CN107901566A - Breathable acrylonitrile-ethylene-styrene copolymer film composite paper and preparation method thereof - Google Patents

Abstract

The invention discloses a preparation method of breathable acrylonitrile-ethylene-styrene copolymer film composite paper, which comprises the following steps: (1) ultrasonically dispersing calcium carbonate, an organic solvent and a titanate coupling agent, and drying to obtain modified calcium carbonate; (2) blending and extruding modified calcium carbonate, micro-nanocrystalline cellulose particles, porous powder quartz, acrylonitrile-ethylene-styrene copolymer, diethyl malonate and dibutyltin maleate; (3) rolling and biaxially stretching the extrudate to obtain a film; (4) heating and hot-pressing the film on the surface of the paper layer; wherein the mass ratio of the modified calcium carbonate to the micro-nano crystalline cellulose particles to the porous quartz powder is 1:1-2: 2-4. The film layer of the breathable acrylonitrile-ethylene-styrene copolymer film composite paper has good tensile strength and good breathability, and the preparation method is simple and easy to realize.

Description

Breathable acrylonitrile-ethylene-styrene copolymer film composite paper and preparation method thereof

technical field

The invention relates to a breathable film, in particular to a breathable acrylonitrile-ethylene-styrene copolymer film composite paper and a preparation method thereof.

Background technique

Any kind of packaging material, including plastic film or edible film, is very important to determine the permeability of oxygen, nitrogen, carbon dioxide and water vapor, especially the packaging material used for fresh fruit and vegetable preservation, its air permeability is very important, because it has A film with suitable air permeability can regulate the physiological metabolism of fruits and vegetables to a certain extent, thereby improving the eating quality of fruits and vegetables and prolonging the shelf life of fruits and vegetables. In this regard, in order to obtain materials with good air permeability, people have carried out Extensive research.

Chinese patent application 201110203184.8 discloses a composition and a preparation method of a low-air-permeable air-permeable membrane. agents and coupling agents. Its advantage is that the nano-micron inorganic filler can improve the mechanical properties of the breathable film, and the surface coupling modified inorganic particles increase the compatibility with the polyolefin matrix resin, but the disadvantage is that the high addition amount (30%-55% ) micron inorganic particles can not be uniformly dispersed in the matrix resin, thus affecting the uniformity of air permeability of the film material.

Chinese patent application 201110125458.6 discloses a polyolefin film and its preparation method, the components of which include: polyolefin resin, pore forming agent and extractant. Its advantage is that the polypropylene hydrocarbon film prepared by the traditional wet method has a small structure and a large number, but it adopts a two-step extraction process with a high volume percentage concentration, and the extraction solvent is N, N'-dimethylformamide, dichloro Methane, chloroform, etc. are highly polluting and toxic solvents, which can cause great harm to the human body and the environment.

Chinese patent application 201710110501.9 discloses a breathable composite film and its preparation method. The composite film is prepared from the following components by weight percentage: 60%-82% polyolefin resin polymer, 2%-8% micronano Crystalline cellulose particles, 0.4%-1% antioxidant, 15%-30% dispersant, 0.1%-0.5% lubricant, 0.2%-1% coupling agent. The preparation method is as follows: uniformly disperse the micro-nanocrystalline cellulose aqueous dispersion and the coupling agent; then add the dispersant and mix evenly, and dry to obtain the pretreated filler; the obtained pretreated filler, polyolefin resin, antioxidant , Lubricant is added to the twin-screw extruder, and the breathable composite film composition is obtained through melt extrusion, cooling and granulation, and the flat film is prepared by hot calendering; then immersed in the cleaning agent, ultrasonicated, and dried; two-way stretching and Heat-setting treatment to obtain a breathable composite film. The composite film has high air permeability and excellent mechanical properties. The disadvantage is that it needs to be immersed in the cleaning agent, and the processing process is cumbersome.

Therefore, it is very necessary to provide a film with simple preparation method and good air permeability.

Contents of the invention

The purpose of this invention is to provide a kind of breathable acrylonitrile-ethylene-styrene copolymer film composite paper and preparation method thereof, the film layer of this breathable acrylonitrile-ethylene-styrene copolymer film composite paper has good tensile strength , and has good gas permeability, and the preparation method is simple and easy to realize.

In order to achieve the above object, the present invention provides a preparation method of air-permeable acrylonitrile-ethylene-styrene copolymer film composite paper, comprising the following steps: (1) calcium carbonate, organic solvent and titanate coupling agent are ultrasonically dispersed, baked Dry to obtain modified calcium carbonate; (2) modify calcium carbonate, micro-nanocrystalline cellulose particles, porous powder quartz, acrylonitrile-ethylene-styrene copolymer, diethyl malonate and dibutyltin maleate blending and extruding; (3) calendering and biaxially stretching the extrudate to obtain a film; (4) heating and pressing the film on the surface of the paper layer; wherein, modified calcium carbonate, micro The mass ratio of nanocrystalline cellulose particles to porous powder quartz is 1:1-2:2-4.

The present invention also provides a breathable acrylonitrile-ethylene-styrene copolymer film composite paper prepared according to the above-mentioned preparation method.

Through the above technical scheme, the present invention modifies the calcium carbonate, and mixes the modified calcium carbonate, micro-nanocrystalline cellulose particles, and porous powder quartz and adds it into the acrylonitrile-ethylene-styrene copolymer as the matrix Among the raw materials for film preparation, a film with good tensile strength and good air permeability is prepared through extrusion, calendering, and biaxial stretching processes, and the film is heated and hot-pressed on the surface of the paper layer to obtain a film composite paper, the preparation method is simple, easy to implement, and has good promotion value.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The invention provides a method for preparing air-permeable acrylonitrile-ethylene-styrene copolymer film composite paper, comprising the following steps: (1) ultrasonically dispersing calcium carbonate, an organic solvent and a titanate coupling agent, and drying to obtain a modified Calcium carbonate; (2) Modified calcium carbonate, micro-nanocrystalline cellulose particles, porous powder quartz, acrylonitrile-ethylene-styrene copolymer, diethyl malonate and dibutyltin maleate are blended, extruded (3) calendering and biaxially stretching the extruded product to obtain a film; (4) heating the film and hot pressing it on the surface of the paper layer; wherein, modified calcium carbonate, micro-nanocrystalline cellulose particles The mass ratio to porous powder quartz is 1:1-2:2-4.

Through the above technical scheme, the present invention modifies the calcium carbonate, and mixes the modified calcium carbonate, micro-nanocrystalline cellulose particles, and porous powder quartz and adds it into the acrylonitrile-ethylene-styrene copolymer as the matrix Among the raw materials for film preparation, a film with good tensile strength and good air permeability is prepared through extrusion, calendering and biaxial stretching processes. The preparation method is simple, easy to implement, and has good promotion value.

In the above technical solution, as long as the above ratio is followed, a film with good air permeability can be obtained, and the addition amount of each component can be adjusted within a wide range by those skilled in the art. In order to make the film have both good tensile strength and good air permeability, preferably, relative to 100 parts by weight of acrylonitrile-ethylene-styrene copolymer, the added modified calcium carbonate, micro-nanocrystalline cellulose particles and the total weight of porous powder quartz is 15-25 parts.

For the specific conditions of the preparation process of the present invention, those skilled in the art can adjust flexibly. In order to improve the tensile strength of the material, and make the film have good air permeability, and reduce the sticking phenomenon in the extrusion process, preferably, the step (3) Conditions for middle calendering include: hot calendering the extrudate at 200-220° C. under a pressure of 20t-40t.

For the specific conditions of the preparation process of the present invention, those skilled in the art can adjust flexibly. In order to improve the tensile strength of the material and make the film have good air permeability, preferably, the conditions of biaxial stretching include: The film is biaxially stretched with a stretch ratio of 1.2-1.8, and then subjected to heat setting treatment at 130-160° C., and the heat setting treatment time is 5-15 minutes.

For the modification of calcium carbonate, those skilled in the art can adjust in a wide range. In order to improve the ratio of modified calcium carbonate to micro-nanocrystalline cellulose particles and porous powder quartz, the air permeability of the film can be improved without reducing The tensile strength of the film, preferably, in step (1), the mass ratio of calcium carbonate, organic solvent and titanate coupling agent is 1:2-3:0.4-0.6.

For the specific process of the modification of calcium carbonate, those skilled in the art can adjust in a wide range, in order to improve the air permeability of the film after improving the ratio of modified calcium carbonate and micro-nanocrystalline cellulose particles, porous powder quartz, Without reducing the tensile strength of the film, preferably, the ultrasonic dispersion time is 10-20 min, and the drying temperature is 40-90°C.

In the above technical scheme, the titanate coupling agent can be selected in a wide range. In order to improve the air permeability of the film after improving the ratio of modified calcium carbonate to micro-nanocrystalline cellulose particles and porous powder quartz, it does not To reduce the tensile strength of the film, preferably, the titanate coupling agent is isopropyl triisostearyl titanate and/or isopropyl trioctanoyl titanate.

In the above technical solution, the organic solvent can be selected in a wide range. Preferably, the organic solvent is one or more of methanol, ethanol, propylene glycol, diethylene glycol, acetone, tetrahydrofuran, and pentaerythritol.

In the above technical solution, the paper layer can be selected in a wide range. In order to make the film layer better bonded to the paper layer, preferably, the paper layer is kraft paper or corrugated paper.

Of course, those skilled in the art can adjust the addition amount of each component in a wide range. In order to make the obtained film have good tensile strength and air permeability, preferably, in parts by weight, relative to 100 parts Acrylonitrile-ethylene-styrene copolymer, 3-4 parts of modified calcium carbonate, 4-6 parts of micro-nanocrystalline cellulose particles, 8-12 parts of porous powder quartz, 3-6 parts of diethyl malonate, 1-2 parts of dibutyltin maleate.

Wherein, in order to make the obtained film have good tensile strength and air permeability, preferably, the particle size distribution of the micro-nanocrystalline cellulose particles is 100nm-50μm.

Wherein, in order to make the obtained film have good tensile strength and gas permeability, preferably, the average diameter of the porous powdered quartz is not greater than 0.8 μm.

For the blending conditions in step (2), those skilled in the art can adjust within a wide range. In order to improve the uniformity of mixing, preferably, in step (2): the blending temperature is 180-195° C. Refining time is 30-40min.

Furthermore, in order to increase the tensile strength of the film, preferably, the extrusion temperature in step (2) is 200-215°C.

The present invention also provides a breathable acrylonitrile-ethylene-styrene copolymer film composite paper prepared according to the above-mentioned preparation method. The film has both tensile strength and good air permeability, and the film is heated and hot-pressed on the surface of the paper layer to obtain the film composite paper. The film composite paper not only has good tensile strength, but also has Good air permeability, very suitable as packaging materials for fruits and vegetables.

The present invention will be described in detail below by way of examples.

Ethylene-propylene-styrene-acrylonitrile copolymer was purchased from Changzhou Andexin Chemical Co., Ltd.; micro-nanocrystalline cellulose particles were purchased from Shanghai Sansi Technology Materials Co., Ltd.; others were commercially available.

Preparation Example 1

In parts by weight, 1 part of calcium carbonate, 2 parts of ethanol and 0.4 part of isopropyl tricaprylyl titanate were ultrasonically dispersed for 20 minutes, and dried at 90° C. to obtain modified calcium carbonate.

Preparation example 2

In parts by weight, 1 part of calcium carbonate, 3 parts of ethanol and 0.6 part of isopropyl triisostearyl titanate were ultrasonically dispersed for 10 minutes, and dried at 40° C. to obtain modified calcium carbonate.

Preparation example 3

In parts by weight, 1 part of calcium carbonate, 2.5 parts of ethanol and 0.5 part of isopropyl triisostearyl titanate were ultrasonically dispersed for 15 minutes, and dried at 70° C. to obtain modified calcium carbonate.

Example 1

The preparation method of breathable acrylonitrile-ethylene-styrene copolymer film composite paper comprises the following steps:

(1) In parts by weight, with 100 parts of acrylonitrile-ethylene-styrene copolymer, 3 parts of modified calcium carbonate in Preparation Example 1, micro-nanocrystalline cellulose particles (particle size distribution is 10 μm-50 μm) 4 Parts, 8 parts of porous powder quartz (average diameter not greater than 0.8 μm), 3 parts of diethyl malonate, 1 part of dibutyltin maleate were blended at 180°C, the mixing time was 30min, and extruded at 200°C ;

(2) The extrudate is hot-calendered at 200°C under a pressure of 20t, and the film obtained after calendering is biaxially stretched to a stretch ratio of 1.2, and then heat-set at 130°C for a heat-setting time of 5min;

(3) The stretched film is heated and hot-pressed on the surface of the paper layer at 180°C.

Example 2

The preparation method of breathable acrylonitrile-ethylene-styrene copolymer film composite paper comprises the following steps:

(1) In parts by weight, with 100 parts of acrylonitrile-ethylene-styrene copolymer, 4 parts of modified calcium carbonate in Preparation Example 2, micro-nanocrystalline cellulose particles (particle size distribution is 100nm-20 μm) 6 Parts, 12 parts of porous powder quartz (average diameter not greater than 0.8μm), 6 parts of diethyl malonate, 2 parts of dibutyltin maleate were blended at 195°C, the mixing time was 40min, and extruded at 215°C ;

(2) The extrudate is hot-calendered at 220°C under a pressure of 40t, and the film obtained after calendering is biaxially stretched to a stretch ratio of 1.8, and then heat-set at 160°C for a heat-setting time of 15min;

(3) The stretched film is heated and hot-pressed on the surface of the paper layer at 170°C.

Example 3

The preparation method of breathable acrylonitrile-ethylene-styrene copolymer film composite paper comprises the following steps:

(1) In parts by weight, with 100 parts of acrylonitrile-ethylene-styrene copolymer, 3.5 parts of modified calcium carbonate in Preparation Example 3, micro-nanocrystalline cellulose particles (particle size distribution is 10-30 μm) 5 parts Parts, 10 parts of porous powder quartz (average diameter not greater than 0.8 μm), 4.5 parts of diethyl malonate, 1.5 parts of dibutyltin maleate were blended at 188 ° C, the mixing time was 35 minutes, and extruded at 205 ° C ;

(2) The extrudate is hot-calendered at 210°C under a pressure of 30t, and the film obtained after calendering is biaxially stretched to a stretch ratio of 1.5, and then heat-set at 145°C for a heat-setting time of 10min;

(3) The stretched film was heated and hot-pressed on the surface of the paper layer at 190°C.

Example 4

Prepare air-permeable acrylonitrile-ethylene-styrene copolymer film composite paper according to the method of embodiment 3, the difference is that 2 parts of modified calcium carbonate in preparation example 3, micro-nanocrystalline cellulose particles (particle size distribution is particle size The distribution is 10-30 μm) 4 parts, porous powder quartz (average diameter is not more than 0.8 μm) 8 parts.

Example 5

Prepare air-permeable acrylonitrile-ethylene-styrene copolymer film composite paper according to the method of embodiment 3, the difference is that 5 parts of modified calcium carbonate in preparation example 3, micro-nanocrystalline cellulose particles (particle size distribution is particle size The distribution is 10-30μm) 5 parts, porous powder quartz (average diameter is not more than 0.8μm) 20 parts.

Example 6

Prepare air-permeable acrylonitrile-ethylene-styrene copolymer film composite paper according to the method of embodiment 3, the difference is, 1 part of modified calcium carbonate in preparation example 3, micro-nanocrystalline cellulose particle (particle size distribution is particle size The distribution is 10-30μm) 2 parts, porous powder quartz (average diameter is not more than 0.8μm) 4 parts.

Comparative example 1

According to the method for embodiment 3, acrylonitrile-ethylene-styrene copolymer film composite paper is prepared, and difference is that 3.5 parts of modified calcium carbonate used in embodiment 3 are changed into 3.5 parts of unmodified calcium carbonate.

Comparative example 2

Acrylonitrile-ethylene-styrene copolymer film composite paper is prepared according to the method of Example 3, and the difference is that the added modified calcium carbonate, micro-nanocrystalline cellulose particles and porous powder quartz are changed to:

5 parts of modified calcium carbonate in Preparation Example 3, 2 parts of micro-nanocrystalline cellulose particles (the particle size distribution is 10-30 μm), and 7 parts of porous powder quartz (average diameter is not more than 0.8 μm).

Comparative example 3

Acrylonitrile-ethylene-styrene copolymer film composite paper is prepared according to the method of Example 3, and the difference is that the added modified calcium carbonate, micro-nanocrystalline cellulose particles and porous powder quartz are changed to:

2 parts of modified calcium carbonate in Preparation Example 3, 8 parts of micro-nanocrystalline cellulose particles (the particle size distribution is 10-30 μm), and 3 parts of porous powder quartz (average diameter is not more than 0.8 μm).

Test example 1

Oxygen transmission rate (unit: mL/m ² , day, standard atmospheric pressure) is measured by an oxygen transmission rate tester model 8001, and the corresponding standard is GB/T1038-2000 Plastic Film and Sheet Gas Permeability Test Method .

After detecting the films prepared in Examples 1-6 and Comparative Examples 1-3, it was found that the order of oxygen transmission rate from high to low is: Example 5, Example 3, Example 2, Example 1 , Example 4, Example 6, Comparative Example 2, Comparative Example 1, and Comparative Example 3, wherein the oxygen transmission rate of Example 5 is the highest at 2950mL/m ² , and Example 3, Example 2 and Example 1 The oxygen transmission rate is close, wherein the oxygen transmission rate of embodiment 3 is 1952mL/m ² , the oxygen transmission rate of embodiment 4 and embodiment 6 is close, and embodiment 6 is 1710mL/m ² ; The oxygen transmission rate of the film in Example 1 and Comparative Example 3 is relatively low, and the oxygen transmission rate of Comparative Example 2 is only 1518mL/m ² .

Test example 2

The water vapor transmission rate (unit: mL/m ² ) is tested with a Model 3/33 water vapor transmission rate tester, and the corresponding standard is GB/T 30412-2013 Water vapor transmission rate of plastic films and sheets Determination.

After detecting the films prepared in Examples 1-6 and Comparative Examples 1-3, it was found that the order of water vapor transmission rate from high to low is: Example 5, Example 3, Example 2, Example 1. Example 4, Example 6, Comparative Example 2, Comparative Example 1, and Comparative Example 3. Among them, Example 5 has the highest water vapor transmission rate of 8.6mL/m ² , and Example 3, Example 2 and The water vapor transmission rate of embodiment 1 is close, wherein the water vapor transmission rate of embodiment 3 is 7.2mL/m ² , the water vapor transmission rate of embodiment 4 and embodiment 6 is close, and embodiment 6 is 6.4mL/m m ² ; the water vapor transmission rate of the films in Comparative Example 2, Comparative Example 1 and Comparative Example 3 was low, and the water vapor transmission rate of Comparative Example 2 was only 4.6mL/m ² .

Test example 3

The parameter of tensile strength (in MPa) is detected by the first part of GB/T1040.1-2006 Determination of tensile properties of plastics.

After detecting the films prepared in Examples 1-6 and Comparative Examples 1-3, it was found that the order of tensile strength from high to low is: Comparative Example 3, Example 3, Example 2, Example 1, Embodiment 6, embodiment 4, embodiment 5, comparative example 1, comparative example 2, wherein, the tensile strength of comparative example 3 is the highest, is 19.2MPa, the tensile strength of embodiment 3, embodiment 2 and embodiment 1 Close, wherein the tensile strength of embodiment 3 is 17.8MPa, the tensile strength of embodiment 4, embodiment 5 and embodiment 6 is close, and embodiment 5 is 14.9MPa; The tensile strength of film in comparative example 2, comparative example 1 The strength is low, and the tensile strength of Comparative Example 2 is only 11.5MPa.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (10)

1. A kind of 1. preparation method of ventilative acrylonitrile ethylene styrene copolymer Film laminated paper, it is characterised in that including with Lower step：

   (1) by calcium carbonate, organic solvent and titanate coupling agent ultrasonic disperse, drying, obtains modified calcium carbonate；

   (2) by modified calcium carbonate, micro nanocrystalline cellulose granules, porous konilite, acrylonitrile ethylene styrene copolymer, third Diethyl adipate and dibutyitin maleate blending, extrusion；

   (3) extrudate is rolled, biaxial tension, film is made；

   (4) film heat and hot pressing is on the surface of paper layer；

   Wherein, the mass ratio of modified calcium carbonate, micro nanocrystalline cellulose granules and porous konilite is 1:1-2:2-4.
2. 2. preparation method according to claim 1, wherein, it is common relative to acrylonitrile-vinyl-styrene of 100 parts by weight Polymers, the total weight parts of the modified calcium carbonate of addition, micro nanocrystalline cellulose granules and porous konilite are 15-25 parts.
3. 3. preparation method according to claim 1 or 2, wherein, the condition of calendering includes in step (3)：Extrudate is existed 200-220 DEG C under the pressure of 20t-40t to carry out hot calender.
4. 4. preparation method according to claim 1 or 2, wherein, the condition of biaxial tension includes：It is thin by what is obtained after calendering Film carries out biaxial tension, and stretching ratio 1.2-1.8, then carries out thermal finalization processing, thermal finalization processing time at 130-160 DEG C For 5-15min.
5. 5. preparation method according to claim 1 or 2, wherein, in step (1), calcium carbonate, organic solvent and titanate esters are even The mass ratio for joining agent is 1:2-3:0.4-0.6；And/or the ultrasonic disperse time is 10-20min, drying temperature is 40-90 DEG C.
6. 6. preparation method according to claim 5, wherein,

   Titanate coupling agent is three caprylyl titanate esters of three iso stearyl titanate esters of isopropyl and/or isopropyl；And/or

   Organic solvent is methanol, the one or more in ethanol, propane diols, diethylene glycol, acetone, tetrahydrofuran, pentaerythrite；

   And/or paper layer is brown paper or corrugated paper.
7. 7. preparation method according to claim 1 or 2, wherein, in parts by weight, relative to 100 parts of acrylonitrile-second Alkene-styrol copolymer, 3-4 parts of modified calcium carbonate, 4-6 parts of micro nanocrystalline cellulose granules, porous konilite 8-12 parts, the third two 3-6 parts of diethyl phthalate, 1-2 parts of dibutyitin maleate.
8. 8. preparation method according to claim 7, wherein, the particle diameter distribution of micro nanocrystalline cellulose granules is 100nm-50 μm；And/or the average diameter of porous konilite is no more than 0.8 μm.
9. 9. preparation method according to claim 1 or 2, wherein, in step (2)：Blending temperature is 180-195 DEG C, is kneaded Time is 30-40min；And/or extrusion temperature is 200-215 DEG C.
10. It is 10. common according to ventilative acrylonitrile-vinyl-styrene that claim 1-9 any one of them preparation methods are prepared Homopolymer film extrusion coating paper.