CN112280137A

CN112280137A - Preparation method of high-toughness and high-strength cosmetic hose packaging film

Info

Publication number: CN112280137A
Application number: CN202011036244.7A
Authority: CN
Inventors: 王良胜; 杜德熙
Original assignee: Tubest Packing Gz Co ltd
Current assignee: Tubest Packing Gz Co ltd
Priority date: 2020-09-27
Filing date: 2020-09-27
Publication date: 2021-01-29

Abstract

The invention discloses a preparation method of a high-toughness and high-strength cosmetic hose packaging film, and particularly relates to a nano silicon dioxide particle graft modified polyethylene composite film. Linear Low Density Polyethylene (LLDPE) is used as a toughening agent to modify the toughness and strength of High Density Polyethylene (HDPE) and is used as a carrier resin of a packaging film; the silane coupling agent is used for carrying out surface modification on the nano silicon dioxide particles so as to improve the interface compatibility of the nano silicon dioxide particles and resin; after being finely ground, the modified nano silicon dioxide is mixed with carrier resin, and the grafted modified polyethylene film is synthesized by a melt blending method. The invention improves the mechanical property of the polyethylene film, particularly improves the toughness and the strength of the film, and is more applicable to the field of soft tube packaging of cosmetics.

Description

Preparation method of high-toughness and high-strength cosmetic hose packaging film

Technical Field

The invention belongs to the field of cosmetic hose packaging, and particularly relates to a nano silicon dioxide particle grafted modified polyethylene composite film.

Background

The soft tube package of cosmetics has higher requirements on the toughness and the strength of the film, and the traditional polyethylene film has printing problems and fine crease phenomena in the field of soft tube package of cosmetics. Polyethylene films are often used as flexible tube packaging materials in industries such as cosmetics, medical products, food packaging and the like due to good waterproof and moistureproof properties, good physical properties, good chemical corrosion resistance, low cost and the like. In the traditional polyethylene preparation method, the rubber toughened plastic is adopted, so that the toughness is increased, and other properties of the material, such as rigidity, strength and the like, slide down greatly; the polymer film material is modified by the high-modulus filler, so that the strength, the thermal deformation temperature and the rigidity are improved, but the toughness of the polymer material is reduced. Therefore, how to simultaneously improve the strength and the toughness of the polymer material becomes a difficult point for researching the cosmetic hose packaging film.

Disclosure of Invention

The invention provides a preparation process of a nano silicon dioxide grafted and modified polyethylene composite film.

In order to solve the technical problems, the invention provides a preparation method of a high-toughness and high-strength cosmetic hose packaging film, which comprises the following steps: preparing carrier resin, namely modifying high-density polyethylene by using linear low-density polyethylene as a toughening agent; and (3) grafting modification, namely, carrying out surface modification on the nano silicon dioxide particles by using a silane coupling agent to improve the interface compatibility of the nano silicon dioxide particles and resin.

In a second aspect, the present invention provides a modified silica as described above, which is finely ground and then melt-blended with a carrier resin as described above to synthesize a graft-modified polyethylene film.

The invention has the beneficial effects that: the linear low-density polyethylene is used as a toughening agent to modify the high-density polyethylene, so that the mechanical property of the carrier resin is obviously improved; the silane coupling agent KH-550 is adopted to modify the surface of the nano silicon dioxide particles, so that the interface compatibility of the nano silicon dioxide particles and resin is improved; finally, the grafted modified polyethylene composite film prepared by the melt blending method has excellent toughness and strength.

To make the aforementioned objects, features and advantages of the present invention more apparent, preferred embodiments are described in detail below with reference to the accompanying drawings. It is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.

Drawings

In order to more clearly illustrate the embodiments or prior art solutions of the present invention, the drawings that are necessary for describing the embodiments or prior art will be briefly described below.

FIG. 1 is a flow chart of a process for preparing a graft-modified polyethylene composite film according to the present invention;

FIG. 2 shows the grafting reaction formula of the silane coupling agent modified nano-silica of the present invention.

Detailed Description

To make the implementation objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Illustrating a specific embodiment

Referring to fig. 1, the invention provides a preparation method of a high-toughness high-strength cosmetic hose packaging film, which is characterized by comprising the following steps: preparing carrier resin, namely modifying high-density polyethylene by using linear low-density polyethylene as a toughening agent; and (3) grafting modification, namely, carrying out surface modification on the nano silicon dioxide particles by using a silane coupling agent to improve the interface compatibility of the nano silicon dioxide particles and resin. And grinding the modified silicon dioxide finely, and synthesizing the grafted modified polyethylene film with the carrier resin by a melt blending method.

Optionally, the preparation of the carrier resin comprises the steps of adding sufficient High Density Polyethylene (HDPE) into a single-screw basic device of a testing machine, adjusting the plasticizing temperature of a single-screw extruder and the rotating speed of three rollers to stably and uniformly extrude a film with the thickness of 0.5mm, weighing the high density polyethylene and linear low density polyethylene with required qualities on an electronic scale, mixing and adding the high density polyethylene and the linear low density polyethylene according to the mass proportion, wherein the Linear Low Density Polyethylene (LLDPE) is respectively 0%, 10%, 20%, 30% and 40%, and obtaining the composite film with the thickness of 0.5mm by calendaring and molding after extrusion. The mechanical properties of the composite films of different proportions were tested by a universal electronic tester, and the test results are shown in table 1.

TABLE 1 mechanical property test results of composite films with different proportions

TABLE 1

It can be seen from table 1 that the mechanical properties of the whole film are obviously improved after the LLDPE resin is added, and the elongation at break is obviously increased in the transverse direction and the longitudinal direction along with the increase of the addition of the LLDPE, because the LLDPE has a branched chain structure more than that of HDPE and is intertwined with each other after blending, when the LLDPE is subjected to tensile force, the intertwined branched chains buffer the tensile force, so that the mechanical properties are improved; when the proportion of LLDPE is too large, the branched chain structure of LLDPE is entangled with itself, and the entanglement degree with HDPE is reduced, so that the elongation at break, the tear strength and the tensile strength are all reduced.

In summary, LLDPE is added into HDPE resin for melt blending modification, so that the mechanical property of the composite film is improved, and when the proportion of HDPE to LLDPE is 8:2, each mechanical property reaches the best, which is the best proportioning scheme.

Optionally, in a grafting modification experiment, the precipitation method nano silicon dioxide powder is placed in a beaker and dried in an oven at 75 ℃ for later use; meanwhile, placing 500ml of beaker in an oven for drying for 12 hours until the weight is constant for standby.

Placing the beaker on an electronic balance scale, and peeling; 3g of dry nano silicon dioxide powder is respectively weighed and placed in four beakers, 40ml of isopropanol is respectively added, a magnetic stirrer is used for quickly and uniformly stirring, so that the nano silicon dioxide and the isopropanol are fully mixed, in the stirring process, the mouth of each beaker is sealed by a preservative film and a rubber band, liquid splashing and solvent volatilization in the stirring process are prevented, and meanwhile, the external environment is isolated.

Measuring silane coupling agent KH-550 with volumes of 3ml, 6ml, 9ml and 12ml by using measuring cylinders with a volume of 20ml respectively, adding 8ml of isopropanol into four test tubes respectively, and uniformly oscillating; then the solution is placed in an ultrasonic cleaner, and ultrasonic dispersion is carried out on the solution for 8 min.

Adding the silane coupling agent/isopropanol mixture subjected to ultrasonic treatment into the uniformly stirred nano silicon dioxide isopropanol solution, heating to 80 ℃, and continuously heating and stirring at a high speed for 30 min.

And (3) performing suction filtration, pouring the heated and stirred suspension into a suction filtration device while the suspension is hot, performing suction filtration on the emulsion while the suction filtration solvent is an organic phase by using an organic filter membrane, and washing the emulsion for three times by using absolute ethyl alcohol to obtain the modified nano-silica solid.

After the surface of the nano-silica is modified, the affinity of the nano-silica to an organic solvent is changed, and the extremely hydrophilic and oleophobic nano-silica is changed into oleophilic and hydrophobic through surface grafting modification, so that the dispersion effect of the nano-silica in the organic solvent is preliminarily judged through the sedimentation effect and sedimentation speed of the nano-powder in the organic solvent.

Respectively weighing 0.05g of unmodified nano-silica and four modified nano-silica powders added with silane coupling agents in different proportions into a test tube, adding 8ml of dimethyl sulfoxide, oscillating, mixing and carrying out ultrasonic treatment for 8 min. The test tube is vertically placed in a test tube rack, after standing and settling for two hours, through observing the turbidity of the solution and the amount of the sediment, the settling speed of the nano powder added with 6ml of silane coupling agent in the organic solvent is the slowest.

In summary, when the mass-to-volume ratio of the nanoparticles to the silane coupling agent is 1:2, the surface graft modification effect of the nano-silica particles is the best.

Optionally, synthesizing a graft modified polyethylene composite film, weighing a certain mass of nano silicon dioxide powder by an electronic analytical balance, and blending and stirring the nano silicon dioxide powder and isopropanol; simultaneously measuring a silane coupling agent with the mass-to-volume ratio of 1:2 to the nano silicon dioxide powder, adding isopropanol, and dispersing in an ultrasonic cleaner for 8 min; adding ultrasonically dispersed silane coupling agent into the nano silicon dioxide/isopropanol emulsion, stirring at high speed for 30min at 80 ℃, placing into an electric heating air blast drying oven, drying at 75 ℃ overnight, and grinding finely for later use.

Taking the matrix resin as HDPE: LLDPE ═ 8: 2. Blending high-density polyethylene and linear low-density polyethylene according to the mass ratio of 8:2, weighing nano silicon dioxide powder with a certain mass, putting the nano silicon dioxide powder into a high-speed mixer, melting and blending uniformly at 160 ℃ and the rotating speed of 55r/min, extruding toughening and reinforcing master batches through a single-screw granulator after complete melting, enabling the mass fraction of the powder to reach 3% according to the required ratio, adding matrix resin, carrying out calendering and molding through a calendering sheet testing machine to obtain a nano silicon dioxide film, and debugging the stretching speed and the extrusion temperature of the calendering sheet testing machine in advance to obtain a uniform and stable composite film with the thickness of 0.5mm and the width of 12 cm.

The mechanical properties of the film materials were tested using a universal electronic tester according to the GB13022-91 standard, and the test results are shown in Table 2.

TABLE 2 mechanical Property test results of film materials

TABLE 2

The research data in the table shows that comparing the performances of the three composite films, the effect of toughening and reinforcing the original composite film can be achieved no matter whether the filled nano silicon dioxide particles are modified, and the overall mechanical property of the modified powder and resin blended composite film is obviously stronger than that of the unmodified powder blended film.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims

1. A preparation method of a high-toughness high-strength cosmetic hose packaging film is characterized by comprising the following steps: preparing carrier resin, namely modifying high-density polyethylene by using linear low-density polyethylene as a toughening agent; and (3) grafting modification, namely, carrying out surface modification on the nano silicon dioxide particles by using a silane coupling agent to improve the interface compatibility of the nano silicon dioxide particles and resin.

2. The production method according to claim 1, wherein the carrier resin is produced by a melt blending method using a mini-type calendering sheet tester JYP-30.

3. The blending method according to claim 2, wherein the raw material ratio of the high density polyethylene to the linear low density polyethylene is 8: 2.

4. The method of claim 1, wherein the graft modification comprises: isopropanol is taken as a solvent, and a silane coupling agent KH-550 and dried nano silicon dioxide are subjected to grafting reaction under certain conditions, namely, hydroxyl on the surface of the silicon dioxide is grafted and substituted to generate oleophylic and hydrophobic groups.

5. The method of claim 1, wherein the grafting reaction has a reaction equation:

6. the preparation method according to claim 4, wherein the reaction conditions of the grafting reaction include ultrasonic dispersion for 8 minutes and stirring at a constant temperature of 80 ℃ for 30 minutes.

7. The preparation method according to claim 4, wherein the mass-volume ratio of the nano-silica powder to the silane coupling agent is 1: 2.

8. A graft-modified polyethylene composite film, characterized in that the modified silica described in claim 1 is finely ground and then melt-blended with the carrier resin described in claim 1 to synthesize a graft-modified polyethylene film.

9. The method according to claim 8, wherein the modified silica powder has a mass fraction of 3%.

10. The toughness and strength of the film are particularly suitable for the field of cosmetic hose packaging.