阅读说明：本技术 一种可降解高阻隔乳液及其制备方法和应用 (Degradable high-barrier emulsion and preparation method and application thereof ) 是由 冯亮 黎坛 王恩飞 李朝辉 于 2021-09-18 设计创作，主要内容包括：本发明提供了一种降解高阻隔乳液及其制备方法和应用,乳液以重量份数计,包括以下原料：70-90份聚3-羟基丁酸酯-3-羟基戊酸酯共聚物(PHBV),100-200份溶剂,5-10份右旋聚乳酸(PDLA),0.1-0.3份引发剂,0.1-0.2份扩链剂,1-5份改性纳米蒙脱土,1-2份聚乙二醇,300-800份水,1-5份乳化剂和0.5-2份水溶性抗菌剂。上述乳液具有优异阻隔性能；还具有优异可降解性；应用在可降解薄膜上,使得薄膜能够达到软包装的阻隔性能,大大扩展可降解薄膜的使用范围,具有优异的应用前景。(The invention provides a degradable high-barrier emulsion and a preparation method and application thereof, wherein the emulsion comprises the following raw materials in parts by weight: 70-90 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate copolymer (PHBV), 100-200 parts of solvent, 5-10 parts of poly (D-lactic acid) (PDLA), 0.1-0.3 part of initiator, 0.1-0.2 part of chain extender, 1-5 parts of modified nano-montmorillonite, 1-2 parts of polyethylene glycol, 800 parts of 300-hydroxy butyrate, 1-5 parts of emulsifier and 0.5-2 parts of water-soluble antibacterial agent. The emulsion has excellent barrier property; also has excellent degradability; the composite material is applied to the degradable film, so that the film can achieve the barrier property of flexible packages, the application range of the degradable film is greatly expanded, and the composite material has excellent application prospect.)

1. A degradable high-barrier emulsion comprises the following raw materials in parts by weight:

70-90 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate copolymer, 100-200 parts of solvent, 5-10 parts of poly (D-lactic acid), 0.1-0.3 part of initiator, 0.1-0.2 part of chain extender, 1-5 parts of modified nano-montmorillonite, 1-2 parts of polyethylene glycol, 300-800 parts of water, 1-5 parts of emulsifier and 0.5-2 parts of water-soluble antibacterial agent.

2. The degradable high-barrier emulsion of claim 1, wherein the number average molecular weight of the poly 3-hydroxybutyrate-3-hydroxyvalerate copolymer is 5000-12000 g/mol.

3. The degradable high-barrier emulsion of claim 1, wherein the solvent is selected from a mixed solvent of chloroform and ethanol;

the initiator is p-toluenesulfonic acid;

the chain extender is selected from basf joncryl ADR-4368-CS;

the molecular weight of the polyethylene glycol is 500-3000 g/mol.

4. The degradable high-barrier emulsion of claim 1, wherein the emulsifier is selected from one or more of tween 20, tween 21, tween 40, tween 41, tween 80, tween 81 and tween 85.

5. The degradable high barrier emulsion of claim 1, wherein the antimicrobial agent is selected from aminopropylbiguanide and/or polyhexamethylene biguanide.

6. A preparation method of the degradable high-barrier emulsion of any one of claims 1 to 5, comprising the following steps:

mixing PHBV, a solvent, PDLA, an initiator and a chain extender, stirring for dissolving, pressurizing and heating for copolymerization reaction to obtain a PHBV/PDLA copolymer;

mixing the modified nano montmorillonite with polyethylene glycol, and uniformly mixing the mixture with a PHBV/PDLA copolymer to obtain a mixture;

mixing water and an emulsifier to obtain a pre-emulsion, mixing the pre-emulsion with the mixture, stirring at a high speed and ultrasonically dispersing to obtain an oil-in-water emulsion, cooling, reducing the pressure, blowing air, adding an antibacterial agent after the content of VOC is reduced to below 30g/L, and reacting to obtain the degradable high-barrier emulsion.

7. The preparation method according to claim 6, wherein the temperature of the copolymerization reaction is 70-90 ℃ and the time of the copolymerization reaction is 2-6 h.

8. The production method according to claim 6, wherein the high-speed stirring speed is 6000 to 20000 rpm;

the frequency of ultrasonic dispersion is 500-200000 Hz, and the power is more than or equal to 1000W.

9. A degradable high-barrier film, which is characterized in that the degradable high-barrier emulsion according to any one of claims 1 to 5 or the degradable high-barrier emulsion prepared by the preparation method according to any one of claims 6 to 8 is coated on the surface of the degradable film.

Technical Field

The invention belongs to the technical field of barrier fluids, and particularly relates to a degradable high-barrier emulsion and a preparation method and application thereof.

Background

In recent years, with the popularization of plastic forbidden requirements at home and abroad, more and more degradable plastics are applied to the lives of people. In the foreseeable future, the comprehensive application of the degradable plastic to people in terms of living aspects is a necessary situation, and the functional high-barrier package can also meet the arrival of the degradable plastic. However, the oxygen transmission capacity and the water vapor transmission capacity of the existing degradable plastic are both one order of magnitude larger than those of the existing conventional high-barrier K film, so that the degradable plastic film cannot be used for high-barrier packaging.

Disclosure of Invention

In view of the above, the present invention aims to provide a degradable high-barrier emulsion, a preparation method and an application thereof, wherein the emulsion enables a degradable film to have high barrier property.

The invention provides a degradable high-barrier emulsion which comprises the following raw materials in parts by weight:

70-90 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate copolymer (PHBV), 100-200 parts of solvent, 5-10 parts of poly (D-lactic acid) (PDLA), 0.1-0.3 part of initiator, 0.1-0.2 part of chain extender, 1-5 parts of modified nano-montmorillonite, 1-2 parts of polyethylene glycol, 800 parts of 300-hydroxy butyrate, 1-5 parts of emulsifier and 0.5-2 parts of water-soluble antibacterial agent.

In the invention, the number average molecular weight of the poly-3-hydroxybutyrate-3-hydroxyvalerate copolymer (PHBV) is 5000-30000 g/mol.

In the present invention, the solvent is selected from a mixed solvent of chloroform and ethanol;

the initiator is p-toluenesulfonic acid;

the chain extender is selected from basf joncrylADR-4368-CS;

the molecular weight of the polyethylene glycol is 500-3000 g/mol.

In the invention, the molecular weight of the poly (D-lactic acid) (PDLA) is 5000-12000 g/mol; the PDLA is added, so that the high-barrier emulsion provided by the invention can be hydrolyzed in the PDLA in nature to generate an acid environment after being discarded, and the action of an antibacterial agent is inhibited in the acid environment, so that the decomposition of PHBV is promoted better, and the control on the degradability of a product is achieved.

In the present invention, the emulsifier is selected from one or more of tween 20, tween 21, tween 40, tween 41, tween 80, tween 81 and tween 85.

In the present invention, the antimicrobial agent is selected from aminopropylbiguanide and/or polyhexamethylene biguanide. The antibacterial grade can provide an antibacterial type for the high-barrier emulsion, and the degradation time is controlled by controlling the addition amount of the antibacterial agent and the PDLA. The use of the antibacterial agent enables the PHBV to maintain barrier properties for a long time under aseptic conditions in an ambient temperature environment.

The invention provides a preparation method of the degradable high-barrier emulsion, which comprises the following steps:

mixing PHBV, a solvent, PDLA, an initiator and a chain extender, stirring for dissolving, pressurizing and heating for copolymerization reaction to obtain a PHBV/PDLA copolymer;

mixing the modified nano montmorillonite with polyethylene glycol, and uniformly mixing the mixture with a PHBV/PDLA copolymer to obtain a mixture;

mixing water and an emulsifier to obtain a pre-emulsion, mixing the pre-emulsion with the mixture, stirring at a high speed and ultrasonically dispersing to obtain an oil-in-water emulsion, cooling, reducing the pressure, blowing air, adding an antibacterial agent after the content of VOC is reduced to below 30g/L, and reacting to obtain the degradable high-barrier emulsion.

In the invention, the temperature of the copolymerization reaction is 70-90 ℃, and the time of the copolymerization reaction is 2-6 h.

In the invention, the high-speed stirring speed is 6000-20000 rpm;

the frequency of ultrasonic dispersion is 500-200000 Hz, and the power is more than or equal to 1000W.

The invention provides a degradable high-barrier film, and the degradable high-barrier emulsion prepared by the method or the degradable high-barrier emulsion prepared by the method in the technical scheme is coated on the surface of the degradable film.

In the invention, the thickness of the emulsion coating is 0.5-5 microns, preferably 1-4 microns; in a specific embodiment, the emulsion coating has a thickness of 2 microns.

In the present invention, the degradable film is preferably a biaxially oriented polylactic acid film (BOPLA).

The invention provides a degradable high-barrier emulsion which comprises the following raw materials in parts by weight: 70-90 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate copolymer (PHBV), 100-200 parts of solvent, 5-10 parts of poly (D-lactic acid) (PDLA), 0.1-0.3 part of initiator, 0.1-0.2 part of chain extender, 1-5 parts of modified nano-montmorillonite, 1-2 parts of polyethylene glycol, 800 parts of 300-hydroxy butyrate, 1-5 parts of emulsifier and 0.5-2 parts of water-soluble antibacterial agent. The emulsion has excellent barrier property; also has excellent degradability; the composite material is applied to the degradable film, so that the film can achieve the barrier property of flexible packages, the application range of the degradable film is greatly expanded, and the composite material has excellent application prospect.

Detailed Description

To further illustrate the present invention, the following examples are provided to describe in detail a degradable high-barrier emulsion and its preparation method and application, but they should not be construed as limiting the scope of the present invention.

Example 1

S1: 75 parts of PHBV with molecular weight of 6000-7000g/mol are taken and stirred and dissolved in 140 parts of solvent (mixed solvent of chloroform and ethanol with volume ratio of 5: 2), 7.5 parts of PDLA is added and dissolved at the same time, 0.15 part of initiator p-toluenesulfonic acid and 0.15 part of chain extender BASF joncrylADR-4368-CS are added and stirred and dissolved. After the dissolution is finished, pressurizing to more than 0.2Mpa, heating to 76 ℃, and carrying out copolymerization reaction for 3.5 hours to generate a PHBV/PDLA copolymer of a macromolecular chain;

s2: stirring and dissolving 2.5 parts of modified nano-montmorillonite and 1.2 parts of 1200g/mol PEG in a proper amount of solvent, and mixing and stirring the solution and the solution obtained in the step S1 uniformly;

s3: adding 2 parts of tween 80 into 400 parts of deionized water, stirring to obtain a pre-emulsion, adding the solution obtained in the step S2 into the pre-emulsion, and performing high-speed stirring and shearing at 12000rpm and ultrasonic dispersion at 1500kHz for 20min to obtain o/w type pickering emulsion;

s4: cooling the emulsion obtained in the step S3 to normal temperature, reducing the pressure by using a vacuum pump, and simultaneously performing air purging to reduce the pressure to be below 5kpa and reduce VOC to be below 30 g/L;

s5, adding 0.7 part of water-soluble aminopropyl biguanide into the emulsion obtained in the step S4, and stirring for reaction for 1 hour to obtain the degradable high-barrier emulsion.

The degradable high-barrier emulsion is coated on a biaxially oriented polylactic acid film (BOPLA) with the coating thickness of 2.0 microns to obtain the degradable high-barrier film.

Example 2

S1: 9000g/mol PHBV82 parts with molecular weight of 7000-charge are taken, stirred and dissolved in 160 parts of solvent (mixed solvent of chloroform and ethanol with the volume ratio of 3: 1), 7 parts of PDLA are added and dissolved, then 0.18 part of initiator p-toluenesulfonic acid and 0.15 part of chain extender BASF joncrylADR-4368-CS are added and stirred and dissolved. After the dissolution is finished, pressurizing to more than 0.2Mpa, heating to 75 ℃, and carrying out copolymerization reaction for 4.5 hours to generate PHBV/PDLA copolymer of macromolecular chains;

s2: stirring and dissolving 2.8 parts of modified nano montmorillonite and 1.5 parts of 1800g/mol PEG in a proper amount of solvent, and mixing and stirring the solution and the solution obtained in the step S1 uniformly;

s3: adding 2.5 parts of tween 21 into 520 parts of deionized water, stirring to obtain a pre-emulsion, adding the solution obtained in the step S2 into the pre-emulsion, and performing high-speed stirring and shearing at 15000rpm and ultrasonic dispersion at 1200kHz for 15min to obtain an o/w type pickering emulsion;

s4: cooling the emulsion obtained in the step S3 to normal temperature, reducing the pressure by using a vacuum pump, and simultaneously performing air purging to reduce the pressure to be below 5kpa and reduce VOC to be below 30 g/L;

s5, adding 0.8 part of water-soluble aminopropyl biguanide into the emulsion obtained in the step S4, and stirring and reacting for 1.2 hours to obtain the degradable high-barrier emulsion.

The degradable high-barrier emulsion is coated on a biaxially oriented polylactic acid film (BOPLA) with the coating thickness of 2.0 microns to obtain the degradable high-barrier film.

Example 3

S1: the molecular weight 7000-10000g/mol PHBV80 parts is taken, stirred and dissolved in 170 parts of solvent (mixed solvent of chloroform and ethanol with the volume ratio of 12: 5), simultaneously PDLA9 parts is added and dissolved, then 0.15 part of initiator p-toluenesulfonic acid and 0.18 part of chain extender BASF joncrylADR-4368-CS are added and stirred and dissolved. After the dissolution is finished, pressurizing to more than 0.2Mpa, heating to 76 ℃, and carrying out copolymerization reaction for 4.0 hours to generate a PHBV/PDLA copolymer of a macromolecular chain;

s2: stirring and dissolving 4.0 parts of modified nano montmorillonite and 1.8 parts of 1500g/mol PEG in a proper amount of solvent, and mixing and stirring the solution and the solution obtained in the step S1 uniformly;

s3: adding 3 parts of tween 41 into 600 parts of deionized water, stirring to obtain a pre-emulsion, adding the solution obtained in the step S2 into the pre-emulsion, and carrying out high-speed stirring and shearing at 18000rpm and ultrasonic dispersion at 1600kHz for 12min to obtain o/w type pickering emulsion;

s4: cooling the emulsion obtained in the step S3 to normal temperature, reducing the pressure by using a vacuum pump, and simultaneously performing air purging to reduce the pressure to be below 5kpa and reduce VOC to be below 30 g/L;

s5, adding 1.2 parts of water-soluble polyhexamethylene biguanide into the emulsion obtained in the step S4, and stirring for reaction for 1.2 hours to obtain the degradable high-barrier emulsion.

The degradable high-barrier emulsion is coated on a biaxially oriented polylactic acid film (BOPLA) with the coating thickness of 2.0 microns to obtain the degradable high-barrier film.

Example 4

S1: 85 parts of PHBV with molecular weight of 6000-7000g/mol are taken and stirred and dissolved in 180 parts of solvent (mixed solvent of chloroform and ethanol with volume ratio of 7: 2), 6 parts of PDLA is added and dissolved at the same time, 0.13 part of initiator p-toluenesulfonic acid and 0.15 part of chain extender BASF joncrylADR-4368-CS are added and stirred and dissolved. After the dissolution is finished, pressurizing to more than 0.2Mpa, heating to 80 ℃, and carrying out copolymerization reaction for 2.5 hours to generate PHBV/PDLA copolymer of macromolecular chains;

s2: stirring and dissolving 2 parts of modified nano montmorillonite and 1.5 parts of 2000g/mol PEG in a proper amount of solvent, and mixing and stirring the solution and the solution obtained in the step S1 uniformly;

s3: adding 2.8 parts of tween 41 into 650 parts of deionized water, stirring to obtain a pre-emulsion, adding the solution obtained in the step S2 into the pre-emulsion, and performing high-speed stirring and shearing at 18000rpm and ultrasonic dispersion at 800kHz for 15min to obtain an o/w type pickering emulsion;

s4: cooling the emulsion obtained in the step S3 to normal temperature, reducing the pressure by using a vacuum pump, and simultaneously performing air purging to reduce the pressure to be below 5kpa and reduce VOC to be below 30 g/L;

s5, adding 0.8 part of water-soluble polyhexamethylene biguanide into the emulsion obtained in the step S4, and stirring for reaction for 1 hour to obtain the degradable high-barrier emulsion.

The degradable high-barrier emulsion prepared in the embodiment 1-4 is coated on a biaxially oriented polylactic acid film (BOPLA) with the coating thickness of 2.0 microns to obtain the degradable high-barrier film.

TABLE 1 Performance test results for films prepared in examples 1-4

	Test standard	Unit of	Example 1	Example 2	Example 3	Example 4
							Oxygen transmission rate	GB/T 19789-2005	cm3/m2*24h	24.6	22.5	21.7	22.3
Antibacterial property	QB/T 2591-2003	％	98.3	99.2	99	97.5
							Time of degradation	GB/T 19277.1-2011	day	143	138	125	136

From the above examples, the invention provides a degradable high-barrier emulsion, which comprises the following raw materials in parts by weight: 70-90 parts of poly 3-hydroxybutyrate-3-hydroxyvalerate copolymer (PHBV), 100-200 parts of solvent, 5-10 parts of poly (D-lactic acid) (PDLA), 0.1-0.3 part of initiator, 0.1-0.2 part of chain extender, 1-5 parts of modified nano-montmorillonite, 1-2 parts of polyethylene glycol, 800 parts of 300-hydroxy butyrate, 1-5 parts of emulsifier and 0.5-2 parts of water-soluble antibacterial agent. The emulsion has excellent barrier property; also has excellent degradability; the composite material is applied to the degradable film, so that the film can achieve the barrier property of flexible packages, the application range of the degradable film is greatly expanded, and the composite material has excellent application prospect.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.