A kind of manufacturing process of degradable blister packaging material

Abstract

The invention relates to the technical field of degradation of blister packaging materials, and discloses a manufacturing process of a degradable blister packaging material. The invention comprises the following steps: taking isophthalic acid as a raw material to prepare o-nitrobenzyl dicarboxylate, taking o-nitrobenzyl dicarboxylate as a raw material to prepare o-nitrobenzyl alcohol, carrying out an esterification reaction between the alcoholic hydroxyl group of the o-nitrobenzyl alcohol and the carboxylic acid functional group of α-bromo-4-chlorophenylacetic acid to generate a degradable initiator monomer, carrying out an esterification polymerization reaction between the chlorine functional group of the degradable initiator monomer and the carboxylic acid functional group of 1,3-phenylenediacetic acid to generate a degradable initiator polymer, taking the o-nitrobenzyl dicarboxylate as an initiator and styrene as a reaction monomer, and manufacturing the degradable blister packaging material through an atom transfer free radical polymerization reaction. The main chain of the blister packaging material has an o-nitrobenzyl ester group that can be degraded by ultraviolet light, and also contains a benzyl ester and a carboxyl ester group that can be degraded by chemical means, so that the material can be chemically degraded through a hydrolysis reaction, and can also be photodegraded through ultraviolet light irradiation.

Description

Technical Field

[0001] The invention relates to the technical field of degradation of blister packaging materials, in particular to a manufacturing process of degradable blister packaging materials. Background Art

[0002] The emergence of degradable polymer materials provides a new direction for solving the problem of waste plastic pollution. It is an environmentally friendly material, also known as "green material". The degradation of polymer materials refers to the process in which the polymer undergoes a change in molecular structure under certain environmental conditions (such as light, heat, microorganisms, etc.), resulting in a decrease in relative molecular weight until it is completely degraded. There are two main types of degradable polymer materials, namely blended type and synthetic type.

[0003] Among them, the blended degradable polymer material has the risk of leaking photosensitizer when used, which will pollute the surrounding environment, thus limiting its scope of use. Synthetic degradable polymer materials are degradable polymers that introduce degradable groups into the main chain or side chain of olefin polymers to make them degradable. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] The invention provides a process for manufacturing a degradable blister packaging material. The main chain of the manufactured degradable blister packaging material contains an o-nitrobenzyl ester group that can be degraded by ultraviolet light, and also contains a benzyl ester and a carboxyl ester group that can be chemically degraded by a hydrolysis reaction, and can also be photodegraded by ultraviolet light irradiation.

[0006] (II) Technical solution

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A process for manufacturing a degradable blister packaging material comprises the following steps:

[0009] Step 1, synthesizing a degradable initiator polymer, the synthesis mechanism and method thereof are as follows:

[0010] Step 1-1, preparing o-nitrobenzene dicarboxylate using isophthalic acid as a raw material;

[0011] Step 1-2, preparing o-nitrobenzyl alcohol by using o-nitrodicarboxylic acid benzene as a raw material;

[0012] Step 1-3, generating a degradable initiator monomer by esterification reaction between the alcoholic hydroxyl group of o-nitrodibenzyl alcohol and the carboxylic acid functional group of α-bromo-4-chlorophenylacetic acid;

[0013] Step 1-4, generating a degradable initiator polymer by esterification reaction between the chlorine functional group of the degradable initiator monomer and the carboxylic acid functional group of 1,3-benzenedioic acid;

[0014] Step 2, using a degradable initiator polymer as an initiator and styrene as a reaction monomer, to manufacture a degradable blister packaging material through an atom transfer free radical polymerization reaction, and the manufacturing process is as follows:

[0015] Catalyst, 2,2-bipyridine bpy, 8-13 parts of degradable initiator polymer, a stirrer and 200-500 parts of styrene monomer are added in sequence to a sealed tube with a spherical bottom, and the tube is frozen with liquid nitrogen, vacuumed, nitrogen-filled, and thawed. The tube is vacuum sealed, and the polymerization tube is placed in an oil bath for reaction and then taken out to obtain a degradable blister packaging material.

[0016] Preferably, in step 1-4, the chlorine functional group of the degradable initiator monomer is subjected to an esterification reaction with the carboxylic acid functional group of 1,3-benzenedioic acid to generate a degradable initiator polymer, and the specific synthesis steps are as follows:

[0017] Weigh 270-540 parts of a degradable initiator monomer and dissolve it in N,N-dimethylformamide, add 92-138 parts of tetramethylguanidine under ice bath conditions, add 78-156 parts of 1,3-phenylenediacetic acid after stirring, and react by stirring to obtain a degradable initiator polymer.

[0018] Preferably, in the step 1-4, the reaction is stirred at 20-35° C. for 12-18 hours, and then precipitated in methanol, washed and dried to obtain a degradable initiator polymer.

[0019] Preferably, in the step 2, liquid nitrogen freezing, vacuuming, nitrogen passing, and thawing are repeated three times, and then the tube is vacuum sealed, and the polymerization tube is placed in an oil bath at 100-120° C. for reaction for 8-15 hours and then taken out to obtain a degradable blister packaging material.

[0020] (III) Beneficial technical effects

[0021] Compared with the prior art, the present invention has the following beneficial technical effects:

[0022] The invention uses isophthalic acid as a raw material to prepare o-nitrobenzene dicarboxylate, uses o-nitrobenzene dicarboxylate as a raw material to prepare o-nitrobenzyl alcohol, generates a degradable initiator monomer by an esterification reaction between an alcoholic hydroxyl group of the o-nitrobenzyl alcohol and a carboxylic acid functional group of alpha-bromo-4-chlorophenylacetic acid, generates an esterification polymerization reaction between a chlorine functional group of the degradable initiator monomer and a carboxylic acid functional group of 1,3-phenylenediacetic acid, generates a degradable initiator polymer, uses the degradable initiator polymer as an initiator, uses styrene as a reaction monomer, and manufactures a degradable blister packaging material by an atom transfer free radical polymerization reaction, and the number average molecular weight M of the degradable initiator polymer is 200 %. n，GPC , and the number average molecular weight M after the degradation experiment n，GPC After comparison, it was found that the number average molecular weight M n，GPC After the degradation experiment was carried out, it was significantly reduced, proving that the degradable blister packaging material has the degradation function;

[0023] And because the main chain of the synthesized degradable blister packaging material contains an o-nitrobenzyl ester group that can be degraded by ultraviolet light, and also contains benzyl ester and carboxyl ester groups that can be chemically degraded, it can not only be chemically degraded by hydrolysis reaction, but also be photodegraded by ultraviolet light irradiation. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is the chemical structure of benzene o-nitrodicarboxylate;

[0025] Figure 2 is the chemical structure of o-nitrodibenzyl alcohol;

[0026] Figure 3 is the chemical structure of the degradable initiator monomer;

[0027] Figure 4 It is the chemical structure of the degradable initiator polymer. DETAILED DESCRIPTION

[0028] Embodiment 1:

[0029] A process for manufacturing a degradable blister packaging material comprises the following steps:

[0030] Step 1, synthesizing a degradable initiator polymer, the synthesis mechanism and method thereof are as follows:

[0031] Step 1-1, using isophthalic acid as a raw material to prepare o-nitrobenzene dicarboxylate, the chemical structure of which is as follows Figure 1 As shown, the specific synthesis steps are as follows:

[0032] Weigh 660 mg of isophthalic acid into a 50 mL single-necked flask, add 10 mL of 98% sulfuric acid, and place in an ice bath for 30 min. Slowly drop 5 mL of concentrated nitric acid into the system in a constant pressure dropping funnel. During the addition of nitric acid, control the system temperature below 0°C. After the addition is complete, place the system at room temperature to react for 12 h. After washing in an ice water bath, add a saturated sodium bicarbonate solution, adjust the pH value to 7, filter, wash, collect the filter residue, wash with methanol, collect the product by centrifugation, and dry it under vacuum to obtain o-nitrobenzene dicarboxylate;

[0033] Step 1-2, using o-nitrodicarboxylic acid benzene as a raw material to prepare o-nitrodibenzyl alcohol, the chemical structure of which is as follows: Figure 2 As shown, the specific synthesis steps are as follows:

[0034] 800 mg of o-nitrodicarboxylic acid benzene was dissolved in 50 mL of tetrahydrofuran, and 18 g of borane tetrahydrofuran complex was slowly added to the above tetrahydrofuran in an ice bath over 1 hour. After the addition was completed, the mixture was reacted at room temperature for 48 hours under nitrogen flow, the borane tetrahydrofuran complex and tetrahydrofuran were removed, and the mixture was extracted with ethyl acetate. The organic phases were combined, washed and dried to obtain o-nitrodibenzyl alcohol.

[0035] Step 1-3, the alcoholic hydroxyl group of o-nitrodibenzyl alcohol and the carboxylic acid functional group of α-bromo-4-chlorophenylacetic acid undergo esterification reaction to generate a degradable initiator monomer, the chemical structure of which is as follows: Figure 3 As shown, the specific synthesis steps are as follows:

[0036] 1 g of α-bromo-4-chlorophenylacetic acid, 12 mg of 4-dimethylaminopyridine, 270 mg of o-nitrobenzyl alcohol and 50 mL of dry and dehydrated dichloromethane were added to a 250 mL round-bottom flask in sequence, and the round-bottom flask was placed in an ice-water bath for cooling. Within 0.5 h, 247 mg of dicyclohexylcarbodiimide dissolved in 10 mL of anhydrous dichloromethane was added to the cooled reaction solution. The reaction mixture was stirred at 0° C. for 0.5 h, and then the ice-water bath was removed. The reaction was continued to stir at room temperature for 24 h, and then filtered, concentrated, and separated by column chromatography (petroleum ether / ethyl acetate=30 / 1) to obtain a degradable initiator monomer;

[0037] Step 1-4, the chlorine functional group of the degradable initiator monomer undergoes an esterification reaction with the carboxylic acid functional group of 1,3-phenylenediacetic acid to generate a degradable initiator polymer, the chemical structure of which is as follows: Figure 4 As shown, the specific synthesis steps are as follows:

[0038] Weigh 270 mg of a degradable initiator monomer and dissolve it in 10 mL of N,N-dimethylformamide, add 92 mg of tetramethylguanidine under ice bath conditions, stir for 5 min, then add 78 mg of 1,3-phenylenediacetic acid, stir and react at 25° C. for 12 h, then precipitate in methanol, wash and dry to obtain a degradable initiator polymer;

[0039] Step 2, using a degradable initiator polymer as an initiator and styrene as a reaction monomer, to manufacture a degradable blister packaging material through an atom transfer free radical polymerization reaction, and the manufacturing process is as follows:

[0040] 14.4 mg CuBr, 46.9 mg 2,2-bipyridine bpy, 83 mg degradable initiator polymer, a stirrer and 2 g styrene monomer were added to a 5 mL sealed tube with a spherical bottom. The tube was frozen with liquid nitrogen, vacuumed, passed through nitrogen and thawed for three times. The tube was sealed under vacuum. The polymerization tube was placed in an oil bath at 110° C. for reaction for 8 h and then taken out. The tube was cooled with cold water and the sealed tube was opened. The catalyst CuBr was removed by neutral alumina chromatography using tetrahydrofuran as solvent and the degradable blister packaging material was obtained by precipitation with methanol.

[0041] Degradation performance of degradable blister packaging materials:

[0042] The gel permeation chromatography (GPC) of the degradable blister packaging material prepared in Example 1 was tested, and the number average molecular weight M n，GPC =1.31×10 4 g / moL, molecular weight distribution is M w / M n =1.27;

[0043] The chemical degradation test method is as follows: 100 mg of degradable blister packaging material is dissolved in 3 mL of THF, and then 10 mg of sodium hydroxide and 3 mL of distilled water are added, and the reaction is refluxed for 24 hours. After the reaction is completed, the solvent is evaporated, and a hydrochloric acid aqueous solution is added. The precipitate is filtered using a 0.22 um microporous filter membrane, and after washing and drying, its permeability gel chromatography (GPC) is tested, and the number average molecular weight M n，GPC =1600g / moL;

[0044] The UV degradation test method is as follows: 100 mg of degradable blister packaging material is weighed and dissolved in 10 mL of tetrahydrofuran, then spread on a clean glass plate and dry naturally, ensuring that the film thickness is as uniform as possible. The film thickness is measured with a vernier caliper. Finally, the sample on the glass plate is placed under a 365 nm UV lamp (5 mW / cm 2 ) for 10 h, and tested by gel permeation chromatography (GPC), the number average molecular weight M n，GPC =2200g / moL;

[0045] It can be seen that in Example 1, a degradable initiator polymer is used as an initiator to manufacture a degradable blister packaging material through an atom transfer radical polymerization reaction. Since the synthesized degradable blister packaging material has an o-nitrobenzyl ester group that can be degraded by ultraviolet light, and also contains a benzyl ester and a carboxyl ester group that can be chemically degraded, it can not only be chemically degraded by a hydrolysis reaction, but also be photodegraded by ultraviolet light irradiation;

[0046] Embodiment 2:

[0047] A process for manufacturing a degradable blister packaging material comprises the following steps:

[0048] Step 1, synthesizing a degradable initiator polymer, the synthesis mechanism and method thereof are as follows:

[0049] Step 1-1, the synthesis step of preparing o-nitrobenzene dicarboxylate using isophthalic acid as raw material is shown in Example 1;

[0050] Step 1-2, the synthesis step of preparing o-nitrobenzyl alcohol by using o-nitrodicarboxylic acid benzene as raw material is shown in Example 1;

[0051] Step 1-3, the synthesis step of generating a degradable initiator monomer by esterification reaction between the alcoholic hydroxyl group of o-nitrobenzyl alcohol and the carboxylic acid functional group of α-bromo-4-chlorophenylacetic acid is shown in Example 1;

[0052] Step 1-4, the chlorine functional group of the degradable initiator monomer undergoes an esterification reaction with the carboxylic acid functional group of 1,3-benzenedioic acid to generate a degradable initiator polymer. The specific synthesis steps are as follows:

[0053] 540 mg of a degradable initiator monomer was weighed and dissolved in 20 mL of N,N-dimethylformamide, 138 mg of tetramethylguanidine was added under ice bath conditions, and the mixture was stirred for 30 min. Then, 78 mg of 1,3-phenylenediacetic acid was added, and the mixture was stirred at 20° C. for 18 h. The mixture was then precipitated in methanol, washed, and dried to obtain a degradable initiator polymer;

[0054] Step 2, using a degradable initiator polymer as an initiator and styrene as a reaction monomer, to manufacture a degradable blister packaging material through an atom transfer free radical polymerization reaction, and the manufacturing process is as follows:

[0055] 14.4 mg CuBr, 46.9 mg 2,2-bipyridine bpy, 83 mg degradable initiator polymer, a stirrer and 2.6 g styrene monomer were added to a 5 mL sealed tube with a spherical bottom. The tube was frozen with liquid nitrogen, vacuumed, passed through nitrogen and thawed. After three times, the tube was sealed in vacuum. The polymerization tube was placed in a 120°C oil bath for reaction for 10 hours, then taken out, cooled with cold water, and the sealed tube was opened. The catalyst CuBr was removed by neutral alumina chromatography using tetrahydrofuran as solvent, and the degradable blister packaging material was obtained by precipitation with methanol. The number average molecular weight M n，GPC =1.87×10 4 g / moL, molecular weight distribution is M w / M n =1.30, the number average molecular weight after chemical degradation experiment M n，GPC =1800g / moL, number average molecular weight M after UV degradation experiment n，GPC =2500g / mol;

[0056] It can be seen that in Example 2, a degradable initiator polymer is used as an initiator to manufacture a degradable blister packaging material through atom transfer radical polymerization reaction, and chemical degradation can also be achieved through hydrolysis reaction, and photodegradation can be achieved through ultraviolet light irradiation;

[0057] Embodiment 3:

[0058] A process for manufacturing a degradable blister packaging material comprises the following steps:

[0059] Step 1, synthesizing a degradable initiator polymer, the synthesis mechanism and method thereof are as follows:

[0060] Step 1-1, the synthesis step of preparing o-nitrobenzene dicarboxylate using isophthalic acid as raw material is shown in Example 1;

[0061] Step 1-2, the synthesis step of preparing o-nitrobenzyl alcohol by using o-nitrodicarboxylic acid benzene as raw material is shown in Example 1;

[0062] Step 1-3, the synthesis step of generating a degradable initiator monomer by esterification reaction between the alcoholic hydroxyl group of o-nitrobenzyl alcohol and the carboxylic acid functional group of α-bromo-4-chlorophenylacetic acid is shown in Example 1;

[0063] Step 1-4, the chlorine functional group of the degradable initiator monomer undergoes an esterification reaction with the carboxylic acid functional group of 1,3-benzenedioic acid to generate a degradable initiator polymer. The specific synthesis steps are as follows:

[0064] Weigh 270 mg of a degradable initiator monomer and dissolve it in 20 mL of N,N-dimethylformamide, add 138 mg of tetramethylguanidine under ice bath conditions, stir for 5 min, then add 156 mg of 1,3-phenylenediacetic acid, stir and react at 35° C. for 15 h, then precipitate in methanol, wash and dry to obtain a degradable initiator polymer;

[0065] Step 2, using a degradable initiator polymer as an initiator and styrene as a reaction monomer, to manufacture a degradable blister packaging material through an atom transfer free radical polymerization reaction, and the manufacturing process is as follows:

[0066] 14.4 mg CuBr, 46.9 mg 2,2-bipyridine bpy, 125 mg degradable initiator polymer, a stirrer and 5 g styrene monomer were added to a 5 mL sealed tube with a spherical bottom. Liquid nitrogen freezing, vacuum pumping, nitrogen passing and thawing were repeated three times, and the tube was sealed in vacuum. The polymerization tube was placed in a 100°C oil bath for reaction for 15 hours, then taken out, cooled with cold water, and the sealed tube was opened. The catalyst CuBr was removed by neutral alumina chromatography using tetrahydrofuran as the solvent, and the degradable blister packaging material was obtained by precipitation with methanol. The number average molecular weight M n，GPC =3.76×10 4 g / moL, molecular weight distribution is M w / M n =1.35, the number average molecular weight after chemical degradation experiment M n，GPC =4600g / moL, the number average molecular weight after UV degradation experiment M n，GPC =5100g / moL;

[0067] It can be seen that in Example 3, a degradable initiator polymer is used as an initiator to manufacture a degradable blister packaging material through atom transfer radical polymerization reaction, and chemical degradation can also be achieved through hydrolysis reaction, and photodegradation can be achieved through ultraviolet light irradiation.

Claims

1. A process for manufacturing a degradable blister packaging material, characterized in that: The following steps are involved: Step 1, synthesizing a degradable initiator polymer, the synthesis mechanism and method thereof are as follows: Step 1-1, preparing o-nitrobenzene dicarboxylate using isophthalic acid as a raw material; Step 1-2, preparing o-nitrobenzyl alcohol by using o-nitrodicarboxylic acid benzene as a raw material; Step 1-3, generating a degradable initiator monomer by esterification reaction between the alcoholic hydroxyl group of o-nitrodibenzyl alcohol and the carboxylic acid functional group of α-bromo-4-chlorophenylacetic acid; Step 1-4, generating a degradable initiator polymer by esterification reaction between the chlorine functional group of the degradable initiator monomer and the carboxylic acid functional group of 1,3-phenylenediacetic acid; Step 2, using a degradable initiator polymer as an initiator and styrene as a reaction monomer, to manufacture a degradable blister packaging material through an atom transfer free radical polymerization reaction, and the manufacturing process is as follows: A catalyst, 2,2-bipyridine bpy, 8-13 parts by weight of a degradable initiator polymer, a stirrer and 200-500 parts by weight of a styrene monomer are sequentially added into a sealed tube with a spherical bottom, and the tube is frozen with liquid nitrogen, vacuumed, nitrogen-passed, and thawed. The tube is vacuum sealed, and the polymerization tube is placed in an oil bath for reaction and then taken out to obtain a degradable blister packaging material.

2. A process for manufacturing a degradable blister packaging material according to claim 1, characterized in that: In step 1-4, the chlorine functional group of the degradable initiator monomer undergoes an esterification reaction with the carboxylic acid functional group of 1,3-benzenedioic acid to generate a degradable initiator polymer. The specific synthesis steps are as follows: 270-540 parts by weight of a degradable initiator monomer is weighed and dissolved in N,N-dimethylformamide, 92-138 parts by weight of tetramethylguanidine is added under ice bath conditions, and after stirring, 78-156 parts by weight of 1,3-benzenedioic acid is added, and the mixture is stirred for reaction to obtain a degradable initiator polymer.

3. A process for manufacturing a degradable blister packaging material according to claim 2, characterized in that: In the step 1-4, the reaction is stirred at 20-35° C. for 12-18 hours, and then precipitated in methanol, washed, and dried to obtain a degradable initiator polymer.

4. The process for manufacturing a degradable blister packaging material according to claim 1, characterized in that: The step 2, liquid nitrogen freezing - vacuuming - nitrogen passing - thawing, is repeated three times, and then the tube is sealed in vacuum, and the polymerization tube is placed in a 100-120° C. oil bath for reaction for 8-15 hours and then taken out to obtain a degradable blister packaging material.

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