阅读说明：本技术 一种阻燃防毒耐高温聚丙烯共挤膜及其制备方法 (Flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extrusion film and preparation method thereof ) 是由 张�杰 陈祯 张婷婷 任玮 韩德孝 孙红月 肖大君 楚鑫鑫 于 2020-03-30 设计创作，主要内容包括：本发明公开了一种阻燃防毒耐高温聚丙烯共挤膜及其制备方法。该共挤膜包括由外至内的外层、黏合层、中间层、黏合层和内层；外层原料为聚烯烃树脂、阻燃剂和色母粒的共混物；黏合层原料为马来酸酐改性聚丙烯聚合物、乙烯-甲基丙烯酸共聚物、线型低密度聚乙烯或乙烯-醋酸乙烯共聚物中的任意一种；中间层原料为聚偏二氯乙烯、乙烯-乙烯醇共聚物或聚酰胺中的任意一种；内层原料为增韧树脂、阻燃剂和色母粒的共混物。该方法是将各层原料通过多层共挤出复合设备采用多层共挤出复合工艺制备得到五层共挤膜。本发明将阻燃、防毒、耐高温集成到聚丙烯薄膜中,阻燃性、耐热老化性、阻隔性、抗撕裂性优异,手感柔软,适用于防护装备和生化包装材料领域。(The invention discloses a flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extrusion film and a preparation method thereof. The co-extrusion film comprises an outer layer, an adhesive layer, a middle layer, an adhesive layer and an inner layer from outside to inside; the outer layer is made of a blend of polyolefin resin, a flame retardant and color master batches; the raw material of the adhesive layer is any one of maleic anhydride modified polypropylene polymer, ethylene-methacrylic acid copolymer, linear low density polyethylene or ethylene-vinyl acetate copolymer; the material of the middle layer is any one of polyvinylidene chloride, ethylene-vinyl alcohol copolymer or polyamide; the inner layer is made of a blend of toughened resin, a flame retardant and color master batch. The method is characterized in that raw materials of each layer are subjected to multilayer coextrusion compounding equipment to prepare the five-layer coextrusion film by adopting a multilayer coextrusion compounding process. The flame-retardant, anti-virus and high-temperature-resistant polypropylene film integrates flame retardance, heat aging resistance, barrier property and tear resistance into a polypropylene film, is excellent in flame retardance, heat aging resistance, barrier property and tear resistance, is soft in hand feeling, and is suitable for the fields of protective equipment and biochemical packaging materials.)

1. A flame-retardant, gas-resistant and high-temperature-resistant polypropylene co-extrusion film is characterized by comprising an outer layer, an adhesive layer, a middle layer, an adhesive layer and an inner layer from outside to inside;

the outer layer is made of a blend of polyolefin resin, a flame retardant and color master batches; the raw material of the adhesive layer is any one of maleic anhydride modified polypropylene polymer, ethylene-methacrylic acid copolymer, linear low density polyethylene or ethylene-vinyl acetate copolymer; the material of the middle layer is any one of polyvinylidene chloride, ethylene-vinyl alcohol copolymer or polyamide; the inner layer is made of a blend of toughened resin, a flame retardant and color master batch.

2. The flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extrusion film as claimed in claim 1, wherein the outer layer raw material is a blend of 100 parts by weight of polyolefin resin, 12-25 parts by weight of flame retardant and 4-8 parts by weight of color master batch; the inner layer is made of a blend of 100 parts by weight of toughened resin, 12-25 parts by weight of flame retardant and 4-8 parts by weight of color master batch.

3. The flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extrusion film according to claim 1 or 2, wherein the polyolefin resin is composed of polypropylene homo-polymer resin and toughening resin.

4. The flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extrusion film as claimed in claim 1 or 2, wherein the polyolefin resin comprises 100 parts by weight of polypropylene homopolymerization resin and 60-300 parts by weight of toughening resin.

5. The flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extrusion film according to claim 3 or 4, wherein the toughening resin is at least one of polypropylene copolymer resin, low density polyethylene, linear low density polyethylene, polyolefin plastomer or polyolefin elastomer.

6. The flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extruded film according to claim 1 or 2, wherein the flame retardant is at least one of a mixture of metal oxide and halogenated hydrocarbon, phosphate ester or intumescent flame retardant.

7. The flame-retardant, gas-resistant and high-temperature-resistant polypropylene co-extruded film according to claim 6, wherein the mixture of the metal oxide and the halogenated hydrocarbon is a mixture of decabromodiphenyl ether and antimony oxide; the phosphate is dimethyl methylphosphonate.

8. The flame-retardant, gas-resistant and high-temperature-resistant polypropylene co-extrusion film according to claim 1 or 2, which is characterized in that the thickness of the co-extrusion film is 50-250 um, the thickness of the outer layer is 20-100 um, the thickness of the bonding layer is 5-15 um, the thickness of the middle layer is 5-30 um, and the thickness of the inner layer is 20-100 um.

9. A preparation method of the flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extruded film as recited in any one of claims 1 to 8 is characterized in that the method comprises the following steps: the flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extruded film is prepared by adopting a multi-layer co-extrusion composite process for the raw materials of each layer according to any one of claims 1 to 8.

10. The preparation method of the flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extrusion film according to claim 9, which is characterized in that the method specifically comprises the following steps: respectively adding the raw materials of each layer into respective extruders, respectively melting and plasticizing in the respective extruders, then flowing into a multilayer co-extrusion composite die head and distributing according to a certain interlayer structure, and then carrying out extrusion compounding and cooling molding to obtain the flame-retardant, anti-toxicity and high-temperature resistant polypropylene co-extrusion film;

the processing temperature of the extruder of the outer layer is as follows: the temperature of the first temperature zone is 175-225 ℃, the temperature of the second temperature zone is 175-225 ℃, the temperature of the third temperature zone is 180-220 ℃, and the temperature of the fourth temperature zone is 165-195 ℃;

the extruder processing temperature of the adhesive layer was: the temperature of the first temperature zone is 145-175 ℃, the temperature of the second temperature zone is 180-195 ℃, the temperature of the third temperature zone is 180-195 ℃, and the temperature of the fourth temperature zone is 170-190 ℃;

the extruder processing temperature of the middle layer was: the temperature of the first temperature zone is 165-200 ℃, the temperature of the second temperature zone is 165-200 ℃, the temperature of the third temperature zone is 160-175 ℃, and the temperature of the fourth temperature zone is 145-155 ℃;

the processing temperature of the extruder of the inner layer is as follows: the primary temperature zone is 175-220 ℃, the secondary temperature zone is 175-220 ℃, the tertiary temperature zone is 180-205 ℃, and the quaternary temperature zone is 160-175 ℃;

the processing temperature of the multilayer co-extrusion composite die head is 190-205 ℃.

Technical Field

The invention relates to a polypropylene film, in particular to a flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extrusion film and a preparation method thereof.

Background

The polypropylene film is widely applied to the industries of packaging, chemical engineering, building, textile and the like due to the characteristics of low cost, high barrier, easy forming, stability and the like. The prior art relates to a flame-retardant polypropylene film, a barrier polypropylene film, a low-temperature-resistant polypropylene film and the like of a functional polypropylene film.

The polypropylene product is generally large in thickness, small in structural layer number, mostly a single-layer blending material, and general in barrier property, and is tested by adopting a method of U L94 < Tests for plastics flame retardant rating of thin film for Materials in Devices and applications, the flame retardant polypropylene film still hardly reaches VTM-2 level, and the flame retardance is difficult to realize when the thickness of the thin film is lower.

The prior art relating to the barrier property of polypropylene is numerous, and the prior art is mostly concentrated in the fields of geomembranes, greenhouse films, food packaging films and the like. However, the protection objects are common gases such as oxygen, hydrogen, air, water vapor and the like, and no research report on the military toxicant 'mustard gas' exists at present.

At present, no report of functional polypropylene films applied to protective materials or protective equipment, particularly a high-temperature resistant polypropylene technology, is seen. The protective equipment needs a thin film with soft hand feeling due to the requirement of usability, the hardness of polypropylene is reduced and the toughness is improved by adding toughening resin on the resin formula of the protective equipment, but the potential hazard brought by the protective equipment is that the temperature resistance of the polypropylene film is obviously reduced, and particularly, the surface of the polypropylene film can be discolored, sticky, embrittled and the like when the protective equipment is continuously placed in a high-temperature environment, so that the appearance and the use reliability of the protective equipment are influenced.

Therefore, when the polypropylene is applied to protective equipment as a barrier film, the polypropylene cannot give consideration to flame retardance, gas defense, high temperature resistance and flexibility at the same time, so that the excellent performance of the polypropylene film cannot be exerted, and the application range of the polypropylene film is limited.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing a flame-retardant, anti-toxic and high-temperature-resistant polypropylene co-extruded film and a preparation method thereof.

The technical scheme for solving the technical problem of the co-extruded film is to provide the flame-retardant, anti-poison and high-temperature-resistant polypropylene co-extruded film which is characterized by comprising an outer layer, an adhesive layer, a middle layer, the adhesive layer and an inner layer from outside to inside;

the outer layer is made of a blend of polyolefin resin, a flame retardant and color master batches; the raw material of the adhesive layer is any one of maleic anhydride modified polypropylene polymer, ethylene-methacrylic acid copolymer, linear low density polyethylene or ethylene-vinyl acetate copolymer; the material of the middle layer is any one of polyvinylidene chloride, ethylene-vinyl alcohol copolymer or polyamide; the inner layer is made of a blend of toughened resin, a flame retardant and color master batch.

The technical scheme for solving the technical problems of the method is to provide a preparation method of a flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extruded film, which is characterized by comprising the following steps: and preparing the flame-retardant, anti-toxin and high-temperature-resistant polypropylene co-extruded film by adopting a multi-layer co-extrusion composite process for the raw materials of each layer.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the invention, the flame retardance, the gas defense and the high temperature resistance are integrated into the polypropylene film, the prepared flame-retardant, gas defense and high temperature resistance polypropylene film has good flame retardance (more than VTM-2 level), excellent barrier property to mustard gas (the liquid-gas protection time of the mustard gas is more than 150min), and the surface of the film is not sticky and crisp after aging for 24 hours at 125 ℃, and has excellent heat and aging resistance.

(2) The polypropylene film has good hand feeling and physical and mechanical properties, overcomes the defects of poor flame resistance, brittle and hard hand feeling, poor tear resistance and poor folding resistance of the existing polypropylene film, and improves the usability of the polypropylene film; the compatibility technical problems of flame retardance, gas defense and high temperature resistance of the existing polypropylene film are solved, the polypropylene film can be applied to products such as protective equipment, high temperature cooking resistant film materials, hazardous chemical packaging materials, biochemical warfare agent barrier bags, shed films, flexible shelters, protective tents and the like, and the product value and market potential of the polypropylene film are improved.

(3) The method adopts a multi-layer co-extrusion composite process, is formed in one step, has no solvent pollution, is clean and environment-friendly, and is rapid and efficient.

Detailed Description

Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.

The invention provides a flame-retardant, gas-resistant and high-temperature-resistant polypropylene co-extrusion film (referred to as a co-extrusion film for short), which is characterized in that the co-extrusion film adopts a multi-layer co-extrusion composite process to obtain a five-layer structure film material which sequentially comprises an outer layer, an adhesive layer, a middle layer, the adhesive layer and an inner layer from outside to inside;

the outer layer is made of a blend of polyolefin resin, a flame retardant and color master batches; the raw material of the adhesive layer is any one of maleic anhydride modified polypropylene polymer, ethylene-methacrylic acid copolymer, linear low density polyethylene or ethylene-vinyl acetate copolymer; the material of the middle layer is any one of polyvinylidene chloride, ethylene-vinyl alcohol copolymer or polyamide; the inner layer is made of a blend of toughened resin, a flame retardant and color master batch.

The polyolefin resin consists of polypropylene homopolymerization resin and toughening resin;

the toughening resin is at least one of polypropylene copolymer resin, low density polyethylene, linear low density polyethylene (LL DPE), polyolefin plastomer or polyolefin elastomer;

the flame retardant is at least one of a mixture of metal oxide and halogenated hydrocarbon, phosphate ester or intumescent flame retardant; the mixture of the metal oxide and the halogenated hydrocarbon is a mixture of decabromodiphenyl ether and antimony oxide; the phosphate is dimethyl methylphosphonate.

Preferably, the outer layer raw material is a blend of 100 parts by weight of polyolefin resin, 12-25 parts by weight of flame retardant and 4-8 parts by weight of color master batch; the inner layer is made of a blend of 100 parts by weight of toughened resin, 12-25 parts by weight of flame retardant and 4-8 parts by weight of color master batch;

preferably, the polyolefin resin consists of 100 parts by weight of polypropylene homopolymerization resin and 60-300 parts by weight of toughening resin;

the thickness of crowded membrane altogether is 50 ~ 250um, and wherein outer thickness is 20 ~ 100um, and the thickness of adhesion layer is 5 ~ 15um, and the thickness in intermediate level is 5 ~ 30um, and the thickness of inlayer is 20 ~ 100 um.

The invention also provides a preparation method (method for short) of the flame-retardant, anti-virus and high-temperature-resistant polypropylene co-extruded film, which is characterized by comprising the following steps: and (3) preparing the raw materials of each layer by multilayer coextrusion compounding equipment through a multilayer coextrusion compounding process to obtain the flame-retardant, anti-toxicity and high-temperature-resistant polypropylene coextrusion film.

In the multilayer coextrusion composite process, the processing temperature of an extruder of the outer layer is as follows: the temperature of the first temperature zone is 175-225 ℃, the temperature of the second temperature zone is 175-225 ℃, the temperature of the third temperature zone is 180-220 ℃, and the temperature of the fourth temperature zone is 165-195 ℃; the extruder processing temperature of the adhesive layer was: the temperature of the first temperature zone is 145-175 ℃, the temperature of the second temperature zone is 180-195 ℃, the temperature of the third temperature zone is 180-195 ℃, and the temperature of the fourth temperature zone is 170-190 ℃; the extruder processing temperature of the middle layer was: the temperature of the first temperature zone is 165-200 ℃, the temperature of the second temperature zone is 165-200 ℃, the temperature of the third temperature zone is 160-175 ℃, and the temperature of the fourth temperature zone is 145-155 ℃; the processing temperature of the extruder of the inner layer is as follows: the primary temperature zone is 175-220 ℃, the secondary temperature zone is 175-220 ℃, the tertiary temperature zone is 180-205 ℃, and the quaternary temperature zone is 160-175 ℃; the processing temperature of the multilayer co-extrusion composite die head is 190-205 ℃.

The multilayer coextrusion compounding device comprises a coextrusion flat film production line or a coextrusion tube film production line;

the multilayer coextrusion composite process comprises a coextrusion blow molding film forming method, a coextrusion casting film forming method and the like;

the method specifically comprises the following steps: and respectively adding the raw materials of each layer into respective extruders, respectively melting and plasticizing in the respective extruders, then flowing into the same multilayer co-extrusion composite die head, uniformly distributing in the die head according to a certain interlayer structure, and then carrying out extrusion compounding and cooling molding to obtain the flame-retardant, anti-toxicity and high-temperature resistant polypropylene co-extrusion film.

When a co-extrusion pipe film production line is adopted, raw materials of all layers are respectively added into respective extruders, respectively melted and plasticized by the respective extruders of all layers, flow into a multi-layer co-extrusion tubular composite die head and are uniformly distributed in the die head according to a certain interlayer structure, and after extrusion and inflation cooling at a die opening, the flame-retardant, gas-defense and high-temperature-resistant polypropylene co-extrusion film is obtained.

When a co-extrusion flat film production line is adopted, raw materials of all layers are respectively added into respective extruders, respectively melted and plasticized by the respective extruders of all layers, flow into a multi-layer co-extrusion casting composite die head and are uniformly distributed in the die head according to a certain interlayer structure, and after extrusion and casting cooling of a die opening, the flame-retardant, anti-toxicity and high-temperature resistant polypropylene co-extrusion film is obtained.