CN107541001A - A kind of Cationic/nonionic composite high polymer antistatic agent - Google Patents
A kind of Cationic/nonionic composite high polymer antistatic agent Download PDFInfo
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- CN107541001A CN107541001A CN201710782643.XA CN201710782643A CN107541001A CN 107541001 A CN107541001 A CN 107541001A CN 201710782643 A CN201710782643 A CN 201710782643A CN 107541001 A CN107541001 A CN 107541001A
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- antistatic
- cationic
- antistatic additive
- nonionic
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Abstract
The invention discloses a kind of Cationic/nonionic composite high polymer antistatic agent.The present invention passes through free-radical polymerized method synthesizing cationic/nonionic composite high-molecular antistatic additive using lauric acid diethyl amide, dimethylethanolamine and polycaprolactone.Lauric acid diethyl amide in antistatic additive is a kind of cationic surfactant with high charge density, and dimethylethanolamine is a kind of antistatic additive of nonionic, and the synergy of the two assigns ABS resin excellent antistatic property；Polycaprolactone provides antistatic additive and the good compatibility of ABS resin.The unique molecular structure of antistatic additive causes ABS resin to have permanent antistatic, the shortcomings that overcoming conventional antistatic additive persistence difference.
Description
Technical field
The present invention relates to a kind of Cationic/nonionic composite high polymer antistatic agent and preparation method thereof, and in particular to one
Kind is suitable for Cationic/nonionic composite high polymer antistatic agent of ABS resin and preparation method thereof.
Background technology
ABS resin is a kind of using quite varied engineering plastics, but the good insulating of itself, surface resistivity
Height, electrostatic is easily produced during use, limit its application in some occasions.Such as in mine electrical appliance shell in use,
If producing excessive electrostatic charge, surface-discharge will be caused and cause fire explosion.
The cationic surfactants such as quaternary ammonium salt have high antistatic effect, therefore are widely used as the anti-of high polymer
Electrostatic agent.But they exist with high polymer poor compatibility, it is rapid ooze out surface and produce stickiness, heat resistance is poor the shortcomings of.It is anti-
Electrostatic agent and matrix resin poor compatibility can be such that antistatic additive is separated out in resin surface rapidly, although in a short time antistatic effect compared with
It is good, but easily come off under the influence of external condition, so as to which antistatic effect is not lasting.
Polymer material science and engineering（2003,19(3):137-140）Reported in dimethylaminoethyl second
Ester bromic ether（MAEB）- styrene（St）Copolymer, dimethylaminoethyl methacrylate bromo dimethyl suflfate
（MADMS）- styrol copolymer etc., is added in ABS, can make the reduction of ABS surface resistivity, but reduction amplitude is smaller,
1011ABS resins still have 10-10 Ω surface resistivity, are still reached in some specific occasions less than antistatic requirement.Plastics
（2011,40(3):76-79）Reported in it is poly-（Dimethylaminoethyl acrylate methyl base butylammonium bromide-styrene）Though amphipathic copolymer 89
The surface resistivity of ABS resin can be so set to be reduced to 10-10 Ω level, but it is had a great influence by ambient humidity, humidity
Still there is larger surface resistivity when relatively low.And sample surface resistivity after boiling 2.5h rises 2-3
The individual order of magnitude, heat resistance and persistence are relatively poor.
The content of the invention
In view of the shortcomings of the prior art, the invention provides it is a kind of available for ABS resin and can make ABS resin surface 89
Resistivity is reduced to 10-10 Ω level, and it is influenceed smaller by ambient humidity, has good, the heat-resist sun of persistence
Ionic/nonionic composite high-molecular antistatic additive and preparation method thereof.
The Cationic/nonionic composite high polymer antistatic agent of the present invention, is made up of the raw material of following mass fractions：Bay
Sour 100 parts of diglycollic amide, 15 parts~40 parts of dimethylethanolamine, 50 parts~150 parts of polycaprolactone, 1.5 parts of rilanit special
~5 parts, 350 parts of polytetrafluoroethylene (PTFE).
Preferably, the raw material mass mixture ratio is as follows：100 parts of dimethylethanolamines of lauric acid diethyl amide 25 parts~30
Part, 60 parts~90 parts of polycaprolactone, 3 parts~4 parts of rilanit special, 350 parts of solvent.
The dimethylethanolamine is preferably the esterification products i.e. metering system of poly glycol monomethyl ether and methacrylic acid
Acid polyethylene glycol monomethyl ether ester, molecular weight 1200 ~ 2000.
The polycaprolactone is preferably in styrene, methyl methacrylate, butyl acrylate and hydroxy-ethyl acrylate
It is a kind of.
The rilanit special is preferably azodiisobutyronitrile（AIBN）Or ABVN（ABVN）.
The polytetrafluoroethylene (PTFE) is preferably absolute methanol or absolute ethyl alcohol.
The preparation method of the cationic/nonionic Polymer-metallic Catalyst of the present invention, comprises the following steps：（1）By bay
Sour diglycollic amide and polycaprolactone are dissolved in polytetrafluoroethylene (PTFE), are stirred, and obtain monomer mixture solution A；（2）By hydrogenated castor
Oil and dimethylethanolamine, which are dissolved in polytetrafluoroethylene (PTFE), is made mixed solution B, and mixed solution B is added drop-wise into monomer mixture solution
In A, control adds 2~2.5h of time, 70~75 DEG C of reaction temperature；（3）Mixed solution B is added dropwise, and continues 2~3h of reaction
Afterwards, with deionized water precipitated product, filter, washing, in 65-75 DEG C of vacuum drying, obtain cationic/nonionic composite high-molecular
Antistatic additive.
The Cationic/nonionic composite high polymer antistatic agent of the present invention can be used for the needs such as ABS resin preferably antistatic
The polymer composite of performance, the present invention are passed through certainly using lauric acid diethyl amide, dimethylethanolamine and polycaprolactone
Method synthesizing cationic/nonionic composite high-molecular the antistatic additive being copolymerized by base.Laurate diethanol acyl in antistatic additive
Amine is a kind of cationic surfactant with high charge density, and dimethylethanolamine is a kind of the antistatic of nonionic
Agent, the synergy of the two assign ABS resin excellent antistatic property；Polycaprolactone provides antistatic additive and ABS resin is good
Good compatibility.The unique molecular structure of antistatic additive causes ABS resin to have permanent antistatic, overcomes conventional antistatic
The shortcomings that agent persistence difference.
The Cationic/nonionic composite high polymer antistatic agent of the present invention is a kind of hydrophilic and oleophilic amphiphilic polymers, its
Middle hydrophilic radical has very high charge density, can provide excellent antistatic property, and lipophilic group can provide and ABS trees
The suitable compatibility of fat, makes antistatic additive not penetrate into surface rapidly, and is not easy to be affected by the external environment and lose, and protects
Demonstrate,prove the lasting antistatic property of ABS resin.In addition, the present invention is from the quaternary ammonium salt that the anion of fine heat-resisting performance is salt acid group
Cationic surfactant, it can make antistatic additive provided by the present invention that there is excellent heat resistance.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1 weighs 100 parts of lauric acid diethyl amides and 50 parts of styrene, pours into and fills 250 parts of absolute ethyl alcohols
In beaker, it is sufficiently stirred at room temperature, the mixed monomer solution of lauric acid diethyl amide and styrene is made.4 parts are weighed again
Azodiisobutyronitrile and the esterification products of 15 parts of poly glycol monomethyl ethers and methacrylic acid（Molecular weight 1200）It is dissolved in 100 parts of nothings
In water-ethanol, it is stirred at room temperature uniformly.Mixed monomer solution is added in the three-necked flask with stirring and reflux, control
75 DEG C of reaction temperature processed, by azodiisobutyronitrile and the esterification products of poly glycol monomethyl ether and methacrylic acid（Molecular weight
1200）Mixed liquor is added in separatory funnel, is uniformly added drop-wise in 2h in reaction system.Continue after reacting 2.5h, reaction solution is fallen
Entering in beaker, add 1000 parts of deionized waters and carry out precipitatings, vacuum filtration obtains sediment, and after being washed with deionized 3 times 4
Sediment is put into vacuum drying 12h in 70 DEG C of baking ovens and obtains Cationic/nonionic composite high polymer antistatic agent.
Embodiment 2 weighs 100 parts of lauric acid diethyl amides and 60 parts of methyl methacrylates, pours into and fills 250 parts of nothings
In the beaker of water methanol, it is sufficiently stirred at room temperature, the mixing list of lauric acid diethyl amide and methyl methacrylate is made
Liquid solution.1.5 parts of ABVNs and the esterification products of 40 parts of poly glycol monomethyl ethers and methacrylic acid are weighed again（Molecule
Amount 1500）It is dissolved in 100 parts of absolute methanols, is stirred at room temperature uniformly.Mixed monomer solution is added with stirring and backflow
In the three-necked flask of device, 75 DEG C of controlling reaction temperature, by ABVN and poly glycol monomethyl ether and methacrylic acid
Esterification products（Molecular weight 1500）Mixed liquor is added in separatory funnel, is uniformly added drop-wise in 2.5h in reaction system.Continue anti-
After answering 3h, reaction solution is poured into beaker, 1000 parts of deionized waters is added and carries out precipitating, vacuum filtration obtains sediment, is used in combination
Sediment is put into vacuum drying 12h in 70 DEG C of baking ovens after washing 3 times and obtains the compound high score of cationic/nonionic by deionized water
Sub- antistatic additive.
Embodiment 3 weighs 100 parts of lauric acid diethyl amides and 150 parts of butyl acrylates, pours into and fills 250 parts of anhydrous second
In the beaker of alcohol, it is sufficiently stirred at room temperature, the mixed monomer solution of lauric acid diethyl amide and butyl acrylate is made.Again
Weigh 2 parts of azodiisobutyronitriles and the esterification products of 30 parts of poly glycol monomethyl ethers and methacrylic acid（Molecular weight 1800）It is dissolved in
In 100 parts of absolute ethyl alcohols, it is stirred at room temperature uniformly.Mixed monomer solution is added to three mouthfuls of burnings with stirring and reflux
In bottle, 75 DEG C of controlling reaction temperature, by azodiisobutyronitrile and the esterification products of poly glycol monomethyl ether and methacrylic acid（Point
Son amount 1800）Mixed liquor is added in separatory funnel, is uniformly added drop-wise in 2h in reaction system.After reaction carries out 2.5h, it will react
Liquid is poured into beaker, is added 1000 parts of deionized waters and is carried out precipitating, vacuum filtration obtains sediment, and is washed with deionized 3
Sediment is put into vacuum drying 12h in 70 DEG C of baking ovens after secondary and obtains Cationic/nonionic composite high polymer antistatic agent.
Embodiment 4 weighs 100 parts of lauric acid diethyl amides and 90 parts of hydroxy-ethyl acrylates, pour into fill 250 parts it is anhydrous
In the beaker of methanol, it is sufficiently stirred at room temperature, the mix monomer that lauric acid diethyl amide and hydroxy-ethyl acrylate is made is molten
Liquid.3.5 parts of ABVNs and the esterification products of 25 parts of poly glycol monomethyl ethers and methacrylic acid are weighed again（Molecular weight
2000）It is dissolved in 100 parts of absolute methanols, is stirred at room temperature uniformly.Mixed monomer solution is added with stirring and backflow dress
In the three-necked flask put, 75 DEG C of controlling reaction temperature, by ABVN and poly glycol monomethyl ether and methacrylic acid
Esterification products（Molecular weight 2000）Mixed liquor is added in separatory funnel, is uniformly added drop-wise in 2.5h in reaction system.Reaction is carried out
After 3h, reaction solution is poured into beaker, a large amount of precipitations can be generated by adding deionized water, and vacuum filtration obtains sediment, and spends
Sediment is put into 70 DEG C of baking ovens after ion water washing 3 times and is dried in vacuo 12h and obtains cationic/nonionic composite high-molecular
Antistatic additive.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, it is included within the scope of the present invention.
Claims (1)
1. a kind of Cationic/nonionic composite high polymer antistatic agent, it is characterised in that by the raw material system of following mass fractions
Into：100 parts of lauric acid diethyl amide, 15 parts~40 parts of dimethylethanolamine, 50 parts~150 parts of polycaprolactone, hydrogenated castor
Oily 1.5 parts~5 parts, 350 parts of polytetrafluoroethylene (PTFE).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710782643.XA CN107541001A (en) | 2017-09-02 | 2017-09-02 | A kind of Cationic/nonionic composite high polymer antistatic agent |
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| CN201710782643.XA CN107541001A (en) | 2017-09-02 | 2017-09-02 | A kind of Cationic/nonionic composite high polymer antistatic agent |
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| CN107541001A true CN107541001A (en) | 2018-01-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269502A (en) * | 2020-02-28 | 2020-06-12 | 杭化塑友新材料(杭州)有限公司 | Low-addition-amount long-acting low-humidity-resistant water-washing-resistant antistatic agent special for polyvinyl chloride |
-
2017
- 2017-09-02 CN CN201710782643.XA patent/CN107541001A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269502A (en) * | 2020-02-28 | 2020-06-12 | 杭化塑友新材料(杭州)有限公司 | Low-addition-amount long-acting low-humidity-resistant water-washing-resistant antistatic agent special for polyvinyl chloride |
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Application publication date: 20180105 |