CN110305435B - Transparent toughened polylactic acid/acrylic alloy material and preparation raw materials and preparation method thereof - Google Patents
Transparent toughened polylactic acid/acrylic alloy material and preparation raw materials and preparation method thereof Download PDFInfo
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- CN110305435B CN110305435B CN201910698224.7A CN201910698224A CN110305435B CN 110305435 B CN110305435 B CN 110305435B CN 201910698224 A CN201910698224 A CN 201910698224A CN 110305435 B CN110305435 B CN 110305435B
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- toughening agent
- polylactic acid
- alloy material
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08L67/04—Polyesters derived from hydroxycarboxylic 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention belongs to the field of composite materials, and discloses a transparent toughened polylactic acid/acrylic alloy material as well as a preparation raw material and a preparation method thereof. The preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material contain crystalline polylactic acid, polymethyl methacrylate, a transparent toughening agent and a compatilizer, wherein the transparent toughening agent is a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent, the main toughening agent is a rubber toughening agent with a core-shell structure and the particle size of the main toughening agent is less than 180nm, and the auxiliary toughening agent is an ethylene-vinyl acetate copolymer. The polylactic acid/acrylic alloy material prepared from the preparation raw materials provided by the invention has the advantages of high transparency, high temperature resistance and high toughness, and has great industrial application prospects.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a transparent toughened polylactic acid/acrylic alloy material as well as a preparation raw material and a preparation method thereof.
Background
Polylactic acid as a novel biodegradable material has the characteristics of high transparency, good glossiness, excellent processability and the like, and along with the gradual improvement of the attention of people to the environmental protection problem, more and more polylactic acid materials are used for replacing the existing materials in the market. Meanwhile, the polylactic acid itself has the characteristics of heat resistance and high brittleness, which still prevents the wide application of the material.
The polylactic acid and acrylic blended alloy has the advantages of high temperature resistance and high transparency without post-treatment. For example, CN101735582A discloses a polylactic acid/polymethyl methacrylate alloy material, which comprises, by mass, 50 to 90% of polylactic acid, 10 to 50% of polymethyl methacrylate, 0.1 to 2% of a heat stabilizer, and 0.1 to 2% of a lubricant. The polylactic acid/polymethyl methacrylate alloy material is a semitransparent material and has good heat resistance. However, polylactic acid and polymethyl methacrylate both belong to brittle materials and have the defect of insufficient toughness, and the polylactic acid/acrylic alloy material with good transparency, high temperature resistance and high toughness can widen the application field of the new materials.
Disclosure of Invention
The invention aims to overcome the defects that the existing polylactic acid/acrylic alloy material cannot have high transparency, high temperature resistance and high toughness at the same time, and provides a transparent toughened polylactic acid/acrylic alloy material with high transparency, high temperature resistance and high toughness as well as a preparation raw material and a preparation method thereof.
The transparent toughening polylactic acid/acrylic alloy material comprises crystalline polylactic acid, polymethyl methacrylate, a transparent toughening agent and a compatilizer, wherein the transparent toughening agent is a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent, the main toughening agent is a rubber toughening agent with a core-shell structure and the particle size of which is less than 180nm, and the auxiliary toughening agent is an ethylene-vinyl acetate copolymer.
Further, based on the total weight of the raw materials for preparing the transparent toughened polylactic acid/acrylic alloy material, the content of the crystalline polylactic acid is 20-70 wt%, the content of the polymethyl methacrylate is 20-70 wt%, the content of the transparent toughening agent is 5-20 wt%, and the content of the compatilizer is 1-5 wt%.
Further, the weight ratio of the main toughening agent to the auxiliary toughening agent is (2-8): 1.
Further, the shell layer of the main toughening agent is acrylate rubber and the core layer is acrylate rubber or a compound of acrylate rubber and silicone rubber.
Furthermore, the particle size of the main toughening agent is 100-150 nm.
Furthermore, the refractive index of the main toughening agent is 1.47-1.49.
Further, the number average molecular weight of the crystalline polylactic acid is 80000 to 250000.
Further, the number average molecular weight of the polymethyl methacrylate is 50000-200000.
Further, the compatilizer is selected from at least one of acrylonitrile-styrene-maleic anhydride copolymer, acrylonitrile-styrene-GMA copolymer and ethylene-acrylate-GMA copolymer.
The invention also provides a preparation method of the transparent toughened polylactic acid/acrylic alloy material, wherein the preparation method takes the preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material as raw materials and comprises the following steps: the components in the raw materials for preparing the transparent toughened polylactic acid/acrylic alloy material are uniformly mixed, and then the obtained mixture is placed in a double-screw extruder for melt extrusion granulation.
In addition, the invention also provides the transparent toughened polylactic acid/acrylic alloy material prepared by the method.
According to the invention, the composite toughening agent which has a specific particle size and is formed by compounding the rubber toughening agent with the core-shell structure and the ethylene-vinyl acetate copolymer is added into the polylactic acid and the acrylic alloy material, so that the obtained polylactic acid/acrylic alloy material is not only a transparent material and has good toughness, but also can overcome the defect of poor temperature resistance of the polylactic acid, has the characteristics of high transparency, high temperature resistance and high toughness, and is more widely applied to the field of packaging with requirements on transparency.
Detailed Description
The preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material provided by the invention contain crystalline polylactic acid, polymethyl methacrylate, a transparent toughening agent and a compatilizer, and preferably consist of the components. The transparent toughening agent is a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent. The weight ratio of the main toughening agent to the auxiliary toughening agent is preferably (2-8): 1, and more preferably (4-8): 1, so that the main toughening agent and the auxiliary toughening agent can better play a role in synergistic toughening. In addition, the content of the toughening agent is preferably 5-20 wt% based on the total weight of the preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material.
In the invention, the main toughening agent is a rubber toughening agent with a core-shell structure, preferably, the shell layer of the main toughening agent is acrylate rubber and the core layer is acrylate rubber or a compound of acrylate rubber and silicone rubber, and specifically, the shell layer of the main toughening agent is at least one of M-210, SX-006 and the like. The refractive index of the toughening agent is close to that of acrylic, and the light transmittance of the polylactic acid/acrylic alloy material is greatly improved. The particle size of the main toughening agent is less than 180nm, and preferably 100-150 nm. In addition, the refractive index of the main toughening agent is preferably 1.47-1.49.
In the invention, the auxiliary toughening agent is an ethylene-vinyl acetate copolymer, and specifically can be at least one of VINNEX 2525, VINNEX 8880 and the like. The auxiliary toughening agent has good compatibility with polylactic acid and can improve the toughness of the polylactic acid material, so that the transparency and the toughness of the material can be kept in the polylactic acid material.
In the present invention, the crystalline polylactic acid preferably has an optical purity of 96% or more and a number average molecular weight of 80000 to 250000. The content of the crystalline polylactic acid is preferably 20 to 70 wt%.
In the present invention, the number average molecular weight of the polymethyl methacrylate is preferably 50000 to 200000. The content of the polymethyl methacrylate is preferably 20-70 wt%.
The type of the compatibilizer is not particularly limited in the present invention, and may be any of various materials that can improve the compatibility of each component, and specific examples thereof include, but are not limited to: at least one of acrylonitrile-styrene-maleic anhydride copolymer (e.g., SMA800), acrylonitrile-styrene-GMA copolymer (e.g., SAG002, SAG008, etc.), and ethylene-acrylate-GMA copolymer (e.g., AX 8900). The content of the compatilizer is preferably 1-5 wt%.
The invention also provides a preparation method of the transparent toughened polylactic acid/acrylic alloy material, wherein the preparation method takes the preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material as raw materials and comprises the following steps: the components in the raw materials for preparing the transparent toughened polylactic acid/acrylic alloy material are uniformly mixed, and then the obtained mixture is placed in a double-screw extruder for melt extrusion granulation. Wherein, the mixing can adopt manual stirring mixing, and can also adopt various existing mixing devices to carry out mechanical mixing. The mixing conditions are such that the above components form a homogeneous system. In the mixing process, the above components can be mixed in any order, for example, the above components can be added into a mixing container one by one in any order for mixing, or any two or more of the above components can be uniformly mixed and then the other components can be added for continuous uniform mixing. In addition, in the melt extrusion granulation process, the temperature of the adopted double-screw extruder is preferably controlled to be 180-220 ℃, and the screw rotating speed is preferably controlled to be 350-500 r/min.
In addition, the invention also provides the transparent toughened polylactic acid/acrylic alloy material prepared by the method. The transparent toughened polylactic acid/acrylic alloy material has the characteristics of high transparency, high temperature resistance and high toughness, and is very suitable for being used as a packaging material.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Crystalline polylactic acid (the number average molecular weight is 80000), polymethyl methacrylate (the number average molecular weight is 200000), a transparent toughening agent (a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent according to the weight ratio of 4:1, wherein the main toughening agent is M-210 with a core-shell structure, the particle size of the main toughening agent is 100-150 nm, the auxiliary toughening agent is an ethylene-vinyl acetate copolymer, particularly VINNEX 2525, and a compatilizer (an acrylonitrile-styrene-maleic anhydride copolymer, SMA800) are stirred and mixed uniformly, and then the mixture is placed in a double-screw extruder to be melted and extruded for granulation at the temperature of 180-220 ℃ and the screw rotating speed of 350-500 r/min, so that the transparent toughened polylactic acid/acrylic alloy material is obtained. The dosage of each raw material is shown in table 1, and the performance of the transparent toughened polylactic acid/acrylic alloy material is shown in table 2.
Example 2
Crystalline polylactic acid (with the number average molecular weight of 250000), polymethyl methacrylate (with the number average molecular weight of 100000), a transparent toughening agent (a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent according to the weight ratio of 6:1, wherein the main toughening agent is SX-006 with a core-shell structure and has the particle size of 100-150 nm, the auxiliary toughening agent is an ethylene-vinyl acetate copolymer, particularly VIEX NN8880, and a compatilizer (acrylonitrile-styrene-GMA copolymer, SAG002) are stirred and mixed uniformly, and then the mixture is placed in a double-screw extruder to be melted and extruded and granulated at the temperature of 180-220 ℃ and the screw rotating speed of 350-500 r/min, so that the transparent toughened polylactic acid/acrylic alloy material is obtained. The dosage of each raw material is shown in table 1, and the performance of the transparent toughened polylactic acid/acrylic alloy material is shown in table 2.
Example 3
Crystalline polylactic acid (with the number average molecular weight of 130000), polymethyl methacrylate (with the number average molecular weight of 50000), a transparent toughening agent (a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent according to the weight ratio of 6:1, wherein the main toughening agent is SX-006 with a core-shell structure and the particle size of the SX-006 is 100-150 nm, the auxiliary toughening agent is an ethylene-vinyl acetate copolymer, particularly VIEX NN2525), and a compatilizer (an ethylene-acrylate-GMA copolymer, AX8900) are stirred and mixed uniformly, and then the mixture is placed in a double-screw extruder to be subjected to melt extrusion granulation at the temperature of 180-220 ℃ and the screw rotation speed of 350-500 r/min, so that the transparent toughened polylactic acid/acrylic alloy material is obtained. The dosage of each raw material is shown in table 1, and the performance of the transparent toughened polylactic acid/acrylic alloy material is shown in table 2.
Comparative example 1
The transparent toughened polylactic acid/acrylic alloy material is prepared according to the method of the embodiment 2, except that the main toughening agent is replaced by the auxiliary toughening agent (VINNEX 8880) with the same weight part, and the rest conditions are the same as the embodiment 2, so that the reference transparent toughened polylactic acid/acrylic alloy material is obtained. The dosage of each raw material is shown in table 1, and the performance of the transparent toughened polylactic acid/acrylic alloy material is shown in table 2.
Comparative example 2
The transparent toughened polylactic acid/acrylic alloy material is prepared according to the method of the embodiment 2, except that the auxiliary toughening agent is replaced by the main toughening agent (SX-006) with the same weight part, and the rest conditions are the same as the embodiment 2, so that the reference transparent toughened polylactic acid/acrylic alloy material is obtained. The dosage of each raw material is shown in table 1, and the performance of the transparent toughened polylactic acid/acrylic alloy material is shown in table 2.
Comparative example 3
The transparent toughened polylactic acid/acrylic alloy material is prepared according to the method of the embodiment 2, except that the main toughening agent and the auxiliary toughening agent are both replaced by the common toughening agent (ABS high rubber powder HR181) with the same weight part, and the rest conditions are the same as the embodiment 2, so that the reference transparent toughened polylactic acid/acrylic alloy material is obtained. The dosage of each raw material is shown in table 1, and the performance of the transparent toughened polylactic acid/acrylic alloy material is shown in table 2.
TABLE 1 amount of each raw material (wt%)
TABLE 2
From the results, the polylactic acid/acrylic alloy material provided by the invention has the advantages of high transparency, high temperature resistance and high toughness, and has a great industrial application prospect.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (6)
1. A raw material for preparing a transparent toughened polylactic acid/acrylic alloy material, which is characterized in that, the preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material comprise crystalline polylactic acid, polymethyl methacrylate, a transparent toughening agent and a compatilizer, the transparent toughening agent is a composite toughening agent consisting of a main toughening agent and an auxiliary toughening agent, the main toughening agent is a rubber toughening agent with a core-shell structure and a particle size of less than 180nm, the shell layer is acrylic rubber and the core layer is acrylic rubber or a composite of the acrylic rubber and silicone rubber, the refractive index of the main toughening agent is close to that of acrylic, the refractive index of the main toughening agent is 1.47-1.49, the auxiliary toughening agent is an ethylene-vinyl acetate copolymer, and the weight ratio of the main toughening agent to the auxiliary toughening agent is (2-8): 1; the compatilizer is selected from at least one of acrylonitrile-styrene-maleic anhydride copolymer, acrylonitrile-styrene-GMA copolymer and ethylene-acrylate-GMA copolymer; based on the total weight of the preparation raw materials of the transparent toughened polylactic acid/acrylic alloy material, the content of the crystalline polylactic acid is 20-70 wt%, the content of the polymethyl methacrylate is 20-70 wt%, the content of the transparent toughening agent is 5-20 wt%, and the content of the compatilizer is 1-5 wt%.
2. The raw material for preparing the transparent toughened polylactic acid/acrylic alloy material as claimed in claim 1, wherein the particle size of the main toughening agent is 100-150 nm.
3. The raw material for preparing the transparent toughened polylactic acid/acrylic alloy material according to claim 1, wherein the number average molecular weight of the crystalline polylactic acid is 80000-250000.
4. The raw material for preparing the transparent toughened polylactic acid/acrylic alloy material as claimed in claim 1, wherein the number average molecular weight of the polymethyl methacrylate is 50000-200000.
5. A preparation method of a transparent toughened polylactic acid/acrylic alloy material is characterized in that the preparation method takes the preparation raw material of the transparent toughened polylactic acid/acrylic alloy material as claimed in any one of claims 1 to 4 as a raw material and comprises the following steps: the components in the raw materials for preparing the transparent toughened polylactic acid/acrylic alloy material are uniformly mixed, and then the obtained mixture is placed in a double-screw extruder for melt extrusion granulation.
6. The transparent toughened polylactic acid/acrylic alloy material prepared by the method of claim 5.
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| TWI413659B (en) * | 2010-10-05 | 2013-11-01 | Ind Tech Res Inst | Bio-based material composition and optical device employing the same |
| CN105062024B (en) * | 2015-09-23 | 2016-07-20 | 深圳市绿糖科技有限公司 | High transparency high-temperature resistant lactic acid composite material and preparation method thereof |
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| WO2005123831A1 (en) * | 2004-06-16 | 2005-12-29 | Unitika Ltd. | Polylactic acid-containing resin composition and molded body obtained from same |
| CN101983986A (en) * | 2010-10-26 | 2011-03-09 | 中国科学院长春应用化学研究所 | Transparent and toughening polylactic acid resin and method for preparing the same |
| CN102153844A (en) * | 2011-04-21 | 2011-08-17 | 上海锦湖日丽塑料有限公司 | High-impact heat-resisting polylactic resin with high light transmittance and preparation method of high-impact heat-resisting polylactic resin |
| CN102352094A (en) * | 2011-09-20 | 2012-02-15 | 奇瑞汽车股份有限公司 | High-toughness and highly heat-resistant polylactic acid (PLA) alloy material and preparation method thereof |
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