CN111748137B - Low-humidity-resistant antistatic agent special for polyolefin - Google Patents
Low-humidity-resistant antistatic agent special for polyolefin Download PDFInfo
- Publication number
- CN111748137B CN111748137B CN201910235421.5A CN201910235421A CN111748137B CN 111748137 B CN111748137 B CN 111748137B CN 201910235421 A CN201910235421 A CN 201910235421A CN 111748137 B CN111748137 B CN 111748137B
- Authority
- CN
- China
- Prior art keywords
- antistatic agent
- polyoxyethylene ether
- polyolefin
- antistatic
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2003/324—Alkali metal phosphate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of antistatic agents, and discloses a low-humidity-resistant antistatic agent special for polyolefin, which comprises the following components in percentage by mass: 31 to 55 percent of fatty amine polyoxyethylene ether surfactant; 19 to 35 percent of higher fatty alcohol; ionic compounds 3 to 34 percent; 0-5% of nano oxide; and 3-16% of a functional auxiliary dispersing agent. The antistatic agent of the present invention is exclusively used for polyolefin materials, can realize excellent antistatic properties at a small addition amount, and has excellent antistatic properties also at low humidity. In addition, the antistatic agent of the invention is white to light yellow powder or flake in appearance, and hardly influences the transparency and mechanical properties of the product.
Description
Technical Field
The invention relates to the field of antistatic agents, in particular to a low-humidity-resistant antistatic agent special for polyolefin.
Background
Due to its excellent comprehensive properties, polyolefin plastics are widely used in various fields such as household appliances, transportation, electronic appliances, national defense industry and the like. However, since polyolefin plastics generally have electrical insulation properties, the surface resistance of PE and PP, for example, is generally 10 16 ～10 20 Omega. Therefore, once triboelectrically charged, it is not easily eliminated, and static electricity is generated. Due to electrostatic attraction, plastic articles can adsorb dust and other dirt in the air, which affects the aesthetics of the article, and due to the effect of static electricity, adhesion occurs during the manufacture of plastic films. In addition, static electricity causes accidents such as fire, explosion, electric shock, and the like. In order to avoid such accidents, plastic articles used in some applications must be treated to be antistatic.
There are various methods for eliminating the static electricity of the polymer material: such as the addition of conductive fillers, such as carbon black, metal powders; the static electricity is eliminated by using a conductive device in the processing process of the plastic product; coating a conductive coating on the surface of the product; increasing the air humidity during the processing or use of the plastic; adding an antistatic agent. These methods have characteristics and limitations, and in comparison, the method is the simplest and most effective to add an antistatic agent, and has low cost, strong usability and the most common application.
However, the antistatic performance of the currently commonly used surfactant type antistatic agent is greatly influenced by air humidity, and under the condition of lower humidity, the antistatic performance is greatly weakened or even lost, so that the use of the surfactant type antistatic agent has certain limitation. The polymer permanent antistatic agent is slightly affected by humidity, but has high cost and large addition amount, and is only used in some high-end occasions. Therefore, it is important to develop an antistatic agent which is added in a small amount and is less affected by humidity.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a low humidity resistant antistatic agent for polyolefin, which is used exclusively for polyolefin materials, can realize excellent antistatic performance with a small addition amount, and has excellent antistatic performance also at low humidity. In addition, the antistatic agent of the invention is white to light yellow powder or flake in appearance, and hardly influences the transparency and mechanical properties of products.
The specific technical scheme of the invention is as follows: the special antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by mass:
31 to 55 percent of fatty amine polyoxyethylene ether surfactant;
19 to 35 percent of higher fatty alcohol;
3 to 34 percent of ionic compound;
0-5% of nano oxide;
3 to 16 percent of functional dispersion aid.
Although there may be a number of reports in the prior art on the single components of the above-described formulations of the invention, it is intended to be emphasized that the core of the invention is not the development of new antistatic materials, but how to combine them from the existing technologies in order to obtain an antistatic agent which is specific to polyolefin materials and which still has an excellent antistatic effect at low addition levels and low humidity. The formula of the invention is not a simple pieced combination, but a plurality of components can be synergistic in mechanism, and compared with the existing antistatic agent, the antistatic agent has small addition amount and outstanding antistatic effect under low humidity (compared with the prior art, the antistatic agent makes a remarkable progress). Since the chemical field is an experimental science, the factors influencing the technical effects are multifaceted, mutually crossed and complicated, and completely different technical effects can be brought only by replacing a certain composition or modifying a small part of parameters, so that the technical effects are difficult to be expected by a person skilled in the art and can be judged only by experimental data results.
The principle of synergy among the components of the invention is as follows: the complex system of fatty amine polyoxyethylene ether and high-carbon fatty alcohol has good antistatic performance in polyolefin, good compatibility with resin and higher decomposition temperature, and can meet the use requirement of polyolefin at the processing temperature, and in the system of fatty amine and high-carbon fatty alcohol, the invention adds the high-performance auxiliary dispersing agent, and can greatly increase the solubility of ionic compounds and nano oxides in the system under the system melting state, and the solubility of the ionic compounds and the nano oxides can reach more than 20 wt%. The antistatic agent containing high concentration ionic compound and nanometer oxide molten system is added into polyolefin resin, so that the antistatic agent has excellent compatibility with polyolefin and basically has no influence on the mechanical performance and appearance of polyolefin. The high-concentration ionic compound and the nano oxide are dissolved in a fatty amine and high-carbon fatty alcohol system and can be uniformly distributed in the polyolefin, the ionic compound increases the ion concentration in the polyolefin, internal charges are leaked through ion conduction, and the resistance of the polyolefin is reduced. Also, the antistatic agent containing a high concentration of ionic compounds and nano-oxides is uniformly dispersed in the form of molecules in the polymer, and the current is conducted through a mixture of dense and irregular conductors dispersed in the polymer. In this mixture, between any two adjacent conductor particles, there are discontinuous conduction barriers, through which the charge carriers jump from one conductor to the other by means of tunneling, via the barrier separating them. On the other hand, an antistatic agent containing a high concentration of ionic compounds and nano-oxides migrates to the surface of an article with migration of the antistatic agent, increasing the ionic concentration at the surface of the article. Through ion conduction, the surface resistance of the product is reduced, and even if the surface antistatic agent is washed off or wiped off, the internal antistatic agent can also slowly migrate to the surface, so that the polyolefin has a long-term antistatic effect. In addition, the antistatic agent is not sensitive to the environmental humidity, and is determined by the properties of a high-concentration ionic compound and nano oxide aliphatic amine and high-carbon aliphatic alcohol dissolving system, and the high-concentration ionic compound and nano oxide act on the surface and the interior of a product to achieve the antistatic effect. The excellent long-acting low-humidity antistatic performance of the antistatic agent is beyond the reach of other traditional antistatic agents.
Preferably, the fatty amine polyoxyethylene ether surfactant is one or more selected from laurylamine polyoxyethylene ether, cocoamine polyoxyethylene ether, tallow amine polyoxyethylene ether, hydrogenated tallow amine polyoxyethylene ether, stearylamine polyoxyethylene ether and stearylamine polyoxyethylene ether.
Preferably, the molecular formula of the higher fatty alcohol is C n H 2n+1 OH，n＝12～22。
Preferably, the higher fatty alcohol is one or more of dodecanol, octadecanol, behenyl alcohol and the like.
Preferably, the ionic compound is a salt of an alkali metal with an organic acid or an inorganic acid, or a salt of metallic zinc with an organic acid or an inorganic acid.
Preferably, the ionic compound is one or more of lithium acetate, lithium chloride, lithium perchlorate, lithium hexafluorophosphate, potassium acetate, potassium phosphate, potassium thiocyanate, potassium hexafluorophosphate, potassium perchlorate, sodium bromide, sodium perchlorate, sodium hexafluorophosphate and zinc chloride.
Preferably, the nano oxide is a metal nano oxide, such as one or more of zinc oxide, titanium dioxide, tin oxide, and the like.
Preferably, the functional auxiliary dispersant is an ultrafine inorganic oxide or a metal stearate.
Preferably, the metal stearate is one or more of zinc stearate and calcium stearate.
The superfine inorganic oxide is silicon dioxide.
In the preferable case of the above components, the antistatic effect is more excellent.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the existing common antistatic agent, the antistatic agent provided by the invention is white to light yellow powder or flaky object, and the color of the product is not influenced. Meanwhile, the antistatic agent is added in a small amount, the addition amount of the antistatic agent in the polyolefin film is 0.6-1.5%, and the addition amount of the antistatic agent in the sheet is about 1-4%, so that the product can be endowed with good antistatic performance.
2. The antistatic agent of the invention can play an antistatic role under lower humidity, while the antistatic effect of the common polyolefin antistatic agent under low humidity is poor.
3. The antistatic agent has good compatibility with polyolefin and has small influence on the mechanical property of products.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The special antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by mass:
31 to 55 percent of fatty amine polyoxyethylene ether surfactant;
19 to 35 percent of higher fatty alcohol;
3 to 34 percent of ionic compound;
0-5% of nano oxide;
3 to 16 percent of functional dispersion aid.
Preferably, the fatty amine polyoxyethylene surfactant is one or more selected from laurylamine polyoxyethylene ether, cocoamine polyoxyethylene ether, tallow amine polyoxyethylene ether, hydrogenated tallow amine polyoxyethylene ether, stearylamine polyoxyethylene ether and octadecylamine polyoxyethylene ether.
Preferably, the molecular formula of the higher fatty alcohol is C n H 2n+1 OH, n =12 to 22. Further preferably one or more of dodecanol, octadecanol, behenyl alcohol and the like.
Preferably, the ionic compound is a salt of an alkali metal with an organic acid or an inorganic acid, or a salt of metallic zinc with an organic acid or an inorganic acid. More preferably one or more of lithium acetate, lithium chloride, lithium perchlorate, lithium hexafluorophosphate, potassium acetate, potassium phosphate, potassium thiocyanate, potassium hexafluorophosphate, potassium perchlorate, sodium bromide, sodium perchlorate, sodium hexafluorophosphate and zinc chloride.
Preferably, the nano oxide is a metal nano oxide, such as one or more of zinc oxide, titanium dioxide, tin oxide, and the like.
Preferably, the functional dispersion aid is an ultrafine inorganic oxide or a metal stearate. The metal stearate is one or more of zinc stearate and calcium stearate. The superfine inorganic oxide is silicon dioxide.
Example 1
A low humidity resistant antistatic agent specially used for polyolefin, comprising:
46 percent of tallow amine polyoxyethylene ether
28% of octadecanol;
16% of zinc chloride;
2% of nano zinc oxide;
and 8% of zinc stearate.
The preparation method comprises the following steps:
1) Adding tallow amine polyoxyethylene ether, octadecanol, and zinc stearate into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
2) Adding zinc chloride and nano zinc oxide into the melting system, preserving heat and uniformly stirring at a high speed;
3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 2
A low humidity resistant antistatic agent specially used for polyolefin, comprising:
stearyl amine polyoxyethylene ether 43%
26% of behenyl alcohol;
13 percent of potassium thiocyanate;
12% of nano zinc oxide;
6 percent of silicon dioxide.
The preparation method comprises the following steps:
1) Adding tallow amine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 120 ℃.
2) Adding potassium thiocyanate and nano zinc oxide into the melting system, keeping the temperature, stirring and mixing uniformly;
3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 3
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
45% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
15% of potassium hexafluorophosphate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding octadecylamine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 130 ℃.
(2) Adding potassium hexafluorophosphate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 4
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
20% of potassium hexafluorophosphate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding octadecylamine polyoxyethylene, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding potassium hexafluorophosphate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 5
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
35% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
25% of potassium hexafluorophosphate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding octadecylamine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding potassium hexafluorophosphate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 6
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of tallow amine polyoxyethylene ether;
28% of octadecanol;
20% of lithium perchlorate;
12% of calcium stearate;
the preparation method comprises the following steps:
(1) Adding tallow amine polyoxyethylene ether, octadecanol and calcium stearate into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding lithium perchlorate into the melting system, keeping the temperature, stirring and mixing evenly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 7
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of tallow amine polyoxyethylene ether;
28% of octadecanol;
20% of lithium perchlorate;
12% of zinc stearate;
the preparation method comprises the following steps:
(1) Adding tallow amine polyoxyethylene ether, octadecanol and zinc stearate into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding lithium perchlorate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 8
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of tallow amine polyoxyethylene ether;
28% of octadecanol;
20% of lithium perchlorate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding tallow amine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding zinc chloride and nano zinc oxide into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 9
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of tallow amine polyoxyethylene ether;
28% of octadecanol;
20% of lithium stearate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding tallow amine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding lithium stearate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 10
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
tallow amine polyoxyethylene 40%;
28% of octadecanol;
20% of sodium bromide;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding tallow amine polyoxyethylene, octadecanol and zinc stearate into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding sodium bromide into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 11
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of laurylamine polyoxyethylene ether;
28% of octadecanol;
20% of lithium perchlorate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding laurylamine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding lithium perchlorate into the melting system, keeping the temperature, stirring and mixing evenly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 12
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of cocoamine polyoxyethylene ether;
28% of octadecanol;
20% of lithium perchlorate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding the cocoamine polyoxyethylene ether, the octadecanol and the silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding lithium perchlorate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 13
The antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by weight;
40% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
20% of lithium perchlorate;
12% of silicon dioxide;
the preparation method comprises the following steps:
(1) Adding octadecylamine polyoxyethylene ether, octadecanol and silicon dioxide into a reaction kettle, slowly heating to dissolve, and keeping the temperature at 125 ℃.
(2) Adding lithium perchlorate into the melting system, keeping the temperature, stirring and mixing uniformly;
(3) Discharging the materials, and slicing or powdering to obtain the required antistatic agent product.
Example 14
The special antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by mass:
31% of stearylamine polyoxyethylene ether;
31% of behenyl alcohol;
34% of sodium hexafluorophosphate;
1% of nano tin oxide;
3 percent of calcium stearate.
Example 15
The special antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by mass:
55% of cocoamine polyoxyethylene ether;
19 percent of dodecanol;
5% of potassium phosphate;
5% of nano zinc oxide;
16% of zinc stearate.
Example 16
The special antistatic agent for polyolefin with low humidity resistance comprises the following components in percentage by mass:
31% of stearylamine polyoxyethylene ether;
32% of behenyl alcohol;
34% of sodium hexafluorophosphate;
3 percent of calcium stearate.
In order to better verify the antistatic properties of the antistatic agent of the present invention at low humidity, the following comparative examples were prepared.
Comparative example 1
40% of nonylphenol polyoxyethylene ether;
28% of octadecanol;
20% of potassium hexafluorophosphate;
12 percent of silicon dioxide.
Comparative example 2
40% of polyethylene glycol 6000 distearate;
28% of octadecanol;
20% of potassium hexafluorophosphate;
12 percent of silicon dioxide.
Comparative example 3
40% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
20% of calcium chloride;
12 percent of silicon dioxide.
Comparative example 4
40% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
20% of sodium chloride;
12% of silicon dioxide.
Comparative example 5
40% of octadecylamine polyoxyethylene ether;
28% of glyceryl monostearate;
20% of potassium hexafluorophosphate;
12% of silicon dioxide.
Comparative example 6
40% of octadecylamine polyoxyethylene ether;
polyethylene glycol 600028%;
20% of potassium hexafluorophosphate;
12% of silicon dioxide.
Comparative example 7
20% of octadecylamine polyoxyethylene ether;
48% of octadecanol;
20% of potassium hexafluorophosphate;
12% of silicon dioxide.
Comparative example 8
60% of octadecylamine polyoxyethylene ether;
8% of octadecanol;
20% of potassium hexafluorophosphate;
12% of silicon dioxide.
Comparative example 9
50% of octadecylamine polyoxyethylene ether;
30% of octadecanol;
2% of potassium hexafluorophosphate;
18 percent of silicon dioxide.
Comparative example 10
30% of octadecylamine polyoxyethylene ether;
28% of octadecanol;
40% of potassium hexafluorophosphate;
12 percent of silicon dioxide.
Comparative example 11
50% of octadecylamine polyoxyethylene ether;
5% of octadecanol;
25% of potassium hexafluorophosphate;
20 percent of silicon dioxide.
Comparative example 12
23% of octadecylamine polyoxyethylene ether;
45% of octadecanol;
20% of potassium hexafluorophosphate;
12% of silicon dioxide.
Comparative example 13 (conventional PE antistatic formulation 1)
60% of octadecylamine polyoxyethylene ether;
40 percent of zinc stearate,
Comparative example 14 (common PE antistatic agent formulation 2)
50% of cocoamine polyoxyethylene ether;
30% of glyceryl monostearate;
20% of PEG6000 distearate.
Application examples
The antistatic agent prepared in the above example 1 and PE plastic particles are prepared into plastic antistatic master batches with a certain concentration, and then the antistatic master batches and the PE particles are uniformly mixed for film blowing. 2 samples of PE film were made, in which the antistatic agent content was 0.8% and 1%, respectively, and the samples were designated 1 and 2.
Carrying out surface resistance detection on the prepared samples 1 and 2 at the temperature of 23 +/-2 ℃ and in the standard environment of 50 +/-10%, and recording the surface resistance of the samples 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. While 1 and 2 were tested for antistatic properties under low humidity conditions.
Table 1: test results under Standard conditions
Table 2: test results at 30% relative humidity
From the above results, it can be seen that the surface resistance of the product can be significantly reduced by adding a small amount of the antistatic agent of the present invention to the PE film, the product can take effect after 1 day of molding, there is no change in the surface resistance value after half a year, and the PE film has excellent antistatic properties even at low humidity (28% relative humidity). Because of the excellent performance, the antistatic agent has wide application prospect. The data obtained for the antistatic agent of example 1 of the invention at low humidity are remarkable for the antistatic agents of the prior art.
The antistatic agent of examples 3-5 and PE plastic particles were made into plastic antistatic master batches with a certain concentration, and then the antistatic master batches and the PE particles were mixed uniformly and blown into films. 3 PE film samples were prepared, in which the content of antistatic agent was 1%, and the PE film samples were respectively designated 3, 4, and 5.
Carrying out surface resistance detection on the prepared PE film samples 3, 4 and 5 at the temperature of 23 +/-2 ℃ and in the standard environment of 50 +/-10%, and recording the surface resistance of the samples 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. PE film samples 3, 4, 5 were also tested for antistatic performance under low humidity conditions.
Table 3: test results of PE film samples 3, 4, and 5 under standard conditions
Table 4: test results of PE film samples 3, 4, 5 at low relative humidity
From the results of examples 3, 4 and 5, it can be seen that the antistatic agent of the present invention can be added to the PE film in a small amount, so that the surface resistance of the product can be significantly reduced, the product can be formed for 1 day, the surface resistance value does not change after half a year, and the PE film has excellent antistatic properties even at low humidity (28% relative humidity). From table 3 we can see that the antistatic effect of examples 3, 4, 5 is substantially comparable at standard humidity. From Table 4, we can also conclude that the concentration of the ionic compound in the system determines the antistatic performance at low humidity, and the higher the concentration of the ionic compound in the system, the better the antistatic performance at low humidity.
The antistatic agent of examples 6 to 8 and PE plastic particles were prepared into plastic antistatic master batches with a certain concentration, and then the antistatic master batches and the PE particles were mixed uniformly to carry out film blowing. 3 PE film samples were prepared, with 1% antistatic agent in the PE film, and the PE film samples were designated 6, 7, and 8, respectively.
Carrying out surface resistance detection on the prepared PE film samples 6, 7 and 8 at the temperature of 23 +/-2 ℃ in a standard environment of 50 +/-10%, and recording the surface resistance of the samples 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. Meanwhile, the PE film samples 6, 7, 8 were tested for antistatic properties under low humidity conditions.
TABLE 5 test results of PE film samples 6, 7, 8 under standard conditions
Table 6: test results of PE film samples 6, 7, 8 under Low humidity conditions
From the results of examples 6, 7 and 8, it can be seen that the addition of a small amount of the antistatic agent of the present invention to a PE film significantly reduces the surface resistance of the product, and the product can take effect after 1 day of molding, has no change in surface resistance value after half a year, and has excellent antistatic properties even at low humidity (28% relative humidity). From Table 5 we also conclude that the antistatic properties of the antistatic agent products prepared with the systems using different dispersants are substantially identical under standard humidity conditions. As can be seen from Table 6, the antistatic properties of the antistatic agent using silica as a dispersant are superior in the case of low humidity.
The antistatic agent of examples 9 to 10 and PE plastic particles were made into plastic antistatic master batches of a certain concentration, and then the antistatic master batches and the PE particles were mixed uniformly and blown into films. 3 PE film samples were prepared, with 1% antistatic agent in the PE film and 9, 10 for the PE film samples, respectively.
Carrying out surface resistance detection on the prepared PE film samples 9 and 10 at the temperature of 23 +/-2 ℃ and in the standard environment of 50 +/-10%, and recording the surface resistance of the samples 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. Meanwhile, the PE film samples 9 and 10 were tested for antistatic properties under low humidity conditions.
Table 7: test results of samples 9 and 10 under standard conditions
Table 8: test results of samples 9 and 10 under low humidity conditions
As can be seen from Table 7, the surface resistance of the product can be significantly reduced by adding a small amount of the antistatic agent of the present invention to the PE film under standard humidity, and the product can take effect after 1 day of molding without any change in the surface resistance value after half a year. As can be seen from Table 8, the antistatic agent prepared by using lithium stearate and sodium bromide as ionic compounds has a not very good antistatic effect at low humidity, and shows different antistatic properties when the physical and chemical properties of different ionic compounds are different. We need to screen suitable ionic compounds to formulate antistatic agents for optimal effect.
The antistatic agents of examples 11 to 13 and PE plastic particles were mixed to prepare plastic antistatic master batches having a certain concentration, and then the antistatic master batches and the PE particles were mixed uniformly and blown into films. 3 PE film samples were prepared, with 1% antistatic agent in the PE film, and the PE film samples were designated 11, 12, and 13, respectively.
Carrying out surface resistance detection on the prepared PE film samples 11, 12 and 13 at the temperature of 23 +/-2 ℃ and in the standard environment of 50 +/-10%, and recording the surface resistance of the samples at 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. PE film samples 11, 12, 13 were also tested for antistatic performance under low humidity conditions.
Table 9: test results of PE film samples 11, 12, 13 under Standard conditions
Table 10: test results of PE film samples 11, 12, 13 under Low humidity conditions
It can be seen from table 9 that, under standard humidity, the antistatic agent prepared from low-carbon chain fatty amine polyoxyethylene ether can have antistatic effect in a short time in the PE film, and after a period of standing, the antistatic effect of high-carbon chain fatty amine polyoxyethylene ether is better, which is related to the easy migration of low-carbon chain fatty amine polyoxyethylene ether in resin. As can be seen from Table 10, the high carbon chain fatty amine polyoxyethylene ether has better antistatic effect under low humidity, which is probably related to better compatibility and compatibility of the high carbon chain fatty amine polyoxyethylene ether and the ionic compound.
The antistatic agents of examples 11 to 13 and PE plastic particles were prepared into plastic antistatic master batches of a certain concentration, and then the antistatic master batches and PP particles were uniformly mixed and blown into films. 3 PP film samples were prepared, with 1% antistatic agent in the PP film, and the PP film samples were designated 14, 15, and 16, respectively.
Carrying out surface resistance detection on the PP film samples 14, 15 and 16 prepared in the way at the temperature of 23 +/-2 ℃ and in the standard environment of 50 +/-10%, and recording the surface resistance of the samples 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. PP film samples 14, 15, 16 were also tested for antistatic performance under low humidity conditions.
Table 11: test results of PE film samples 14, 15, 16 under standard conditions
Table 12: test results of PE film samples 14, 15, 16 under Low humidity conditions
It can be seen from table 11 that, under standard humidity, the antistatic agent prepared from low-carbon chain fatty amine polyoxyethylene ether can have antistatic effect in a PP film within a short time, and after a period of standing, the antistatic effect of high-carbon chain fatty amine polyoxyethylene ether is better, which is related to the easy migration of low-carbon chain fatty amine polyoxyethylene ether in resin. As can be seen from Table 12, the high carbon chain fatty amine polyoxyethylene ether has better antistatic effect under low humidity, which is probably related to better compatibility and compatibility of the high carbon chain fatty amine polyoxyethylene ether and the ionic compound. By comparing the results in tables 9 and 11, tables 10 and 12, we can see that the antistatic agent of the present invention has the same antistatic effect on PP, but the performance is slightly inferior to that of PE, which is related to the higher crystallinity and glass transition temperature of PP material than that of PE material.
From the above test results, it can be seen that the antistatic agent of the present invention can significantly reduce the surface resistance of the product by adding a small amount of the antistatic agent to polyolefins such as PE and PP, the product can take effect after 1 day of molding, the surface resistance value does not change after half a year, and the antistatic agent has good antistatic performance even at low humidity (relative humidity is lower than 30%). Due to the excellent performances, the antistatic agent has wide application prospect.
Comparative application
And (3) preparing the products prepared in the comparative examples 1-14 and PE plastic particles into plastic antistatic master batches with a certain concentration, uniformly mixing the antistatic master batches and the PE particles, and blowing the film. 14 PE film samples were prepared, and the content of the antistatic agent in the PE film was divided into 1%, and the samples were designated as comparative examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14.
Carrying out surface resistance detection on the prepared comparative samples 1-2 at 23 +/-2 ℃ under a standard environment of 50 +/-10%, and recording the surface resistance of the samples 24 hours, 72 hours, 7 days, 30 days, 90 days and 180 days after production; and compared to a blank. Meanwhile, 1 to 14 were tested for antistatic property under low humidity condition and compared with the blank.
Table 13: test results of comparative example sample under Standard conditions
TABLE 14 test results of comparative samples under low humidity conditions
As can be seen from Table 13, the comparative examples each having a different antistatic agent component exhibited a certain antistatic effect on the PE film under the standard test conditions, but in the case of low humidity, most of the comparative examples had no antistatic property as can be seen from Table 14. Only comparative examples 5, 6, 7, 8, 10 still had some antistatic properties. By comparing the data with the examples, the formulation of the present invention is demonstrated to have excellent antistatic properties at low humidity, and a significant improvement is achieved compared to the comparative examples. In addition, the components and the proportion in the formula of the invention are strictly limited and are not combined at will.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (5)
1. The special antistatic agent for polyolefin with low humidity resistance is characterized by comprising the following components in percentage by mass:
31 to 55 percent of fatty amine polyoxyethylene ether surfactant;
19 to 35 percent of higher fatty alcohol;
ionic compounds 3 to 34%;
0-5% of nano oxide and not 0;
3 to 16 percent of functional auxiliary dispersant;
the fatty amine polyoxyethylene surfactant is selected from one or more of laurylamine polyoxyethylene ether, cocoamine polyoxyethylene ether, tallow amine polyoxyethylene ether, hydrogenated tallow amine polyoxyethylene ether, stearylamine polyoxyethylene ether and octadecylamine polyoxyethylene ether;
the molecular formula of the higher fatty alcohol is C n H 2n+1 OH，n=12～22；
The ionic compound is a salt formed by alkali metal and organic acid or inorganic acid, or a salt formed by metal zinc and organic acid or inorganic acid;
the nano oxide is a metal nano oxide;
the functional auxiliary dispersant is superfine inorganic oxide or metal stearate.
2. The special low-humidity-resistant antistatic agent for polyolefin as claimed in claim 1, wherein the higher fatty alcohol is one or more of dodecanol, octadecanol and behenyl alcohol.
3. The special low-humidity-resistant antistatic agent for polyolefin as claimed in claim 1, wherein the ionic compound is one or more of lithium acetate, lithium chloride, lithium perchlorate, lithium hexafluorophosphate, potassium acetate, potassium phosphate, potassium thiocyanate, potassium hexafluorophosphate, potassium perchlorate, sodium bromide, sodium perchlorate, sodium hexafluorophosphate and zinc chloride.
4. The special antistatic agent for polyolefin with low humidity resistance as claimed in claim 1, wherein the metal stearate is one or more of zinc stearate and calcium stearate.
5. The special antistatic agent for polyolefin with low humidity resistance of claim 1 wherein the ultrafine inorganic oxide is silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910235421.5A CN111748137B (en) | 2019-03-26 | 2019-03-26 | Low-humidity-resistant antistatic agent special for polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910235421.5A CN111748137B (en) | 2019-03-26 | 2019-03-26 | Low-humidity-resistant antistatic agent special for polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111748137A CN111748137A (en) | 2020-10-09 |
| CN111748137B true CN111748137B (en) | 2022-12-02 |
Family
ID=72671497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910235421.5A Active CN111748137B (en) | 2019-03-26 | 2019-03-26 | Low-humidity-resistant antistatic agent special for polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111748137B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773824A (en) * | 2022-05-05 | 2022-07-22 | 广饶县科瑞生物科技有限公司 | Antistatic auxiliary agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3975325A (en) * | 1973-08-27 | 1976-08-17 | Ici United States Inc. | Antistatic agent composition |
| CN1340559A (en) * | 2000-08-29 | 2002-03-20 | 西巴特殊化学品控股有限公司 | Method for decreasing dust deposit on polyolefin film |
| CN1800245A (en) * | 2005-07-26 | 2006-07-12 | 杭州市化工研究院有限公司 | PVC antistatic elasticizer synthesis process |
| JP2008297518A (en) * | 2007-06-04 | 2008-12-11 | Dic Corp | Antistatic agent |
| CN104018345A (en) * | 2014-03-28 | 2014-09-03 | 上海天坛助剂有限公司 | Multi-functional antistatic agent |
| CN104194143A (en) * | 2014-06-24 | 2014-12-10 | 湛江包装材料企业有限公司 | Abrasion-resistant modified anti-static smooth compound nano-masterbatch, as well as preparation method and application thereof |
-
2019
- 2019-03-26 CN CN201910235421.5A patent/CN111748137B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3975325A (en) * | 1973-08-27 | 1976-08-17 | Ici United States Inc. | Antistatic agent composition |
| CN1340559A (en) * | 2000-08-29 | 2002-03-20 | 西巴特殊化学品控股有限公司 | Method for decreasing dust deposit on polyolefin film |
| CN1800245A (en) * | 2005-07-26 | 2006-07-12 | 杭州市化工研究院有限公司 | PVC antistatic elasticizer synthesis process |
| JP2008297518A (en) * | 2007-06-04 | 2008-12-11 | Dic Corp | Antistatic agent |
| CN104018345A (en) * | 2014-03-28 | 2014-09-03 | 上海天坛助剂有限公司 | Multi-functional antistatic agent |
| CN104194143A (en) * | 2014-06-24 | 2014-12-10 | 湛江包装材料企业有限公司 | Abrasion-resistant modified anti-static smooth compound nano-masterbatch, as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《国内外高分子型抗静电剂的研究进展》;刘慧珍 等;《杭州化工》;20170331;第47卷(第1期);5-8 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111748137A (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104844885A (en) | Antistatic masterbatch for engineering plastics and preparation method thereof | |
| CN110669259B (en) | Efficient flame-retardant smoke-suppression environment-friendly bifunctional auxiliary agent and PVC-U material prepared from same | |
| CN111748137B (en) | Low-humidity-resistant antistatic agent special for polyolefin | |
| CN110054883B (en) | Long-acting washable low-temperature-resistant colorless transparent liquid antistatic agent for rubber and plastic and preparation method thereof | |
| CN113861594A (en) | Flame-retardant high-temperature-resistant PVC (polyvinyl chloride) film for graphene electrothermal film and preparation method thereof | |
| CN110483928A (en) | A kind of graphene anti-static plastic preparation method | |
| CN104194145A (en) | Environment-friendly nano modified halogen-free flame retardant polypropylene and preparation method thereof | |
| CN107345033B (en) | Polyvinyl chloride cable composite material and its manufacturing method, cable | |
| CN102702612A (en) | High-flow precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN110591243A (en) | Special flame-retardant synergistic functional master batch for nylon resin modification and preparation method thereof | |
| CN102516681B (en) | Glass-fiber-reinforced AS (acrylonitrile-styrene) resin antistatic material and preparation method | |
| CN103524981A (en) | Modified PBT/ABS (polybutylene terephthalate/acrylonitrile-butadiene-styrene) alloy material | |
| CN112940477A (en) | Scratch-resistant UV-resistant flame-retardant photodiffusion polycarbonate composition and preparation method thereof | |
| CN108976754B (en) | Antistatic flame-retardant composite material and preparation method and application thereof | |
| CN106189244A (en) | A kind of environmentally-friendly transparent type POSS modified calcium zinc stabilizer and preparation method thereof | |
| CN113980298A (en) | Antistatic master batch and preparation method thereof | |
| CN114316556B (en) | High-impact permanent antistatic flame-retardant PC material and preparation method thereof | |
| CN110684267B (en) | Special flame-retardant synergistic functional master batch for styrene resin modification and preparation method thereof | |
| CN110591336B (en) | Special flame-retardant synergistic functional master batch for thermoplastic polyurethane modification and preparation method thereof | |
| CN109705478A (en) | Generation Ⅲ nuclear power station rubber cable semiconductive conductor shielding material | |
| CN115584114A (en) | Polycarbonate alloy composition and preparation method and application thereof | |
| CN110615936B (en) | Special halogen-free flame-retardant synergistic functional master batch for modifying styrene resin and preparation method thereof | |
| CN110607066B (en) | Special halogen-free flame-retardant synergistic functional master batch for modifying polyformaldehyde and preparation method thereof | |
| CN104744764A (en) | Flame-retardant and anti-aging polyethylene powder and preparation method thereof | |
| JP2007009000A (en) | Polyolefin-based resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210908 Address after: 310011 room 300, 3rd floor, building 13, No.7, shihuiba, Gongshu District, Hangzhou City, Zhejiang Province Applicant after: Hangshi technology development (Hangzhou) Co.,Ltd. Address before: 310000 room 315, third floor, building 13, No. 7, lime dam, Gongshu District, Hangzhou City, Zhejiang Province Applicant before: Hanghua Plastic Friends New Materials (Hangzhou) Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |