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CN-121975247-A - Antistatic PVC calendered film and preparation method thereof

CN121975247ACN 121975247 ACN121975247 ACN 121975247ACN-121975247-A

Abstract

The invention relates to the technical field of research and development of antistatic PVC materials, and discloses an antistatic PVC calendered film and a preparation method thereof, and specifically comprises the steps of grafting a secondary amino quaternized linear organosilicon compound and a secondary amino quaternized cage-type organosilicon compound onto a PVC molecular chain through nucleophilic substitution reaction of secondary amine-chlorine to prepare quaternized organosilicon modified PVC; the method comprises the steps of carrying out functional modification treatment on conductive carbon black filler by using 1, 3-propane sultone to obtain sulfonated conductive carbon black filler, mixing quaternized organosilicon modified PVC and sulfonated conductive carbon black filler in the presence of a heat stabilizer, realizing ionic bonding interface compatibility of the conductive carbon black filler and a PVC matrix through electrostatic adsorption, compounding PVC resin, and carrying out a calendaring molding process to obtain the PVC calendaring film.

Inventors

  • CHEN CAI
  • CHEN SHANGPING
  • Mei Yihui
  • LIU SHUANG

Assignees

  • 黄山嘉浩新材料科技有限公司

Dates

Publication Date
20260505
Application Date
20260228

Claims (10)

  1. 1. An antistatic PVC calendered film is characterized by comprising the following raw materials in parts by weight: 30-45 parts of PVC resin; 45-60 parts of quaternized organosilicon modified PVC; 8-12 parts of sulfonated conductive carbon black filler; 0.5-3 parts of heat stabilizer; Wherein the quaternized organosilicon modified PVC is prepared by grafting a secondary amino quaternized linear organosilicon compound and a secondary amino quaternized cage organosilicon compound onto a PVC molecular chain through nucleophilic substitution reaction of secondary amine-chlorine; The sulfonated conductive carbon black filler is prepared by grafting 1, 3-propane sultone to the surface of the hydroxylated conductive carbon black filler through sultone-hydroxyl ring-opening reaction and performing alkali neutralization treatment.
  2. 2. An antistatic PVC calendered film according to claim 1 wherein the secondary amino quaternized linear organosilicon compound has the chemical formula: 。
  3. 3. An antistatic PVC calendered film according to claim 1 wherein the secondary amino quaternized cage organosilicon compound has the chemical formula: 。
  4. 4. an antistatic PVC calendered film according to claim 1 wherein the quaternized silicone modified PVC is formulated from 86-96wt% polyvinyl chloride resin, 2-7wt% secondary amino quaternized linear organosilicon compound and 2-7wt% secondary amino quaternized cage organosilicon compound.
  5. 5. An antistatic PVC calendered film according to claim 1 wherein the mass ratio of 1, 3-propane sultone to hydroxylated conductive carbon black filler in the sulfonated conductive carbon black filler is (0.3-1): 10.
  6. 6. An antistatic PVC calendered film according to claim 5 wherein the particle size of the hydroxylated conductive carbon black filler is 20-30nm.
  7. 7. A method for producing an antistatic PVC calendered film according to any of claims 1-6, comprising the steps of: The method comprises the steps of firstly, carrying out nucleophilic substitution reaction on secondary amine functional groups in secondary amine quaternized linear organosilicon compounds and secondary amine quaternized cage organosilicon compounds and chlorine functional groups on PVC molecular chains to realize grafting modification treatment of the secondary amine quaternized linear organosilicon compounds and the secondary amine quaternized cage organosilicon compounds on PVC resin together, so as to obtain quaternized organosilicon modified PVC; Step two, performing ring-opening reaction on hydroxyl functional groups contained on the surface of the hydroxylated conductive carbon black filler and 1, 3-propane sultone to form sulfonic acid groups, and performing alkali neutralization treatment by using sodium hydroxide to obtain sulfonated conductive carbon black filler; And thirdly, firstly mixing the quaternized organosilicon modified PVC and the sulfonated conductive carbon black filler in the presence of a heat stabilizer, and carrying out electrostatic adsorption on sulfonate groups in the sulfonated conductive carbon black filler and quaternary ammonium salt groups in the quaternized organosilicon modified PVC to realize ionic bonding type interface compatibility of the conductive carbon black filler and a PVC matrix, and then compounding PVC resin, thereby preparing the antistatic PVC calendered film through a calendering process.
  8. 8. The method for producing an antistatic PVC calendered film according to claim 7, wherein the method for producing a secondary amino quaternized linear organosilicon compound is: By the addition reaction of Si-H functional groups of 1,3, 5, 7-octamethyltetrasiloxane and alkenyl functional groups of vinyl dimethyl ethoxysilane, and controlling the mol ratio of 1,3, 5, 7-octamethyltetrasiloxane to vinyldimethylethoxysilane to be 1:2.01-2.05 to generate diethoxy linear silane monomer; The addition reaction of the-NH 2 functional group of (3-aminopropyl) dimethyl ethoxysilane and the alpha, beta-alkenyl functional group of the acryloyloxyethyl trimethyl ammonium chloride is carried out, and the molar ratio of the (3-aminopropyl) dimethyl ethoxysilane to the acryloyloxyethyl trimethyl ammonium chloride is controlled to be 1:0.95-0.99, so that a secondary amino quaternized ethoxysilane monomer is generated; The secondary amino quaternized linear organosilicon compound is produced by the condensation reaction of the silicon ethoxy group of the diethoxy linear silane monomer and the silicon ethoxy group of the secondary amino quaternized ethoxy silane monomer, and controlling the mol ratio of the diethoxy linear silane monomer to the secondary amino quaternized ethoxy silane monomer to be 1:2.01-2.05.
  9. 9. The method for preparing an antistatic PVC calendered film according to claim 8, wherein the method for preparing the secondary amino quaternized cage-type organosilicon compound is as follows: Generating diethoxy cage silane monomer by performing addition reaction on Si-H functional groups of hexamethyl dihydro POSS and alkenyl functional groups of vinyl dimethyl ethoxy silane, and controlling the molar ratio of the hexamethyl dihydro POSS to the vinyl dimethyl ethoxy silane to be 1:2.01-2.05; The secondary amino quaternized cage type organic silicon compound is generated by the condensation reaction of the silicon ethoxy group of the diethoxy cage type silane monomer and the silicon ethoxy group of the secondary amino quaternized ethoxy silane monomer, and controlling the mol ratio of the diethoxy cage type silane monomer to the secondary amino quaternized ethoxy silane monomer to be 1:2.01-2.05.
  10. 10. The preparation method of the antistatic PVC calendered film is characterized in that the preparation method of the hexamethyl dihydro POSS is characterized in that acid is used for catalyzing methyltrimethoxysilane and trimethoxysilane to carry out hydrolytic polycondensation reaction, and the molar ratio of methyltrimethoxysilane to trimethoxysilane is controlled to be 3.01-3.05:1, so that the hexamethyl dihydro POSS is generated.

Description

Antistatic PVC calendered film and preparation method thereof Technical Field The invention relates to the technical field of research and development of antistatic PVC materials, in particular to an antistatic PVC calendered film and a preparation method thereof. Background PVC calendered film is a polymer film material formed by taking polyvinyl chloride (PVC) resin as a matrix and carrying out the procedures of high-speed mixing, open milling, calendering and the like, and is widely applied to a plurality of fields such as packaging, construction, electronics, medical treatment, home decoration and the like because of the advantages of high cost efficiency, high wear resistance, high chemical corrosion resistance, good flame retardance and the like. However, PVC calendered films are extremely susceptible to charge transfer and static buildup due to friction and contact separation during calendering and later processing, transportation and use due to their polymeric insulating properties (volume resistivity typically up to 10 14-1016 Ω and cm). The electrostatic effect not only causes dust accumulation on the surface of the film and impaired appearance, but also causes process faults such as film adhesion, deviation and the like in a high-speed production line. In the electronic field, electrostatic discharge (ESD) can cause component breakdown, and in flammable environments, serious ignition safety hazards exist. The conductive filler is introduced into the PVC material, which is one of important technical paths for realizing antistatic modification, but the interface compatibility of the inorganic conductive filler (such as graphene, carbon nano tube, carbon black and the like) and an organic PVC cotton matrix is limited, agglomeration or interface defects are easy to form when the conductive filler is directly added, and the performance of the material is obviously deteriorated. The research shows that the PVC molecular chain contains a large number of strong-polarity C-Cl bonds, so that the intermolecular force is strong, the material has the defects of high brittleness, poor toughness and insufficient ductility, and is easy to crack in the calendaring process. At present, the flexibility of the PVC calendered film is improved by adding small molecular plasticizers such as phthalate esters (DOP, DBP, DIBP) and the like in industry, but the small molecular plasticizers have long-term stability problems such as easy migration, volatilization, precipitation and the like, so that the physical and mechanical properties of the PVC calendered film are attenuated along with time, and environmental and health risks can be brought. In the prior art, toughening is achieved by introducing a soft segment into a PVC molecular chain, but the mechanical strength (such as tensile strength) of a material is remarkably reduced by introducing a simple soft segment although the impact toughness can be improved. Therefore, how to realize high-efficiency toughening of PVC and maintain the mechanical strength of the PVC, namely, the toughening balance of the material is realized, and the PVC material has important significance for expanding the engineering application value of the PVC material. Disclosure of Invention The invention takes conductive carbon black as antistatic filler, develops quaternized linear organosilicon compound with flexible structure and quaternized cage organosilicon compound with rigid-flexible structure through molecular design, introduces the quaternized linear organosilicon compound into PVC molecular chain through chemical bonding, realizes toughening technical effect through flexible structure on one hand, maintains mechanical strength of material through rigid structure on the other hand, realizes ionic bonding type interfacial compatibility of conductive carbon black filler and PVC matrix through electrostatic adsorption through quaternary ammonium structure on the other hand, and the prepared PVC calendered film product has antistatic effect and shows tough and balanced characteristics. An antistatic PVC calendered film comprises the following raw materials in parts by weight: 30-45 parts of PVC resin; 45-60 parts of quaternized organosilicon modified PVC; 8-12 parts of sulfonated conductive carbon black filler; 0.5-3 parts of heat stabilizer; Wherein the quaternized organosilicon modified PVC is prepared by grafting a secondary amino quaternized linear organosilicon compound and a secondary amino quaternized cage organosilicon compound onto a PVC molecular chain through nucleophilic substitution reaction of secondary amine-chlorine; The sulfonated conductive carbon black filler is prepared by grafting 1, 3-propane sultone to the surface of the hydroxylated conductive carbon black filler through sultone-hydroxyl ring-opening reaction and performing alkali neutralization treatment. Preferably, the formula of the quaternized organosilicon modified PVC comprises 86-96wt% of polyvinyl chloride re