CN115926406B - Full-degradable high-barrier polyester composite film material, preparation method and application - Google Patents
Full-degradable high-barrier polyester composite film material, preparation method and application Download PDFInfo
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 42
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
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- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of polymer composite materials, and discloses a fully-degradable high-barrier polyester composite film material, a preparation method and application thereof, wherein the fully-degradable high-barrier polyester composite film material comprises the following components: p34HB, PLA, PLLA-PBA-PLLA and nano TiO 2 Organic tin catalyst and polyether polyol modified montmorillonite. The fully-degradable high-barrier polyester composite film material has excellent ductility, tensile strength, tear resistance and water-oxygen barrier property, and can be fully degraded in a short time.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a fully-degradable high-barrier polyester composite film material, a preparation method and application thereof.
Background
In the field of packaging, especially packaging films, plastic materials such as PE, PP, PET films are still the main stream of packaging films, and the plastic materials from petroleum base have excellent processability, good mechanical properties and excellent barrier properties of partial materials such as PET. Despite its superior performance, its non-degradability also presents a series of environmental problems. Finding a packaging material that is also excellent in performance and is fully degradable remains a direction of efforts.
In the current degradable materials, besides the paper board, polyesters such as starch, polylactic acid and the like and biomass fibers are still mainstream. Starch has been intensively studied for its inexpensive price and wide sources and various articles for life and industry, such as starch-based films, starch tableware, etc., have been prepared by modification and compounding. However, starch has the natural defects of poor mechanical property and unstable performance, and can only be applied to the field with low requirement on mechanical property. The presence of polylactic acid changes this state of the art. Polylactic acid (PLA) is an aliphatic polyester, and lactic acid (2-hydroxypropionic acid) is used as a basic structural unit. PLA can be prepared by fermenting natural materials such as corn, or by polycondensation of lactic acid. PLA and its end products can be decomposed naturally into CO under composting condition 2 And water, which reduces the discharge amount of solid waste, is a green and environment-friendly biological source material. Polylactic acid has good biodegradability and processability, but is brittle and fragile, lacks elasticity and flexibility, so that the application of the polylactic acid is limited to a great extent, and the film is mainly applied to the packaging aspect, and the barrier property of the polylactic acid film material is poor and cannot be applied to the packaging field requiring good barrier property. For the strength modification of polylactic acid films, a certain research has been carried out at present, and different substances are added into polylactic acid by a blending or chemical modification mode. For example, zhang Wei (Wei Zhang, long Chen, yu Zhang; polymer.2009, 50:1311-1315.) greatly improves the flexibility of polylactic acid by blending the polyamide elastomer with the polylactic acid, but causes a serious decrease in the mechanical properties of the composite material.
Polyhydroxyalkanoate PHA is a new degradable resin which is recently developed, is an intracellular polyester synthesized by a plurality of microorganisms, is a natural high molecular biological material, and has a carbon neutralization index of 100% because the polyhydroxyalkanoate PHA can be completely prepared by fermentation. PHA has good biocompatibility, biodegradability and hot processing performance of plastics, and can realize substitution of plastics in partial scenes. In particular to the 4 th-generation product P34HB of PHA, which is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, the resin has obvious performance advantages, such as better mechanical property and barrier property, compared with the original PHA product in a comprehensive way. Although the performance of P34HB is improved compared with that of the primary PHA product, the mechanical property and the barrier property of the P34HB are still greatly different from those of high-performance plastics such as PET and the like, the cost is also higher, and the optimization of the performance and the cost is still the key of the use of the P34 HB.
Therefore, how to improve the mechanical properties and the water-oxygen barrier property of the degradable film material is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the fully degradable high-barrier polyester composite film material provided by the invention has excellent ductility, tensile strength, tear resistance and water-oxygen barrier property, and can be fully degraded in a short time.
The first aspect of the invention provides a fully-degradable high-barrier polyester composite film material, which comprises the following components: p34HB, PLA, PLLA-PBA-PLLA and nano TiO 2 Organic tin catalyst and polyether polyol modified montmorillonite.
Preferably, the fully-degradable high-barrier polyester composite film material comprises the following components in parts by mass: p34HB52-75 parts, PLA 24-36 parts, PLLA-PBA-PLLA 8-16 parts, nano TiO 2 1-2 parts of organic tin catalyst 0.5-1 part and polyether polyol modified montmorillonite 1.2-3 parts.
Preferably, the molecular structural formula of the P34HB is as follows:
wherein n=200-400, m=100-200.
According to the difference of n and m, the invention can realize differential mechanical property and barrier property, improve the m value and improve the flexibility of the material; the n value is increased, and the strength of the material can be improved. More preferably, n=300-400, m=100-150.
Preferably, the PLLA-PBA-PLLA is a block copolymer of poly (butylene adipate) -L-polylactic acid, the molecular general formula of the block copolymer is PLLAn-PBAm-PLLAn ', n, m, n' is the polymerization degree of each segment, and the molecular structural formula is as follows:
where n=20-32, m=50-100, n' =20-32.
The invention adopts PLLA-PBA-PLLA to greatly improve the compatibility among components and improve the toughness of the composite membrane material.
Preferably, the nano TiO 2 The grain diameter of the catalyst is 10-200nm, and the crystal form is anatase.
The invention adopts nano TiO 2 Can be used as a nucleating agent, effectively improves the crystallization speed of P34HB and PLA and perfects the crystal form, improves the uniformity of spherulites, shortens the spherulites of the P34HB by more than 20 percent, and reduces the crystallization temperature by about 10 ℃.
Preferably, the organotin-based catalyst is dibutyltin dilaurate and/or stannous octoate.
The organic tin catalyst is adopted to catalyze the polyester to realize the transesterification reaction, and particularly can catalyze the reaction among PLLA-PBA-PLLA, PLA and P34HB in a system, thereby being beneficial to improving the compatibility and uniformity of substances.
Preferably, the molecular weight of the PLA is 200000-400000.
Preferably, the particle size of the polyether polyol modified lamellar montmorillonite is 200-400 meshes.
The second aspect of the invention provides a preparation method of the fully-degradable high-barrier polyester composite film material, which comprises the following steps:
mixing the P34HB, the PLA, the PLLA-PBA-PLLA and the nano TiO2, and carrying out melt extrusion to obtain a master batch;
and mixing the master batch, the organotin catalyst and the polyether polyol modified lamellar montmorillonite, and carrying out melt casting to form a film to obtain the full-degradable high-barrier polyester composite film material.
Preferably, the parameters of the melt extrusion include: the melt extrusion temperature is 190-220 ℃, the screw rotation speed is 150-200rad/min, and the residence time is 1-2min.
Preferably, the parameters of the melt-cast film include: the processing temperature is 185-225 ℃, the rotating speed of a casting roller is 0.8-1.2m/min, the rotating speed of a traction roller is 1.1-1.4m/min, the synchronous coefficient of the traction roller is 1-1.5, the tension of a winding roller is 2.5-3.5Kg, the synchronous coefficient of the winding roller is 0.2-0.5, and the temperature of a cooling roller is 20-50 ℃.
Preferably, the components are further included in a step of drying the components prior to mixing the components.
The third aspect of the invention provides the application of the fully-degradable high-barrier polyester composite film material in packaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fully-degradable high-barrier polyester composite film material is based on the good mechanical strength and certain barrier property of P34HB, and high-strength PLA is introduced, and the compatibility is improved by adding PLLA-PBA-PLLA with a wider crystallization temperature area and toughness, and the crystallization forms of the two are regulated; further introduce nano TiO 2 The film-forming agent has the functions of both the reinforcing agent and the crystallization accelerator, and can realize the improvement of the overall crystallization rate, thereby promoting the adjustment of the crystallization during film formation; the organic tin catalyst is added into the composite system, so that the transesterification reaction between polyester groups can be effectively promoted, and the overall uniformity of the composite material can be improved; the polyether polyol modified lamellar montmorillonite is based on the fact that the lamellar montmorillonite can effectively improve interlayer spacing after being modified, and promote dispersion of montmorillonite in a matrix, so that barrier property of the composite membrane material is greatly improved; the invention realizes the comprehensive improvement of the mechanical property and the barrier property of the membrane through the comprehensive action of the components.
(2) The fully-degradable high-barrier polyester composite film material has excellent ductility, tensile strength, tear resistance and water-oxygen barrier property, and can be fully degraded in a short time; wherein the elongation at break is 150-260%, the tensile strength is 24-35MPa, the transverse/longitudinal tearing strength is 82-135MPa, and the length is 25 muThe oxygen permeability of the m-thickness fully-degradable high-barrier polyester composite film material is 220-265cm 3 /(m 2 24 h.0.1 MPa) and a water vapor transmission rate of 125-150 g/(m) 2 24 hr.MPa), and the time required for complete degradation of the fully-degradable high-barrier polyester composite film material with the thickness of 50 mu m is 8-10 weeks under the condition of 25 ℃ of soil composting.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents, apparatus used in the examples below were obtained from conventional commercial sources, unless otherwise specified, or may be obtained by methods known in the art.
The preparation method of the polyether polyol modified montmorillonite used in the following examples can be referred to the preparation method in the invention patent with publication number CN1693549A, and specifically comprises the following steps:
s1, dissolving sodium montmorillonite in deionized water to form a suspension with the weight percent of 10, uniformly stirring, adding cetyltrimethylammonium bromide, stirring and reacting for 4 hours at the temperature of 60 ℃, and standing and hydrating for 24 hours to obtain a mixed solution; wherein, the addition amount of the hexadecyl trimethyl ammonium bromide is 24 percent of the mass of the sodium montmorillonite;
s2, dissolving polyether glycol in dimethylacetamide to form a solution, adding the solution into the mixed solution obtained in the step S1, stirring at a rotating speed of 150rmp, heating to 90 ℃ for dehydration, drying, grinding and sieving to obtain the polyether glycol-modified polyether glycol; wherein the mass of the polyether glycol is 10-30% of the mass of the sodium montmorillonite.
Example 1
The fully-degradable high-barrier polyester composite film material comprises the following components in parts by mass: p34HB52 parts, PLA 24 parts, PLLA-PBA-PLLA 8 parts, nano TiO 2 2 parts of organic tin catalyst 0.6 part and polyether polyol modified montmorillonite 2 parts.
The preparation method of the full-degradable high-barrier polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) P34HB, PLA, PLLA-PBA-PLLA and nano TiO 2 Uniformly mixing at the rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 190-220 ℃, the screw rotation speed is 180rad/min, and the residence time is 1.5min;
(3) Uniformly mixing the master batch with an organotin catalyst and polyether polyol modified lamellar montmorillonite at a rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-215 ℃, the rotating speed of the casting roller is 1m/min, the rotating speed of the traction roller is 1.2m/min, the synchronous coefficient of the traction roller is 1.2, the tension of the winding roller is 2.8Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 20 ℃.
In this embodiment, the following components are used:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=256 and m=142.
The molecular weight of PLA is 250000-350000.
PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and L-polylactic acid, and has the following molecular structural formula:
where n=26, m=85, n' =28.
Nanometer TiO 2 The particle size of the particles is 10nm, and the crystal form is anatase.
The organotin catalyst is a mixture of 50wt% of each of dibutyltin dilaurate and stannous octoate.
The particle size of the adopted polyether polyol modified lamellar montmorillonite is 300 meshes; the molecular weight of the polyether glycol used is 2200, and the mass of the polyether glycol is 22% of that of sodium montmorillonite.
Example 2
The fully-degradable high-barrier polyester composite film material comprises the following components in parts by mass: p34HB 75 parts, PLA 24 parts, PLLA-PBA-PLLA 8 parts, nano TiO 2 1.8 parts of organic tin catalyst 0.6 part and 2 parts of polyether polyol modified lamellar montmorillonite.
The preparation method of the full-degradable high-barrier polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) Uniformly mixing P34HB, PLA, PLLA-PBA-PLLA and nano TiO2 at a rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 195-215 ℃, the screw rotation speed is 180rad/min, and the residence time is 1.5min;
(3) Uniformly mixing the master batch with an organotin catalyst and polyether polyol modified lamellar montmorillonite at a rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-215 ℃, the rotating speed of the casting roller is 1m/min, the rotating speed of the traction roller is 1.2m/min, the synchronous coefficient of the traction roller is 1.2, the tension of the winding roller is 2.9Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 50 ℃.
In this embodiment, the following components are used:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=256 and m=142.
The molecular weight of PLA is 250000-350000.
PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and L-polylactic acid, and has the following molecular structural formula:
where n=26, m=85, n' =28.
Nanometer TiO 2 The grain diameter of the catalyst is 100nm, and the crystal form is anatase.
The organotin catalyst is a mixture of 50wt% of each of dibutyltin dilaurate and stannous octoate.
The particle size of the adopted polyether polyol modified lamellar montmorillonite is 300 meshes; the molecular weight of the polyether glycol used is 2200, and the mass of the polyether glycol is 22% of that of sodium montmorillonite.
Example 3
The fully-degradable high-barrier polyester composite film material comprises the following components in parts by mass: p34HB 62 parts, PLA 32 parts, PLLA-PBA-PLLA 12.5 parts, nano TiO 2 1.5 parts of organotin catalyst 0.8 parts and polyether polyol modified montmorillonite 2.2 parts.
The preparation method of the full-degradable high-barrier polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) Uniformly mixing P34HB, PLA, PLLA-PBA-PLLA and nano TiO2 at a rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 200-220 ℃, the screw rotation speed is 160rad/min, and the residence time is 2min;
(3) Uniformly mixing the master batch with an organotin catalyst and polyether polyol modified lamellar montmorillonite at a rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-215 ℃, the rotating speed of the casting roller is 1.2m/min, the rotating speed of the traction roller is 1.3m/min, the synchronous coefficient of the traction roller is 1.4, the tension of the winding roller is 3.2Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 35 ℃.
In this embodiment, the following components are used:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=325 and m=145.
PLA has a molecular weight of 300000-400000.
PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and L-polylactic acid, and has the following molecular structural formula:
where n=26, m=85, n' =30.
Nanometer TiO 2 The particle size of the particles is 50nm, and the crystal form is anatase.
The organotin catalyst is stannous octoate.
The particle size of the adopted polyether polyol modified lamellar montmorillonite is 250 meshes; the molecular weight of the polyether glycol used is 1800, and the mass of the polyether glycol is 25% of that of sodium montmorillonite.
Example 4
The fully-degradable high-barrier polyester composite film material comprises the following components in parts by mass: p34HB52 parts, PLA36 parts, PLLA-PBA-PLLA 16 parts, nano TiO 2 2 parts of organotin catalyst, 1 part of polyether polyol modified lamellar montmorillonite and 3 parts of polyether polyol modified lamellar montmorillonite.
The preparation method of the full-degradable high-barrier polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) Uniformly mixing P34HB, PLA, PLLA-PBA-PLLA and nano TiO2 at a rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 200-220 ℃, the screw rotation speed is 180rad/min, and the residence time is 1.5min;
(3) Uniformly mixing the master batch with an organotin catalyst and polyether polyol modified lamellar montmorillonite at a rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-220 ℃, the rotating speed of the casting roller is 1.1m/min, the rotating speed of the traction roller is 1.3m/min, the synchronous coefficient of the traction roller is 1.2, the tension of the winding roller is 3Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 35 ℃.
In this embodiment, the following components are used:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=350, m=124.
The molecular weight of PLA is 250000-350000.
PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and L-polylactic acid, and has the following molecular structural formula:
where n=28, m=80, n' =28.
Nanometer TiO 2 The grain diameter of the catalyst is 200nm, and the crystal form is anatase.
The organotin catalyst is dibutyl tin dilaurate.
The particle size of the adopted polyether polyol modified lamellar montmorillonite is 300 meshes; the molecular weight of the polyether glycol used is 1800, and the mass of the polyether glycol is 26% of that of sodium montmorillonite.
Comparative example 1 (differing from example 3 in that PLLA-PBA-PLLA was absent)
The polyester composite film material comprises the following components in parts by mass: p34HB 62 parts, PLA 32 parts, nano TiO 2 1.5 parts of organotin catalyst 0.8 parts and polyether polyol modified montmorillonite 2.2 parts.
The preparation method of the polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) Uniformly mixing P34HB, PLA and nano TiO2 at a rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 200-220 ℃, the screw rotation speed is 160rad/min, and the residence time is 2min;
(3) Uniformly mixing the master batch with an organotin catalyst and polyether polyol modified lamellar montmorillonite at a rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-215 ℃, the rotating speed of the casting roller is 1.2m/min, the rotating speed of the traction roller is 1.3m/min, the synchronous coefficient of the traction roller is 1.4, the tension of the winding roller is 3.2Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 35 ℃.
In this comparative example, the components used are specifically as follows:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=325 and m=145.
PLA has a molecular weight of 300000-400000.
Nanometer TiO 2 The particle size of the particles is 50nm, and the crystal form is anatase.
The organotin catalyst is stannous octoate.
The particle size of the adopted polyether polyol modified lamellar montmorillonite is 250 meshes; the molecular weight of the polyether glycol used is 1800, and the mass of the polyether glycol is 25% of that of sodium montmorillonite.
Comparative example 2 (differing from example 2 in that no organotin-based catalyst was contained)
The polyester composite film material comprises the following components in parts by mass: p34HB 75 parts, PLA 24 parts, PLLA-PBA-PLLA 8 parts, nano TiO 2 1.8 parts of polyether polyol modified lamellar montmorillonite and 2 parts of polyether polyol modified lamellar montmorillonite.
The preparation method of the polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) Uniformly mixing P34HB, PLA, PLLA-PBA-PLLA and nano TiO2 at a rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 195-215 ℃, the screw rotation speed is 180rad/min, and the residence time is 1.5min;
(3) Uniformly mixing the master batch and polyether polyol modified lamellar montmorillonite at the rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-215 ℃, the rotating speed of the casting roller is 1m/min, the rotating speed of the traction roller is 1.2m/min, the synchronous coefficient of the traction roller is 1.2, the tension of the winding roller is 2.9Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 50 ℃.
In this comparative example, the components used are specifically as follows:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=256 and m=142.
The molecular weight of PLA is 250000-350000.
PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and L-polylactic acid, and has the following molecular structural formula:
where n=26, m=85, n' =28.
Nanometer TiO 2 The grain diameter of the catalyst is 100nm, and the crystal form is anatase.
The particle size of the adopted polyether polyol modified lamellar montmorillonite is 300 meshes; the molecular weight of the polyether glycol used is 2200, and the mass of the polyether glycol is 22% of that of sodium montmorillonite.
Comparative example 3 (differing from example 3 in the use of other types of modified montmorillonite)
The polyester composite film material comprises the following components in parts by mass: p34HB 62 parts, PLA 32 parts, PLLA-PBA-PLLA 12.5 parts, nano TiO 2 1.5 parts of organotin catalyst 0.8 parts and hexadecyl trimethyl ammonium bromide modified montmorillonite 2.2 parts.
The preparation method of the polyester composite film material comprises the following steps:
(1) Vacuum drying the components at 50deg.C for 24 hr;
(2) Uniformly mixing P34HB, PLA, PLLA-PBA-PLLA and nano TiO2 at a rotating speed of 200rmp, and then carrying out melt extrusion and granulating to obtain a master batch; wherein, the parameters of the melt extrusion are as follows: the melt extrusion temperature is 200-220 ℃, the screw rotation speed is 160rad/min, and the residence time is 2min;
(3) Uniformly mixing the master batch with an organotin catalyst and cetyl trimethyl ammonium bromide modified montmorillonite at the rotating speed of 150rmp, and then carrying out melt casting to form a film to obtain a fully-degradable high-barrier polyester composite film material; wherein, parameters of the melt casting film forming are as follows: the processing temperature is 195-215 ℃, the rotating speed of the casting roller is 1.2m/min, the rotating speed of the traction roller is 1.3m/min, the synchronous coefficient of the traction roller is 1.4, the tension of the winding roller is 3.2Kg, the synchronous coefficient of the winding roller is 0.4, and the temperature of the cooling roller is 35 ℃.
In this comparative example, the components used are specifically as follows:
p34HB is a copolymer of 3-hydroxybutyric acid and 4-hydroxybutyric acid, and its molecular structural formula is as follows:
where n=325 and m=145.
PLA has a molecular weight of 300000-400000.
PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and L-polylactic acid, and has the following molecular structural formula:
where n=26, m=85, n' =30.
Nanometer TiO 2 The particle size of the particles is 50nm, and the crystal form is anatase.
The organotin catalyst is stannous octoate.
The adopted hexadecyl trimethyl ammonium bromide modified montmorillonite has the particle size of 250 meshes and is not modified by polyether glycol; the preparation method comprises the following steps: dissolving sodium montmorillonite in deionized water to form 10wt% suspension, stirring uniformly, adding cetyltrimethylammonium bromide, stirring at 60 ℃ for reaction for 4 hours, and standing for hydration for 24 hours to obtain cetyltrimethylammonium bromide modified montmorillonite; wherein, the addition amount of the hexadecyl trimethyl ammonium bromide is 24 percent of the mass of the sodium montmorillonite.
Performance testing
The polyester composite film materials prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to the related mechanical properties, water-oxygen barrier properties and degradability tests, and the results are shown in Table 1.
TABLE 1
As can be seen from the data in table 1:
compared with example 3, comparative example 1 was significantly reduced in both strength and water-oxygen barrier properties due to the absence of PLLA-PBA-PLL;
compared with the example 2, the comparative example 2 has no ester exchange reaction due to no addition of the organotin catalyst, so that the strength and the water-oxygen barrier property of the catalyst are obviously reduced;
compared with the example 3, the comparative example 3 adopts other types of modified montmorillonite, the mechanical property is reduced, the barrier property for oxygen is obviously reduced, and the invention is proved to obviously improve the barrier property for oxygen by adopting the specific modified montmorillonite.
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these are intended to be included in the scope of the present invention as defined in the appended claims.
Claims (7)
1. The full-degradable high-barrier polyester composite film material is characterized by comprising the following components in parts by mass: p34HB52-75 parts, PLA 24-36 parts, PLLA-PBA-PLLA 8-16 parts, nano TiO 2 1-2 parts of organotin catalyst 0.5-1 part and polyether polyol modified lamellar montmorillonite 1.2-3 parts;
the molecular structural formula of the P34HB is as follows:
；
wherein n=200-400, m=100-200;
the PLLA-PBA-PLLA is a block copolymer of polybutylene adipate and levorotatory polylactic acid, the molecular general formula of the PLLA-PBAm-PLLAn ', n, m, n' is the polymerization degree of each segment, and the molecular structural formula is as follows:
；
wherein n=20-32, m=50-100, n' =20-32;
the preparation method of the polyether polyol modified lamellar montmorillonite comprises the following steps:
s1, dissolving sodium montmorillonite in deionized water to form a suspension with the weight percent of 10, uniformly stirring, adding cetyltrimethylammonium bromide, stirring and reacting for 4 hours at the temperature of 60 ℃, and standing and hydrating for 24 hours to obtain a mixed solution; wherein, the addition amount of the hexadecyl trimethyl ammonium bromide is 24 percent of the mass of the sodium montmorillonite;
s2, dissolving polyether glycol in dimethylacetamide to form a solution, adding the solution into the mixed solution obtained in the step S1, stirring at a rotating speed of 150rpm, heating to 90 ℃ for dehydration, drying, grinding and sieving to obtain the polyether glycol-modified polyether glycol; wherein the mass of the polyether glycol is 10-30% of the mass of the sodium montmorillonite.
2. The fully degradable high barrier polyester composite film material according to claim 1, wherein the nano TiO 2 The grain diameter of the catalyst is 10-200nm, and the crystal form is anatase.
3. The fully degradable high barrier polyester composite film material according to claim 1, wherein the organotin-based catalyst is dibutyltin dilaurate and/or stannous octoate.
4. A method for preparing the fully degradable high barrier polyester composite film material as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
combining the P34HB, the PLA, the PLLA-PBA-PLLA and the nano TiO 2 Mixing, and melt-extruding to obtain master batch;
and mixing the master batch, the organotin catalyst and the polyether polyol modified lamellar montmorillonite, and carrying out melt casting to form a film to obtain the full-degradable high-barrier polyester composite film material.
5. The method of claim 4, wherein the parameters of melt extrusion include: the melt extrusion temperature is 190-220 ℃, the screw rotation speed is 150-200rad/min, and the residence time is 1-2min.
6. The method according to claim 4, wherein the parameters of the melt-cast film formation include: the processing temperature is 185-225 ℃, the rotating speed of a casting roller is 0.8-1.2m/min, the rotating speed of a traction roller is 1.1-1.4m/min, the synchronous coefficient of the traction roller is 1-1.5, the tension of a winding roller is 2.5-3.5Kg, the synchronous coefficient of the winding roller is 0.2-0.5, and the temperature of a cooling roller is 20-50 ℃.
7. Use of the fully degradable high barrier polyester composite film material of any one of claims 1 to 3 in packaging.
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| CN102501529A (en) * | 2011-11-18 | 2012-06-20 | 佛山佛塑料科技集团股份有限公司 | Biaxial drawing polylactic acid compound film with barrier property and preparation method thereof |
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