CN115521593B - High-toughness environment-friendly transparent composite film material and preparation method thereof - Google Patents
High-toughness environment-friendly transparent composite film material and preparation method thereof Download PDFInfo
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- CN115521593B CN115521593B CN202111639261.4A CN202111639261A CN115521593B CN 115521593 B CN115521593 B CN 115521593B CN 202111639261 A CN202111639261 A CN 202111639261A CN 115521593 B CN115521593 B CN 115521593B
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 21
- 239000004626 polylactic acid Substances 0.000 claims abstract description 21
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 20
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- -1 polybutylene terephthalate Polymers 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 11
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 11
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000002118 epoxides Chemical class 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 3
- 229940067597 azelate Drugs 0.000 claims description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 19
- 230000003078 antioxidant effect Effects 0.000 abstract description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2431/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a high-toughness environment-friendly transparent composite film material, which comprises the following preparation raw materials in parts by weight: 71-138 parts of polyester polymer, 0.1-5 parts of crystallization auxiliary agent, 0.1-1.5 parts of chain extender and 0.1-5 parts of stabilizer. The invention can improve the mechanical property of polymer melt and improve the tearing resistance and the tensile property by adopting the epoxy chain extender and the polyvinyl acetate with the viscosity of 4-6 ten thousand Pa.s, and can improve the transparency of the composite film and the bonding capability with paper products by adopting the oxide type inorganic nucleating agent to react with polylactic acid with the molecular weight of 2-25 ten thousand daltons so as to recrystallize the polymer melt. Meanwhile, the anti-aging capability of the composite membrane is improved and the service life of the composite membrane is prolonged by adopting the synergistic effect of the hindered phenol antioxidant and the phosphite antioxidant.
Description
Technical Field
The invention relates to a high-toughness environment-friendly transparent composite film material, relates to C08L, and particularly relates to the field of compositions of high-molecular compounds.
Background
Along with the continuous acceleration of the life pace of people, various disposable products are produced, the serious environmental pollution problem is caused by the large-scale use of the disposable products, the large-scale paper plastic products can be recycled by the outer paper products, but the inner plastic products are made of polyethylene or polypropylene, the recycling can not be realized, the disposable products are not degradable, and the separation cost of the paper products and the plastic products is high, so that the large number of disposable paper plastic products are polluted by waste. The environment-friendly degradable lactic acid polymer is adopted as the paper plastic product for film coating, so that the biodegradation of the paper plastic product can be realized, but the mechanical property of the lactic acid polymer is poor, and the prepared film coated product has poor tensile property and impact resistance, so that the polylactic acid film needs to be modified.
The Chinese patent No. 202011011516.8 discloses a degradable polyester synthetic paper and a preparation method thereof, which adopts the mixed synergistic effect of polyester material, polylactic acid and polypropylene, improves the degradation performance of the product, reduces the density of the synthetic paper, lightens the product, but the introduced polypropylene cannot be decomposed in the environment, and cannot realize complete degradation of the composite paper. Chinese patent No. CN202011493666.7 discloses an antioxidant degradable film and its preparation method, wherein hydrophobic filler and titanium dioxide are introduced to improve water resistance and mechanical strength of polyester material, but excessive filler addition can reduce compatibility of filler and polymer, and affect mechanical properties of polymer film.
Disclosure of Invention
In order to prepare the transparent composite film material with good degradation effect and good mechanical property, the first aspect of the invention provides a high-toughness environment-friendly transparent composite film material, which comprises the following preparation raw materials in parts by weight: 71-138 parts of polyester polymer, 0.1-5 parts of crystallization auxiliary agent, 0.1-1.5 parts of chain extender and 0.1-5 parts of stabilizer.
As a preferred embodiment, the polyester polymer is selected from one or a combination of several of polylactic acid, polybutylene terephthalate, polyethylene terephthalate, polyarylate and polyvinyl acetate.
As a preferred embodiment, the polyester-based polymer is a combination of polylactic acid, polybutylene terephthalate, and polyvinyl acetate.
As a preferred embodiment, the weight ratio of polylactic acid, polybutylene terephthalate, and polyvinyl acetate is (70-98): (0.5-30): (0.5-10).
As a preferred embodiment, the weight ratio of polylactic acid, polybutylene terephthalate and polyvinyl acetate is (70-92): (2-25): (3-8).
As a preferred embodiment, the weight ratio of polylactic acid, polybutylene terephthalate and polyvinyl acetate is 92:2:3.
as a preferred embodiment, the polylactic acid has a molecular weight of 2 to 25 kilodaltons and a melt index of 1 to 30g/10min at 190 ℃.
As a preferred embodiment, the polybutylene terephthalate is selected from one or a combination of several of polybutylene adipate terephthalate, polybutylene azelate terephthalate and polybutylene sebacate terephthalate.
As a preferred embodiment, the polybutylene adipate-terephthalate has a melt flow rate of 2.5 to 4.5g/10min at 190 ℃.
As a preferred embodiment, the polyvinyl acetate has a viscosity at room temperature of 40000-60000pa.s.
As a preferred embodiment, the crystallization aid is a nucleating agent selected from one or a combination of several of inorganic nucleating agents, organic nucleating agents, polymer nucleating agents and beta-crystal nucleating agents.
As a preferred embodiment, the inorganic nucleating agent is selected from one or a combination of several of oxide nucleating agent, rare earth metal nucleating agent, calcium carbonate nucleating agent, mica nucleating agent and carbon black nucleating agent.
As a preferred embodiment, the nucleating agent is an oxide nucleating agent. The oxide nucleating agent is adopted to react with polylactic acid and polybutylene adipate terephthalate, so that the polymer can be recrystallized in a melt state, the dispersion compatibility among polymer melts is increased, and the transparency and the melt strength of the polymer are improved.
As a preferred embodiment, the chain extender is selected from one or a combination of a plurality of difunctional acid derivatives, acid anhydrides, epoxides, alcohol chain extenders, amine chain extenders and ether chain extenders.
As a preferred embodiment, the chain extender is a low molecular weight epoxide.
The applicant finds that polylactic acid and polybutylene adipate terephthalate are jointly reacted in the experimental process, the molecular mass of a polymer is reduced due to thermal degradation and hydrolysis in the preparation process, the number of carboxyl ends is increased, a generated polymer melt is easy to crack, the film forming difficulty is high, the brittleness of the generated film material is high, wrinkles and fish eyes are easy to shrink in the cooling process of the film coating material, the tearing strength of the film coating layer is low, the mechanical property is poor, the mechanical property of the polymer melt can be improved by introducing an epoxy chain extender and polyvinyl acetate with the viscosity of 4-6 ten thousand Pa.s, the tearing resistance and the tensile property are improved, and the possible reasons are hypothesized as follows: the polymer melt generates a large number of carboxyl ends due to degradation reaction in the high-temperature processing process, the reaction activity is strong, the polyvinyl acetate and the chain extender can react among the carboxyl ends, the hydroxyl groups and the amino groups after being introduced, and the thermally decomposed small molecular weight polymers are repolymerized, so that 'bridging' is formed among the small molecular weight polymers to improve the molecular weight of the polymers, thereby increasing the viscosity of a polymer system, improving the melt strength and improving the tensile property and the tearing resistance of the laminated layer.
As a preferred embodiment, the stabilizer includes an antioxidant and an ultraviolet absorber.
As a preferred embodiment, the weight ratio of the antioxidant to the ultraviolet absorber is 1: (0.3-0.8).
As a preferred embodiment, the weight ratio of the antioxidant to the ultraviolet absorber is 1:0.5.
as a preferred embodiment, the antioxidant is selected from one or a combination of several of amine-type antioxidants, phenol-type antioxidants, phosphoric acid compound antioxidants and heterocyclic molecular antioxidants.
As a preferred embodiment, the antioxidant is a combination of a hindered phenol antioxidant and a phosphoric acid compound antioxidant.
As a preferred embodiment, the hindered phenol type antioxidant is a combination of antioxidant 1076 and antioxidant 168.
As a preferred embodiment, the weight ratio of antioxidant 1076 to antioxidant 168 is 1: (1-1.5).
As a preferred embodiment, the weight ratio of antioxidant 1076 to antioxidant 168 is 1:1.2.
in a preferred embodiment, the ultraviolet absorber is one selected from the group consisting of a benzophenone ultraviolet absorber, a triazine ultraviolet absorber, a phosphoramide ultraviolet absorber, and a hindered amine ultraviolet absorber.
As a preferred embodiment, the ultraviolet absorber is a hindered amine ultraviolet absorber.
The second aspect of the invention provides a preparation method of a high-toughness environment-friendly transparent composite film material, which comprises the following steps:
(1) The preparation raw materials are weighed according to the weight parts and mixed by a high-speed mixer, and the mixing speed is 500-1500rpm. Mixing for 5-20min to obtain a mixture;
(2) Adding the mixture obtained in the step 1 into a double-screw extruder for shearing dispersion, extruding and granulating, wherein the temperature of the double-screw extruder is 140-240 ℃, the rotating speed is 200-500rpm, and the ratio of the length of the screw to the diameter of the screw is (35-55): 1.
as a preferred embodiment, the high-speed mixer has a mixing speed of 500-1200rpm, a mixing time of 5-20min, a twin-screw extruder temperature of 190-220 ℃, a twin-screw extruder speed of 250-400rpm, and a screw length to diameter ratio of (36-52): 1.
the applicant found that in the high-speed mixing process of the high-speed mixer, the stabilizer with low melting point, the crystallization aid and the chain extender can be coated on the surface of the polyester polymer due to frictional heat, so that the dispersion of the aid in the polymer melt is uniform, the mixture is further uniformly mixed by matching the temperature and the rotating speed of the double-screw extruder, and the mechanical property of the melt is improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the high-toughness environment-friendly transparent composite film material, the mechanical property of a polymer melt can be improved by adopting the epoxy chain extender and the polyvinyl acetate with the viscosity of 4-6 ten thousand Pa.s, and the tearing resistance and the tensile property are improved.
(2) According to the high-toughness environment-friendly transparent composite film material, the oxide type inorganic nucleating agent is adopted to react with polylactic acid with the molecular weight of 2-25 ten thousand daltons, so that the polymer melt is recrystallized, and the transparency of the composite film and the binding capacity with paper products are improved.
(3) According to the high-toughness environment-friendly transparent composite film material, the ageing resistance of the composite film is improved and the service life of the composite film is prolonged by adopting the synergistic effect of the hindered phenol antioxidant and the phosphite antioxidant.
(4) The high-toughness environment-friendly transparent composite film material provided by the invention can be biodegraded under certain conditions by adopting polylactic acid, polybutylene terephthalate and polyvinyl acetate for combined blending, and has no environmental protection and pressure maintaining capability.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In addition, the raw materials used are commercially available unless otherwise indicated.
Example 1
The high-toughness environment-friendly transparent composite film material comprises the following preparation raw materials in parts by weight: 97 parts of polyester polymer, 0.5 part of crystallization auxiliary agent, 0.5 part of chain extender and 2 parts of stabilizer.
The polyester polymer is a combination of polylactic acid, polybutylene terephthalate and polyvinyl acetate, and the weight ratio is 92:2:3, a step of; the polylactic acid has a molecular weight of 3.8 kilodaltons, a melt index of 4.5g/10min at 190 ℃ and is available from Nature works, USA under the trade mark 4032D; the polybutylene terephthalate is polybutylene adipate terephthalate, and the melt flow rate at 190 ℃ is 4.5g/10min, and is purchased from Jin Huizhao long with the trade name Ecoworld; the polyvinyl acetate has a viscosity of 50000Pa.s at room temperature and is purchased from Beijing Oriental petrochemical Co., ltd, and the model is BJ-235.
The crystallization aid is an oxide nucleating agent, and is purchased from Ruiqite and has the brand name RQT-CH.
The chain extender is a low molecular weight epoxide, commercially available from Jiayi under the brand SG-20.
The stabilizer comprises an antioxidant and an ultraviolet absorber, and the weight ratio is 1:0.5.
the antioxidant is a combination of an antioxidant 1076 and an antioxidant 168, and the weight ratio is 1:1.2; the ultraviolet absorber is a hindered amine ultraviolet absorber, the model is UV-770, and the ultraviolet absorber is purchased from BASF corporation of Germany.
The preparation method of the high-toughness environment-friendly transparent composite film material comprises the following steps:
(1) The preparation raw materials are weighed according to parts by weight, mixed by a high-speed mixer, and the mixing speed is 1200rpm. Mixing for 5min to obtain a mixture;
(2) Adding the mixture obtained in the step 1 into a double-screw extruder for shearing dispersion, extruding and granulating, wherein the temperature of the double-screw extruder is 210 ℃, the rotating speed is 350rpm, and the ratio of the length of the screw to the diameter of the screw is 45:1.
example 2
The preparation method of the high-toughness environment-friendly transparent composite film material comprises the following specific steps of example 1, wherein the specific steps are that the combination of polylactic acid, polybutylene adipate, and polyvinyl acetate is 85:7:5.
the mixing speed of the high-speed mixer was 500rpm, the mixing time was 20min, the temperature of the twin-screw extruder was 220℃and the rotational speed of the twin-screw extruder was 360rpm.
Example 3
A high-toughness environment-friendly transparent composite film material and a preparation method thereof are provided, and the specific steps are the same as in example 1, wherein the difference is 98 parts of polyester polymer, 0.7 part of crystallization auxiliary agent, 0.3 part of chain extender and 1 part of stabilizer.
Polylactic acid, polybutylene adipate terephthalate and polyvinyl acetate, wherein the weight ratio of the polylactic acid to the polybutylene adipate to the polyvinyl acetate is 70:25:3.
the mixing speed of the high-speed mixer was 500rpm, the mixing time was 15min, the twin-screw extruder temperature was 190℃and the twin-screw extruder speed was 400rpm.
Example 4
A high-toughness environment-friendly transparent composite film material and a preparation method thereof are provided, and the specific steps are the same as in example 1, wherein the difference is 98 parts of polyester polymer, 0.7 part of crystallization auxiliary agent, 0.8 part of chain extender and 0.5 part of stabilizer.
Polylactic acid, polybutylene adipate terephthalate and polyvinyl acetate, wherein the weight ratio of the polylactic acid to the polybutylene adipate to the polyvinyl acetate is 80:10:8.
the mixing speed of the high-speed mixer was 1000rpm, the mixing time was 10min, the temperature of the twin-screw extruder was 190℃and the rotational speed of the twin-screw extruder was 250rpm.
Performance test:
the composite membrane material particles prepared in examples 1-4 are prepared into a high-toughness environment-friendly transparent composite membrane by adopting the prior art.
1. Tensile strength: the tensile strength of the prepared transparent composite film is tested according to the GB/T13022 standard.
2. Elongation at break: the elongation at break of the transparent composite film prepared according to the GB/T13022 standard test.
3. Right angle tear Strength: the right angle tear strength of the prepared transparent composite film is tested according to GB/T16578 standard.
4. Biological decomposition rate: the prepared transparent composite film is tested according to GB/T19277.1 standard for biological decomposition rate. Tests were performed according to the above criteria and the test results are shown in table 1.
TABLE 1
Claims (3)
1. The high-toughness environment-friendly transparent composite film material is characterized by comprising the following preparation raw materials in parts by weight: 71-138 parts of polyester polymer, 0.1-5 parts of crystallization auxiliary agent, 0.1-1.5 parts of chain extender and 0.1-5 parts of stabilizer;
the polyester polymer is a combination of polylactic acid, polybutylene terephthalate and polyvinyl acetate;
the polybutylene terephthalate is selected from one or a combination of a plurality of polybutylene adipate terephthalate, polybutylene azelate terephthalate and polybutylene sebacate terephthalate;
the molecular weight of the polylactic acid is 3.8 ten thousand daltons, and the melt index at 190 ℃ is 4.5g/10min;
the viscosity of the polyvinyl acetate at room temperature is 40000-60000Pa.s;
the nucleating agent is an oxide nucleating agent;
the chain extender is a low molecular weight epoxide.
2. The high-toughness environmentally friendly transparent composite film material according to claim 1, wherein the polybutylene adipate-terephthalate has a melt flow rate of 2.5-4.5g/10min at 190 ℃.
3. A method for preparing the high-toughness environment-friendly transparent composite film material according to any one of claims 1-2, which is characterized by comprising the following steps:
(1) Weighing the preparation raw materials in parts by weight, mixing by using a high-speed mixer at 500-1500rpm for 5-20min to obtain a mixture;
(2) Adding the mixture obtained in the step 1 into a double-screw extruder for shearing dispersion, extruding and granulating, wherein the temperature of the double-screw extruder is 140-240 ℃, the rotating speed is 200-500rpm, and the ratio of the length of the screw to the diameter of the screw is (35-55): 1.
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