CN110218444A - A kind of preparation method of DOPO grafting carbon nanotube is fire-retardant and antistatic for nylon 6 - Google Patents
A kind of preparation method of DOPO grafting carbon nanotube is fire-retardant and antistatic for nylon 6 Download PDFInfo
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- CN110218444A CN110218444A CN201910643106.6A CN201910643106A CN110218444A CN 110218444 A CN110218444 A CN 110218444A CN 201910643106 A CN201910643106 A CN 201910643106A CN 110218444 A CN110218444 A CN 110218444A
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- nylon
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- retardant
- antistatic
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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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/017—Additives being an antistatic agent
Abstract
The present invention relates to a kind of preparation methods of DOPO grafting carbon nanotube for the fire-retardant and antistatic of nylon 6.It is added in PA6 it is characterized in that being grafted MWCNTs by DOPO so that material reaches the antistatic standard and UL94V-2 grade of GB12158-2006 " otherwise electrostatic accident general directive/guide " and GJB3007-1997 " antistatic workspace technical requirements ", while additive amount is less does not influence the original physical property of material.Effect of the invention is that by add DOPO-MWCNTs method prepare it is a kind of with traditional nylon 6 compared with have better flame resistance, antistatic property, thermal stability and heat-resisting quantity polymer.Equipment used is simple, and easy to implement and operation, produces in existing general material molding equipment.It is widely used in the multiple fields such as building, medical, industrial goods, clothes, all kinds of joint products.
Description
Technical field
The present invention relates to a kind of preparation methods of DOPO grafting carbon nanotube for the fire-retardant and antistatic of nylon 6, belongs to
Engineering plastics technical field.
Technical background
PA6 be it is a kind of there are high intensity, self-lubricating, wear-resisting and resistant to chemical etching etc. excellent properties, be the maximum work of yield
Engineering plastics are mainly used for electronic apparatus and auto parts and components etc., have a wide range of applications in engineering field.PA6 itself is special
Property determine its volume resistivity with higher, UL-94 off grade, easily accumulation electrostatic, there are security risks.In certain special necks
Under domain, such as explosive, inflammable, high abrasion use environment, it is bigger to generally require not only intensity, but also flame-retardant and anti-static performance is more
High PA6 modified material.It is exactly carbon black (CB) in the antistatic modified material of most common PA6, but the big influence material of additional amount
Self character is not suitable for many occasions.
For the application for PA6 after accumulating electrostatic, easy release electrostatic generates spark and Electrostatic Absorption dust, is firing
After burning, wink speed generates a large amount of heat and poisonous and hazardous flue gas, easily causes serious consequence to lives and properties.Pass through
DOPO is grafted MWCNTs, improves the fire-retardant and antistatic property of PA6, reduces the generation of hidden danger, promotes flame retardant property simultaneously for body
The control of product resistivity in a certain range, reaches antistatic effect.
Summary of the invention
For problem of the prior art mentioned above, the present invention provides a kind of preparation method of DOPO grafting carbon nanotube
For the fire-retardant and antistatic of nylon 6.DOPO-MWCNTs, which is added, can significantly improve the flame-retardant and anti-static performance of PA6, reach
Resisting for GB12158-2006 " otherwise the general directive/guide of electrostatic accident " and GJB3007-1997 " antistatic workspace technical requirements " is quiet
Electric standard, UL-94V-2 maintain the original excellent properties of material.
The present invention is achieved by the following technical programs:
A kind of preparation method of DOPO grafting carbon nanotube is fire-retardant and antistatic for nylon 6, mainly by matrix PA6 tree
Rouge, multi-walled carbon nanotube MWCNTs and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO composition comprising
With following numbers are as follows:
100 parts of PA6
1-10 parts of DOPO-MWCNTs
6 composite material of antistatic nylon, is prepared by the following method to obtain:
(1) by 12h dry at 100 parts of nylon 6,1-10 parts of DOPO, 1-10 parts of MWCNTs in an oven 80 DEG C, in case subsequent
It uses；
(2) above-mentioned DOPO and ethyl alcohol are placed in four neck round-bottom flasks equipped with blender.Solvent is heated to 20-120
DEG C, it is slowly added to formaldehyde, while being stirred at reflux 5-30 hours.After reaction, by remaining DOPO-CH2OH is filtered and at 50 DEG C
Under be dried in vacuum overnight；
(3) in the 500ml round-bottomed flask equipped with condenser, MWCNT is dispersed in a certain proportion of sulfuric acid of 150ml
In the mixture of (98wt%) and nitric acid (68wt%).Dispersion is flowed back 4 hours under ultrasonic vibration at 15-80 DEG C.So
Afterwards, it dilutes dispersions obtained and filter in water.By solid product (MWCNT-COOH) washing to certain pH, and at 40 DEG C
Under be dried in vacuum overnight；
(4) MWCNT-COOH, SOCl 2 and DMF are dispersed 2-6 hours with certain proportion in ultrasonic bath, and certain
At a temperature of flow back 24 hours.Then unreacted SOCl 2 is removed by distillation, and at room temperature by remaining MWCNT-COCl
It is dry；
(5) MWCNT-COCl the and DOPO-CH 2OH of calculation amount is added in glass flask and is dispersed with toluene.Then will
Mixture stirs certain time under 2 atmosphere of N at a certain temperature.Filtration product DOPO-MWCNTs is simultaneously dried under vacuum.
(6) 100 parts of nylon 6 of above-mentioned drying, 1-10 parts of DOPO-MWCNTs are uniformly mixed in batch mixer
(7) uniformly mixed material is added in single screw extrusion machine and squeezes out, is granulated；
(8) in 200-250 DEG C of tablet press machine, 5-25Mpa pressure lower sheeting examination is made in 3-20 minutes in the nylon 6 being granulated
Sample tests its mechanical property, flame retardant property and antistatic property respectively.
The present invention has excellent fire-retardant and antistatic property, simultaneously as additive amount is few, the mechanical property of nylon 6 does not have yet
It has a significant impact.
Equipment used in the present invention is simple, and easy to implement and operation, produces on existing general molding equipment.
Antistatic nylon 6 of the invention can be widely applied to the multiple fields such as explosive, inflammable, high abrasion.
Hereinafter, being illustrated in conjunction with specific embodiments to the preparation method of flame-retardant and anti-static nylon 6 of the invention.
Specific embodiment
The embodiment of the present invention provides a kind of flame-retardant and anti-static nylon 6 composite material comprising has following numbers are as follows: Buddhist nun
6 100 parts of dragon；1-10 parts of DOPO-MWCNTs.
Embodiment one
1) 100 parts of nylon, 6,1 parts of DOPO-MWCNTs are uniformly mixed；
2) single screw extrusion machine is added in uniformly mixed material, the temperature in each area of single screw extrusion machine is respectively as follows: an area
220 DEG C, two 230 DEG C of areas, three 240 DEG C of areas, four 230 DEG C of areas.；
3) in 230 DEG C, 18Mpa pressure lower sheeting 12 minutes required sample was made, to it in above-mentioned 2) resulting nylon 6
It is tested for the property.Its performance is as shown in Table 1.
Embodiment two
1) 100 parts of nylon, 6,3 parts of DOPO-MWCNTs are uniformly mixed；
2) single screw extrusion machine is added in uniformly mixed material, the temperature in each area of single screw extrusion machine is respectively as follows: an area
220 DEG C, two 230 DEG C of areas, three 240 DEG C of areas, four 230 DEG C of areas.；
3) in 230 DEG C, 18Mpa pressure lower sheeting 12 minutes required sample was made, to it in above-mentioned 2) resulting nylon 6
It is tested for the property.Its performance is as shown in Table 1.
Embodiment three
1) 100 parts of nylon, 6,5 parts of DOPO-MWCNTs are uniformly mixed；
2) single screw extrusion machine is added in uniformly mixed material, the temperature in each area of single screw extrusion machine is respectively as follows: an area
220 DEG C, two 230 DEG C of areas, three 240 DEG C of areas, four 230 DEG C of areas.；
3) in 230 DEG C, 18Mpa pressure lower sheeting 12 minutes required sample was made, to it in above-mentioned 2) resulting nylon 6
It is tested for the property.Its performance is as shown in Table 1.
Example IV
1) 100 parts of nylon, 6,7 parts of DOPO-MWCNTs are uniformly mixed；
2) single screw extrusion machine is added in uniformly mixed material, the temperature in each area of single screw extrusion machine is respectively as follows: an area
220 DEG C, two 230 DEG C of areas, three 240 DEG C of areas, four 230 DEG C of areas.；
3) in 230 DEG C, 18Mpa pressure lower sheeting 12 minutes required sample was made, to it in above-mentioned 2) resulting nylon 6
It is tested for the property.Its performance is as shown in Table 1.
Embodiment five
1) 100 parts of nylon, 6,9 parts of DOPO-MWCNTs are uniformly mixed；
2) single screw extrusion machine is added in uniformly mixed material, the temperature in each area of single screw extrusion machine is respectively as follows: an area
220 DEG C, two 230 DEG C of areas, three 240 DEG C of areas, four 230 DEG C of areas.；
3) in 230 DEG C, 18Mpa pressure lower sheeting 12 minutes required sample was made, to it in above-mentioned 2) resulting nylon 6
It is tested for the property.Its performance is as shown in Table 1.
As seen from the above table, applied to test performance flame retardant property and the volume electricity of the embodiment batten of technical solution of the present invention
Resistance rate (VR) is greatly improved than pure PA6, and the mechanical property of material also meets the mechanical property generally required.Namely
It says, PA6 composite material of the present invention also keeps its mechanical property while flame-retardant and anti-static, and satisfaction is applied just usually
Constant value has high innovative value.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that above example merely to being illustrated, the range being not intended to be limiting of the invention.The skill of this field
Art personnel are it should be understood that can without departing from the scope and spirit of the present invention modify to above embodiments.This hair
Bright range is defined by the following claims.
Claims (4)
1. a kind of preparation method of DOPO grafting carbon nanotube is fire-retardant and antistatic for nylon 6, it is characterised in that under having
State mass fraction:
6 100 parts of nylon
1-10 parts of DOPO grafting carbon nanotube DOPO-MWCNTs, with reinforced nylon 6 flame-retardant and anti-static performance；
Silane resin acceptor kh-550 0.5%-5%, reacts with HGP-2, improves the compatibility of HGP-2 and nylon 6.
2. flame-retardant and anti-static nylon 6 according to claim 1, which is characterized in that including high temperature resistance, good mechanics
There is GB12158-2006 " otherwise the general directive/guide of electrostatic accident " and GJB3007-1997 " to prevent quiet for performance, UL-94 V-2 grade
Electric workspace technical requirements " anti-static thermoplastic engineering plastics.
3. flame-retardant and anti-static nylon 6 according to claim 1, which is characterized in that the polymer material has good
Mechanical property, good mechanical property include: that at conditions of low strain, polyamide has excellent fatigue performance and stagnant damage
Lose few: other engineering plastics of 6 modular ratio same rigidity of nylon are high, have high impact properties.
4. a kind of flame-retardant and anti-static nylon 6 composite material is used to prepare fire-retardant anti-as described in any one of claim 1-3
Electrostatic nylon 6 composite material, it is characterised in that be prepared by the following method to obtain:
(1) by 12h dry at 100 parts of nylon 6,1-10 parts of DOPO, 1-10 parts of MWCNTs in an oven 80 DEG C, make in case subsequent
With；
(2) above-mentioned DOPO and ethyl alcohol are placed in four neck round-bottom flasks equipped with blender.Solvent is heated to 20-120 DEG C, is delayed
It is slow that formaldehyde is added, while being stirred at reflux 5-30 hours.After reaction, by remaining DOPO-CH2OH filtering and the vacuum at 50 DEG C
It is dried overnight；
(3) in the 500ml round-bottomed flask equipped with condenser, MWCNT is dispersed in a certain proportion of sulfuric acid of 150ml (98wt%)
In the mixture of nitric acid (68wt%).Dispersion is flowed back 4 hours under ultrasonic vibration at 15-80 DEG C.Then, by gained
Dispersion is diluted and is filtered in water.By solid product (MWCNT-COOH) washing to certain pH, and at 40 DEG C, vacuum is dry
It is dry overnight；
(4) MWCNT-COOH, SOCl 2 and DMF are dispersed 2-6 hours with certain proportion in ultrasonic bath, and in certain temperature
Lower reflux 24 hours.Then unreacted SOCl2 is removed by distillation, and remaining MWCNT-COCl is dried at room temperature for；
(5) MWCNT-COCl of calculation amount and 2 OH of DOPO-CH is added in glass flask and is dispersed with toluene.Then it will mix
It closes object and stirs certain time at a certain temperature under 2 atmosphere of N.Filtration product DOPO-MWCNTs is simultaneously dried under vacuum.
(6) 100 parts of nylon 6 of above-mentioned drying, 1-10 parts of DOPO-MWCNTs are uniformly mixed in batch mixer
(7) uniformly mixed material is added in single screw extrusion machine and squeezes out, is granulated；
(8) in 200-250 DEG C of tablet press machine, 5-25Mpa pressure lower sheeting sample is made in 3-20 minutes in the nylon 6 being granulated, point
Its mechanical property, flame retardant property and antistatic property are not tested.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910643106.6A CN110218444A (en) | 2019-07-17 | 2019-07-17 | A kind of preparation method of DOPO grafting carbon nanotube is fire-retardant and antistatic for nylon 6 |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910643106.6A CN110218444A (en) | 2019-07-17 | 2019-07-17 | A kind of preparation method of DOPO grafting carbon nanotube is fire-retardant and antistatic for nylon 6 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225902A (en) * | 2020-10-26 | 2021-01-15 | 长春工业大学 | DDP polyphosphate flame retardant and preparation method thereof |
| CN113737522A (en) * | 2021-09-06 | 2021-12-03 | 江阴市宏勇医疗科技发展有限公司 | Antistatic antifriction non-woven fabrics |
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| CN102181074A (en) * | 2011-03-23 | 2011-09-14 | 同济大学 | Carbon nano tube containing 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) base group and preparation method thereof |
| CN102382453A (en) * | 2011-09-28 | 2012-03-21 | 深圳市科聚新材料有限公司 | Antistatic nylon material and preparation method thereof |
| CN102899742A (en) * | 2012-11-07 | 2013-01-30 | 东华大学 | Electrically conductive composite fiber containing carbon nanotubes and preparation method of fiber |
| CN106221209A (en) * | 2016-08-25 | 2016-12-14 | 江苏百利达股份有限公司 | A kind of nylon66 fiber/carbon nanotube conducting composite and preparation method thereof |
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| US20180201751A1 (en) * | 2016-02-26 | 2018-07-19 | Lg Chem, Ltd. | Carbon composite material and method for producing same |
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2019
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102181074A (en) * | 2011-03-23 | 2011-09-14 | 同济大学 | Carbon nano tube containing 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) base group and preparation method thereof |
| CN102382453A (en) * | 2011-09-28 | 2012-03-21 | 深圳市科聚新材料有限公司 | Antistatic nylon material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225902A (en) * | 2020-10-26 | 2021-01-15 | 长春工业大学 | DDP polyphosphate flame retardant and preparation method thereof |
| CN113737522A (en) * | 2021-09-06 | 2021-12-03 | 江阴市宏勇医疗科技发展有限公司 | Antistatic antifriction non-woven fabrics |
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