CN112126127A

CN112126127A - Antistatic agent and preparation method thereof

Info

Publication number: CN112126127A
Application number: CN202011072279.6A
Authority: CN
Inventors: 柳观波; 汪锋平; 郑晓虎; 柳岸俊
Original assignee: Hangzhou Lin'an Dechang Electrostatic Technology Co ltd
Current assignee: Hangzhou Lin'an Dechang Electrostatic Technology Co ltd
Priority date: 2020-10-09
Filing date: 2020-10-09
Publication date: 2020-12-25
Anticipated expiration: 2040-10-09
Also published as: CN112126127B

Abstract

The application relates to the technical field of plastic product additives, in particular to an antistatic agent and a preparation method thereof, and the antistatic agent is mainly prepared from the following raw materials in parts by mass: 35-45 parts of octadecylamine; 10-15 parts of ethylene oxide gas; 30-40 parts of monoglyceride; 2-3 parts of borate; 0.5-1 part of polyol. The specific preparation method is S1: weighing the octadecylamine in parts by weight, heating and melting at the temperature of 70-75 ℃, and then feeding into a reaction kettle; s2: controlling the temperature of the reaction kettle to be 140-150 ℃, introducing ethylene oxide gas into the molten octadecylamine, and reacting for 1.5-2 h; s3: adding the glyceryl laurate, the borate and the glycerol in parts by mass into a reaction kettle, and stirring for 1-1.5h at the temperature of 100-; s4: and (3) cooling the temperature of the reaction kettle to 80-85 ℃, discharging while the reaction kettle is hot, and cooling to obtain the target antistatic agent. After the antistatic agent prepared by the method is blended into a molded product, the antistatic agent has better antistatic capability and can reduce the influence of surface abrasion on the antistatic performance.

Description

Antistatic agent and preparation method thereof

Technical Field

The application relates to the technical field of molded product additives, in particular to an antistatic agent and a preparation method thereof.

Background

Antistatic agents are additives that are added to plastics or applied to the surface of molded articles to reduce static buildup. Antistatic agents can be classified into an internal type and an external type according to the method of use, and the internal type is mainly used for plastics.

Antistatic agents generally have the characteristics of surfactants, and structurally have both polar groups and nonpolar groups, and can be classified into cationic antistatic agents, anionic antistatic agents, and nonionic antistatic agents according to the principle of antistatic. The non-ionic antistatic agent is mainly represented by ethoxylated aliphatic alkylamine, is widely applied to polyethylene, polypropylene, ABS and other styrene polymers, has an antistatic effect, and has the advantages of good dispersibility, good shipping performance, good processability and the like.

The antistatic agent for the biaxially oriented polypropylene film in the alpine region and the preparation method thereof, disclosed in Chinese patent with application number CN201610035947.5, comprise the following raw materials: modifier, monoglyceride, antioxidant and polypropylene; the modifier is obtained by compounding ethoxylated octadecyl amine, N-di (hydroxyethyl) cocoamide and alkyl amine borate; the preparation method of the antistatic agent comprises the following steps: (1) reacting octadecyl amine, N, N-di (hydroxyethyl) cocoamide, alkyl amine borate and ethylene oxide to obtain a modifier; (2) uniformly mixing the modifier, monoglyceride, antioxidant and polypropylene to obtain a mixture; (3) adding the mixture into an extruder, and melting and extruding to prepare the antistatic master batch; (4) cooling, drying, granulating and bagging the antistatic master batch prepared in the step (3) to obtain the antistatic agent; the reaction in the step (1) is an addition reaction of octadecyl amine, N, N-di (hydroxyethyl) cocoamide and alkyl amine borate after being mixed in a high-speed mixer and then with ethylene oxide; in the step (1), the weight part ratio of the octadecyl amine, the N, N-di (hydroxyethyl) cocoamide and the alkyl amine borate is 9:1: 2. The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.

After the antistatic agent is blended with the plastic master batch, the antistatic agent can be dragged to the surface of the plastic product by the hydrophilic group to form a molecular layer with conductive capability in the preparation process of the plastic product, so that the antistatic effect is achieved. The antistatic agent disclosed in the publication has a structure of an antistatic component on the surface of a plastic product which is not dense enough, and after the surface of the plastic product is abraded, the overall antistatic ability is greatly reduced in a short period.

Disclosure of Invention

In order to reduce the reduction of the antistatic capability of the surface of a plastic product after abrasion, the application provides an antistatic agent and a preparation method thereof.

In a first aspect, the present application provides an antistatic agent, using the following technical scheme:

an antistatic agent is mainly prepared from the following raw materials in parts by mass:

35-45 parts of octadecylamine;

10-15 parts of ethylene oxide gas;

30-40 parts of monoglyceride;

2-3 parts of borate;

0.5-1 part of polyol.

By adopting the technical scheme, the N, N-dihydroxyethyl octadecylamine is prepared from the ethylene oxide and the octadecylamine. The N, N-dihydroxyethyl octadecylamine, the monoglyceride and the boric acid ester can play a compounding synergistic effect, play an antistatic role in multiple modes, have small dependence on environmental humidity and have better stability and abrasion resistance.

N, N-dihydroxyethyl octadecylamine, monoglyceride and borate all have hydrophilic groups and lipophilic groups, and are taken as antistatic agents to be mixed into a high polymer material, in the forming process of the high polymer material, the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate can form dense orientation arrangement on the surface of the high polymer material, the lipophilic groups extend into the high polymer material, the hydrophilic groups extend out of the high polymer material, and in the curing process of the high polymer material, under the traction of the hydrophilic groups, the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate can form a monomolecular layer on the surface of the high polymer material. The hydrophilic groups of the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the boric acid ester can absorb moisture in air, and are combined with water molecules through hydrogen bonds to form a conductive layer, so that the antistatic effect is achieved.

The N, N-dihydroxyethyl octadecylamine contains longer fat long chains, the motion capability of the fat long chains is stronger, the movement and the transmission of protons are facilitated among molecules, and generated static charges are conducted and released through ion conduction. The N, N-dihydroxyethyl octadecylamine is distributed on the surface of a polymer material in a fine layer rib shape to form a conductive surface layer, and is almost distributed in a sphere shape at the center part of the polymer to form a core-shell structure which is taken as a passage for leaking static charges, so that the antistatic performance can be better under the condition of lower humidity.

And oxygen atoms in hydroxyl groups of the N, N-dihydroxyethyl octadecylamine and the monoglyceride can generate coordinate bonds with boron atoms in the borate, so that the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate are crosslinked, a multi-layer latticed long-chain conductive structure is formed on the surface and inside of the high polymer material, proton conduction is easier, the antistatic capability is further improved, and the influence of environmental humidity on the antistatic capability is further reduced. Compared with an antistatic layer consisting of independent molecules, the crosslinked net structure still has better antistatic capability even if the surface layer is worn. Because the N, N-dihydroxyethyl octadecylamine has two hydroxyl groups with the same environment and the steric hindrance on the hydroxyl groups is small, the coordination bond formed between the N, N-dihydroxyethyl octadecylamine and the boric acid ester is more compact and stable, the network structure is more stable, and the crosslinking degree is higher.

The raw material also contains polyol, and the polyhydroxy structure of the polyol can continuously form coordination bonds with a plurality of boron atoms, so that the cross-linking among the molecules of the raw materials is assisted, the formed reticular conducting layer is more compact, and the stability is further improved. And hydroxyl on the polyalcohol can also generate hydrogen bonds with oxygen atoms in the N, N-dihydroxyethyl octadecylamine and the monoglyceride, so that the cross-linking of long-chain macromolecules is promoted, and the stability of a grid structure is further improved.

The present application may be further configured in a preferred example to: the borate ester includes at least one of an ethoxylated monoglyceride of borate or a monoglyceride of borate fatty acid ester.

By adopting the technical scheme, the ethoxylated boric acid monoglyceride and the boric acid monoglyceride fatty acid ester are only bonded with the hydroxyl on one glycerin, the side of a boron atom far away from the glycerin still has sufficient space, and the boron atom has relatively small steric hindrance while having the antistatic property, so that the ethoxylated boric acid monoglyceride and the boric acid monoglyceride fatty acid ester can form crosslinking with N, N-dihydroxyethyl octadecylamine and monoglyceride conveniently.

The present application may be further configured in a preferred example to: the polyhydric alcohol comprises tetrol and pentol.

By adopting the technical scheme, the erythritol and the pentadiol have more hydroxyl groups and smaller molecular volume, and can be quickly and uniformly distributed among the long chains of the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate during the reaction, so that the crosslinking effect among the long chains is improved.

The present application may be further configured in a preferred example to: the polyol also includes pentaerythritol.

By adopting the technical scheme, the molecules of pentaerythritol are in a tetrahedral type, and the steric hindrance between every two hydroxyl groups is small, so that the pentaerythritol can better act between long chains of N, N-dihydroxyethyl octadecylamine, monoglyceride and borate.

The present application may be further configured in a preferred example to: the number of carbon atoms of the aliphatic chain of the monoglyceride is 16-18.

By adopting the technical scheme, the carbon chain length of the monoglyceride with the fatty chain carbon content of 16-18 is similar to that of the carbon chain in the N, N-dihydroxyethyl octadecylamine, and the oleophylic capacity of the carbon chain is similar to that of the carbon chain in the N, N-dihydroxyethyl octadecylamine, so that the distribution of the monoglyceride and the N, N-dihydroxyethyl octadecylamine is more uniform, the synergism between the monoglyceride and the N, N-dihydroxyethyl octadecylamine is more easily generated, and the integral antistatic capacity is improved.

The present application may be further configured in a preferred example to: the raw material also comprises 5-10 parts by mass of calcium carbonate.

Through adopting above-mentioned technical scheme, because the antistatic agent behind the finished product is the solid particle to because contain more hydrophilic group in the antistatic agent, moisture in the easy absorption air, consequently produce the adhesion and agglomerate between the solid particle easily, after adding calcium carbonate, calcium carbonate can form one deck calcareous layer on antistatic agent finished product solid particle surface, reduces the viscidity of solid particle, thereby prevents the bonding between the granule, makes finished product antistatic agent solid particle more easily preserve.

In a second aspect, the present application provides a method for preparing an antistatic agent, which adopts the following technical scheme:

a preparation method of an antistatic agent comprises the following steps:

s1: weighing the octadecylamine in parts by weight, heating and melting at the temperature of 70-75 ℃, and then feeding into a reactor;

s2: controlling the temperature of the reaction kettle to be 140-;

s3: adding the monoglyceride, the calcium carbonate, the borate and the polyol in parts by mass into a reactor of S2, and stirring for 1-1.5h at the temperature of 100-110 ℃;

s4: and (3) cooling the temperature of the reaction kettle to 80-85 ℃, discharging while the reaction kettle is hot, and cooling to obtain the target antistatic agent.

By adopting the technical scheme, the S1 and S2 are the process steps of preparing the N, N-dihydroxyethyl octadecylamine by octadecylamine and ethylene oxide gas, the ethylene oxide gas is directly introduced into the molten octadecylamine for reaction, and no other external substances are added, so that the prepared N, N-dihydroxyethyl octadecylamine has higher purity and subsequent purification operation is not needed; and the reaction temperature is controlled to be 140 ℃ and 150 ℃, and the yield of macromolecular amine in the N, N-dihydroxyethyl octadecylamine can be improved at the reaction temperature. And step S3, mixing N, N-dihydroxyethyl octadecylamine, monoglyceride, borate and polyalcohol to generate crosslinking, forming a net-shaped macromolecular structure, and uniformly compounding calcium carbonate among the antistatic agents.

The present application may be further configured in a preferred example to: in the step S3, a vacuum process is performed during the stirring process.

By adopting the technical scheme, under the condition of the operation temperature of 100-110 ℃ in S3, the small molecular substances which are not completely reacted in the N, N-dihydroxyethyl octadecylamine can be gasified and pumped out by vacuumizing, so that the content of the macromolecular amine in the target antistatic agent is increased, and the antistatic effect of the product is improved. And because the raw materials contain a small amount of water, the water in the reactant can be pumped out through the vacuum pumping in the S3, so that the purity of the product is improved.

In summary, the present application includes at least one of the following beneficial technical effects:

1. the antistatic agent prepared by the method has three antistatic components of N, N-dihydroxyethyl octadecylamine, monoglyceride and borate, and the three components can be matched and crosslinked to form a multilayer net structure, so that the antistatic agent can play an antistatic role in multiple modes, has low dependence on environmental humidity and has better stability and abrasion resistance.

2. The raw materials also contain polyhydric alcohol, so that mutual crosslinking can be generated among the boric acid esters, and hydrogen bonds can be generated between the boric acid esters and oxygen atoms in the raw materials, and the binding capacity among the raw materials is improved.

3. Calcium carbonate is also contained in the raw materials, and can form a calcium layer on the surfaces of finished antistatic agent particles to prevent the particles from being bonded.

4. According to the preparation method, the molten octadecylamine and the ethylene oxide are directly reacted, so that impurities in the product are reduced, the product purity is higher, the product is vacuumized in the stirring process, the small molecular amine and the water generated in the reaction can be removed, and the antistatic effect of the prepared product is improved.

Detailed Description

Preparation example

Preparation example 1: the preparation of the boric acid monoglyceride comprises the following steps:

s1: weighing 20kg of glycerol, adding the glycerol into a reaction kettle, heating at 60 ℃, and stirring;

s2: adding 10kg of borax into glycerol by taking nitrogen as protective gas, adjusting the temperature of a reaction kettle to be 100 ℃ after the borax and the glycerol are uniformly mixed, carrying out condensation reflux until no more condensed water flows out, and vacuumizing for 1h to obtain a crude product;

s3: filtering the crude product while the crude product is hot, and then fractionating to obtain the boric acid monoglyceride.

Preparation example 2: the preparation of ethoxylated boric acid monoglyceride (one of boric acid esters) comprises the following steps:

s1: 10kg of the monoglyceride borate obtained in production example 1 and 20kg of ethyl acetate were added to a reaction kettle, and 0.5kg of boron trifluoride was added as a catalyst, and the solution was heated to 130 ℃ in the reaction kettle;

s2: introducing 5kg of ethylene oxide into the boric acid monoglyceride solution by taking nitrogen as a protective gas, wherein the reaction time is 3 hours;

s3: and filtering the mixed solution after reaction, and distilling to obtain the ethoxylated boric acid monoglyceride.

Preparation example 3: preparation of boric acid monoglyceride octadecanoic acid ester (one of boric acid esters) by adopting the following steps:

s1: 10kg of the monoglyceride of boric acid obtained in production example 1 and a sufficient amount of dimethyl fumarate were charged in a reaction vessel, and 0.8kg of DMF (dimethylformamide) was added as a catalyst;

s2: adding 20kg of stearic acid into the reaction kettle, heating the solution to 120 ℃, and continuously discharging condensed water by carrying out condensation reflux in the heating process, wherein the reaction time is 4 hours;

s3: filtering the mixed solution after reaction, and distilling to obtain the boric acid monoglyceride octadecanoic acid ester.

Examples

Example 1: an antistatic agent, the components and the amount thereof are shown in Table 1,

raw materials of 35kg of octadecylamine, 10kg of ethylene oxide, 30kg of monoglyceride, 2kg of boric acid ester and 0.5kg of polyalcohol; wherein monoglyceride is glyceryl laurate, borate is trioctadecyl borate, and polyalcohol is glycerol.

The antistatic agent is prepared by the following method:

s1: weighing the octadecylamine with the mass, heating and melting at the temperature of 75 ℃, and then sending into a reaction kettle;

s2: controlling the temperature of the reaction kettle to be 140 ℃, uniformly and slowly introducing the ethylene oxide gas in parts by mass into the molten octadecylamine, and reacting for 2 hours to obtain N, N-dihydroxyethyl octadecylamine;

s3: adding the glyceryl laurate, the boric acid ester and the glycerol in parts by weight into a reaction kettle, and compounding and stirring at the temperature of 100 ℃ for 1 h;

s4: cooling the reaction kettle to 80 ℃, discharging while the reaction kettle is hot, and cooling to obtain the target antistatic agent;

s5: and slicing and packaging the target antistatic agent.

Example 2: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the amounts of the components are different and the components and their amounts are shown in table 1.

Example 3: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that boric acid ester is boric acid monoglyceride stearate, and the components and the using amount thereof are shown in table 1.

Example 4: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the boric acid ester is ethoxylated boric acid monoglyceride, and the components and the use amount thereof are shown in table 1.

Example 5: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the boric acid ester is a mixture of boric acid monoglyceride octadecanoic acid ester and ethoxylated boric acid monoglyceride, and the components and the amounts thereof are shown in table 1.

Example 6: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the polyol is a mixture of erythritol and pentadiol, and the components and the amounts thereof are shown in Table 1.

Example 7: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the polyol is a mixture of erythritol, pentadiol and pentaerythritol, and the components and the amounts thereof are shown in Table 1.

Example 8: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that hexadecanoic glyceride is used as glyceride, and the components and the using amount thereof are shown in table 1.

Example 9: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the glyceride is octadecanoic acid glyceride, and the components and the using amount thereof are shown in table 1.

Example 10: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the glyceride is a mixture of hexadecanoic glyceride and octadecanoic glyceride, and the components and the use amount thereof are shown in Table 1.

Example 11: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that 8kg of calcium carbonate was further added to the reaction vessel in the step of S3, and the components and the amounts thereof were as shown in Table 1.

Example 12: an antistatic agent for a polymer, which is a polymer,

the difference from the example 1 is that the boric acid ester is a mixture of boric acid monoglyceride octadecanoic acid ester and ethoxylated boric acid monoglyceride, the polyol is a mixture of erythritol, pentanol and pentaerythritol, the glyceride is a mixture of hexadecanoic acid glyceride and octadecanoic acid glyceride, and the components and the using amount thereof are shown in the table 1;

8kg of calcium carbonate was also added to the reaction kettle in step S3.

Example 13: an antistatic agent for a polymer, which is a polymer,

the difference from example 12 is that in step S3, evacuation treatment of the reaction vessel was performed while heating and stirring.

Examples 1-13 the amounts of each component used are shown in table 1 below.

TABLE 1 Components and amounts (kg) of examples 1-14

Comparative example

Comparative example 1: an antistatic agent for a polymer, which is a polymer,

raw materials comprise 7.5kg of octadecyl amine, 0.83kg of N, N-di (hydroxyethyl) cocoamide, 1.67kg of alkylolamine borate, 1.25kg of ethylene oxide, 7.5kg of glyceryl laurate, 0.28kg of tris (2, 4-di-tert-butyl) phenyl phosphite and 74.7kg of polypropylene;

prepared by the following steps:

s1: adding octadecyl amine, N-di (hydroxyethyl) cocoamide and alkyl alcohol amine borate into a high-speed mixer, mixing, then sending into a reaction kettle, uniformly introducing ethylene oxide into the mixture at the temperature of 120 ℃, and reacting for 6 hours to obtain a modifier;

s2: uniformly mixing a modifier, glyceryl laurate, tris (2, 4-di-tert-butyl) phenyl phosphite and polypropylene to obtain a mixture, adding the mixture into a THJ-high-rotation-speed high-torque co-rotating parallel double-screw mixing extruder, and melting and extruding to prepare an antistatic master batch;

s3: and (5) cooling, drying, pelletizing and circularly drying the antistatic master batch prepared in the step S2 to obtain the antistatic agent.

Comparative example 2: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the starting material does not contain monoglycerides, borate esters and polyols;

is prepared by the following steps:

s1: weighing octadecylamine in the mass part shown in the following table 2, heating and melting at the temperature of 75 ℃, and then feeding into a reaction kettle;

s3: cooling the reaction kettle to 80 ℃, discharging while the reaction kettle is hot, and cooling to obtain the antistatic agent;

s4: and slicing and packaging the target antistatic agent.

Comparative example 3: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the starting material does not contain borate esters and polyols.

In step S3, only glyceryl laurate is added to the reaction vessel.

Comparative example 4: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the feedstock does not contain glycerides and polyols;

only trioctadecyl borate is added to the reaction vessel in step S3.

Comparative example 5: an antistatic agent for a polymer, which is a polymer,

the difference from example 1 is that the starting material does not contain a polyol;

only glyceryl laurate and trioctadecyl borate are added to the reaction vessel in step S3.

Comparative examples 2-5 the amounts of each component are shown in table 2 below.

TABLE 2 comparative examples 2-5 with respect to the groups and amounts (kg)

Performance test

Preparation of test samples:

the antistatic agents prepared in examples 1 to 13 and comparative examples 1 to 5 were mixed with the PVC master batch using a mixer, respectively, and then heated to be melted using an extruder and extrusion-molded, cut to prepare antistatic PVC sheets having a side length of 20cm by 20cm, wherein the amount of each group of the antistatic agents was 3%, and the PVC sheets to which the antistatic agents of examples 1 to 13 and comparative examples 1 to 5 were added were numbered as test samples 1 to 13 and comparative examples 1 to 5, respectively.

Test one: antistatic Property test

The test principle is as follows: the surface resistance of the antistatic PVC plate prepared by each test group is measured under different humidity environments, the antistatic capability of each test group can be compared by comparing the surface resistance, and the lower the surface resistance is, the better the antistatic capability is.

Test subjects: test samples 1-13, control samples 1-4.

Test equipment: type ACL-800 megohmmeters.

The test steps are as follows: controlling the environmental temperature to be 23 ℃ and the environmental humidity to be 50% RH, placing the antistatic PVC plate prepared by each test group in the environment, and after 1h, respectively measuring the surface resistance of each group by using a megohmmeter to obtain and record first test data; and then controlling the environmental temperature to be 23 ℃ and the environmental humidity to be 12% RH, placing the antistatic PVC plate prepared by each test group in the environment, and after 1h, respectively measuring the surface resistance of each group by using a megohmmeter to obtain and record second test data. The test data are shown in table 3 below.

Table 3 surface resistance recording table (omega) for each group of PVC plate under different environmental humidity

Comparing the data of the test sample 1 and the control sample 1 in table 3, it can be found that the surface resistance in the test sample 1 is greater than the control sample 1, and the rate of change of the surface resistance of the test sample 1 is smaller than the control sample 1 under the low humidity condition. This shows that the antistatic effect of the antistatic agent prepared in example 1 is superior to that of control 1, and the antistatic agent of example 1 is less affected by the ambient humidity.

Comparing the data of test samples 1-2, test samples 3-5, control sample 2 and control sample 4 in table 3, it was found that the surface resistance in test samples 3-5 was smaller than that of test samples 1-2, and that control samples 2 and 4 were higher. This shows that the addition of boric acid ester can improve the antistatic effect of the product, and boric acid monoglyceride stearate and ethoxylated boric acid monoglyceride are preferably used as boric acid ester. The reason is that oxygen atoms in hydroxyl groups of the N, N-dihydroxyethyl octadecylamine and the monoglyceride can generate coordinate bonds with boron atoms in the borate ester, so that the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate ester are crosslinked, a multi-layer grid-shaped long-chain conductive structure is formed on the surface and inside of the high polymer material, and the proton conduction is easier.

The ethoxylated boric acid monoglyceride and the boric acid monoglyceride fatty acid ester are only bonded with one hydroxyl on glycerol, a sufficient space is still formed on one side of a boron atom far away from the glycerol, the steric hindrance on the boron atom is relatively small while the ethoxylated boric acid monoglyceride and the boric acid monoglyceride have an antistatic property, and the ethoxylated boric acid monoglyceride and the boric acid monoglyceride are convenient to form cross-linking with N, N-dihydroxyethyl octadecylamine and monoglyceride, so that a formed mesh conductive layer is more compact, and the antistatic capability is improved.

Comparing the data of test samples 1-2, test samples 6-7 and control sample 5 in Table 3, it was found that the surface resistance was lower in test samples 6-7 than in test samples 1-2, while the highest in control sample 5. This shows that the addition of a polyol improves the antistatic effect of the product, and that the use of erythritol, pentanol and pentaerythritol as the polyol is more preferable. This is probably because the polyol's polyhydroxy structure is able to continuously form coordination bonds with multiple boron atoms, thereby assisting in cross-linking between the raw material molecules and making the formed network conductive layer denser.

Compared with glycerol, the erythritol and the pentadiol have more hydroxyl groups and relatively smaller molecular volume, and can be uniformly distributed among long chains of the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate, pentaerythritol molecules form a regular tetrahedron type, and steric hindrance among the hydroxyl groups is smaller, so that the pentaerythritol can better act on the N, N-dihydroxyethyl octadecylamine, the monoglyceride and the borate.

Comparing the data of test samples 1-2, test samples 8-10, control sample 2 and control sample 3 in Table 3, it was found that the surface resistance was less in test samples 8-10 than in test samples 1-2, and that control samples 2 and 3 were higher than in test samples 1-2. This shows that the addition of the mono-glycol can improve the antistatic effect of the product, and the selection of the hexadecanoic glyceride and the octadecanoic glyceride as the monoglyceride is the more preferable scheme. The reason is probably that the carbon chain length of the monoglyceride with the fatty chain carbon content of 16-18 is similar to that of the carbon chain in the N, N-dihydroxyethyl octadecylamine, and the oleophylic capacity of the carbon chain is similar to that of the carbon chain in the N, N-dihydroxyethyl octadecylamine, so that the distribution of the monoglyceride and the N, N-dihydroxyethyl octadecylamine is more uniform, the synergism between the monoglyceride and the N, N-dihydroxyethyl octadecylamine is more easily generated, and the integral antistatic capacity is improved.

Comparing the data of test sample 1-2 and test sample 11 in table 3, the surface resistances of test sample 1-2 and test sample 11 were found to be similar, which indicates that the antistatic effect of the product was not negatively affected by the addition of calcium carbonate.

Comparing the data in test samples 1-11 and test sample 12 in table 3, the lowest surface resistance was found in test sample 12, which illustrates the best antistatic effect achieved by using both the boric acid monoglyceride octadecanoate and ethoxylated boric acid monoglyceride as the borate ester, butanetetraol, pentanol and pentaerythritol as the polyol, and hexadecanoic acid glyceride and octadecanoic acid glyceride as the monoglyceride, example 12 being the best solution.

Comparing the data of test sample 12 and test sample 13 in table 3, it was found that the surface resistance of test sample 13 was lower, which indicates that the antistatic effect of the product was improved by performing the vacuum pumping in step S3. The reason is that the small molecular substances which are completely reacted in the N, N-dihydroxyethyl octadecylamine can be gasified and pumped out by vacuumizing, so that the content of the macromolecular amine in the target antistatic agent is increased, and the antistatic effect of the product is improved. And because the raw materials contain a small amount of water, water in reactants can be pumped out through the vacuum pumping in the S3, so that the product has higher purity.

And (2) test II: the test principle of the abrasion resistance test is as follows: the surface of the antistatic PVC plate of each experimental group is processed to form a wear surface with the same degree, then the surface resistance at the wear surface is measured, and the abrasion resistance of each experimental group aiming at the antistatic capability can be compared by comparing the magnitude of the surface resistance change before and after wear.

Test subjects: test samples 1-13, control samples 1-5.

Test equipment: ACL-800 type megohmmeter, MD3215S1ST-150 bench grinder, the grinding wheel is CBN grinding wheel with 40% of grinding rate.

The test steps are as follows: and (3) grinding the surfaces of the antistatic PVC plates of all groups by using a grinding machine, uniformly grinding the surface of each PVC plate twice to form a wear surface, and measuring and recording the surface resistance of the wear surface of each group of PVC plates by using a megohmmeter under the conditions that the ambient temperature is 23 ℃ and the ambient humidity is 50% RH. The time interval from grinding to surface resistance measurement is controlled within 1 h.

Data processing: in the first test, each set of data measured under the conditions that the ambient temperature is 23 ℃ and the ambient humidity is 50% RH was taken as the resistance value before wear, each set of data measured in the present test was taken as the resistance value after wear, the increase ratio of the resistance value before and after wear was calculated, and the test data are shown in table 4 below.

TABLE 4 comparison table of surface resistance before and after abrasion of each group of PVC plates

Comparing the data of the test sample 1 and the control sample 1 in table 4, it can be found that the resistance increase ratio of the test sample 1 is smaller than that of the control sample 1. The conclusion of the first test shows that, compared with the control sample 1, the antistatic agent prepared by the test sample 1 still has better antistatic capability after being worn, the influence of surface wear on the antistatic agent of the test sample 1 is smaller, and the anti-wear capability of the antistatic agent of the test sample 1 is stronger.

Comparing the data of test samples 1-2, test samples 3-5, and control samples 2-4 in Table 4, it can be seen that the ratio of increase in resistance of test samples 3-5 is smaller than that of test samples 1-2, the ratio of increase in resistance of control samples 2 and 3 is larger, and the ratio of increase in resistance of control sample 3 is significantly lower than that of control samples 2-3. The conclusion of the first test shows that after the boric acid ester is added, the conductive layer on the surface of the PVC plate is thicker and more compact due to the generation of the crosslinked multi-layer latticed structure, and still has a good antistatic effect after being worn. The boric acid ester is boric acid monoglyceride stearate and ethoxylated boric acid monoglyceride, which has better effect.

Comparing the data of test samples 1 to 2, test samples 6 to 7 and control sample 5 in Table 4, it was found that the resistance increase ratio of test samples 6 to 7 was smaller than that of test samples 1 to 2, and the resistance increase ratio of control sample 5 was the largest. The conclusion of the first test shows that after the polyol is added, the formed reticular conducting layer is more compact, so that the influence of abrasion on the electric resistance performance of the product is further reduced. More preferably, the polyhydric alcohol is erythritol, pentanol or pentaerythritol.

Comparing the data of test samples 1-2, test samples 8-10, control samples 2-3 and control sample 5 in Table 4, it was found that the resistance increase ratio of test samples 8-10 was smaller than that of test samples 1-2, and the resistance increase ratio of control samples 2-3 to control sample 5 was larger. The conclusion of the first test shows that after monoglyceride is added, the monoglyceride can be crosslinked with borate, so that the overall crosslinking degree is improved, the influence of abrasion on the electric resistance of the product is further reduced, and a better scheme is provided for selecting hexadecanoic glyceride and octadecanoic glyceride. Meanwhile, the resistance increase ratio of the control sample 3 is relatively smaller than that of the control sample 2, which shows that under the condition of not adding borate ester, the influence of abrasion on the electric resistance performance of the product can be reduced to a certain extent by simply adding monoglyceride.

Comparing the data of the test sample 12 and the test sample 13 in table 4, it is found that the resistance increase ratio of the test sample 13 is smaller than that of the test sample 12, and the conclusion of the first test shows that the influence of abrasion on the antistatic capability of the product can be further reduced after the concentration of the active ingredients in the antistatic agent is increased by the vacuum pumping operation in the step S3.

And (3) test III: test principle of anti-caking capacity of antistatic agent particles: the anti-adhesion capability can be judged by placing each group of antistatic agent particles for a long time in the same environment and observing whether the antistatic agent particles are bonded or not.

Test subjects: test sample 1 and test sample 11.

The test steps are as follows: two groups of prepared target antistatic agent particles are placed in an environment with the temperature of 23 +/-3 ℃ and the humidity of 50% RH +/-5% RH, the conditions of the particles of the two groups are observed every day, the days for starting the bonding phenomenon of the two groups of samples are recorded, and the test data are shown in the following table 5.

TABLE 5 two sets of days to begin adhesion

As can be seen from the data in the table, the number of days to start the bonding of test sample 11 is significantly greater than that of test sample 1, which indicates that the anti-bonding ability of the antistatic agent particles is greatly improved after the addition of calcium carbonate. The reason is that after the calcium carbonate is added, the calcium carbonate can form a calcium layer on the surface of the finished product solid particles of the antistatic agent, so that the viscosity of the antistatic agent particles after water absorption is reduced, the adhesion among the particles is prevented, and the finished product solid particles of the antistatic agent are easier to store.

The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.

Claims

1. An antistatic agent characterized by: the material is mainly prepared from the following raw materials in parts by mass:

35-45 parts of octadecylamine;

10-15 parts of ethylene oxide gas;

30-40 parts of monoglyceride;

2-3 parts of borate;

0.5-1 part of polyol.

2. An antistatic agent according to claim 1, characterized in that: the borate ester includes at least one of an ethoxylated monoglyceride of borate or a monoglyceride of borate fatty acid ester.

3. An antistatic agent according to claim 1, characterized in that: the polyol includes at least one of erythritol or pentadiol.

4. An antistatic agent according to claim 3, characterized in that: the polyol also includes pentaerythritol.

5. An antistatic agent according to claim 1, characterized in that: the number of carbon atoms of the aliphatic chain of the monoglyceride is 16-18.

6. An antistatic agent according to claim 1, characterized in that: the raw material also comprises 5-10 parts by mass of calcium carbonate.

7. A process for the preparation of an antistatic agent according to any of claims 1 to 6, characterized in that: the method comprises the following steps:

s2: controlling the temperature of the reaction kettle to be 140-;

8. The method for preparing an antistatic agent according to claim 7, wherein: in the step S3, a vacuum process is performed during the stirring process.