CN113150445A - Water-blocking oxygen-blocking polyolefin material and preparation method and application thereof - Google Patents
Water-blocking oxygen-blocking polyolefin material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/123—Unsaturated polyimide precursors the unsaturated precursors comprising halogen-containing substituents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/14—Gas barrier composition
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Abstract
The invention provides a water-blocking and oxygen-blocking polyolefin material and a preparation method and application thereof. The water-blocking oxygen-blocking polyolefin material is prepared from the following raw materials in parts by weight: 65-80 parts of polypropylene, 20-35 parts of fluorine modified polyimide containing a carbazole structure, 0.2-1 part of peroxide initiator and 0.5-3 parts of antioxidant; the fluorine modified polyimide containing the carbazole structure is obtained by reacting diamine containing the carbazole structure with fluorine-containing dianhydride and then sealing the end with maleic anhydride; the molar ratio of diamine containing a carbazole structure to fluorine-containing dianhydride is 1-2: 1. According to the invention, the fluorine modified polyimide containing the carbazole structure is introduced, so that the prepared material has good water-blocking and oxygen-blocking effects.
Description
Technical Field
The invention belongs to the field of plastic packaging, and particularly relates to a water-blocking and oxygen-blocking polyolefin material as well as a preparation method and application thereof.
Background
Barrier properties are a basic requirement for packaging materials, and can prevent the invasion of substances outside the package, such as oxygen, water vapor, bacteria and the like, and prevent the substances inside the package from escaping. Particularly oxygen-sensitive pharmaceutical, medical and food packaging, require high barrier properties to prevent oxygen ingress or to scavenge trapped oxygen internally to avoid oxidation of the product and to extend the shelf life of the goods.
Polyolefin materials such as PE and PP are commonly used as packaging materials, but since these materials have low polarity, they are known from the principle of similarity and compatibility that nonpolar polymer materials easily transmit nonpolar gas and therefore have high air permeability. The barrier property of the polymer film can be improved by improving the crystallinity of the polymer or the order of molecular chain arrangement, reducing the free volume and the like, but the high crystallinity affects the transparency of the material.
Polar polymers such as polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polylactic acid (PLA), polyethylene 2, 5-furandicarboxylate (PEF), polyethylene naphthalate (PEN), copolyamide (MXD6), and the like, are similarly barrier packaging materials, and although the air permeability is low, these high barrier materials have some disadvantages that are somewhat difficult to overcome, such as a sharp decrease in barrier properties under high humidity conditions with PVA and EVOH; PVDC contains chlorine element, and toxic substances are generated during incineration; PLA and PEF are hard and brittle and have low impact strength; PEN and MXD6 are expensive and are subject to foreign restrictions, etc.; and the water resistance of polar polymer materials is generally inferior to that of polyolefins.
The blending of the high-barrier material with PE and PP can make up for the deficiencies of the materials and reduce the cost, but the compatibility of the high-polarity barrier material and the nonpolar polyolefin is poor, the continuity of the high-barrier material can be damaged by the blending of the materials, the barrier property can be influenced, and the water resistance of the polyolefin can also be influenced by the introduction of the polar material. The multilayer co-extrusion technology can compound the high barrier material layer between the polyolefin layers, can improve the adhesive force between the high barrier material layer and the polyolefin layers through an adhesive, and keeps the continuity of the barrier material, but the process has high requirements on equipment and high cost.
Therefore, it is desirable to provide a polyolefin material with good water and oxygen resistance and low production cost.
Disclosure of Invention
The invention aims to solve the problems of poor water and oxygen resistance or high production cost of a packaging material in the prior art, and provides a water and oxygen resistant polyolefin material with good water and oxygen resistance and low production cost. According to the invention, the fluorine modified polyimide containing the carbazole structure is introduced, so that the prepared material has good water-blocking and oxygen-blocking effects.
The invention also aims to provide a preparation method of the water-blocking and oxygen-blocking polyolefin material.
The invention also aims to provide the application of the water-blocking and oxygen-blocking polyolefin material in preparing medicine packaging boxes or food packaging boxes.
In order to solve the technical problems, the invention adopts the following technical scheme:
a water-blocking oxygen-blocking polyolefin material is prepared from the following raw materials in parts by weight:
the fluorine modified polyimide containing the carbazole structure is obtained by reacting diamine containing the carbazole structure with fluorine-containing dianhydride and then sealing the end with maleic anhydride;
the molar ratio of diamine containing a carbazole structure to fluorine-containing dianhydride is 1-2: 1.
According to the invention, fluorine modified polyimide containing a carbazole structure is introduced into a polypropylene chain segment through double bonds of maleic anhydride, and the carbazole structure contains a rigid plane, so that the regularity, rigidity and inter-chain cohesion of a polymer chain are increased by introducing the carbazole structure, and the filling efficiency of the chain segment is improved, so that the barrier property of the polymer is improved, and the problem of the reduction of mechanical property and barrier property caused by poor compatibility is solved because imide containing the carbazole structure is grafted on polypropylene. The plastic package for food generally requires steaming and boiling for 30min at the temperature of more than 121 ℃ to kill bacteria, the polyimide structure can improve the heat resistance of the material, and the introduction of fluorine can improve the water resistance of the packaging material, especially the water resistance under high humidity.
The fluorine modified polyimide containing the carbazole structure is prepared by synthesizing diamine containing the carbazole structure and fluorine-containing dianhydride into polyimide with primary amine groups at two ends and then sealing the polyimide with maleic anhydride. The invention further discovers through further research that: the molecular weight of the fluorine modified polyimide containing the carbazole structure affects the degree of crosslinking of the material, and further affects the water-blocking and oxygen-blocking performance of the material, so that a specific raw material ratio (the molar ratio of diamine containing the carbazole structure to fluorine-containing dianhydride is 1-2: 1) is required to control the molecular weight of the fluorine modified polyimide containing the carbazole structure: when the molar ratio of diamine containing a carbazole structure to fluorine-containing dianhydride is larger, the molecular weight of the obtained fluorine modified polyimide containing the carbazole structure is small, more maleic anhydride double bonds can be reacted under the same dosage, and the crosslinking degree of a system is larger; when the molar ratio of the two is small, the molecular weight of the obtained fluorine modified polyimide containing the carbazole structure is large, and after the fluorine modified polyimide is blended and reacted with polypropylene, the distribution of the polyimide is more concentrated, the distribution continuity is poor, and the gas barrier property is reduced.
More preferably, the molar ratio of the diamine containing the carbazole structure to the fluorine-containing dianhydride is 1.07-1.5: 1.
Preferably, the diamine containing a carbazole structure is one or a combination of several of 9H-carbazole-2, 7-diamine, 9H-carbazole-3, 6-diamine, 9-methyl-9H-carbazole-3, 6-diamine, 9-ethyl-9H-carbazole-3, 6-diamine, or 4, 4' - (9H-carbazole-3, 6-diyl) dianiline.
The fluorine-containing dianhydride is a substance having two acid anhydride groups at both ends, and a fluorine group is provided on a linking group connecting the two acid anhydride groups. It is to be inferred from the principle that the type of the acid anhydride is not limited. Preferably, the fluorine-containing dianhydride is fluorine-containing dianhydride with phthalic anhydride at two ends. The fluorine-containing dianhydride with two ends of phthalic anhydride is commercial fluorine-containing dianhydride. Further preferably, the fluorine-containing dianhydride is one or a combination of two of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride (also known as hexafluoro dianhydride) or bisphenol AF dianhydride.
Preferably, the molar ratio of primary amino groups to maleic anhydride remaining after the reaction of the diamine containing a carbazole structure and the fluorine-containing dianhydride is 1: 1. The invention adopts maleic anhydride to react with the residual primary amino group, maleic anhydride double bonds are introduced at two ends of a molecular chain, and the maleic anhydride double bonds can be copolymerized with polypropylene under the action of an initiator to play a role in crosslinking.
The polyolefins of the present invention are selected from the non-polar polyolefins commonly used in packaging materials. Preferably one or a combination of polyethylene or polypropylene; further preferred is polypropylene.
Preferably, the initiator is a peroxide initiator; further preferably one or a combination of more of dicumyl peroxide, benzoyl peroxide tert-butyl peroxide and methyl ethyl ketone peroxide.
Antioxidants with better compatibility with the system of the present invention can be used in the present invention, including but not limited to, one or more of antioxidant 1010 (pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), antioxidant 264(2, 6-di-tert-butyl-p-cresol), or antioxidant 1076 (octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate).
The preparation method of the water-blocking oxygen-blocking polyolefin material comprises the following steps:
s1, preparation of fluorine modified polyimide containing carbazole structure
S11, dissolving diamine containing a carbazole structure in a solution, adding fluorine-containing dianhydride, carrying out a pre-reaction at 20-35 ℃ to generate amic acid, adding a catalyst, and heating to 140-160 ℃ to carry out ring closure on the amic acid to obtain polyimide;
s12, adding maleic anhydride into the product obtained in the step S11, reacting at the temperature of 20-40 ℃ to enable the maleic anhydride to be subjected to ring opening to be changed into maleic amide acid, continuing to heat to the temperature of 140-160 ℃ to enable the maleic amide acid to be subjected to ring closing to obtain polyimide, and cooling, purifying and drying to obtain the fluorine modified polyimide containing the carbazole structure;
s2, preparation of water-blocking and oxygen-blocking polyolefin material
And melting, blending and extruding polyolefin, fluorine modified polyimide containing a carbazole structure obtained from S1, an initiator and an antioxidant to obtain the water-blocking and oxygen-blocking polyolefin material.
Preferably, the temperature of the melt blending in the step S2 is 140-170 ℃.
Preferably, the temperature of the extrusion in the step S2 is 160-220 ℃.
The application of the water-blocking and oxygen-blocking polyolefin material in preparing medicine packaging boxes or food packaging boxes is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, diamine containing a carbazole structure reacts with fluorine-containing dianhydride and is capped with maleic anhydride to obtain fluorine modified polyimide containing the carbazole structure, and double bonds of maleic anhydride at two ends react with polypropylene for copolymerization, so that the compatibility of the fluorine modified polyimide containing the carbazole structure and the polypropylene is effectively improved, a crosslinking effect is achieved, and the mechanical strength of the material is enhanced. The carbazole structure has high rigidity and plays a role in filling and blocking, and the fluorine modified polyimide containing the carbazole structure is stably dispersed in a polypropylene system through a crosslinking structure, so that the gas barrier property can be effectively improved. Fluorine is excellent in hydrophobicity, and introduction of the fluorine can improve water resistance and avoid influence on water resistance of polypropylene and oxygen resistance under high-humidity conditions due to introduction of polar groups. The synergistic effect among the carbazole structure, the maleic anhydride double bond and the fluorine element remarkably improves the water-blocking and oxygen-blocking performance of the material, particularly the water-blocking and oxygen-blocking performance under the high-temperature and high-humidity condition, wherein the oxygen transmission rate of the material can be as low as 0.270cm under the condition of 80% RH humidity3/(pkg.0.1 MPa.24 h), with conventional polypropylene material (0.54 cm)3Compared with pkg.0.1 Mpa.24 h, the oxygen transmission rate is reduced by 50 percent; the water-resistant and oxygen-resistant film has the oxygen transmission rate equivalent to that under the condition of 0% RH humidity, and has excellent water-resistant and oxygen-resistant performance.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The polypropylene used in the examples and comparative examples was Taiwan PP-1024.
Examples 1 to 11
The embodiment provides a series of water-blocking and oxygen-blocking polyolefin materials, and the preparation method comprises the following steps:
s1, preparation of fluorine modified polyimide containing carbazole structure
S11, dissolving diamine containing a carbazole structure in dimethyl sulfoxide, slowly adding fluorine-containing dianhydride at the temperature of 20-35 ℃, reacting for 10-15 h, adding triethylamine catalyst, and then continuously heating to 140-160 ℃ for reacting for 4-6 h;
s12, cooling to 20-40 ℃, adding maleic anhydride to react for 12-16 h, then heating to 140-160 ℃, further reacting for 4-6 h, cooling, purifying and drying to obtain the fluorine modified polyimide containing the carbazole structure;
s2, preparation of water-blocking and oxygen-blocking polyolefin material
And melting and blending polypropylene, fluorine modified polyimide containing a carbazole structure obtained from S1, an initiator and an antioxidant at 140-170 ℃, and extruding at 160-220 ℃ to obtain the water-blocking and oxygen-blocking polyolefin material.
It should be noted that, under the above reaction temperature and time conditions, the structure of the product is less affected.
The specific formula is detailed in tables 1-3.
TABLE 1 raw materials and amounts (mol) of fluorine-modified polyimides containing carbazole structure
TABLE 2 materials and amounts of Water-and oxygen-blocking Polypropylene materials I (g)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Polypropylene | 65 | 80 | 67 | 75 | 75 | 75 | 75 |
| PI-1 | 35 | 20 | 33 | 25 | — | — | — |
| PI-6 | — | — | — | — | 25 | — | — |
| PI-7 | — | — | — | — | — | 25 | — |
| PI-8 | — | — | — | — | — | — | 25 |
| Dicumyl peroxide | 0.8 | 1.0 | — | — | — | — | — |
| Methyl ethyl ketone peroxide | — | — | 0.2 | 0.4 | 0.4 | 0.4 | 0.4 |
| Antioxidant 1010 | 3.0 | — | — | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant 264 | — | 1.0 | 2.0 | — | — | — | — |
。
TABLE 3 raw materials and amounts II (g) of water-and oxygen-blocking polypropylene materials
| Example 8 | Example 9 | Example 10 | Example 11 | |
| Polypropylene | 75 | 75 | 75 | 75 |
| PI-2 | 25 | — | — | — |
| PI-3 | — | 25 | — | — |
| PI-4 | — | — | 25 | — |
| PI-5 | — | — | — | 25 |
| Methyl ethyl ketone peroxide | 0.4 | 0.4 | 0.4 | 0.4 |
| Antioxidant 1010 | 0.5 | 0.5 | 0.5 | 0.5 |
。
Comparative example 1
This comparative example is different from example 4 in that PI-1 is replaced with PI-9 having a smaller molar ratio of diamine containing a carbazole structure to fluorine-containing dianhydride.
Comparative example 2
Compared with example 4, the difference of the comparative example is that PI-1 is replaced by PI-10 with larger molar ratio of diamine containing carbazole structure and fluorine-containing dianhydride.
Comparative example 3
This comparative example is compared to example 4, except that PI-1 was replaced with PI-11, which does not contain fluorine.
Comparative example 4
This comparative example is compared with example 4, except that PI-1 is replaced with PI-12 which does not contain a carbazole structure.
Comparative example 5
This comparative example is compared to example 4, except that PI-1 was replaced with PI-13 without maleic anhydride.
The plastics prepared in the above examples and comparative examples were subjected to a performance test.
1. Melt index: the assay is carried out according to GB/T3682-2000, and the specific assay conditions are as follows: 230 ℃ and 2.16 kg.
2. And (3) testing mechanical properties: the tensile strength and elongation at break of the polypropylene material sheet were measured according to GB/T1040.3-2006.
3. Barrier properties: the polypropylene materials of the examples and comparative examples were prepared into 100ml plastic bottles and tested for oxygen transmission rate at 0% RH and 80% RH, respectively, according to GB/T31354-2014 at 23 ℃; according to GB31355-2014, the water vapor transmission rate is tested, and the test conditions are as follows: 38 ℃ and 90% RH.
The test results are detailed in table 4.
Table 4 results of performance testing
As can be seen from the results of table 4: in the embodiment, the polypropylene material has good oxygen resistance, and the oxygen transmission rate is lower than 0.35cm under the humidity of 0% RH and 80% RH3/(pkg.0.1 MPa.24 h), much smaller than unmodified PP-1024 polypropylene (0.54 cm)3/(pkg · 0.1Mpa · 24 h)); the water vapor transmission amount is not changed greatly, the excellent water resistance of the polypropylene is maintained, and the tensile property of the material meets the use requirement.
Comparative example 1 because the molar ratio of diamine containing carbazole structure to fluorine-containing dianhydride is less than 1, namely the molar ratio of fluorine-containing dianhydride is greater than diamine containing carbazole structure, resulting in that the copolymer has no residual amino group and can react with maleic anhydride to introduce double bonds, the synthesized fluorine modified polyimide containing carbazole structure can not be grafted with polyolefin, and because the compatibility of the fluorine modified polyimide containing carbazole structure and polyolefin is poor, the gas barrier and water blocking performance is obviously reduced; in the comparative example 2, because the molar ratio of diamine containing a carbazole structure to fluorine-containing dianhydride is greater than 2, the molecular weight of the prepared fluorine modified polyimide containing the carbazole structure is smaller, and part of diamine containing the carbazole structure cannot react with fluorine-containing dianhydride but directly reacts with maleic anhydride, on one hand, an effective barrier is not formed due to scattered distribution of the carbazole structure playing a role in filling and blocking, and the gas barrier effect is slightly poor, on the other hand, the content of fluorine-containing dianhydride is lower, and the water resistance is also reduced; comparative example 3 since the modified polyimide does not contain fluorine, the oxygen transmission rate of the obtained polypropylene material is increased under 80% RH, and the water vapor transmission rate is increased remarkably; comparative example 4 because the modified polyimide does not contain a carbazole structure, regularity, rigidity, inter-chain cohesion of a molecular chain, low filling rate of a chain segment, and poor barrier property; in comparative example 5, the modified polyimide is not terminated with maleic anhydride, so that the water and oxygen blocking performance of the obtained polypropylene material is obviously reduced, and the tensile strength is also obviously reduced, because the compatibility of the fluorine modified polyimide containing a carbazole structure and polypropylene is poor, and when no maleic anhydride is grafted and crosslinked, gaps exist between interfaces due to poor compatibility of the system.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The water-blocking and oxygen-blocking polyolefin material is characterized by comprising the following raw materials in parts by weight:
the fluorine modified polyimide containing the carbazole structure is obtained by reacting diamine containing the carbazole structure with fluorine-containing dianhydride and then sealing the end with maleic anhydride;
the molar ratio of diamine containing a carbazole structure to fluorine-containing dianhydride is 1-2: 1.
2. The water and oxygen blocking polyolefin material according to claim 1, wherein the molar ratio of the diamine containing the carbazole structure to the fluorine-containing dianhydride is 1.07-1.5: 1.
3. The water-blocking and oxygen-blocking polyolefin material according to claim 1, wherein the diamine containing carbazole structure is one or more of 9H-carbazole-2, 7-diamine, 9H-carbazole-3, 6-diamine, 9-methyl-9H-carbazole-3, 6-diamine, 9-ethyl-9H-carbazole-3, 6-diamine, or 4, 4' - (9H-carbazole-3, 6-diyl) dianiline.
4. The water and oxygen blocking polyolefin material according to claim 1, wherein the fluorine-containing dianhydride is a fluorine-containing dianhydride with phthalic anhydride at both ends.
5. The water and oxygen-blocking polyolefin material according to claim 1, wherein the fluorine-containing dianhydride is one or a combination of two of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride or bisphenol AF dianhydride.
6. The water and oxygen-blocking polyolefin material according to claim 1, wherein the polyolefin is one or a combination of polyethylene and polypropylene.
7. The water and oxygen blocking polyolefin material according to claim 1, wherein the initiator is one or a combination of dicumyl peroxide, benzoyl tert-butyl peroxide or methyl ethyl ketone peroxide.
8. The water and oxygen blocking polyolefin material according to claim 1, wherein the antioxidant is one or a combination of antioxidants 1010, 264 or 1076.
9. A method for preparing a water and oxygen blocking polyolefin material as claimed in any one of claims 1 to 8, comprising the steps of:
s1, preparation of fluorine modified polyimide containing carbazole structure
S11, dissolving diamine containing a carbazole structure in a solution, adding fluorine-containing dianhydride, carrying out a pre-reaction at 20-35 ℃ to generate amic acid, adding a catalyst, and heating to 140-160 ℃ to carry out ring closure on the amic acid to obtain polyimide;
s12, adding maleic anhydride into the product obtained in the step S11, reacting at the temperature of 20-40 ℃ to enable the maleic anhydride to be subjected to ring opening to be changed into maleic amide acid, continuing to heat to the temperature of 140-160 ℃ to enable the maleic amide acid to be subjected to ring closing to obtain polyimide, and cooling, purifying and drying to obtain the fluorine modified polyimide containing the carbazole structure;
s2, preparation of water-blocking and oxygen-blocking polyolefin material
And (2) blending and extruding polyolefin, fluorine modified polyimide containing a carbazole structure obtained from S1, an initiator and an antioxidant to obtain the water-blocking and oxygen-blocking polyolefin material.
10. Use of the water-and oxygen-blocking polyolefin material according to any one of claims 1 to 8 for the preparation of pharmaceutical packaging boxes or food packaging boxes.
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