Degradable PA6 composite modified plastic

Abstract

The present application relates to a kind of degradable PA6 composite modified plastics, belong to composite material technical field;The present application is by preparing a modifier with double bond in structure, and using the modifier to modify PBAT, effectively solve the uneven distribution problem of polar additive in PBAT-PA6 composite plastics, and provide good antibacterial performance and ultraviolet light aging resistance for composite plastics, in addition, the modifier of the present application can also improve the polarity of modified PBAT, and using the ionic-dipole interaction of quaternary ammonium salt structure in structure and the polar amide bond in PA6 is formed, the adhesion between modified PBAT phase and PA6 phase is enhanced, the compatibility between modified PBAT and PA6 is improved, and then the mechanical properties of PBAT-PA6 composite plastics as a whole is improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite materials, and particularly relates to a degradable PA6 composite modified plastic, and more particularly to a PA6-PBAT composite plastic. BACKGROUND

[0002] PBAT, namely polybutylene adipate terephthalate, is a petroleum-based biodegradable plastic, which can be completely decomposed into carbon dioxide and water in a natural environment, does not cause pollution to the environment, and has good ductility, heat resistance and impact resistance, and is widely used in the fields of packaging materials and agricultural mulching films.

[0003] Although PBAT has many excellent properties, the mechanical properties and gas barrier properties thereof are relatively poor, and the blending modification of PBAT by adding an appropriate amount of PA6 (polyamide 6) can effectively solve these shortcomings, and the composite plastic obtained after modification still belongs to degradable materials and has a broad research prospect; however, the chemical structure of the two materials has a large difference in polarity, PBAT has weak polarity, and the structure mainly has ester groups, while PA6 is a polar polymer and contains a large number of amide groups in the molecular chain, and direct blending often has poor modification effect, in addition, due to the large difference in polarity between the two, polar additives (such as antibacterial agents and ultraviolet absorbers) often preferentially dissolve and enrich in the PA6 micro area with stronger polarity, which seriously affects the modification effect of the additive on the whole composite plastic, in order to solve the above technical defects, the application provides a degradable PA6 composite modified plastic. SUMMARY

[0004] The purpose of the application is to provide a degradable PA6 composite modified plastic for solving the problems mentioned in the background.

[0005] The purpose of the application can be achieved by the following technical solutions.

[0006] A degradable PA6 composite modified plastic comprises the following raw materials in mass fraction: 75-85 parts of modified PBAT, 15-25 parts of polyamide 6, and 0.2-0.4 parts of an antioxidant.

[0007] The modified PBAT has a modifier of the application grafted in the molecular chain, and the modifier has a reactive double bond, a pyridyl quaternary ammonium salt structure and an ortho-hydroxy benzophenone structure.

[0008] Further, the degradable PA6 composite modified plastic can be prepared by the following preparation method.

[0009] The modified PBAT, the polyamide 6 and the antioxidant are mixed and then added to a twin-screw extruder for melt extrusion at a temperature of 230-240 DEG C to obtain the degradable PA6 composite modified plastic.

[0010] Further, the antioxidant used in the step of preparing the degradable PA6 composite modified plastic is one of antioxidant 1010, antioxidant 1035 and antioxidant 1076.

[0011] Further, the modified PBAT used in the step of preparing the degradable PA6 composite modified plastic can be prepared by the following steps:

[0012] After mixing the PBAT, the modifier, the initiator and the antioxidant, the modified PBAT is obtained by melt extrusion in a twin-screw extruder at a temperature of 150-160℃.

[0013] Further, the initiator used in the step of preparing the modified PBAT is at least one of benzoyl peroxide and dicumyl peroxide.

[0014] Further, the antioxidant used in the step of preparing the modified PBAT is antioxidant 168.

[0015] Further, the preferred mass ratio of the PBAT, the modifier, the initiator and the antioxidant used in the step of preparing the modified PBAT is 100:3-4:0.15-0.25:0.1.

[0016] Further, the modifier used in the step of preparing the modified PBAT can be prepared by the following steps:

[0017] The aromatic acyl chloride and the phenol derivative successively undergo esterification reaction and Fries rearrangement reaction to obtain an ultraviolet absorber, then olefin undergoes a Wulff-Ziegler reaction to obtain a halogenated olefin, and finally the halogenated olefin and the ultraviolet absorber undergo quaternary ammonium salt reaction to obtain the modifier.

[0018] Further, the aromatic acyl chloride used in the step of preparing the modifier is one of nicotinoyl chloride and isonicotinoyl chloride, and is preferably isonicotinoyl chloride.

[0019] Further, the phenol derivative used in the step of preparing the modifier is one of 3-dodecyloxyphenol and 4-dodecyloxyphenol.

[0020] Further, the olefin used in the step of preparing the modifier is one of 2-methyl-1-dodecene and 2-methyl-1-tetradecene.

[0021] The beneficial effects of the present application are:

[0022] The modifier prepared by the application has a structure of o-hydroxybenzophenone, which can form reversible intramolecular hydrogen bonds to absorb the energy of ultraviolet light and convert it into heat energy when irradiated by ultraviolet light; in addition, the modifier of the application also has a structure of pyridine-based quaternary ammonium salt, which not only has good antibacterial performance, but also can integrate the quaternary ammonium salt structure into the conjugated system of o-hydroxybenzophenone, significantly enhancing the intramolecular electron-donating and electron-withdrawing effect, reducing the energy gap, and enabling the molecule to absorb longer-wavelength ultraviolet light, realizing red shift of the absorption spectrum, and covering the entire ultraviolet spectrum range. The modification of PBAT using the modifier of the application can effectively improve the overall antibacterial performance and ultraviolet light aging resistance of PBAT-PA6 composite plastics.

[0023] The modifier prepared by the application has a structure of o-hydroxybenzophenone, which can form reversible intramolecular hydrogen bonds to absorb the energy of ultraviolet light and convert it into heat energy when irradiated by ultraviolet light; in addition, the modifier of the application also has a structure of pyridine-based quaternary ammonium salt, which not only has good antibacterial performance, but also can integrate the quaternary ammonium salt structure into the conjugated system of o-hydroxybenzophenone, significantly enhancing the intramolecular electron-donating and electron-withdrawing effect, reducing the energy gap, and enabling the molecule to absorb longer-wavelength ultraviolet light, realizing red shift of the absorption spectrum, and covering the entire ultraviolet spectrum range. The modification of PBAT using the modifier of the application can effectively improve the overall antibacterial performance and ultraviolet light aging resistance of PBAT-PA6 composite plastics.

[0024] The modifier prepared by the application has a structure of o-hydroxybenzophenone, which can form reversible intramolecular hydrogen bonds to absorb the energy of ultraviolet light and convert it into heat energy when irradiated by ultraviolet light; in addition, the modifier of the application also has a structure of pyridine-based quaternary ammonium salt, which not only has good antibacterial performance, but also can integrate the quaternary ammonium salt structure into the conjugated system of o-hydroxybenzophenone, significantly enhancing the intramolecular electron-donating and electron-withdrawing effect, reducing the energy gap, and enabling the molecule to absorb longer-wavelength ultraviolet light, realizing red shift of the absorption spectrum, and covering the entire ultraviolet spectrum range. The modification of PBAT using the modifier of the application can effectively improve the overall antibacterial performance and ultraviolet light aging resistance of PBAT-PA6 composite plastics. DETAILED DESCRIPTION

[0025] The technical solutions of the application will be described clearly and completely below by combining with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor belong to the protection scope of the application.

[0026] Among them, all raw materials of the application have no special restrictions on their sources, and can be purchased on the market or prepared according to the conventional methods well known to those skilled in the art.

[0027] Among them, the room temperature condition is 25±5℃.

[0028] Example 1

[0029] A degradable PA6 composite modified plastic comprises the following raw materials in mass fraction: 75 parts of modified PBAT, 15 parts of polyamide 6, 0.2 parts of antioxidant 1010.

[0030] The modified PBAT can be prepared by the following steps:

[0031] The 100 parts of PBAT, 3 parts of modifier, 0.15 parts of benzoyl peroxide and 0.1 parts of antioxidant 168 are mixed and then added into a double screw extruder to be melt-extruded at a temperature of 150 DEG C to obtain the modified PBAT.

[0032] The modifier is prepared by the following steps:

[0033] S1, 2.8 parts of 3-dodecyloxyphenol, 1.2 parts of triethylamine and 20 parts of dichloromethane are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, a solution prepared by mixing 1.4 parts of nicotinoyl chloride and 10 parts of dichloromethane is added dropwise into the three-necked flask at room temperature, the reaction is carried out at room temperature for 6 hours after the dropwise addition is completed, the three-necked flask is cooled to room temperature after the reaction is completed, 20 parts of 10% dilute hydrochloric acid is added into the three-necked flask, and the organic layer is separated, dried and evaporated to remove the solvent to obtain an esterification product, 3.2 parts of the esterification product, 2.2 parts of aluminum trichloride and 15 parts of o-dichlorobenzene are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 130 DEG C for 6 hours, the three-necked flask is cooled to room temperature after the reaction is completed, 30 parts of 10% dilute hydrochloric acid is added into the three-necked flask, the mixed solution is evaporated to remove the solvent, and the remaining solid is recrystallized to obtain the ultraviolet absorber;

[0034] S2, 1.8 parts of 2-methyl-1-dodecene, 1.8 parts of N-bromosuccinimide, 0.4 parts of benzoyl peroxide and 20 parts of carbon tetrachloride are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 60 DEG C for 10 hours, the solid is separated by filtration after the reaction is completed, and the remaining reaction solution is evaporated to remove the solvent to obtain the halogenated alkene;

[0035] S3, 2.5 parts of the ultraviolet absorber, 1.8 parts of the halogenated alkene and 15 parts of acetonitrile are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 40 DEG C for 48 hours, the solvent is evaporated after the reaction is completed, the remaining solid is washed with petroleum ether and dried to obtain the modifier;

[0036] The degradable PA6 composite modified plastic is prepared by the following preparation method:

[0037] 75 parts of the modified PBAT, 15 parts of polyamide 6 and 0.2 parts of antioxidant 1010 are mixed and then added into a double screw extruder to be melt-extruded at a temperature of 230 DEG C to obtain the degradable PA6 composite modified plastic.

[0038] Example 2

[0039] The degradable PA6 composite modified plastic comprises the following raw materials in mass fraction: 80 parts of modified PBAT, 20 parts of polyamide 6, 0.3 parts of antioxidant 1035;

[0040] The modified PBAT can be prepared by the following steps:

[0041] The modified PBAT is obtained by mixing 100 parts of PBAT, 3.5 parts of modifier, 0.2 parts of dicumyl peroxide and 0.1 parts of antioxidant 168, and then melt-extruding in a twin-screw extruder at a temperature of 155 DEG C.

[0042] The modifier is prepared by the following steps:

[0043] S1, 2.8 parts of 4-dodecyloxyphenol, 1.6 parts of triethylamine and 20 parts of dichloromethane are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, a solution prepared by mixing 1.4 parts of isonicotinyl chloride and 10 parts of dichloromethane is added dropwise into the three-necked flask at room temperature, the reaction is carried out at room temperature for 7 hours after the dropwise addition is completed, the reaction is cooled to room temperature after the reaction is completed, 20 parts of 10% dilute hydrochloric acid is added into the three-necked flask, and the organic layer is separated, dried and distilled to remove the solvent to obtain an esterification product, 3.2 parts of the esterification product, 2.4 parts of aluminum trichloride and 15 parts of o-dichlorobenzene are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 140 DEG C for 5 hours, the reaction is cooled to room temperature after the reaction is completed, 30 parts of 10% dilute hydrochloric acid is added into the three-necked flask, the mixture is distilled to remove the solvent, and the remaining solid is recrystallized to obtain an ultraviolet absorber;

[0044] S2, 2.1 parts of 2-methyl-1-tetradecene, 1.8 parts of N-bromosuccinimide, 0.4 parts of benzoyl peroxide and 20 parts of carbon tetrachloride are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 70 DEG C for 8 hours, the solid is separated by filtration after the reaction is completed, the remaining reaction liquid is distilled to remove the solvent to obtain a halogenated alkene;

[0045] S3, 2.5 parts of the ultraviolet absorber, 2.0 parts of the halogenated alkene and 15 parts of acetonitrile are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 55 DEG C for 24 hours, the solvent is distilled off after the reaction is completed, the remaining solid is washed with petroleum ether and dried to obtain the modifier;

[0046] The degradable PA6 composite modified plastic is prepared by the following preparation method:

[0047] 80 parts of modified PBAT, 20 parts of polyamide 6, 0.3 parts of antioxidant 1035 are mixed and then added into a double screw extruder to be melt-extruded at a temperature of 235°C to obtain the degradable PA6 composite modified plastic.

[0048] Example 3

[0049] A degradable PA6 composite modified plastic, comprising the following raw materials in parts by mass: 85 parts of modified PBAT, 25 parts of polyamide 6, 0.4 parts of antioxidant 1076;

[0050] The modified PBAT can be prepared by the following steps:

[0051] 100 parts of PBAT, 4 parts of modifier, 0.25 parts of dicumyl peroxide, and 0.1 parts of antioxidant 168 are mixed and then added into a double screw extruder to be melt-extruded at a temperature of 160°C to obtain the modified PBAT;

[0052] The modifier is prepared by the following steps:

[0053] S1, 5.6 parts of 3-dodecyloxyphenol, 2.4 parts of triethylamine, and 35 parts of dichloromethane are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, a solution prepared by mixing 2.8 parts of isonicotinyl chloride and 15 parts of dichloromethane is added dropwise into the three-necked flask at room temperature, the reaction is carried out at room temperature for 8 hours after the dropwise addition is completed, the three-necked flask is cooled to room temperature after the reaction is completed, 30 parts of 10% dilute hydrochloric acid is added into the three-necked flask, and the organic layer is separated, dried, and subjected to rotary evaporation to remove the solvent to obtain an esterification product, 6.5 parts of the esterification product, 4.4 parts of aluminum trichloride, and 30 parts of o-dichlorobenzene are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 150°C for 4 hours, the three-necked flask is cooled to room temperature after the reaction is completed, 50 parts of 10% dilute hydrochloric acid is added into the three-necked flask, the mixed solution is subjected to rotary evaporation to remove the solvent, and the remaining solid is recrystallized to obtain the ultraviolet absorber;

[0054] S2, 3.6 parts of 2-methyl-1-dodecene, 3.6 parts of N-bromosuccinimide, 0.8 parts of benzoyl peroxide, and 40 parts of carbon tetrachloride are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 80°C for 6 hours, the solid is separated by filtration after the reaction is completed, and the remaining reaction solution is subjected to rotary evaporation to remove the solvent to obtain the halogenated alkene;

[0055] S3, 5.2 parts of the ultraviolet absorber, 4.4 parts of the halogenated alkene, and 30 parts of acetonitrile are mixed in a three-necked flask equipped with a thermometer and a reflux condenser, the reaction is carried out at a temperature of 80°C for 6 hours, the solvent is removed by rotary evaporation after the reaction is completed, the remaining solid is washed with petroleum ether and then dried to obtain the modifier.

[0056] The degradable PA6 composite modified plastic is prepared by the following preparation method:

[0057] According to the mass fraction, 85 parts of modified PBAT, 25 parts of polyamide 6, 0.4 parts of antioxidant 1076 are mixed and then added into a double screw extruder to be melt-extruded at a temperature of 240℃ to obtain the degradable PA6 composite modified plastic.

[0058] Comparative Example 1

[0059] The difference between the present comparative example and Example 1 is that the PBAT is not modified, but the unmodified PBAT is used to replace the modified PBAT in the raw materials, and the ultraviolet absorber and bacteriostatic agent are supplemented according to the proportion.

[0060] A degradable PA6 composite modified plastic comprises the following raw materials in mass fraction: 75 parts of PBAT, 15 parts of polyamide 6, 0.2 parts of antioxidant 1010, 1 part of 2-hydroxy-4-n-octyloxybenzophenone, and 1.25 parts of dimethyl benzyl alkyl ammonium chloride;

[0061] The degradable PA6 composite modified plastic is prepared by the following preparation method:

[0062] According to the mass fraction, 75 parts of PBAT, 15 parts of polyamide 6, 1 part of 2-hydroxy-4-n-octyloxybenzophenone, 1.25 parts of dimethyl benzyl alkyl ammonium chloride, and 0.2 parts of antioxidant 1010 are mixed and then added into a double screw extruder to be melt-extruded at a temperature of 230℃ to obtain the degradable PA6 composite modified plastic.

[0063] Experimental Example

[0064] The degradable PA6 composite modified plastics in Examples 1-3 and Comparative Example 1 are respectively subjected to the following performance tests, and the test results are shown in Tables 1 and 2;

[0065] Mechanical property test: the tensile strength and elongation at break of each component of the degradable PA6 composite modified plastic are tested according to the national standard GB / T 1040.2-2006 “Determination of tensile properties of plastics”;

[0066] UV aging resistance test: 500h UV accelerated aging test is carried out according to the national standard GB / T 16422.3 “Laboratory light source exposure test method for plastics Part 3: fluorescent UV lamp”, and then the tensile strength and elongation at break of each component of the degradable PA6 composite modified plastic after accelerated aging are tested according to the national standard GB / T 1040.2-2006 “Determination of tensile properties of plastics”, and the tensile strength retention rate and elongation at break retention rate of each component of the degradable PA6 composite modified plastic after accelerated aging are calculated;

[0067] Bacteriostatic performance test: refer to the national standard GB / T 31402-2023 "Determination of antibacterial activity on the surface of plastics and other non-porous materials" to test the bacteriostatic rate of each component degradable PA6 composite modified plastics on escherichia coli and staphylococcus aureus.

[0068]

[0069]

[0070] It can be seen from Tables 1 and 2 that the modifier of the application effectively improves the compatibility between PBAT and PA6, and in turn improves the overall mechanical properties of the composite material. Compared with the modification method of directly adding bacteriostatic agents and ultraviolet absorbers, the use of the modifier of the application can better improve the overall ultraviolet aging resistance and bacteriostatic performance of the material.

[0071] The above description of disclosed embodiments enables one of ordinary skill in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those of ordinary skill in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Therefore, the application is not to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A degradable PA6 composite modified plastic, characterized in that, The modified PBAT, polyamide 6, and antioxidant are mixed and then fed into a double-screw extruder to melt extrude at a temperature of 230-240 DEG C to obtain the degradable PA6 composite modified plastic. The aromatic acyl chloride and the phenol derivative are sequentially subjected to esterification and Fries rearrangement to obtain an ultraviolet absorber, then the olefin is subjected to a Wulff-Ziegler reaction to obtain a halogenated olefin, and finally the halogenated olefin and the ultraviolet absorber are subjected to a quaternary ammonium salt reaction to obtain the modifier. The modified PBAT, polyamide 6, and antioxidant are mixed and then fed into a double-screw extruder to melt extrude at a temperature of 230-240 DEG C to obtain the degradable PA6 composite modified plastic.

2. The degradable PA6 composite modified plastic according to claim 1, characterized in that, The modified PBAT, polyamide 6, and antioxidant are mixed and then fed into a double-screw extruder to melt extrude at a temperature of 230-240 DEG C to obtain the degradable PA6 composite modified plastic.

3. The degradable PA6 composite modified plastic according to claim 1, characterized in that, The antioxidant used in the step of preparing the degradable PA6 composite modified plastic is one of antioxidant 1010, antioxidant 1035, and antioxidant 1076. The modified PBAT used in the step of preparing the degradable PA6 composite modified plastic is prepared by the following steps:

4. The degradable PA6 composite modified plastic according to claim 3, characterized in that, The PBAT, modifier, initiator, and antioxidant are mixed and then fed into a double-screw extruder to melt extrude at a temperature of 150-160 DEG C to obtain the modified PBAT.

5. The degradable PA6 composite modified plastic according to claim 3, characterized in that, The initiator used in the step of preparing the modified PBAT is at least one of benzoyl peroxide and dicumyl peroxide. The antioxidant used in the step of preparing the modified PBAT is antioxidant 168.

6. The degradable PA6 composite modified plastic according to claim 5, characterized in that, The mass ratio of the PBAT, modifier, initiator, and antioxidant used in the step of preparing the modified PBAT is 100:3-4:0.15-0.25:0.

1.

7. The degradable PA6 composite modified plastic according to claim 5, characterized in that, The modified PBAT used in the step of preparing the degradable PA6 composite modified plastic is prepared by the following steps:

8. The degradable PA6 composite modified plastic according to claim 5, characterized in that, The aromatic acyl chloride and the phenol derivative are sequentially subjected to esterification and Fries rearrangement to obtain an ultraviolet absorber, then the olefin is subjected to a Wulff-Ziegler reaction to obtain a halogenated olefin, and finally the halogenated olefin and the ultraviolet absorber are subjected to a quaternary ammonium salt reaction to obtain the modifier.

9. The degradable PA6 composite modified plastic according to claim 8, characterized in that, The aromatic acyl chloride used in the step of preparing the modifier is one of nicotinoyl chloride and isonicotinoyl chloride; the phenol derivative used in the step of preparing the modifier is one of 3-dodecyloxyphenol and 4-dodecyloxyphenol; and the olefin used in the step of preparing the modifier is one of 2-methyl-1-dodecene and 2-methyl-1-tetradecene. ​ 10. The degradable PA6 composite modified plastic according to claim 9, characterized in that, ​

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