WO2019210684A1

WO2019210684A1 - Environmentally-friendly lldpe winding film

Info

Publication number: WO2019210684A1
Application number: PCT/CN2018/118794
Authority: WO
Inventors: 顾黎明
Original assignee: 苏州聚慧邦新材料科技有限公司
Priority date: 2018-05-02
Filing date: 2018-11-30
Publication date: 2019-11-07
Also published as: CN108517069A

Abstract

Disclosed by the present invention is an environmentally-friendly LLDPE winding film, which is made from the following raw materials in parts by weight: 130-150 parts of LLDPE, 1-2 parts of zinc cyanurate, 17-20 parts of citric acid, 13-20 parts of n-butanol, 2-3 parts of calcium palmitate, 30-40 parts of an organic montmorillonite dispersion liquid, 0.1 -0.2 parts of a catalyst, 0.8-1 part of monoglycerol monostearate and 1-2 parts of zinc stearate. In the present invention, an n-butanol solution of calcium palmitate is used to treat a LLDPE matrix, which may effectively improve the heat resistant stability thereof, and then citric acid is introduced so as to react under the action of a catalyst to obtain a plasticizer-modified matrix raw material; by mean of the described reaction, the bonding strength between a matrix and the raw materials is improved.

Description

An environmentally friendly LLDPE stretch film

Technical field

The invention belongs to the field of membranes, and in particular relates to an environmentally friendly LLDPE wound film.

Background technique

Stretch film is mainly used for the sale and transportation of various products. Its main function is to stabilize, cover and protect the product, so the stretch film must have high puncture resistance, good shrinkage and shrinkage stress. The initial stretch film is mainly made of PVC. With the continuous improvement of the performance requirements of the stretched film, the PVC stretch film is gradually reduced, and various polyethylene stretch films are developing rapidly. Polyethylene stretch film is a kind of tough material. It is widely used in the whole package of wine, cans, mineral water, various beverages, cloth and other products. The product is flexible, anti-impact and anti-impact. Strong tearing, not easy to break, not afraid of tide, and high shrinkage.

technical problem

However, most of the current stretch film only pursues the production cost, and many plasticizers containing halogen are used, which causes environmental pollution, and long-term use also causes certain damage to the human body.

Technical solution

It is an object of the present invention to provide an environmentally friendly LLDPE wound film in view of the deficiencies and deficiencies of the prior art.

To achieve the above object, the present invention adopts the following technical solutions:

An environmentally friendly LLDPE stretch film made of the following raw materials by weight:

130-150 parts of LLDPE, 1-2 parts of zinc cyanurate, 17-20 parts of citric acid, 13-20 parts of n-butanol, 2-3 parts of calcium palmitate, 30-40 parts of organic montmorillonite dispersion, catalyst 0.1 -0.2 parts, 0.8-1 part of monostearate monoester, and 1-2 parts of zinc stearate.

The environmentally friendly LLDPE wound film of the present invention is obtained by the following steps:

(1) taking n-butanol, calcium palmitate mixture, stirring at 60-65 ° C for 20-30 minutes, adding 5-7 times the weight of the mixture in deionized water, stirring evenly, to obtain an alcohol solution;

(2) taking monoglyceryl monostearate, adding to the above alcohol solution, stirring uniformly, adding LLDPE, ultrasonicing for 3-4 minutes to obtain a LLDPE dispersion;

(3) taking zinc cyanurate, adding it to deionized water with a weight of 10-17 times, adding citric acid, feeding it to the reaction kettle, adding the above LLDPE dispersion, adjusting the temperature of the reaction vessel to 90-95 ° C, adding catalyst , the mixture is stirred for 3-5 hours, and the discharge is cooled to obtain a plasticized LLDPE dispersion;

(4) taking the above organic montmorillonite dispersion, mixing with the plasticized LLDPE dispersion, stirring at 60-70 ° C for 1-2 hours, suction filtration, washing the precipitate with water, drying at room temperature to obtain modified LLDPE;

(5) The above-mentioned modified LLDPE is mixed with zinc stearate, stirred uniformly, sent to the extruder, and cast into a film to obtain the environmentally friendly LLDPE wound film.

The catalyst of the present invention is p-toluenesulfonic acid.

The organic montmorillonite dispersion according to the present invention is composed of the following raw materials by weight:

60-70 parts of montmorillonite powder, 6-8 parts of oxidized polyethylene wax, 1-2 parts of castor oil polyoxyethylene ether, 10-14 parts of acetic anhydride, 0.01-0.02 parts of acid catalyst, 20-30 parts of chloroform; The acid catalyst is a sulfuric acid solution having a concentration of 96-98%.

The organic montmorillonite dispersion of the present invention is obtained by the following steps:

(1) taking oxidized polyethylene wax, adding it to chloroform, feeding it into a constant temperature water bath of 55-60 ° C, stirring for 1-2 hours, discharging and cooling to obtain a chloroform solution;

(2) Take acetic anhydride, add 60-70 times its weight to deionized water, stir evenly, add montmorillonite powder, raise the temperature to 80-90 ° C, add the above acid catalyst, add the stirring after the addition 2-3 hours, get montmorillonite dispersion;

(3) The above chloroform solution and the montmorillonite dispersion are mixed, sonicated for 10-20 minutes, the chloroform is distilled off, and the castor oil polyoxyethylene ether is added to obtain the organic montmorillonite dispersion.

Beneficial effect

In the organic montmorillonite dispersion of the invention, the montmorillonite powder is firstly acetylated by acetic anhydride, and concentrated sulfuric acid is used as a catalyst, and then blended with a chloroform solution of oxidized polyethylene wax to castor oil polyoxyethylene. The ether is a dispersing agent, further plasticizing the montmorillonite, improving the surface activity thereof, thereby improving the dispersion compatibility with the polymer matrix and improving the quality of the finished wrapping film.

The invention adopts the n-butanol solution of calcium palmitate to treat the LLDPE matrix, and can effectively improve the heat resistance stability thereof, and then reacts under the action of the catalyst by introducing citric acid to obtain a plasticizer-modified matrix raw material, through which the reaction is carried out. The invention not only improves the bonding strength between the substrate and the raw materials, but also eliminates the need to additionally add a plasticizer raw material, and the citric acid ester obtained by the reaction has good environmental protection, no toxic and harmful substances are released, and the use safety is good.

BEST MODE FOR CARRYING OUT THE INVENTION

实施例Example 11

Weigh the following materials in parts by weight:

150 parts of LLDPE, 2 parts of zinc cyanurate, 20 parts of citric acid, 20 parts of n-butanol, 3 parts of calcium palmitate, 40 parts of organic montmorillonite dispersion, 0.2 parts of catalyst p-toluenesulfonic acid, glycerol monostearate 1 part of monoester and 2 parts of zinc stearate.

The environmentally friendly LLDPE stretch film is obtained by the following steps:

(1) taking n-butanol, calcium palmitate mixture, stirring at 65 ° C for 30 minutes, adding 7 times the weight of the mixture of deionized water, stirring evenly, to obtain an alcohol solution;

(2) taking monoglyceryl monostearate, adding to the above alcohol solution, stirring uniformly, adding LLDPE, ultrasonic for 3 minutes, to obtain a LLDPE dispersion;

(3) Taking zinc cyanurate, adding it to deionized water with a weight of 17 times, adding citric acid, feeding it to the reaction vessel, adding the above LLDPE dispersion, adjusting the temperature of the reaction vessel to 95 ° C, adding the catalyst, and stirring and stirring 5 After hours, the discharge is cooled to obtain a plasticized LLDPE dispersion;

(4) taking the above organic montmorillonite dispersion, mixing with the plasticized LLDPE dispersion, stirring at 70 ° C for 2 hours, suction filtration, washing the precipitate with water, drying at room temperature to obtain modified LLDPE;

(5) taking the above modified LLDPE, mixing with zinc stearate, stirring uniformly, feeding into an extruder, casting into a film, that is, the environmentally friendly LLDPE wrapping film is obtained.

Among them, the organic montmorillonite dispersion is made of the following raw materials by weight:

70 parts of montmorillonite powder, 8 parts of oxidized polyethylene wax, 2 parts of castor oil polyoxyethylene ether, 14 parts of acetic anhydride, 0.02 parts of acid catalyst of sulfuric acid solution having a concentration of 98%, and 30 parts of chloroform;

The preparation method of the organic montmorillonite dispersion is the following steps:

(1) taking oxidized polyethylene wax, adding it to chloroform, feeding it into a constant temperature water bath at 60 ° C, stirring for 2 hours, discharging and cooling to obtain a chloroform solution;

(2) Take acetic anhydride, add it to deionized water with 70 times its weight, stir evenly, add montmorillonite powder, raise the temperature to 90 °C, add the above acid catalyst dropwise, stir and stir for 3 hours. Montmorillonite dispersion;

(3) The above chloroform solution and the montmorillonite dispersion are mixed, sonicated for 20 minutes, and the chloroform is distilled off, and the castor oil polyoxyethylene ether is added to obtain the organic montmorillonite dispersion.

实施例Example 22

Weigh the following materials in parts by weight:

130 parts of LLDPE, 1 part of zinc cyanurate, 17 parts of citric acid, 13 parts of n-butanol, 2 parts of calcium palmitate, 30 parts of organic montmorillonite dispersion, 0.1 part of catalyst p-toluenesulfonic acid, monostearic acid 0.8 parts of monoglyceride and 1 part of zinc stearate.

(1) taking n-butanol, calcium palmitate mixture, stirring at 60 ° C for 20 minutes, adding 5 times the weight of the mixture of deionized water, stirring evenly, to obtain an alcohol solution;

(3) Take zinc cyanurate, add it to deionized water 10 times its weight, add citric acid, send it to the reaction kettle, add the above LLDPE dispersion, adjust the temperature of the reaction kettle to 90 ° C, add catalyst, keep stirring 3 After hours, the discharge is cooled to obtain a plasticized LLDPE dispersion;

(4) taking the above organic montmorillonite dispersion, mixing with the plasticized LLDPE dispersion, stirring at 60 ° C for 1 hour, suction filtration, washing the precipitate with water, drying at room temperature to obtain modified LLDPE;

The organic montmorillonite dispersion is composed of the following raw materials by weight:

60 parts of montmorillonite powder, 6 parts of oxidized polyethylene wax, 1 part of castor oil polyoxyethylene ether, 10 parts of acetic anhydride, 0.01 parts of acid catalyst of sulfuric acid solution having a concentration of 96%, and 20 parts of chloroform;

The organic montmorillonite dispersion is prepared by the following steps:

(1) taking oxidized polyethylene wax, adding it to chloroform, feeding it into a constant temperature water bath at 55 ° C, stirring for 1 hour while holding, cooling the output to obtain a chloroform solution;

(2) Take acetic anhydride, add it to deionized water with 60 times its weight, stir evenly, add montmorillonite powder, raise the temperature to 80 °C, add the above acid catalyst dropwise, stir and stir for 2 hours. Montmorillonite dispersion;

(3) The above chloroform solution and the montmorillonite dispersion are mixed, sonicated for 10 minutes, and the chloroform is distilled off, and the castor oil polyoxyethylene ether is added to obtain the organic montmorillonite dispersion.

Performance tests were performed on the environmentally friendly LLDPE stretched films prepared in Examples 1 and 2:

Tensile strength at break: 25-30MPa;

Elongation at break: 310-400%;

Heat shrinkage rate (130 ° C × 20 seconds) MD: > 60.

Claims

An environmentally friendly LLDPE stretch film characterized in that it is made of the following raw materials by weight:

130-150 parts of LLDPE, 1-2 parts of zinc cyanurate, 17-20 parts of citric acid, 13-20 parts of n-butanol, 2-3 parts of calcium palmitate, 30-40 parts of organic montmorillonite dispersion, catalyst 0.1 -0.2 parts, 0.8-1 part of monostearate monoester, and 1-2 parts of zinc stearate.
An environmentally friendly LLDPE wound film according to claim 1, which is obtained by the following steps:

(1) taking n-butanol, calcium palmitate mixture, stirring at 60-65 ° C for 20-30 minutes, adding 5-7 times the weight of the mixture in deionized water, stirring evenly, to obtain an alcohol solution;

(2) taking monoglyceryl monostearate, adding to the above alcohol solution, stirring uniformly, adding LLDPE, ultrasonicing for 3-4 minutes to obtain a LLDPE dispersion;

(3) taking zinc cyanurate, adding it to deionized water with a weight of 10-17 times, adding citric acid, feeding it to the reaction kettle, adding the above LLDPE dispersion, adjusting the temperature of the reaction vessel to 90-95 ° C, adding catalyst , the mixture is stirred for 3-5 hours, and the discharge is cooled to obtain a plasticized LLDPE dispersion;

(4) taking the above organic montmorillonite dispersion, mixing with the plasticized LLDPE dispersion, stirring at 60-70 ° C for 1-2 hours, suction filtration, washing the precipitate with water, drying at room temperature to obtain modified LLDPE;

(5) The above-mentioned modified LLDPE is mixed with zinc stearate, stirred uniformly, sent to the extruder, and cast into a film to obtain the environmentally friendly LLDPE wound film.
The environmentally friendly LLDPE wound film according to claim 1 or 2, wherein the catalyst is p-toluenesulfonic acid.
The environmentally-friendly LLDPE wound film according to claim 1 or 2, wherein the organic montmorillonite dispersion is composed of the following raw materials by weight:

60-70 parts of montmorillonite powder, 6-8 parts of oxidized polyethylene wax, 1-2 parts of castor oil polyoxyethylene ether, 10-14 parts of acetic anhydride, 0.01-0.02 parts of acid catalyst, 20-30 parts of chloroform; The acid catalyst is a sulfuric acid solution having a concentration of 96 to 98%.
The environmentally friendly LLDPE wound film according to claim 4, wherein the organic montmorillonite dispersion is obtained by the following steps:

(1) taking oxidized polyethylene wax, adding it to chloroform, feeding it into a constant temperature water bath of 55-60 ° C, stirring for 1-2 hours, discharging and cooling to obtain a chloroform solution;

(2) Take acetic anhydride, add 60-70 times its weight to deionized water, stir evenly, add montmorillonite powder, raise the temperature to 80-90 ° C, add the above acid catalyst, add the stirring after the addition 2-3 hours, get montmorillonite dispersion;

(3) The above chloroform solution and the montmorillonite dispersion are mixed, sonicated for 10-20 minutes, the chloroform is distilled off, and the castor oil polyoxyethylene ether is added to obtain the organic montmorillonite dispersion.