speed is 15 rpm.
Embodiment 3
Ingredient includes in parts by weight：65.9 parts of polyformaldehyde, 6 parts of melamine borate salt, melamine contracting pyrophosphate
10 parts, 4 parts of pentaerythritol bisphosphorate melamine salt, 3 parts of graphene, 2 parts of carbon fiber, four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic ester] 0.1 part of pentaerythritol ester, 1 part of melamine, 8 parts of polyester-type thermoplastic polyurethane elastomer.
Step of preparation process is as follows：
（1）Polyester-type thermoplastic polyurethane elastomer is put into kneading machine, by melamine borate salt, melamine after melting
Amine contracting pyrophosphate, pentaerythritol bisphosphorate melamine salt are added in kneading machine, treat thermoplastic polyurethane elastomer with it is fire-retardant
Agent is taken out after being sufficiently mixed, and forms fire retardant coating.Technological parameter：The preceding roll temperature of kneading machine is 175 DEG C, rear roll temperature is
185 DEG C, roller speed for 30 rpm, mixing time be 30 min.
（2）Polyester-type thermoplastic polyurethane elastomer is put into kneading machine, graphene is added to mixing after melting
It in machine, is taken out after thermoplastic polyurethane elastomer is sufficiently mixed with antistatic agent, forms antistatic agent coating.Technique is joined
Number：Preceding roll temperature is 175 DEG C, rear roll temperature is 185 DEG C, roller speed is 35 rpm, mixing time is 45 min.
（3）Dried fire retardant coating, antistatic agent coating, polyformaldehyde and melamine, antioxidant is abundant
Twin-screw extruder barrel is added to after mixing, carbon fiber is added in from side feeding, after double screw extruder melt blending, is drawn
Flame-retardant and anti-static polyformaldehyde composite material is prepared after item, pelletizing, drying.Technological parameter：Double screw extruder barrel zone temperature is
170 DEG C ~ 185 DEG C, head temperature be 180 DEG C, screw speed is 200 rpm, feeding rotating speed is 15 rpm.
Embodiment 4
Ingredient includes in parts by weight：68.7 parts of polyformaldehyde, 6 parts of ammonium polyphosphate, 6 parts of melamine borate salt, Ji Wusi
4 parts of alcohol biphosphonate melamine salt, 3 parts of carbon nanotubes, 2 parts of graphene, 2 parts of carbon fiber, four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic ester] 0.3 part of pentaerythritol ester, 2 parts of melamine, 6 parts of polyester-type thermoplastic polyurethane elastomer.
Step of preparation process is as follows：
（1）Polyester-type thermoplastic polyurethane elastomer is put into kneading machine, by ammonium polyphosphate, melamine borate after melting
Salt, pentaerythritol bisphosphorate melamine salt are added in kneading machine, treat that thermoplastic polyurethane elastomer is sufficiently mixed with fire retardant
After take out, formed fire retardant coating.Technological parameter：The preceding roll temperature of kneading machine is 170 DEG C, rear roll temperature is 180 DEG C, roller speed
It is 30 min for 30 rpm, mixing time.
（2）Polyester-type thermoplastic polyurethane elastomer is put into kneading machine, is added carbon nanotubes, graphene after melting
Enter into kneading machine, taken out after thermoplastic polyurethane elastomer is sufficiently mixed with antistatic agent, form antistatic agent coating.
Technological parameter：Preceding roll temperature is 175 DEG C, rear roll temperature is 180 DEG C, roller speed is 35 rpm, mixing time is 45 min.
（3）Dried fire retardant coating, antistatic agent coating, polyformaldehyde and melamine, antioxidant is abundant
Twin-screw extruder barrel is added to after mixing, carbon fiber is added in from side feeding, after double screw extruder melt blending, is drawn
Flame-retardant and anti-static polyformaldehyde composite material is prepared after item, pelletizing, drying.Technological parameter：Double screw extruder barrel zone temperature 170
DEG C ~ 185 DEG C, head temperature be 180 DEG C, screw speed is 175 rpm, feeding rotating speed is 13 rpm.
The performance of the flame-retardant and anti-static polyformaldehyde composite material of the preparation of the embodiment of the present invention 1 ~ 4 is tested, as a result
As shown in table 1.
The performance indicator of 1 embodiment of table, 1 ~ 4 sample
| Detection project | Testing standard | Pure polyformaldehyde | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength（MPa） | GB/T1040 | 62.3 | 52.5 | 47.6 | 44.6 | 48.3 |
| Notch impact strength（KJ/m2） | GB/T1843 | 6.2 | 5.4 | 4.7 | 4.1 | 4.9 |
| Fire-retardant rank | UL94 | HB | V-2 | V-1 | V-0 | V-1 |
| Surface resistivity/Ω | GB/T 1410 | 1016 | 1010 | 103 | 107 | 104 |
Claims (9)
1. a kind of flame-retardant and anti-static polyformaldehyde composite material, which is characterized in that ingredient includes in parts by weight：Polyformaldehyde 65
~ 79.9 parts, 12 ~ 20 parts of nitrogen phosphorus fire retardant, 3 ~ 8 parts of antistatic agent, 0.1 ~ 0.5 part of antioxidant, 1 ~ 3 part of melamine, bulking agent 4
~ 8 parts.
2. a kind of flame-retardant and anti-static polyformaldehyde composite material according to claim 1, which is characterized in that the nitrogen phosphorus is fire-retardant
Agent is ammonium polyphosphate, one kind or several in melamine condensed phosphoric esters, melamine borate salt, melamine contracting pyrophosphate
Kind and the compound of pentaerythritol bisphosphorate melamine salt.
A kind of 3. flame-retardant and anti-static polyformaldehyde composite material according to claim 1, which is characterized in that the antistatic agent
For the compound of one or more of conductive black, carbon nanotubes, graphene and carbon fiber.
4. a kind of flame-retardant and anti-static polyformaldehyde composite material according to claim 1, which is characterized in that the antioxidant is
Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, three ［ 2,4- di-tert-butyl-phenyls ］ phosphite esters,
One or more of triethylene-glycol double [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester].
5. a kind of flame-retardant and anti-static polyformaldehyde composite material according to claim 1, which is characterized in that the bulking agent is
Polyether-type or polyester-type thermoplastic polyurethane elastomer.
6. a kind of preparation method of flame-retardant and anti-static polyformaldehyde composite material of claim 1-5 any one of them, feature exist
In step of preparation process is as follows：
(1) a certain amount of bulking agent is weighed in proportion to be put into kneading machine, be added to the nitrogen phosphorus fire retardant of compounding after melting
It in kneading machine, is taken out after bulking agent is sufficiently mixed with fire retardant, forms fire retardant coating；
(2) weigh a certain amount of bulking agent in proportion to be put into kneading machine, by conductive black, carbon nanotubes, graphite after melting
One or more of alkene is added in kneading machine, is taken out after bulking agent is sufficiently mixed with antistatic agent, forms antistatic agent
Coating；
(3) dried fire retardant coating, antistatic agent coating, polyformaldehyde and melamine, antioxidant are sufficiently mixed
After be added to twin-screw extruder barrel, carbon fiber is added in from side feeding, and after double screw extruder melt blending, tie rod is cut
Flame-retardant and anti-static polyformaldehyde composite material is prepared in grain, drying.
7. a kind of preparation method of flame-retardant and anti-static polyformaldehyde composite material according to claim 6, which is characterized in that
Technological parameter in step (1)：The preceding roll temperature of kneading machine is 168 ~ 175 DEG C, rear roll temperature is 175 ~ 185 DEG C, roller speed be 20 ~
30 rpm, mixing time are 30 min.
8. a kind of preparation method of flame-retardant and anti-static polyformaldehyde composite material according to claim 6, which is characterized in that
Step（2）In technological parameter：The preceding roll temperature of kneading machine is 168 ~ 175 DEG C, rear roll temperature is 175 ~ 185 DEG C, roller speed be 25 ~
35 rpm, mixing time are 45 min.
9. a kind of preparation method of flame-retardant and anti-static polyformaldehyde composite material according to claim 6, which is characterized in that
Technological parameter in step (3)：Double screw extruder barrel zone temperature is 170 DEG C ~ 185 DEG C, head temperature is 180 DEG C, screw rod turns
Speed is 150 ~ 200 rpm, feeding rotating speed is 12 ~ 15 rpm.
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Cited By (5)
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|---|---|---|---|---|
| CN111057344A (en) * | 2019-12-04 | 2020-04-24 | 兖矿集团有限公司 | Flame-retardant polyformaldehyde and preparation method thereof |
| CN111117147A (en) * | 2020-01-15 | 2020-05-08 | 东莞市耐格美塑胶制品有限公司 | Permanently anti-static surface matte reinforced POM (polyoxymethylene) board and preparation method thereof |
| CN112724594A (en) * | 2020-12-30 | 2021-04-30 | 甘肃泰尔精细化工有限公司 | Antistatic polyformaldehyde and preparation method thereof |
| CN114989552A (en) * | 2022-05-20 | 2022-09-02 | 江西江铜碳纳米材料有限公司 | Alloy prepared based on coating modified carbon method and preparation method thereof |
| CN115073878A (en) * | 2022-08-15 | 2022-09-20 | 广东盟信塑胶实业有限公司 | Carbon nanotube grafted flame-retardant antistatic polyformaldehyde composite material and preparation method thereof |
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| CN111057344A (en) * | 2019-12-04 | 2020-04-24 | 兖矿集团有限公司 | Flame-retardant polyformaldehyde and preparation method thereof |
| CN111117147A (en) * | 2020-01-15 | 2020-05-08 | 东莞市耐格美塑胶制品有限公司 | Permanently anti-static surface matte reinforced POM (polyoxymethylene) board and preparation method thereof |
| CN112724594A (en) * | 2020-12-30 | 2021-04-30 | 甘肃泰尔精细化工有限公司 | Antistatic polyformaldehyde and preparation method thereof |
| CN114989552A (en) * | 2022-05-20 | 2022-09-02 | 江西江铜碳纳米材料有限公司 | Alloy prepared based on coating modified carbon method and preparation method thereof |
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