CN115521593A - 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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- CN115521593A CN115521593A CN202111639261.4A CN202111639261A CN115521593A CN 115521593 A CN115521593 A CN 115521593A CN 202111639261 A CN202111639261 A CN 202111639261A CN 115521593 A CN115521593 A CN 115521593A
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- composite film
- nucleating agent
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- transparent composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000002667 nucleating agent Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 21
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 20
- 239000004626 polylactic acid Substances 0.000 claims abstract description 20
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 18
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 18
- 229920000728 polyester Polymers 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 polybutylene terephthalate Polymers 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229940067597 azelate Drugs 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000003484 crystal nucleating agent Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 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
- 229920001230 polyarylate Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 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
- 239000003963 antioxidant agent Substances 0.000 abstract description 20
- 230000003078 antioxidant effect Effects 0.000 abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 238000012360 testing method Methods 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
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 150000001412 amines Chemical class 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 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
- 239000010452 phosphate Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-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
- 230000006978 adaptation Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000005665 alkyl butylene group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 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
- 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
- 238000010030 laminating Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004408 titanium dioxide 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 adopts the epoxy chain extender and the polyvinyl acetate with the viscosity of 4-6 ten thousand Pa.s to improve the mechanical property of the polymer melt and the tearing resistance and the tensile property, and adopts the reaction of the oxide inorganic nucleating agent and the polylactic acid with the molecular weight of 2-25 ten thousand daltons to ensure that the polymer melt is recrystallized, thereby improving the transparency of the composite film and the bonding capability with paper products. Meanwhile, the hindered phenol antioxidant and the phosphite antioxidant are adopted to realize the synergistic effect, so that the aging resistance of the composite film is improved, and the service life of the composite film is prolonged.
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 high-molecular compound compositions.
Background
With the continuous acceleration of the pace of life of people, various disposable products come into operation, the problem of serious environmental pollution is caused by the use of a large amount of disposable products, although the outer paper products of a large amount of paper-plastic products can be recycled, the inner plastic products are made of polyethylene or polypropylene, cannot be recycled and are not degradable, the cost for separating the paper products from the plastic products is high, and the environment is polluted by the abandonment of a large amount of disposable paper-plastic products. The biodegradable film is coated on the paper-plastic product by adopting the environment-friendly degradable lactic acid polymer, 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 coated film product has poor tensile property and impact resistance, so that the polylactic acid film needs to be modified.
The invention Chinese patent CN202011011516.8 discloses a degradable polyester synthetic paper and a preparation method thereof, which adopts the mixed synergistic effect of a polyester material, polylactic acid and polypropylene to improve the degradation performance of the product, reduce the density of the synthetic paper and lighten the product, but the introduced polypropylene can not be decomposed in the environment and can not realize complete degradation of the composite paper product. The Chinese invention patent CN202011493666.7 discloses an antioxidant degradable film and a preparation method thereof, the water resistance and the mechanical strength of a polyester material are improved by introducing hydrophobic filler and titanium dioxide, but the compatibility of the filler and a polymer is reduced due to the excessive addition of the filler, and the mechanical property of the polymer film is influenced.
Disclosure of Invention
In order to prepare a transparent composite film material with good degradation effect and good mechanical property, the invention provides a high-toughness environment-friendly transparent composite film material in a first aspect, 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.
In a preferred embodiment, the polyester-based polymer is selected from one or more of polylactic acid, polybutylene terephthalate, polyethylene terephthalate, polyarylate and polyvinyl acetate.
In a preferred embodiment, the polyester-based polymer is a combination of polylactic acid, polybutylene terephthalate, and polyvinyl acetate.
In a preferred embodiment, the weight ratio of polylactic acid, polybutylene terephthalate, polyvinyl acetate is (70-98): (0.5-30): (0.5-10).
In a preferred embodiment, the polylactic acid, polybutylene terephthalate, polyvinyl acetate are present in a weight ratio of (70-92): (2-25): (3-8).
In a preferred embodiment, the weight ratio of polylactic acid, polybutylene terephthalate, polyvinyl acetate is 92:2:3.
as a preferred embodiment, the molecular weight of the polylactic acid is 2 to 25 ten thousand daltons, and the melt index at 190 ℃ is 1 to 30g/10min.
In a preferred embodiment, the poly (alkylene acid) butylene terephthalate is selected from one or more 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 to 60000pa.s.
As a preferred embodiment, the crystallization aid is a nucleating agent, and the nucleating agent is selected from one or a combination of several of an inorganic nucleating agent, an organic nucleating agent, a polymeric nucleating agent and a beta-crystal nucleating agent.
In a preferred embodiment, the inorganic nucleating agent is selected from one or more of an oxide nucleating agent, a rare earth metal nucleating agent, a calcium carbonate nucleating agent, a mica nucleating agent and a 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 the polylactic acid and the 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 more of bifunctional 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 weight of a polymer is reduced due to thermal degradation and hydrolysis in the preparation process, the number of terminal carboxyl groups is increased, the 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 spraying material, the tear resistance of the film spraying 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 tear resistance and the tensile property are improved, and the probable reason is guessed as follows: the polymer melt generates a large amount of terminal carboxyl groups due to degradation reaction in the high-temperature processing process, the reaction activity is strong, after the polyvinyl acetate and the chain extender are introduced, the terminal carboxyl groups, the hydroxyl groups and the amino groups can react, the thermally decomposed small molecular weight polymer is polymerized again, and the molecular weight of the polymer is improved by forming bridges among small molecular weight polymers, so that the viscosity of a polymer system is increased, the melt strength is improved, and the tensile property and the tear resistance of a laminating layer are improved.
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.
in a preferred embodiment, the antioxidant is selected from one or a combination of several of amine antioxidant, phenol antioxidant, phosphate compound antioxidant and heterocyclic molecular antioxidant.
As a preferred embodiment, the antioxidant is a combination of a hindered phenol type antioxidant and a phosphate compound antioxidant.
In a preferred embodiment, the hindered phenol antioxidant is a combination of antioxidant 1076 and antioxidant 168.
As a preferred embodiment, the weight ratio of the antioxidant 1076 to the antioxidant 168 is 1: (1-1.5).
As a preferred embodiment, the weight ratio of the antioxidant 1076 to the antioxidant 168 is 1:1.2.
in a preferred embodiment, the ultraviolet absorber is selected from one of a benzophenone ultraviolet absorber, a triazine ultraviolet absorber, a phosphoramide ultraviolet absorber, and a hindered amine ultraviolet absorber.
In a preferred embodiment, the uv absorber is a hindered amine uv 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) Weighing the preparation raw materials in parts by weight, and mixing by using a high-speed mixer at the mixing speed of 500-1500rpm. Mixing for 5-20min to obtain 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 to the diameter of a screw is (35-55): 1.
in a preferred embodiment, the mixing speed of the high-speed mixer is 500-1200rpm, the mixing time is 5-20min, the temperature of the twin-screw extruder is 190-220 ℃, the rotating speed of the twin-screw extruder is 250-400rpm, and the ratio of the length to the diameter of the screw is (36-52): 1.
the applicant finds that in the high-speed mixing process of the high-speed mixer, due to frictional heat, the stabilizer with a low melting point, the crystallization auxiliary agent and the chain extender are coated on the surface of the polyester polymer, so that the auxiliary agent is uniformly dispersed in the polymer melt, and the temperature and the rotating speed of the twin-screw extruder are matched to further uniformly mix the mixture, so that 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 epoxy chain extender and the polyvinyl acetate with the viscosity of 4-6 ten thousand Pa.s are adopted, so that the mechanical property of a polymer melt can be improved, and the tear resistance and the tensile property can be improved.
(2) According to the high-toughness environment-friendly transparent composite film material, an oxide type inorganic nucleating agent is adopted to react with polylactic acid with the molecular weight of 2-25 ten thousand daltons, so that a polymer melt is recrystallized, and the transparency of the composite film and the binding capacity of the composite film with a paper product are improved.
(3) According to the high-toughness environment-friendly transparent composite film material, the aging 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 disclosed by the invention can be biodegraded under a certain condition by adopting the combined blending of polylactic acid, poly-alkyl acid butylene terephthalate and polyvinyl acetate, and has no environmental protection pressure.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
A 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 assistant, 0.5 part of chain extender and 2 parts of stabilizer.
The polyester polymer is a combination of polylactic acid, poly alkyl butylene terephthalate and polyvinyl acetate, and the weight ratio is 92:2:3; the molecular weight of the polylactic acid is 3.8 kilodaltons, the melt index at 190 ℃ is 4.5g/10min, and the polylactic acid is purchased from NatureWorks in the United states and has the trade mark of 4032D; the poly (butylene terephthalate) adipate is poly (butylene adipate terephthalate), the melt flow rate is 4.5g/10min at 190 ℃, the poly (butylene terephthalate) is purchased from Jin Huizhao Longe, and the mark is Ecoworld; the polyvinyl acetate has the viscosity of 50000Pa.s at room temperature, is purchased from Beijing Oriental petrochemical Co., ltd, and has the model of BJ-235.
The crystallization aid is an oxide nucleating agent which is purchased from Ruiqi and has a mark of RQT-CH.
The chain extender is a low molecular weight epoxide available from easy and good sources under the designation SG-20.
The stabilizer comprises an antioxidant and an ultraviolet absorbent, and the weight ratio of the antioxidant to the ultraviolet absorbent 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 absorbent is hindered amine ultraviolet absorbent with the model number of UV-770, and is purchased from BASF company in Germany.
A preparation method of a high-toughness environment-friendly transparent composite film material comprises the following steps:
(1) Weighing the preparation raw materials in parts by weight, and mixing by using a high-speed mixer at the mixing speed of 1200rpm. Mixing for 5min to obtain 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 to the diameter of a screw is 45:1.
example 2
The specific steps of the high-toughness environment-friendly transparent composite film material are the same as those of example 1, and the difference is that the weight ratio of the combination of polylactic acid, polybutylene adipate terephthalate and polyvinyl acetate is 85:7:5.
the mixing speed of the high-speed mixer is 500rpm, the mixing time is 20min, the temperature of the double-screw extruder is 220 ℃, and the rotating speed of the double-screw extruder is 360rpm.
Example 3
The specific steps of the preparation method are the same as example 1, and the differences are that the preparation method comprises 98 parts of polyester polymer, 0.7 part of crystallization auxiliary agent, 0.3 part of chain extender and 1 part of stabilizer.
The composition of polylactic acid, polybutylene adipate terephthalate and polyvinyl acetate in a weight ratio of 70:25:3.
the mixing speed of the high-speed mixer is 500rpm, the mixing time is 15min, the temperature of the double-screw extruder is 190 ℃, and the rotating speed of the double-screw extruder is 400rpm.
Example 4
The specific steps of the high-toughness environment-friendly transparent composite film material are the same as those of example 1, and the differences are that 98 parts of polyester polymer, 0.7 part of crystallization auxiliary agent, 0.8 part of chain extender and 0.5 part of stabilizer.
The composition of polylactic acid, polybutylene adipate terephthalate and polyvinyl acetate in a weight ratio of 80:10:8.
the mixing speed of the high-speed mixer is 1000rpm, the mixing time is 10min, the temperature of the double-screw extruder is 190 ℃, and the rotating speed of the double-screw extruder is 250rpm.
And (3) performance testing:
the composite film material particles prepared in the embodiments 1 to 4 are prepared into a high-toughness environment-friendly transparent composite film 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: and testing the elongation at break of the prepared transparent composite film according to the GB/T13022 standard.
3. Right angle tear strength: the right-angle tear strength of the transparent composite film prepared according to the GB/T16578 standard test.
4. The biological decomposition rate: and testing the biological decomposition rate of the prepared transparent composite film according to the GB/T19277.1 standard. The tests were carried out according to the above criteria and the test results are shown in table 1.
TABLE 1
Claims (10)
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.
2. The high-toughness environment-friendly transparent composite film material as claimed in claim 1, wherein the polyester polymer is selected from one or more of polylactic acid, polybutylene terephthalate, polyethylene terephthalate, polyarylate and polyvinyl acetate.
3. The high-toughness environment-friendly transparent composite film material as claimed in claim 2, wherein the molecular weight of the polylactic acid is 2-25 ten thousand daltons, and the melt index at 190 ℃ is 1-30g/10min.
4. The high-toughness environment-friendly transparent composite film material as claimed in claim 2, wherein the polyalkyl acid butylene terephthalate is selected from one or more of polybutylene adipate terephthalate, polybutylene azelate terephthalate and polybutylene sebacate terephthalate.
5. The high toughness, environmentally friendly transparent composite film material of claim 4, wherein said polybutylene adipate-terephthalate has a melt flow rate of 2.5-4.5g/10min at 190 ℃.
6. The high-toughness environment-friendly transparent composite film material as claimed in claim 2, wherein the viscosity of the polyvinyl acetate at room temperature is 40000-60000pa.s.
7. The high-toughness environment-friendly transparent composite film material as claimed in claim 1, wherein said crystallization aid is a nucleating agent, and said nucleating agent is selected from one or a combination of several of inorganic nucleating agent, organic nucleating agent, polymeric nucleating agent and beta-crystal nucleating agent.
8. The high-toughness environment-friendly transparent composite film material as claimed in claim 7, wherein the inorganic nucleating agent is selected from one or more of an oxide nucleating agent, a rare earth metal nucleating agent, a calcium carbonate nucleating agent, a mica nucleating agent and a carbon black nucleating agent.
9. The high-toughness environment-friendly transparent composite film material as claimed in claim 1, wherein the chain extender is selected from one or more of bifunctional acid derivatives, acid anhydrides, epoxides, alcohol chain extenders, amine chain extenders and ether chain extenders.
10. A method for preparing a high-toughness environment-friendly transparent composite film material according to any one of claims 1 to 9, which is characterized by comprising the following steps of:
(1) Weighing the preparation raw materials in parts by weight, and mixing by using a high-speed mixer at the mixing speed of 500-1500rpm. Mixing for 5-20min to obtain 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 to the diameter of a screw is (35-55): 1.
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