CN111944291A - Polylactic resin composition and preparation method thereof - Google Patents

Polylactic resin composition and preparation method thereof Download PDF

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CN111944291A
CN111944291A CN202010914716.8A CN202010914716A CN111944291A CN 111944291 A CN111944291 A CN 111944291A CN 202010914716 A CN202010914716 A CN 202010914716A CN 111944291 A CN111944291 A CN 111944291A
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polylactic acid
resin composition
acid resin
weight
parts
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CN111944291B (en
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林跃
朱荣华
梁伟
汪伦合
罗狄
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Zhejiang Heinuoer Biomaterials Co ltd
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Zhejiang Heinuoer Biomaterials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J2467/04—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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

Abstract

The present invention relates to a polylactic acid resin composition, characterized in that the polylactic acid resin composition comprises (a) about 20 to 60 parts by weight of polylactic acid; (B) about 40 to about 80 parts by weight of a toughening agent; (C) about 0.1 to about 7 parts by weight of a reactive compatibilizer; (D) about 0.1 to about 3 parts by weight of a rare earth modifier; (E) about 4 to about 15 parts by weight of a reinforcing agent; and (F) about 0.2 to about 2 parts by weight of an opening agent. The invention also relates to a preparation method and application of the polylactic acid resin composition.

Description

Polylactic resin composition and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polylactic acid resin composition and a preparation method thereof, and application of the polylactic acid resin composition in the field of packaging materials.
Background
Among the biodegradable materials, the non-polylactic acid (PLA) Morus is currently most widely used and most industrialized. The raw material of PLA is from renewable green plants, and can be degraded into CO harmless to the environment in a short period of time no matter compost treatment or landfill treatment2And H2O and thus does not negatively affect the environment. However, polylactic acid has disadvantages such as brittleness, hardness, and low heat seal strength, and thus has limited use in the packaging field.
CN103589124A discloses a fully biodegradable PLA/PBAT composite film and a preparation method thereof, bifunctional oxazoline and bifunctional isocyanate compound are used to respectively react with terminal carboxyl and terminal hydroxyl of polyester material, so as to improve the performance of the alloy, but a chain extender with low molecular weight is used, so that the reaction efficiency is low, the possibility that bifunctional group reacts with only one substance (such as PLA) exists, and the heat seal performance of the film is not considered.
CN101245178A discloses a method for preparing a biodegradable polyester composite material with a compatibilization function, which adopts a method of extending a chain of a diisocyanate chain extender to a micromolecule diol end-capped polylactic acid and a biodegradable polyester, and then uses a block copolymer in a blending system of the polylactic acid and the corresponding polyester to play a role in compatibilization.
Disclosure of Invention
In one aspect, the present invention relates to a polylactic acid resin composition, wherein the polylactic acid resin comprises:
(A) about 20 to about 60 parts by weight of polylactic acid;
(B) about 40 to about 80 parts by weight of a toughening agent;
(C) about 0.1 to about 7 parts by weight of a reactive compatibilizer;
(D) about 0.1 to about 3 parts by weight of a rare earth modifier;
(E) about 4 to about 15 parts by weight of a reinforcing agent; and
(F) about 0.2 to about 2 parts by weight of an opening agent.
In one embodiment, the polylactic acid is selected from poly-L-lactic acid, poly-D-lactic acid, poly- (D, L) -lactic acid and mixtures thereof, preferably poly-L-lactic acid; and/or
The polylactic acid has a number average molecular weight of about 2 to 20 ten thousand; and/or
A melt index of about 2 to 100g/10 min; and/or
Melting point of about 120-; and/or
The optical rotation is about 80-99%.
In one embodiment, the toughening agent is selected from the group consisting of polybutylene adipate/terephthalate, polybutylene succinate/adipate, polyhydroxyalkanoates, and combinations thereof, preferably polybutylene adipate/terephthalate or polybutylene succinate.
In one embodiment, the reactive compatibilizer comprises an acrylate compound and an oxazoline compound.
In a preferred embodiment, the reactive compatibilizer is a polymer, particularly a diblock copolymer or triblock copolymer, of an acrylate monomer or combination thereof and an oxazoline monomer or combination thereof.
In a more preferred embodiment, the reactive compatibilizer polymer is present in a crosslinked form.
In one embodiment, the acrylate monomer is selected from methyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate or isooctyl methacrylate, preferably from methyl methacrylate, ethyl methacrylate or isooctyl methacrylate; the oxazoline monomer is selected from 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline or 2-isopropenyl-5-methyl-2-oxazoline, and preferably 2-vinyl-2-oxazoline or 2-vinyl-4-methyl-2-oxazoline.
In another embodiment, the mass ratio of the acrylate compound to the oxazoline compound in the reactive compatibilizer is from about 3:1 to about 25:1, and preferably about 9: 1.
In one embodiment, the reactive compatibilizer has a number average molecular weight of about 0.5 to 15 ten thousand; and/or a melt index of about 2 to 40g/10 min; and/or a melting point of about 70-120 ℃.
In one embodiment, the rare earth modifier is selected from the group consisting of lanthanide rare earth modifiers, cerium-based rare earth modifiers, actinide rare earth modifiers, and combinations thereof, preferably lanthanide rare earth modifiers or cerium-based rare earth modifiers.
In one embodiment, the reinforcing agent is selected from calcium carbonate whiskers, calcium sulfate whiskers, magnesium sulfate whiskers, and combinations thereof, preferably calcium carbonate whiskers or calcium sulfate whiskers.
In one embodiment, the opening agent is selected from the group consisting of oleamide, erucamide, silica, silicone powder, and combinations thereof, preferably selected from oleamide or silicone powder.
In another aspect, the present invention relates to the use of the polylactic acid resin composition of the present invention in the field of packaging materials.
In yet another aspect, the present invention relates to a method for preparing the polylactic acid resin composition of the present invention, comprising the steps of:
(1) providing each component substance according to the weight ratio and uniformly mixing;
(2) the mixed materials are subjected to melt blending, extrusion and granulation to obtain the polylactic resin composition;
and optionally blowing the product obtained in the step (2) into a film, and carrying out melt extrusion, drawing, cooling and rolling to obtain the film of the polylactic acid resin composition.
In yet another aspect, the present invention relates to the use of a reactive compatibilizer for preparing a polylactic acid resin composition.
Detailed Description
The present invention will be described in further detail below. Such description is for the purpose of illustration and not for the purpose of limitation. Other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways. Various modifications and alterations can be made by those skilled in the art without departing from the spirit of the invention.
General definitions and terms
All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety if not otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the definitions provided herein will control.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated.
When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a pair of upper and lower preferable values or specific values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. When numerical ranges are recited herein, unless otherwise stated, the stated ranges are meant to include the endpoints thereof, and all integers and fractions within the ranges. The scope of the invention is not limited to the specific values recited when defining a range. For example, "1-8" encompasses 1, 2, 3, 4, 5, 6, 7, 8, as well as any subrange consisting of any two values therein, e.g., 2-6, 3-5.
The terms "about" and "approximately," when used in conjunction with a numerical variable, generally mean that the value of the variable and all values of the variable are within experimental error (e.g., within 95% confidence interval for the mean) or within ± 10% of the specified value, or more.
The terms "comprising," "including," "having," "containing," or "involving," and other variations thereof herein, are inclusive or open-ended and do not exclude additional unrecited elements or method steps. It will be understood by those skilled in the art that terms such as "including" and "comprising" encompass the meaning of "consisting of …. The expression "consisting of …" excludes any element, step or ingredient not specified. The expression "consisting essentially of …" means that the scope is limited to the specified elements, steps or components, plus optional elements, steps or components that do not materially affect the basic and novel characteristics of the claimed subject matter. It is to be understood that the expression "comprising" covers the expressions "consisting essentially of …" and "consisting of …".
The term "selected from …" means that one or more elements in the later listed groups are independently selected and may include a combination of two or more elements.
The terms "optionally" or "optionally" as used herein mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
When values or range ends are described herein, it is to be understood that the disclosure includes the particular values or ends recited.
The term "one or more" or "at least one" as used herein refers to one, two, three, four, five, six, seven, eight, nine or more.
Unless otherwise indicated, the terms "combination thereof" and "mixture thereof" refer to a multi-component mixture of the elements described, such as two, three, four, and up to the maximum possible multi-component mixture.
Furthermore, no number of elements or components of the invention has been previously indicated and no limitation on the number of occurrences (or presence) of an element or component is intended. Thus, it should be read to include one or at least one and singular forms of a component or ingredient also include the plural unless the numerical value explicitly indicates the singular.
The term "number average molecule" as used hereinThe amount "is alternatively referred to as the number average molar mass. If the molecular weight in the polymer is MjHas a mole fraction of xjNumber of molecules NjNumber average molecular weight
Figure BDA0002664594680000041
Is composed of
Figure BDA0002664594680000042
Wherein
Figure BDA0002664594680000043
The measurement can be carried out by methods such as end group measurement, gel chromatography, membrane osmometry, vapor osmometry, boiling point elevation, mass spectrometry, etc. Molecular weights described herein are number average molecular weights unless otherwise specified. The number average molecular weight and the distribution thereof in the present invention can be measured, for example, by using a Gel Permeation Chromatograph (GPC) or a mass spectrometer.
The term "diblock copolymer" or "diblock copolymer" as used herein refers to a block copolymer having two distinct polymer blocks, such as an acrylate-oxazoline copolymer. Accordingly, "triblock copolymer" or "triblock copolymer" refers to a block copolymer having three distinct polymer blocks, such as acrylate a-acrylate B-oxazoline.
The term "repeating unit" as used herein refers to a combination of atoms linked in a manner on a polymer chain that is the basic unit that makes up the polymer chain.
The terms "L-lactic acid" and "D-lactic acid", "poly-L-lactic acid" and "poly-D-lactic acid" as used herein refer to lactic acid or polylactic acid which are optically isomers of each other, i.e., the optical configurations of the two are opposite. The determination of the D or L configuration of compounds containing asymmetric carbon atoms is determined by Fisher's projection formula, and generally, compounds with a D-isomer are D-isomers and compounds with a L-isomer are L-isomers.
Polylactic acid resin composition
In one aspect, the present invention is directed to a polylactic acid resin composition comprising: (A) about 20 to about 60 parts by weight of polylactic acid; (B) about 40 to about 80 parts by weight of a toughening agent; (C) about 0.1 to about 7 parts by weight of a reactive compatibilizer; (D) about 0.1 to about 3 parts by weight of a rare earth modifier; (E) about 4 to about 15 parts by weight of a reinforcing agent; and (F) about 0.2 to about 2 parts by weight of an opening agent.
(A) Polylactic acid
Polylactic acid is a polymer obtained by polymerizing lactic acid as a main raw material, which is also called polylactide and is a novel biodegradable material. Lactic acid, polylactic acid and a preparation process thereof are exemplified as follows.
Figure BDA0002664594680000044
Wherein the configuration of the raw material lactic acid determines the configuration of the polymer polylactic acid, and n represents the number of repeating units. The poly-L-lactic acid can be obtained by taking L-lactic acid as a raw material and carrying out polymerization reaction. The poly-D-lactic acid can be obtained by taking D-lactic acid as a raw material and carrying out polymerization reaction. Poly- (D, L) -lactic acid can be obtained by taking (D, L) -lactic acid as a raw material and carrying out polymerization reaction.
In one embodiment, poly-L-lactic acid is used. In another embodiment, poly-D-lactic acid is used. In yet another embodiment, poly- (D, L) -lactic acid is used. In one embodiment, a mixture of two or more of poly-L-lactic acid, poly-D-lactic acid and poly- (D, L) -lactic acid is used.
The number average molecular weight and/or melt index of the polylactic acid of the present invention is selected such that it is suitable for use in an extrusion/injection molding process.
In one embodiment, the polylactic acid has a number average molecular weight of about 2 to 20 ten thousand. In a preferred embodiment, the polylactic acid has a number average molecular weight of about 10 to 20 ten thousand. And in a more preferred embodiment from about 10 to about 15 million. For example, about 2 ten thousand, about 2.5 ten thousand, about 3.5 ten thousand, about 4.5 ten thousand, about 5.5 ten thousand, about 6.5 ten thousand, about 7.5 ten thousand, about 8.5 ten thousand, about 9.5 ten thousand, about 10.5 ten thousand, about 11.5 ten thousand, about 12.5 ten thousand, about 13.5 ten thousand, about 14.5 ten thousand, about 15.5 ten thousand, about 16.5 ten thousand, about 17.5 ten thousand, about 18.5 ten thousand, about 19.5 ten thousand, about 20 ten thousand. The suitable number average molecular weight of polylactic acid facilitates the blow extrusion of the polylactic acid resin composition.
The number average molecular weight described above was determined using gel permeation chromatography. The specific determination method is as follows: the number average molecular weight of polylactic acid was obtained by dissolving polylactic acid in chloroform at a concentration of 0.25% by weight, and measuring by gel permeation chromatography (instrument model: Viscotek TDA 305) using polystyrene as a standard material.
In one embodiment, the polylactic acid has a melt index of about 2 to 100g/10 min. In a preferred embodiment, the polylactic acid has a melt index of about 2 to 10g/10 min. For example, about 2g/10min, about 3g/10min, about 4g/10min, about 5g/10min, about 6g/10min, about 7g/10min, about 8g/10min, about 9g/10min, about 10g/10min, about 15g/10min, about 20g/10min, about 25g/10min, about 30g/10min, about 35g/10min, about 40g/10min, about 45g/10min, about 50g/10min, about 55g/10min, about 60g/10min, about 65g/10min, about 70g/10min, about 75g/10min, about 80g/10min, about 85g/10min, about 90g/10min, about 95g/10min, about 100g/10 min. A suitable melt index of polylactic acid facilitates the blow extrusion of the polylactic acid resin composition.
The melt index can be determined using methods customary in the art, for example by measuring the number of grams of melt flowing out within 10min at 160 ℃ under a load of 2.16kg using a melt index tester (MFI-1211).
In one embodiment, the melting point of polylactic acid is about 120-180 ℃. In a preferred embodiment, the melting point of polylactic acid is about 140-160 ℃. For example, about 120 deg.C, about 125 deg.C, about 130 deg.C, about 135 deg.C, about 140 deg.C, about 145 deg.C, about 150 deg.C, about 155 deg.C, about 160 deg.C, about 165 deg.C, about 170 deg.C, about 175 deg.C, about 180 deg.C. An excessively high melting point of polylactic acid lowers the heat seal strength of the film of the polylactic acid resin composition, which is disadvantageous for heat sealing of the film of the polylactic acid resin composition. An excessively low melting point of polylactic acid is disadvantageous for processing of the polylactic acid resin composition.
The melting point can be determined using methods customary in the art, for example using a differential scanning calorimeter (DSC, TA apparatus), with a temperature rise rate of, for example, 10 ℃/min.
In one embodiment, poly-L-lactic acid or poly-D-lactic acid is used, wherein the optical purity of the polylactic acid is about 80-99%. In a preferred embodiment, the optical purity of the polylactic acid is about 90-95%. For example about 80%, about 82%, about 84%, about 86%, about 88%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 98%, about 99%.
In one embodiment, the polylactic acid resin composition of the present invention contains polylactic acid in an amount of about 20 to 60 parts by weight. In a preferred embodiment, the polylactic acid resin composition of the present invention contains about 30 to 50 parts by weight of polylactic acid. For example, about 20 parts by weight, about 25 parts by weight, about 30 parts by weight, about 35 parts by weight, about 40 parts by weight, about 45 parts by weight.
(B) Toughening agent
The toughening agent used in the invention is a degradable polyester toughening agent, which is a polyester toughening material capable of being completely degraded into carbon dioxide and water under the composting condition. The toughening agent is a biodegradable high molecular polymer which can reduce the brittleness of the composite material and improve the impact resistance of the composite material, the molecular chain of the toughening agent contains active groups which are better compatible with matrix resin or can generate chemical reaction with the matrix resin, and the biological toughening agent with flexible chain segments is introduced into the polylactic acid resin composition, so that the impact resistance of the composite material can be improved. The toughening agents used conventionally are styrene-butadiene-styrene (SBS), ethylene-methyl acrylate-glycidyl methacrylate (EMA), methacrylic acid-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene copolymer (ABS) and the like, the toughening agents are difficult to degrade in natural environment and have poor compatibility with polylactic acid, and when the toughening agents are added into the polylactic acid to a certain proportion, the toughening effect of the polylactic acid is not remarkably improved.
The toughening agent has good compatibility with polylactic acid, can be biodegraded, and can be well dispersed in the polylactic acid.
In one embodiment, the toughening agent of the present invention is selected from the group consisting of polybutylene adipate/terephthalate (Poly (butylene-co-terephthalate), PBAT), polybutylene succinate (Poly (butylene succinate), PBS), polybutylene succinate/adipate (PBSA), Polyhydroxyalkanoate (PHA), and combinations thereof. In a preferred embodiment, the toughening agent of the present invention is selected from the group consisting of polybutylene adipate/terephthalate, polybutylene succinate, and combinations thereof. In a more preferred embodiment, the toughening agent of the present invention is polybutylene adipate/terephthalate or polybutylene succinate.
In one embodiment, the content of the toughening agent in the polylactic acid resin composition of the present invention is about 40 to 80 parts by weight. In a preferred embodiment, the toughening agent is present in the inventive polylactic acid resin composition in an amount of about 45 to 65 parts by weight. For example, about 40 parts by weight, about 45 parts by weight, about 50 parts by weight, about 55 parts by weight, about 60 parts by weight, about 65 parts by weight, about 70 parts by weight, about 75 parts by weight, about 80 parts by weight.
(C) Reactive compatibilizer
The compatilizer is a compatilizer which contains reactive groups, and the incompatible two components are promoted to be combined together by virtue of intermolecular bonding force, so that the stable blend is obtained.
In one embodiment, the reactive compatibilizer of the present invention comprises an acrylate compound and an oxazoline compound.
In a preferred embodiment, the reactive compatibilizer of the present invention is a polymer formed from an acrylate monomer or combination thereof and an oxazoline monomer or combination thereof.
In a more preferred embodiment, the reactive compatibilizer of the present invention is a diblock copolymer or triblock copolymer formed from an acrylate monomer or combination thereof and an oxazoline monomer or combination thereof.
In a particularly preferred embodiment, the polymer of the reactive compatibilizer of the present invention is present in a crosslinked form.
After the polymerization of the polymer monomers to form the diblock or triblock copolymers, the copolymers may be further reacted to form a crosslinked product having a spatial network structure in the presence of, for example, a crosslinking agent. Reactive compatibilizers of the prior art are typically monomeric compounds, such as 1, 3-phenylene-bis (2-oxazoline) or 2, 2' -bis (2-oxazoline), which link the polymers through reactive groups at both ends of the molecular structure. In contrast, the reactive compatibilizer of the present application is a polymer having a network structure, which has a plurality of reactive groups on a segment of the polymer having a network structure, and can be linked to other components through each of the reactive groups, thereby forming a composition having a complicated structure and superior properties.
In a preferred embodiment of the present invention, the reactive compatibilizer with a spatial network structure is added to the polylactic acid resin composition, such that oxazoline groups therein can react with carboxyl groups at the ends of the polymer, thereby increasing the compatibility between the polylactic acid and the degradable polyester, wherein polyethylene glycol groups can further improve the toughness of the material, and the mechanical properties of the polylactic acid resin composition can be better improved. And the heat sealing property of the film of the polylactic resin composition is improved without adding an additional heat sealing modifier, so that the film of the polylactic resin composition with higher heat sealing strength can be obtained.
In one embodiment, the acrylate monomer is selected from methyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, or isooctyl methacrylate. In a preferred embodiment, the acrylate monomer is selected from methyl methacrylate, ethyl methacrylate or isooctyl methacrylate.
In one embodiment, the oxazoline monomer is selected from the group consisting of 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-methyl-2-oxazoline. In a preferred embodiment, the oxazoline monomer is 2-vinyl-2-oxazoline or 2-vinyl-4-methyl-2-oxazoline.
In a preferred embodiment, the crosslinking agent is selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and combinations thereof.
In one embodiment, the reactive compatibilizer has a number average molecular weight of about 0.5 to 15 ten thousand. In a preferred embodiment, the number average molecular weight of the reactive compatibilizer is about 4 to 13 ten thousand. In a more preferred embodiment, the number average molecular weight of the reactive compatibilizer is about 7 to 12 ten thousand.
In one embodiment, the melt index of the reactive compatibilizer is about 2 to about 40g/10 min. In a preferred embodiment, the melt index of the reactive compatibilizer is about 4 to 20g/10 min.
In one embodiment, the melting point of the reactive compatibilizer is about 70 to 120 ℃. In a preferred embodiment, the melting point of the reactive compatibilizer is about 80 to 110 ℃.
In one embodiment, the mass ratio of the acrylate compound to the oxazoline compound in the reactive compatibilizer is from about 3:1 to about 25: 1. In a preferred embodiment, the mass ratio of the acrylate-based compound to the oxazoline-based compound is about 9: 1. The appropriate mass ratio of the acrylate compound to the oxazoline compound is beneficial to obtaining the reactive compatilizer with higher reaction activity.
In one embodiment, the content of the reactive compatibilizer in the polylactic acid resin composition of the present invention is about 0.1 to 7 parts by weight. In a preferred embodiment, the reactive compatibilizer is present in an amount of about 0.2 to about 5 parts by weight. For example, about 0.2 parts by weight, about 0.4 parts by weight, about 0.6 parts by weight, about 0.8 parts by weight, about 1 part by weight, about 1.5 parts by weight, about 2 parts by weight, about 2.5 parts by weight, about 3 parts by weight, about 3.5 parts by weight, about 4 parts by weight, about 4.5 parts by weight, about 5 parts by weight.
In one embodiment, the reactive compatibilizer of the present invention is formed by initiating a copolymerization reaction of the acrylate monomer and the oxazoline monomer by an initiator.
In a preferred embodiment, after the initiator initiates the copolymerization reaction of the acrylate monomer and the oxazoline monomer to obtain the copolymer, the cross-linking agent is added to obtain the cross-linked polymer product. Such a process is advantageous for obtaining a reactive compatibilizer having a suitable molecular weight and reactivity.
The method of preparing the reactive compatibilizer of the present invention may, for example, comprise the steps of:
(1) mixing acrylic monomer, oxazoline monomer and initiator in solvent, and protecting atmosphere (such as N)2) Under the protection of (3), heating and stirring to carry out free radical polymerization reaction; after a certain period of reaction, a crosslinking agent is optionally added for further reaction.
(2) Extracting the product of step (1) and drying.
In one embodiment, the acrylic monomer and oxazoline monomer used in step (1) are as defined above. In one embodiment, the mass ratio of the acrylate compound and the oxazoline compound added in step (1) is as described above.
The initiator is also called as free radical initiator, and refers to a kind of compound which is easy to be decomposed into free radicals by heating, and can be used for initiating free radical polymerization and copolymerization of alkene and diene monomers, and can also be used for crosslinking curing of unsaturated polyester and high molecular crosslinking polymerization.
In one embodiment, the initiator used in step (1) is an initiator commonly used in polymerization reactions in the art, including, but not limited to, organic peroxide initiators, inorganic peroxide initiators, azo-type initiators, and redox initiators. In a preferred embodiment, the initiator used in step (1) is an organic peroxide initiator or an azo-type initiator. In a particular embodiment, the initiator used in step (1) is selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, benzoyl t-butyl peroxide, methyl ethyl ketone peroxide, dilauroyl peroxide, and combinations thereof. In a preferred embodiment, the initiator used in step (1) is azobisisobutyronitrile or benzoyl oxide.
In one embodiment, the mass ratio of the acrylate compound and the oxazoline compound to the initiator added in step (1) is from about 35:1 to about 650: 1. In a preferred embodiment, the mass ratio of the acrylate compound and the oxazoline compound to the initiator added in step (1) is from about 100:1 to about 143: 1. Too low initiator content may not sufficiently initiate the copolymerization reaction of step (1), while too high initiator content may cause too severe copolymerization reaction, making it difficult to control the direction of reaction, and making it difficult to obtain a product having a target number of repeating units.
The crosslinking agent is also called a bridging agent, and is usually a substance having a plurality of functional groups in a molecule (e.g., organic dibasic acid, polyhydric alcohol, etc.), or a compound having a plurality of unsaturated double bonds in a molecule (e.g., divinylbenzene and diisocyanate, N-Methylenebisacrylamide (MBA), etc.). In the polymerization reaction, the crosslinking agent may be fed together with the monomer to carry out the polymerization reaction, or may be fed when the polymerization reaction has proceeded to some extent (when a certain number of functional groups remain in the linear molecules of the polymer produced).
In one embodiment, the crosslinking agent used in step (1) is selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, and combinations thereof. In a preferred embodiment, the crosslinking agent used in step (1) is polyethylene glycol diacrylate. In another preferred embodiment, the crosslinking agent used in step (1) is a polyethylene glycol diacrylate having a molecular weight of about 308, about 508, about 708, or about 908. The molecular weight of a suitable cross-linking agent is advantageous to obtain a reactive compatibilizer having a suitable degree of cross-linking. Too low molecular weight of the cross-linking agent can cause too violent cross-linking reaction, which results in too high cross-linking degree of the obtained reactive compatilizer and is not beneficial to playing the role of compatibilization. Too high molecular weight causes too mild crosslinking reaction, resulting in insufficient crosslinking degree of the obtained reactive compatibilizer and being not favorable for compatibilization.
In one embodiment, the mass ratio of the acrylate compound and the oxazoline compound to the crosslinking agent added in step (1) is from about 20:1 to about 120: 1. In a preferred embodiment, the mass ratio of the acrylate compound and the oxazoline compound to the crosslinking agent added in step (1) is from about 30:1 to about 80: 1. Suitable crosslinker content can result in a suitable degree of crosslinking of the reactive compatibilizer.
In one embodiment, the stirring temperature of step (1) is about 70-120 deg.C, such as about 70 deg.C, about 75 deg.C, about 80 deg.C, about 85 deg.C, about 90 deg.C, about 95 deg.C, about 100 deg.C, about 105 deg.C, about 110 deg.C, about 115 deg.C, about 120 deg.C.
In one embodiment, the time for the polymerization reaction in step (1) is about 6 to 12 hours, for example about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, about 11 hours, about 12 hours.
In one embodiment, the time for the crosslinking reaction in step (1) is about 3 to 5 hours, for example about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours.
In one embodiment, the solvent in step (1) is a solvent that can dissolve the acrylic monomer, the oxazoline monomer, and the initiator. In a preferred embodiment, the solvent in step (1) is selected from the group consisting of toluene, benzene, methylene chloride, chloroform, and combinations thereof. In a more preferred embodiment, the solvent in step (1) is toluene.
In a preferred embodiment, the amount of the solvent used in step (1) is 3 to 15ml of solvent per 1g of the mixture.
In one embodiment, step (2) comprises the steps of:
(2.1) cooling the product obtained by the reaction in the step (1) to room temperature, then using absolute ethyl alcohol to precipitate, separating out white solid, centrifuging, and carrying out suction filtration to obtain white solid;
and (2.2) washing the white solid obtained in the step (2.1) with absolute ethyl alcohol for 3 times, and drying to obtain the reactive compatilizer.
(D) Rare earth modifier
The rare earth modifier is a mixture of rare earth oxide and rare earth organic complex, wherein rare earth ions of the rare earth modifier have strong coordination capacity with carboxyl oxygen atoms in the polylactic acid and the toughening agent, and various coordination forms such as monodentate chelation, bidentate bridging and the like are formed, so that the rare earth complex forms special structures such as layered, infinite chain and space network polymers in the polymers, and the compatibility of two phases of the polylactic acid and the toughening agent is further improved.
In one embodiment, the rare earth modifier used in the polylactic acid resin composition of the present invention is selected from the group consisting of lanthanide rare earth modifiers, cerium rare earth modifiers, actinide rare earth modifiers, and combinations thereof. In a preferred embodiment, the rare earth modifier used in the polylactic acid resin composition of the present invention is selected from the group consisting of lanthanide rare earth modifiers, cerium-based rare earth modifiers, and combinations thereof. In a more preferred embodiment, the rare earth modifier used in the polylactic acid resin composition of the present invention is a lanthanoid rare earth modifier or a cerium-based rare earth modifier.
In one embodiment, the rare earth modifier is present in an amount of about 0.1 to 3 parts by weight. In a preferred embodiment, the rare earth modifier is present in an amount of about 0.5 to 2 parts by weight. For example, about 0.1 parts by weight, about 0.3 parts by weight, about 0.5 parts by weight, about 0.8 parts by weight, about 1.0 parts by weight, about 1.3 parts by weight, about 1.5 parts by weight, about 1.7 parts by weight, about 2 parts by weight, about 2.2 parts by weight, about 2.4 parts by weight, about 2.6 parts by weight, about 2.7 parts by weight, about 3 parts by weight. Excessive rare earth modifier results in excessive chelating action of the rare earth modifier with other components, which is not favorable for blow molding extrusion of the polylactic acid resin composition. And too little rare earth modifier is not favorable for the rare earth modifier to fully perform chelation with other components, cannot improve the compatibility of each component in the composition, and is further not favorable for obtaining the polylactic resin composition with good mechanical property and heat sealing property.
(E) Reinforcing agent
Reinforcing agents, also known as reinforcing materials, are substances added to resins that are capable of tightly binding the resin and significantly improving the mechanical properties of the article. In addition, the reinforcing agent can effectively increase the strength performance of the material, reduce the cost of the composite material, reduce the using amount of the opening agent, prevent the opening agent from being separated out and improve the heat seal performance of the polymer film.
The reinforcing agent used in the present invention is a reinforcing agent commonly used in the art. In a preferred embodiment, the reinforcing agent is an inorganic whisker. In a more preferred embodiment, the set of reinforcing agents is selected from the group consisting of calcium carbonate whiskers, calcium sulfate whiskers, magnesium sulfate whiskers, and combinations thereof. In a particularly preferred embodiment, the reinforcing agent is selected from calcium carbonate whiskers, calcium sulfate whiskers, and combinations thereof. In a more preferred embodiment, the reinforcing agent is calcium carbonate whiskers or calcium sulfate whiskers.
In a preferred embodiment, the reinforcing agent is calcium carbonate whiskers having a length of about 20 to 80 μm, preferably about 30 μm or about 40 μm. For example, about 20 μm, about 30 μm, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm.
In another preferred embodiment, the reinforcing agent is calcium sulfate whiskers having a length of about 40 to 100 μm, preferably about 50 μm or about 60 μm. For example, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm, about 90 μm, about 100 μm.
In one embodiment, the enhancer is present in an amount of about 4 to about 15 parts by weight. In a preferred embodiment, the reinforcing agent is present in an amount of about 5 to about 12 parts by weight. For example, about 4 parts by weight, about 5 parts by weight, about 6 parts by weight, about 7 parts by weight, about 8 parts by weight, about 9 parts by weight, about 10 parts by weight, about 11 parts by weight, about 12 parts by weight, about 13 parts by weight, about 14 parts by weight, about 15 parts by weight.
(F) Opening agent
The opening agent is also called slipping agent, and mainly has the functions of reducing the friction coefficient of the film, changing the sliding property and the anti-adhesion property of the film and improving the opening performance of the film.
In one embodiment, the opening agent used in the present invention is selected from the group consisting of oleamide, erucamide, silica, silicone powder, and combinations thereof. In a preferred embodiment, the opening agent used in the present invention is selected from the group consisting of oleamide, silicone powder, and combinations thereof.
In one embodiment, the opening agent is present in an amount of about 0.2 to 2 parts by weight. In a preferred embodiment, the opening agent is present in an amount of about 0.4 to 1.5 parts by weight. For example, about 0.5 parts by weight, about 0.6 parts by weight, about 0.7 parts by weight, about 0.8 parts by weight, about 0.9 parts by weight, about 1 part by weight, about 1.1 parts by weight, about 1.2 parts by weight, about 1.3 parts by weight, about 1.4 parts by weight, about 1.5 parts by weight, about 1.6 parts by weight, about 1.7 parts by weight, about 1.8 parts by weight, about 1.9 parts by weight, about 2 parts by weight. Too much of the opening agent may lower the heat seal strength of the film of the polylactic acid resin composition and may cause slippage of the screw of the film blowing machine. Too little opening agent is not favorable for opening of the film of the polylactic acid resin composition.
Preparation method
The invention also relates to a method for preparing the polylactic acid resin composition, which comprises the following steps:
(1) providing each component substance according to the weight ratio and uniformly mixing;
(2) the mixed materials are melted, blended, extruded and granulated;
in the step (1), the used component substances comprise polylactic acid, a toughening agent, a reactive compatilizer, a rare earth modifier, a reinforcing agent and an opening agent.
In a preferred embodiment, the components are uniformly mixed by high speed stirring, for example using a high speed stirrer. The stirring temperature is about 20-60 ℃. The stirring time is about 20-60 min. For example, stirring at 50 ℃ for 10 min. In a more preferred embodiment, the stirring temperature is about 25-30 ℃. The mixing temperature is reduced, and the mixing time is prolonged, so that a better mixing effect is obtained.
The temperature of the melt blending in the step (2) is such that the polylactic acid has proper fluidity, so that the components can be uniformly dispersed in the polylactic acid matrix, and the components are not degraded or volatilized. In one embodiment, the temperature of the melt blending is about 140-170 ℃. For example, about 140 deg.C, about 145 deg.C, about 150 deg.C, about 155 deg.C, about 160 deg.C, about 165 deg.C, about 170 deg.C.
The time for melt blending should not be too short to allow for uniform mixing of the added components and should not be too long to avoid degradation or volatilization of the components. In one embodiment, the time for melt blending is from about 20 to 80 seconds.
The melt blending apparatus generally employs a single-screw extruder, a twin-screw extruder, and preferably a twin-screw extruder. In a specific embodiment, the heating temperatures of the sections of the extruder from the feed port to the discharge port of the die in the melt blending of the step (2) are set to 140 ℃, 155 ℃, 160 ℃ and 170 ℃ in this order.
In one embodiment, the method for preparing a polylactic acid resin composition of the present invention further comprises the step (3): and (3) blowing the product obtained in the step (2) into a film, and carrying out melt extrusion, traction, cooling and rolling to obtain the film of the polylactic resin composition.
The film processing equipment of step (3) is equipment commonly used in the art, and is usually a common film blowing machine. And (3) setting the heating temperatures of all sections of the film blowing machine from the feed inlet to the discharge outlet of the die head to be 140 ℃, 145 ℃, 160 ℃ and 165 ℃ in sequence.
In a preferred embodiment, the extrusion temperature in step (3) is about 140-. For example, about 140 deg.C, about 145 deg.C, about 150 deg.C, about 155 deg.C, about 160 deg.C, about 165 deg.C, about 170 deg.C.
In a preferred embodiment, the blown film in step (3) has a blow-up ratio of from about 2:1 to about 6: 1. An excessively high blow-up ratio affects the processing stability, causes unevenness in the thickness of the film, and is liable to cause wrinkles. Too low a blow-up ratio may degrade the mechanical properties and gloss of the film.
In one embodiment, the film of the polylactic acid resin composition obtained by the process of the present invention has a thickness of about 5 to 60 μm, preferably about 10 to 50 μm, and more preferably about 20 to 40 μm. For example about 5 μm, about 10 μm, about 15 μm, about 20 μm, about 25 μm, about 30 μm, about 35 μm, about 40 μm, about 45 μm, about 50 μm, about 55 μm, about 60 μm.
Properties of polylactic acid resin composition
The properties of the polylactic acid resin composition of the present invention can be measured by the following methods.
The mechanical properties of the polylactic acid resin composition of the present invention can be characterized by tensile strength and elongation at break. Heat seal properties can be characterized by seal strength. Stability can be characterized by the mechanical and thermal properties of the composition over time. The optical properties can be indicated by observing the gloss of the product. The tensile strength and elongation at break of the film of the polylactic acid resin composition of the present invention can be measured using means conventional in the art, for example, using GB/T1040.3-2006. The degree of heat-resistance, which may reflect the heat-resistant properties of the films of the polylactic acid resin composition, is measured using means conventional in the art, for example using QB/T2358-1998. The thickness of the film of the polylactic acid resin composition of the present invention can be measured by a conventional manner in the art, for example, by using GB/T6672-2001. In the present invention, the elongation at break of the film of the polylactic acid resin composition is measured under conditions of 30 ℃ and 70% humidity after 90 days, and the difference in the elongation at break of the film of the polylactic acid resin composition between before and after 90 days is used to determine the stability of the film of the polylactic acid resin composition.
In one embodiment, a film of a polylactic acid resin composition is obtained by the method for producing a film of a polylactic acid resin composition of the present invention, and the film is subjected to the following tests: transverse tensile strength, longitudinal tensile strength, transverse elongation at break, longitudinal elongation at break, and heat and strength.
In one embodiment, the film of the polylactic acid resin composition of the present invention has a tensile strength in the transverse direction of about 20 to 35MPa, preferably about 25 to 32 MPa. For example about 26MPa, about 27MPa, about 28MPa, about 29MPa, about 30MPa, about 31MPa, about 32 MPa. Higher transverse tensile strength indicates that the material has higher mechanical strength, but excessively high transverse tensile strength indicates that the material has poorer toughness.
In one embodiment, the film of the polylactic acid resin composition of the present invention has a tensile strength in the machine direction of about 25 to 40MPa, preferably about 28 to 38 MPa. For example about 27MPa, about 28MPa, about 29MPa, about 30MPa, about 31MPa, about 32MPa, about 33MPa, about 34MPa, about 35MPa, about 36MPa, about 37MPa, about 38 MPa. Higher longitudinal tensile strength indicates that the material has higher mechanical strength, but too high longitudinal tensile strength indicates that the material has poorer toughness.
In one embodiment, the film of the polylactic acid resin composition of the present invention has an elongation at break in the transverse direction of about 330% to 480%, preferably about 330% to 470%. For example, about 330%, about 332%, about 338%, about 342%, about 345%, about 346%, about 350%, about 355%, about 360%, 364%, about 368%, about 370%, about 375%, about 380%, about 382%, about 386%, about 388%, about 390%, about 393%, about 395%, about 398%, about 400%, about 403%, about 405%, about 408%, about 410%, about 413%, about 415%, about 418%, about 420%, about 423%, about 425%, about 428%, about 430%, about 433%, about 436%, about 437%, about 440%, about 443%, about 446%, about 448%, about 450%, about 454%, about 456%, about 458%, about 460%, about 464%, about 466%, about 468%, about 470%.
In one embodiment, the film of the polylactic acid resin composition of the present invention has an elongation at break in the machine direction of about 250% to 430%, preferably about 255% to 420%. For example, about 250%, about 255%, about 256%, about 260%, about 265%, about 270%, about 275%, about 280%, about 285%, about 290%, about 295%, about 300%, about 310%, about 320%, about 330%, about 340%, about 350%, about 352%, about 355%, about 358%, about 360%, about 363%, about 365%, about 367%, about 370%, about 373%, about 375%, about 378%, about 380%, about 383%, about 385%, about 388%, about 390%, about 393%, about 395%, about 397%, about 400%, about 403%, about 405%, about 409%, about 411%, about 413%, about 415%, about 418%, about 420%.
In one embodiment, the film of the polylactic acid resin composition of the present invention has a heat seal strength of about 10 to 20N/15mm, preferably about 12 to 18N/15 mm. For example, about 10N/15mm, about 11N/15mm, about 12N/15mm, about 13N/15mm, about 14N/15mm, about 15N/15mm, about 16N/15mm, about 17N/15mm, about 18N/15mm, about 19N/15mm, about 20N/15 mm.
In one embodiment, the film of the polylactic acid resin composition of the present invention has a transverse elongation at break of about 230% to 420%, preferably about 230% to 410%, under the condition of 30 ℃ and 70% humidity after 90 days. For example, about 230%, about 234%, about 240%, about 245%, about 250%, about 255%, about 260%, about 261%, about 265%, about 267%, about 270%, about 275%, about 280%, about 281%, about 284%, about 286%, about 288%, about 290%, about 294%, about 298%, about 302%, about 306%, about 310%, about 314%, about 318%, about 322%, about 326%, about 330%, about 334%, about 340%, about 344%, about 348%, about 352%, about 356%, about 360%, about 364%, about 368%, about 372%, about 374%, about 378%, about 382%, about 384%, about 385%, about 388%, about 390%, about 394%, about 398%, about 402%, about 405%, about 408%, about 410%.
In one embodiment, the film of the polylactic acid resin composition of the present invention has an elongation at break in the machine direction of about 200 to 390%, preferably about 200 to 380%, under the condition of 30 ℃ and 70% humidity after 90 days. For example, about 200%, about 201%, about 205%, about 210%, about 215%, about 220%, about 221%, about 226%, about 225%, about 230%, about 232%, about 237%, about 238%, about 243%, about 245%, about 250%, about 253%, about 255%, about 260%, about 270%, about 275%, about 280%, about 285%, about 290%, about 295%, about 300%, about 305%, about 310%, about 315%, about 320%, about 325%, about 330%, about 335%, about 336%, about 340%, about 343%, about 345%, about 350%, about 355%, about 358%, about 362%, about 365%, about 369%, about 372%, about 376%, about 380%.
In one embodiment, the film of the polylactic acid resin composition of the present invention has a heat seal strength of about 10 to 20N/15mm, preferably about 10 to 16N/15 mm. For example, about 10N/15mm, about 11N/15mm, about 12N/15mm, about 13N/15mm, about 14N/15mm, about 15N/15mm, about 16N/15mm, about 17N/15mm, about 18N/15mm, about 19N/15mm, about 20N/15 mm.
In one embodiment, the transverse elongation at break of the film obtained from the polylactic acid resin composition of the present invention is reduced by about 10% to 30%, preferably about 12% to 30%, 90 days after the film is prepared. For example about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%.
In one embodiment, the elongation at break in the machine direction of the film obtained from the polylactic acid resin composition of the present invention is reduced by about 5 to 35%, preferably about 7 to 29% after 90 days of preparing the film. For example, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%.
In one embodiment, the heat seal strength of the film obtained from the polylactic acid resin composition of the present invention is reduced by about 5% to 25%, preferably about 6% to 16%, after 90 days of preparing the film. For example about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%.
The film of the polylactic acid resin composition of the present invention can be used in the field of materials, for example, as a packaging material.
When the film of the polylactic acid resin composition of the present invention is used as a packaging material, it has one or more of the following:
(1) a transverse tensile strength of about 20 to 35 MPa;
(2) a tensile strength in the machine direction of about 25 to 40 MPa;
(3) a transverse elongation at break of about 330% to 480%;
(4) an elongation at break in the machine direction of about 250% to 430%;
(5) a heat seal strength of about 10-20N/15 mm;
(6) the transverse elongation at break is reduced by only about 10-30% after 90 days;
(7) the longitudinal elongation at break decreased only about 5% -35% after 90 days;
(8) the heat seal strength decreased only about 5% to 25% after 90 days.
The invention also relates to the use of the reactive compatibilizer of the present invention for preparing a polylactic acid resin composition, wherein the polylactic acid resin composition has the structure as described above.
Advantageous effects
The polylactic acid resin composition of the invention is prepared by free radical copolymerization and in-situ crosslinking to form a reactive compatilizer with a crosslinking structure, so that the reactive compatilizer has a plurality of reactive functional groups, and the polylactic acid and the toughener are connected through chemical bonds. Meanwhile, the reactive compatilizer has soft chain segments, and the toughness of the composition can be further improved. In addition, the rare earth modifier is added, and the compatibility of the polylactic acid and the toughening agent is further improved through various coordination modes such as chelation, bridging and the like. And a certain amount of reinforcing agent is used in a matching way, so that the product has good mechanical strength and toughness.
In addition, the good compatibility of the components in the polylactic acid resin composition also improves the heat sealing performance of the film of the polylactic acid resin composition, so that the film of the invention has good heat sealing strength, and therefore, compared with the prior art, the film of the polylactic acid resin composition of the invention has better heat sealing performance.
In addition, the addition of the reactive compatibilizer, the reinforcing agent and the rare earth modifier also improves the stability of the film of the polylactic acid resin composition, and the elongation at break and the heat seal strength of the polylactic acid resin composition are only partially reduced after 90 days of product preparation.
The polylactic resin composition has wide application range and simple preparation process, is suitable for large-scale production and application, and has wide application prospect.
Examples
The present invention will be described in further detail with reference to specific examples.
It should be noted that the following examples are only for clearly illustrating the technical solutions of the present invention, and are not intended to limit the present invention. It will be apparent to those skilled in the art that other variations and modifications may be made in the foregoing disclosure without departing from the spirit or essential characteristics of the invention, and it is not desired to exhaustively enumerate all embodiments, but rather those obvious variations and modifications are within the scope of the invention. Unless otherwise indicated, both the instrumentation and reagent materials used herein are commercially available.
Material
Polylactic acid: linear poly-L-lactic acid (PLLA) with an optical purity of 92%, Zhejiang Haizhen biomaterial GmbH, trade name REVODE101L, and the physical properties are shown in Table 1 below.
TABLE 1
Tensile strength Elongation at break Notched impact strength Number average molecular weight Molecular weight distribution Melting Point Melt index
Unit of MPa ％ KJ/m2 All the details of - ℃ g/10min
Numerical value 65 5 3.2 13.5 1.2 145 5
The molecular weights and their distributions in table 1 above were measured using GPC.
Melting points were measured using a differential scanning calorimeter (Q10): 5-10mg of sample is taken, cooled to 0 ℃, maintained for 3min and raised to 200 ℃ at the speed of 10 ℃/min.
The melt index was measured using a melt index tester (MFI-1211): the grams of polylactic acid melt run-off were measured at 190 ℃ under a 2.16kg load for 10 min.
PBAT: poly (butylene adipate/terephthalate) was obtained from Hangzhou Xinfukezhi, Inc.
PBS: polybutylene succinate, purchased from Xinjiang blue mountain Tunghe chemical industry Co., Ltd.
Methyl methacrylate: purchased from jinan constant new materials, inc.
Ethyl methacrylate: purchased from jinan constant new materials, inc.
Isooctyl methacrylate: purchased from jinan constant new materials, inc.
2-vinyl-2-oxazoline: purchased from Hubei Xinkang pharmaceutical chemical Co., Ltd.
2-vinyl-4-methyl-2-oxazoline: hubei Xinkang pharmaceutical chemical Co., Ltd.
Azobisisobutyronitrile: purchased from denna incorporated.
Benzoyl peroxide: purchased from denna incorporated.
1, 3-phenylene-bis (2-oxazoline): purchased from Kjen chemical Co., Ltd.
Methyl diisocyanate: purchased from Kjen chemical Co., Ltd.
Reinforcing agent: calcium carbonate whiskers and calcium sulfate whiskers were purchased from yowa new materials science and technology ltd.
Rare earth modifier: lanthanide series rare earth modifiers and cerium series rare earth modifiers were purchased from Baotou rare earth research institute.
An opening agent: oleamide was purchased from Oimengteng New materials science and technology, Inc. Silicone powder was purchased from Asource industries, Inc. of Dongguan.
The present invention is not particularly limited with respect to the sources of the other raw materials used above, and is generally commercially available.
Preparation of reactive compatibilizer
The invention prepares four reaction type compatilizers M1, M2, M3 and M4 with different components, wherein M1 and M2 are reaction type compatilizers with a cross-linking structure, and M3 and M4 are reaction type compatilizers with a chain structure.
The reactive compatibilizer M1 can be prepared by the following method:
(1) mixing methyl methacrylate, ethyl methacrylate, 2-ethylene-2-oxazoline and azobisisobutyronitrile in toluene under protective gas such as N2Heating to 80 ℃ under the protection of (1), stirring, carrying out free radical polymerization reaction for 6h, then adding polyethylene glycol diacrylate, and continuing to react for 4 h. Wherein the mass ratio of methyl methacrylate to ethyl methacrylate to 2-vinyl-2-oxazoline to azobisisobutyronitrile to polyethylene glycol diacrylate is 60:30:10:1.2: 2.
(2) Cooling the reaction liquid in the step (1) to room temperature, precipitating by using absolute ethyl alcohol, separating out white solid, centrifuging, and performing suction filtration to obtain white solid; the white solid is washed with absolute ethyl alcohol for 3 times and dried to obtain the reactive compatilizer M1.
The reactive compatibilizer M2 can be prepared by the following method:
(1) mixing isooctyl methacrylate, ethyl methacrylate, 2-vinyl-4-methyl-2-oxazoline and benzoyl peroxide in toluene under protective gas such as N2Heating to 90 ℃ under the protection of (1), stirring, carrying out free radical polymerization reaction for 8h, then adding polyethylene glycol diacrylate, and continuing to react for 3 h. Wherein the mass ratio of the isooctyl methacrylate to the ethyl methacrylate to the 2-vinyl-4-methyl-2-oxazoline to the benzoyl peroxide to the polyethylene glycol diacrylate is 45:30:25:0.7: 2.5.
(2) Cooling the reaction liquid in the step (1) to room temperature, precipitating by using absolute ethyl alcohol, separating out white solid, centrifuging, and performing suction filtration to obtain white solid; the white solid is washed with absolute ethyl alcohol for 3 times and dried to obtain the reactive compatilizer M2.
The reactive compatibilizer M3 can be prepared by the following method:
(1) mixing methyl methacrylate, ethyl methacrylate, 2-ethylene-2-oxazoline and azobisisobutyronitrile in toluene under protective gas such as N2Heating to 80 ℃ under the protection of (1), stirring, and carrying out free radical polymerization for 8 h. Wherein the mass ratio of the methyl methacrylate to the ethyl methacrylate to the 2-vinyl-2-oxazoline to the azobisisobutyronitrile is 60:30:10: 1.2.
(2) Cooling the reaction liquid in the step (1) to room temperature, precipitating by using absolute ethyl alcohol, separating out white solid, centrifuging, and performing suction filtration to obtain white solid; the white solid is washed with absolute ethyl alcohol for 3 times and dried to obtain the reactive compatilizer M3.
The reactive compatibilizer M4 can be prepared by the following method:
(1) mixing isooctyl methacrylate, ethyl methacrylate, 2-vinyl-4-methyl-2-oxazoline and benzoyl peroxide in toluene under protective gas such as N2Heating to 90 ℃ under the protection of (1), stirring, and carrying out free radical polymerization for 10 h. Wherein the mass ratio of the isooctyl methacrylate to the ethyl methacrylate to the 2-vinyl-4-methyl-2-oxazoline to the benzoyl peroxide is 45:30:25: 0.7.
(2) Cooling the reaction liquid in the step (1) to room temperature, precipitating by using absolute ethyl alcohol, separating out white solid, centrifuging, and performing suction filtration to obtain white solid; the white solid is washed with absolute ethyl alcohol for 3 times and dried to obtain the reactive compatilizer M4.
Preparation of film of polylactic acid resin composition
The components of the film of the polylactic acid resin composition were arranged according to tables 2 and 3, wherein the contents of the components are expressed in parts by weight.
TABLE 2
Figure BDA0002664594680000171
TABLE 3
Figure BDA0002664594680000181
The polylactic acid, the toughening agent, the reactive compatibilizer, the reinforcing agent, the rare earth modifier and the opening agent in the amounts shown in tables 2 and 3 were uniformly mixed by a high-speed mixer to obtain a blend material premix. And melting and blending the obtained blending material premix by a double-screw extrusion granulator, and granulating the extruded material by a granulator after cooling by air. The heating temperatures of the sections of the extruder from the feed inlet to the discharge outlet of the die head are set to be 140 ℃, 155 ℃, 160 ℃ and 170 ℃ in sequence. Then the obtained granules pass through a film blowing machine, and are subjected to melt extrusion, traction cooling and rolling, and the heating temperatures of all sections from the feed inlet to the discharge outlet of the die head are set to be 140 ℃, 145 ℃, 160 ℃ and 165 ℃ in sequence, so that the film of the polylactic resin composition is prepared.
Testing
Films of the polylactic acid resin compositions in examples and comparative examples were subjected to thickness test with reference to GB/T6672-2001, and the film thickness of each set of examples and comparative examples was 30 μm.
The films of the polylactic acid resin composition are subjected to mechanical property tests with reference to GB/T1040.3-2006.
The films of the polylactic acid resin composition were tested for heat seal strength with reference to QB/T2358-1998.
And in the film blowing process, observing the brightness condition of the film surface.
The samples in the examples and comparative examples were tested for elongation at break and heat seal strength after 90 days at 30 ℃ and 70% humidity with reference to GB/T1040.3-2006 and QB/T2358-1998.
Results
Table 4 is a list of the results of the tests of elongation at break in the transverse direction (%), tensile strength in the transverse direction (MPa), elongation at break in the longitudinal direction (%), tensile strength in the longitudinal direction (MPa), heat seal strength (N/15mm) and brightness for the examples and comparative examples.
TABLE 4
Figure BDA0002664594680000191
As shown in Table 4, the examples all had suitable tensile strengths and higher elongations at break, with tensile strengths in the transverse direction of 27-32MPa and tensile strengths in the longitudinal direction of 29-38 MPa. The tensile strength in the transverse direction of the samples of comparative examples 1 to 10 was 19 to 26MPa, and the tensile strength in the longitudinal direction was 25 to 30MPa, and it can be seen that the tensile strength of the comparative examples is generally lower than that of the examples. Examples 1-8 had elongation at break in the transverse direction of 382% -470% and elongation at break in the machine direction of 367% -418%. Examples 9-12 had elongation at break in the transverse direction of 332% to 364% and elongation at break in the machine direction of 255% to 265%. Comparative examples 1-10 have elongation at break in the transverse direction of 180% to 270% and elongation at break in the machine direction of 165% to 234%, all generally lower than the examples. The samples of examples 1-12 therefore have better toughness than the samples of comparative examples 1-10. Therefore, after the reactive compatilizer, the reinforcing agent and the rare earth modifier are added into the polylactic acid resin composition, the obtained product has better mechanical property. In comparative example 9, the compatibilizer 2-ethylene-2-oxazoline was added, while in comparative example 10, the compatibilizers 1, 3-phenylene-bis (2-oxazoline) and methyl diisocyanate, whose molecular weights were lower than those of the reactive compatibilizers M1 and M2 used in examples 1 to 8, were added. The mechanical properties of the films of comparative examples 9-10 are significantly poorer than those of the compatibilizers used in examples 1-8.
In addition, examples 1-12 had higher heat seal strengths of 12-17N/15mm, while comparative examples 1-10 had relatively lower heat seal strengths of 5-10N/15 mm. Therefore, after the reactive compatilizer, the reinforcing agent and the rare earth modifier are added into the polylactic acid resin composition, the obtained product has better heat sealing performance.
In addition, the samples of examples 1-12 generally had better shine and were better identified when used as packaging materials than the samples of comparative examples 1-10.
Further, the reactive compatibilizers used in examples 9 to 12 had a chain structure, while the reactive compatibilizers used in examples 1 to 8 had a crosslinked network structure, and the films of the corresponding polylactic acid resin compositions had generally better elongation at break in the transverse direction and elongation at break in the longitudinal direction. Therefore, the use of the reactive compatibilizer having a crosslinked structure can improve the toughness of the polylactic acid resin composition. Examples 1 to 8 and examples 9 to 12 have tensile strength and heat seal strength close to each other, and therefore the spatial structure of the reactive compatibilizer does not significantly affect the mechanical strength and heat seal properties of the polylactic acid resin composition.
The evaluation method of the stability of the polylactic acid resin composition is as follows: the samples of examples 1 to 12 and comparative examples 1 to 10 were again tested for elongation at break and heat seal strength after 90 days under conditions of 30 ℃ and 70% humidity with reference to GB/T1040.3-2006 and QB/T2358-1998, and compared for the degree of reduction, the smaller the degree of reduction, the better the stability of the samples.
Table 5 is a table showing the results of the test of elongation at break and heat seal strength after 90 days for the samples of examples and comparative examples under the conditions of 30 ℃ and 70% humidity.
Table 6 is a table listing the reduction in elongation at break and heat seal strength after 90 days compared to that before 90 days for the samples of examples and comparative examples.
TABLE 5
Figure BDA0002664594680000211
TABLE 6
Figure BDA0002664594680000221
As shown in tables 5 and 6, after 90 days, the elongation at break in the transverse direction of examples 1 to 12 was reduced by only 12% to 30%, the elongation at break in the longitudinal direction was reduced by only 7% to 29%, the heat seal strength was reduced by only 6% to 17%, and the corresponding samples also had better service properties. While the comparative examples 1 to 10 have elongation at break in the transverse direction reduced by 41 to 63%, elongation at break in the longitudinal direction reduced by 41 to 66%, and heat seal strength reduced by 20 to 65%, the corresponding samples substantially lose their usability. It can be seen that the mechanical properties (including transverse elongation at break and longitudinal elongation at break) and heat sealability (heat seal strength) of examples 1-12 are generally significantly reduced after 90 days compared to comparative examples 1-10. In addition, in comparative examples 9 and 10, good stability was not achieved using unmodified small molecule oxazoline chain extenders and isocyanate chain extenders. Therefore, after the reactive compatilizer, the reinforcing agent and the rare earth modifier are added into the polylactic acid resin composition, the obtained product has better stability. In addition, the mechanical properties and heat sealability of examples 1 to 8 and 9 to 12 were reduced to a similar extent, and it was found that the steric structure of the reactive compatibilizer did not significantly affect the stability of the polylactic acid resin composition.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, which is defined by the claims appended hereto, as well as the appended claims.

Claims (15)

1. A polylactic acid resin composition, characterized in that the polylactic acid resin comprises:
(A) about 20 to about 60 parts by weight of polylactic acid;
(B) about 40 to about 80 parts by weight of a toughening agent;
(C) about 0.1 to about 7 parts by weight of a reactive compatibilizer;
(D) about 0.1 to about 3 parts by weight of a rare earth modifier;
(E) about 4 to about 15 parts by weight of a reinforcing agent; and
(F) about 0.2 to about 2 parts by weight of an opening agent.
2. The polylactic acid resin composition according to claim 1,
the polylactic acid is selected from poly-L-lactic acid, poly-D-lactic acid, poly- (D, L) -lactic acid and a mixture thereof, preferably poly-L-lactic acid; and/or
The polylactic acid has a number average molecular weight of about 2 to 20 ten thousand; and/or
A melt index of about 2 to 100g/10 min; and/or
Melting point of about 120-; and/or
The optical rotation is about 80-99%.
3. The polylactic acid resin composition according to claim 1 or 2,
the toughening agent is selected from the group consisting of polybutylene adipate/terephthalate, polybutylene succinate/adipate, polyhydroxyalkanoates, and combinations thereof,
preference is given to polybutylene adipate/terephthalate or polybutylene succinate.
4. The polylactic acid resin composition according to any one of claims 1 to 3,
the reactive compatilizer comprises an acrylate compound and an oxazoline compound.
5. The polylactic acid resin composition according to any one of claims 1 to 4,
the reactive compatilizer is a polymer formed by acrylate monomers or a combination of the acrylate monomers and oxazoline monomers or a combination of the acrylate monomers and the oxazoline monomers, in particular to a diblock copolymer or a triblock copolymer.
6. The polylactic acid resin composition according to claim 5, wherein the polymer is present in a crosslinked form.
7. The polylactic acid resin composition according to any one of claims 4 to 6,
the acrylate monomer is selected from methyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate or isooctyl methacrylate,
preferably selected from methyl methacrylate, ethyl methacrylate or isooctyl methacrylate;
the oxazoline monomer is selected from 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline or 2-isopropenyl-5-methyl-2-oxazoline,
2-vinyl-2-oxazoline or 2-vinyl-4-methyl-2-oxazoline are preferred.
8. The polylactic acid resin composition according to any one of claims 4 to 7,
in the reactive compatibilizer, the mass ratio of the acrylate compound to the oxazoline compound is about 3:1 to about 25:1, and preferably about 9: 1.
9. The polylactic acid resin composition according to any one of claims 1 to 8,
the number average molecular weight of the reactive compatibilizer is about 0.5 to 15 ten thousand; and/or
A melt index of about 2 to 40g/10 min; and/or
The melting point is about 70-120 ℃.
10. The polylactic acid resin composition according to any one of claims 1 to 9,
the rare earth modifier is selected from lanthanide rare earth modifiers, cerium rare earth modifiers, actinide rare earth modifiers and combinations thereof, and preferably lanthanide rare earth modifiers or cerium rare earth modifiers.
11. The polylactic acid resin composition according to any one of claims 1 to 10,
the reinforcing agent is selected from calcium carbonate whiskers, calcium sulfate whiskers, magnesium sulfate whiskers and a combination thereof, and calcium carbonate whiskers or calcium sulfate whiskers are preferred.
12. The polylactic acid resin composition according to any one of claims 1 to 11,
the opening agent is selected from the group consisting of oleamide, erucamide, silica, silicone powder, and combinations thereof, preferably oleamide or silicone powder.
13. Use of the polylactic acid resin composition according to any one of claims 1 to 12 for the field of packaging materials.
14. A method of preparing the polylactic acid resin composition of any of claims 1 to 13, comprising the steps of:
(1) providing each component substance according to the weight ratio and uniformly mixing;
(2) the mixed materials are subjected to melt blending, extrusion and granulation to obtain the polylactic resin composition;
and optionally blowing the product obtained in the step (2) into a film, and carrying out melt extrusion, drawing, cooling and rolling to obtain the film of the polylactic acid resin composition.
15. Use of the reactive compatibilizer defined in any one of claims 4 to 9 to prepare a polylactic acid resin composition.
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