Antistatic film and preparation method thereof
By modifying the combination of lignin, cellulose and copolymers, a film with excellent antistatic properties was prepared, which solved the problem of poor effect of existing antistatic films when humidity changes, and achieved the goal of good performance and simple process under different environmental conditions.
Patent Information
- Application Number
- CN202410712128.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-02-29
- Filing Date
- 2024-06-04
- Publication Date
- 2025-03-11
AI Technical Summary
The existing antistatic films have poor antistatic effects when the environmental humidity changes, and are complex in process and high in cost.
A film with excellent antistatic properties was prepared by combining modified lignin and modified cellulose with acrylonitrile-butadiene-styrene copolymer, nanosilica, quaternary ammonium salt and polyethylene glycol through esterification and film formation.
It achieves good antistatic effect under different ambient humidity conditions, and the process is relatively simple and the cost is low, and it is suitable for electronics, aviation and other fields.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of antistatic films, in particular to an antistatic film and a preparation method thereof. Background Art
[0002] Functional films generally have a special function that general films do not have and can meet special application needs, such as antistatic films, anti-rust pen films, etc., to better meet the needs of slow-moving goods packaging, or other performance. The use of conductive fillers can not only produce antistatic plastic films, but also the antistatic is less affected by environmental humidity. The use of antistatic agents to prepare antistatic films has the characteristics of simple process and low price. They are widely used in electronics, aviation, military and other fields. For example, in the document "Preparation and Performance Study of Antistatic ABS Composite Materials", lignin is a natural polymer with aromatic rings and is abundant in output. Sodium lignin sulfonate contains a benzene ring structure similar to acrylonitrile-butadiene-styrene copolymer in its molecules, and blending with it can improve the antistatic effect. Summary of the invention
[0003] 1. Technical issues to be solved
[0004] In view of the deficiencies in the prior art, the present invention provides an antistatic film and a preparation method thereof, which have good antistatic effect.
[0005] (II) Technical solution
[0006] To achieve the above purpose, the present invention provides the following technical solution: an antistatic film, which comprises the following components by weight: 20-40 parts of modified lignin, 15-25 parts of modified cellulose, 40-50 parts of acrylonitrile-butadiene-styrene copolymer, 5-10 parts of nano-silicon dioxide, 6-12 parts of quaternary ammonium salt, and 3-6 parts of polyethylene glycol.
[0007] Preferably, the preparation method of the modified lignin is: adding ε-caprolactone to an ethanol solution to fully dissolve it, slowly adding sodium lignin sulfonate after dissolution, reacting at 80-110°C for 3-6h, continuing to add L-arginine for stirring, and then adding dibutyltin dilaurate catalyst, reacting at 90-130°C for 10-24h to obtain modified lignin.
[0008] Preferably, the mass ratio of the ε-caprolactone, sodium lignin sulfonate, L-arginine, and dibutyltin dilaurate catalyst is 20-30:100:10-15:2-3.
[0009] Preferably, the preparation method of the modified cellulose is: adding cellulose to an ethylenediamine solvent for dissolution, then adding alkenyl succinic anhydride and stannous octoate catalyst thereto, reacting at 60-90°C for 3-6h, distilling under reduced pressure after the reaction, filtering and drying to obtain modified cellulose.
[0010] Preferably, the mass ratio of the cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 30-50:60-80:3-6.
[0011] Preferably, the quaternary ammonium salt is 2,3-epoxypropyltrimethylammonium chloride or octadecyltrimethylammonium chloride.
[0012] Preferably, the antistatic film comprises the following preparation method:
[0013] (1) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then adding dibutyltin dilaurate as a catalyst to carry out esterification reaction at 60-90° C. for 8-16 hours to obtain initial material A;
[0014] (2) 40-50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 5-10 parts by weight of inorganic filler, 6-12 parts by weight of quaternary ammonium salt, 3-6 parts by weight of polyethylene glycol, and 50-80 parts by weight of initial material A are stirred and mixed, and added into a film forming machine to obtain an antistatic film.
[0015] Preferably, the mass ratio of the modified cellulose, the modified lignin, and the dibutyltin dilaurate catalyst in (1) is 30-50:60-70:5-10.
[0016] (III) Beneficial technical effects
[0017] The invention comprises the following steps: epsilon-caprolactone and sodium lignin sulfonate are reacted to obtain sodium lignin sulfonate grafted with epsilon-caprolactone, and then modified lignin is obtained under the action of a dibutyltin dilaurate catalyst; cellulose is reacted with alkenyl succinic anhydride under the action of a stannous octoate catalyst to obtain modified cellulose; modified cellulose and modified lignin are reacted under the action of a dibutyltin dilaurate catalyst to obtain initial material A, and the initial material A is mixed with acrylonitrile-butadiene-styrene copolymer, nano silicon dioxide, 2,3-epoxypropyltrimethylammonium chloride and polyethylene glycol, and the mixture is added into a film-forming machine to obtain an antistatic film.
[0018] Sodium lignin sulfonate molecules contain a large number of benzene rings and have a similar structure to acrylonitrile-butadiene-styrene copolymers, so they have good compatibility. The presence of sulfonic acid groups makes sodium lignin sulfonate have good water solubility. It can be used in antistatic films to disperse static charges on the surface of materials and improve surface antistatic properties. ε-caprolactone reacts with sodium lignin sulfonate to improve the dispersibility of sodium lignin sulfonate in antistatic films and maintain good mechanical properties. Cellulose is grafted with acid anhydride to obtain modified cellulose and react with modified lignin to obtain an antistatic mixture. Cellulose has good antistatic properties. A large number of hydrophilic groups can form a hydrated film, effectively reducing resistance and charge surface density, thereby achieving an antistatic effect. The amino acids also have a good antistatic effect and play a good antistatic role on the film. DETAILED DESCRIPTION
[0019] Example 1
[0020] (1) adding ε-caprolactone to an ethanol solution to fully dissolve it, slowly adding sodium lignin sulfonate dropwise after dissolution, reacting at 80° C. for 3 h, continuing to add L-arginine for stirring, and then adding dibutyltin dilaurate catalyst, wherein the mass ratio of ε-caprolactone, sodium lignin sulfonate, L-arginine, and dibutyltin dilaurate catalyst is 20:100:10:2, and reacting at 90° C. for 10 h to obtain modified lignin;
[0021] (2) adding cellulose to an ethylenediamine solvent for dissolution, and then adding alkenyl succinic anhydride and stannous octoate catalyst thereto, wherein the mass ratio of cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 30:60:3, reacting at 60° C. for 3 h, distilling under reduced pressure after the reaction, filtering and drying to obtain modified cellulose;
[0022] (3) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then continuing to add dibutyltin dilaurate catalyst, wherein the mass ratio of modified cellulose, modified lignin and dibutyltin dilaurate catalyst is 30:60:5, and performing esterification reaction at 60° C. for 8 hours to obtain initial material A;
[0023] (4) 40 parts by weight of acrylonitrile-butadiene-styrene copolymer, 10 parts by weight of nano-silicon dioxide, 12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride, 6 parts by weight of polyethylene glycol, and 80 parts by weight of initial material A were stirred and mixed, and added into a film forming machine to obtain an antistatic film.
[0024] Example 2
[0025] (1) adding ε-caprolactone to an ethanol solution to fully dissolve it, slowly adding sodium lignin sulfonate dropwise after dissolution, reacting at 110° C. for 6 h, continuing to add L-arginine for stirring, and then adding dibutyltin dilaurate catalyst, wherein the mass ratio of ε-caprolactone, sodium lignin sulfonate, L-arginine, and dibutyltin dilaurate catalyst is 30:100:15:3, reacting at 130° C. for 24 h, and obtaining modified lignin;
[0026] (2) adding cellulose to an ethylenediamine solvent for dissolution, and then adding alkenyl succinic anhydride and stannous octoate catalyst thereto, wherein the mass ratio of cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 50:80:6, reacting at 90° C. for 6 hours, distilling under reduced pressure after the reaction, filtering and drying to obtain modified cellulose;
[0027] (3) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then continuing to add dibutyltin dilaurate catalyst, wherein the mass ratio of modified cellulose, modified lignin and dibutyltin dilaurate catalyst is 50:70:10, and performing esterification reaction at 90° C. for 16 hours to obtain initial material A;
[0028] (4) 50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 10 parts by weight of nano-silicon dioxide, 12 parts by weight of octadecyltrimethylammonium chloride, 6 parts by weight of polyethylene glycol, and 80 parts by weight of initial material A were stirred and mixed, and added into a film forming machine to obtain an antistatic film.
[0029] Example 3
[0030] (1) adding ε-caprolactone to an ethanol solution to fully dissolve it, slowly adding sodium lignin sulfonate dropwise after dissolution, reacting at 95° C. for 4.5 hours, continuing to add L-arginine for stirring, and then adding dibutyltin dilaurate catalyst, wherein the mass ratio of ε-caprolactone, sodium lignin sulfonate, L-arginine, and dibutyltin dilaurate catalyst is 25:100:12.5:2.5, reacting at 110° C. for 17 hours, and obtaining modified lignin;
[0031] (2) adding cellulose to an ethylenediamine solvent for dissolution, and then adding alkenyl succinic anhydride and stannous octoate catalyst thereto, wherein the mass ratio of cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 40:70:4.5, reacting at 75° C. for 4.5 hours, distilling under reduced pressure after the reaction, filtering and drying to obtain modified cellulose;
[0032] (3) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then continuing to add dibutyltin dilaurate catalyst, wherein the mass ratio of modified cellulose, modified lignin and dibutyltin dilaurate catalyst is 40:65:7.5, and performing esterification reaction at 75° C. for 12 hours to obtain initial material A;
[0033] (4) 45 parts by weight of acrylonitrile-butadiene-styrene copolymer, 7.5 parts by weight of nano-silicon dioxide, 18 parts by weight of octadecyltrimethylammonium chloride, 4.5 parts by weight of polyethylene glycol, and 65 parts by weight of initial material A were stirred and mixed, and added into a film forming machine to obtain an antistatic film.
[0034] Example 4
[0035] (1) adding ε-caprolactone to an ethanol solution to fully dissolve it, slowly adding sodium lignin sulfonate dropwise after dissolution, reacting at 80° C. for 3 h, continuing to add L-arginine for stirring, and then adding dibutyltin dilaurate catalyst, wherein the mass ratio of ε-caprolactone, sodium lignin sulfonate, L-arginine, and dibutyltin dilaurate catalyst is 20:100:10:2, and reacting at 90° C. for 10 h to obtain modified lignin;
[0036] (2) adding cellulose to an ethylenediamine solvent for dissolution, and then adding alkenyl succinic anhydride and stannous octoate catalyst thereto, wherein the mass ratio of cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 30:60:3, reacting at 60° C. for 3 h, distilling under reduced pressure after the reaction, filtering and drying to obtain modified cellulose;
[0037] (3) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then continuing to add dibutyltin dilaurate catalyst, wherein the mass ratio of modified cellulose, modified lignin and dibutyltin dilaurate catalyst is 50:70:10, and performing esterification reaction at 90° C. for 16 hours to obtain initial material A;
[0038] (4) 45 parts by weight of acrylonitrile-butadiene-styrene copolymer, 7.5 parts by weight of nano-silicon dioxide, 18 parts by weight of octadecyltrimethylammonium chloride, 4.5 parts by weight of polyethylene glycol, and 65 parts by weight of initial material A were stirred and mixed, and added into a film forming machine to obtain an antistatic film.
[0039] Example 5
[0040] (1) adding ε-caprolactone to an ethanol solution to fully dissolve it, slowly adding sodium lignin sulfonate dropwise after dissolution, reacting at 110° C. for 6 h, continuing to add L-arginine for stirring, and then adding dibutyltin dilaurate catalyst, wherein the mass ratio of ε-caprolactone, sodium lignin sulfonate, L-arginine, and dibutyltin dilaurate catalyst is 30:100:15:3, reacting at 130° C. for 24 h, and obtaining modified lignin;
[0041] (2) adding cellulose to an ethylenediamine solvent for dissolution, and then adding alkenyl succinic anhydride and stannous octoate catalyst thereto, wherein the mass ratio of cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 50:80:6, reacting at 90° C. for 6 hours, distilling under reduced pressure after the reaction, filtering and drying to obtain modified cellulose;
[0042] (3) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then continuing to add dibutyltin dilaurate catalyst, wherein the mass ratio of modified cellulose, modified lignin and dibutyltin dilaurate catalyst is 40:65:7.5, and performing esterification reaction at 75° C. for 12 hours to obtain initial material A;
[0043] (4) 40 parts by weight of acrylonitrile-butadiene-styrene copolymer, 10 parts by weight of nano-silicon dioxide, 12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride, 6 parts by weight of polyethylene glycol, and 80 parts by weight of initial material A were stirred and mixed, and added into a film forming machine to obtain an antistatic film.
[0044] Comparative Example 1
[0045] 40 parts by weight of acrylonitrile-butadiene-styrene copolymer, 10 parts by weight of nano-silicon dioxide, 12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride and 6 parts by weight of polyethylene glycol were stirred and mixed, and added into a film-forming machine to obtain an antistatic film.
[0046] According to SJ / T10694-2006, the antistatic film of Examples 1-5 and Comparative Example 1 was tested for antistatic properties. The point-to-point resistance test results are shown in Table 1. 5 to 1×10 9 Ω is qualified.
[0047] Table 1: Point-to-point resistance test results.
[0048] project Resistance(Ω) Example 1 <![CDATA[1.56×10 7 ]]> Example 2 <![CDATA[1.52×10 7 ]]> Example 3 <![CDATA[1.65×10 7 ]]> Example 4 <![CDATA[1.35×10 7 ]]> Example 5 <![CDATA[1.63×10 7 ]]> Comparative Example 1 <![CDATA[3×10 9 ]]>
[0049] It can be seen from Table 1 that the antistatic film of the present invention has a good antistatic effect.
[0050] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. An antistatic film, characterized in that: The antistatic film comprises the following components by weight: 20-40 parts of modified lignin, 15-25 parts of modified cellulose, 40-50 parts of acrylonitrile-butadiene-styrene copolymer, 5-10 parts of nano silicon dioxide, 6-12 parts of quaternary ammonium salt and 3-6 parts of polyethylene glycol.
2. The antistatic film according to claim 1, characterized in that The preparation method of the modified lignin is as follows: ε-caprolactone is added to an ethanol solution to fully dissolve it, sodium lignin sulfonate is slowly added dropwise after dissolution, reacts at 80-110° C. for 3-6 hours, L-arginine is continuously added for stirring, and then dibutyltin dilaurate is added as a catalyst, and reacts at 90-130° C. for 10-24 hours to obtain the modified lignin.
3. The antistatic film according to claim 2, characterized in that The mass ratio of the ε-caprolactone, sodium lignin sulfonate, L-arginine and dibutyltin dilaurate catalyst is 20-30:100:10-15:2-3.
4. The antistatic film according to claim 1, characterized in that The preparation method of the modified cellulose comprises: adding cellulose into ethylenediamine solvent for dissolution, adding alkenyl succinic anhydride and stannous octoate catalyst thereto, reacting at 60-90° C. for 3-6 hours, performing reduced pressure distillation after the reaction, filtering and drying to obtain the modified cellulose.
5. The antistatic film according to claim 4, characterized in that The mass ratio of the cellulose, alkenyl succinic anhydride and stannous octoate catalyst is 30-50:60-80:3-6.
6. The antistatic film according to claim 1, characterized in that The quaternary ammonium salt is 2,3-epoxypropyltrimethylammonium chloride or octadecyltrimethylammonium chloride.
7. A method for preparing an antistatic film according to any one of claims 1 to 6, characterized in that: The antistatic film comprises the following preparation method: (1) adding modified cellulose and modified lignin to N,N-dimethylformamide solvent and stirring evenly, and then adding dibutyltin dilaurate as a catalyst to carry out esterification reaction at 60-90° C. for 8-16 hours to obtain initial material A; (2) 40-50 parts by weight of acrylonitrile-butadiene-styrene copolymer, 5-10 parts by weight of inorganic filler, 6-12 parts by weight of quaternary ammonium salt, 3-6 parts by weight of polyethylene glycol, and 50-80 parts by weight of initial material A are stirred and mixed, and added into a film forming machine to obtain an antistatic film.
8. The antistatic film according to claim 7, characterized in that The mass ratio of the modified cellulose, the modified lignin and the dibutyltin dilaurate catalyst in (1) is 30-50:60-70:5-10.