CN111303600A - Polylactic acid/Zn+Heat-resistant composite material and preparation method thereof - Google Patents
Polylactic acid/Zn+Heat-resistant composite material and preparation method thereof Download PDFInfo
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- CN111303600A CN111303600A CN202010329594.6A CN202010329594A CN111303600A CN 111303600 A CN111303600 A CN 111303600A CN 202010329594 A CN202010329594 A CN 202010329594A CN 111303600 A CN111303600 A CN 111303600A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses polylactic acid/Zn+The heat-resistant composite material comprises polylactic acid and 0.2-1% of Zn+，Zn+Is one of zinc chloride, zinc stearate or zinc acetate; polylactic acid/Zn+The preparation method of the heat-resistant composite material comprises the following steps: mixing polylactic acid and Zn+Drying the raw materials in a vacuum drying oven at 40 ℃ for 12 h; mixing polylactic acid with Zn+Melt blending, and banburying in a torque rheometer at 190 ℃ for 10 min; and (3) performing compression molding on the mixture obtained by banburying in a vacuum film pressing machine at 180 ℃. The invention has the advantages that: adding a small amount of Zn+The crystallinity and the Vicat softening temperature of the polylactic acid can be simultaneously improved, the use temperature of the material is improved, and the application range of the polylactic acid material is widened; zn+As polylactic acid modifierThe price is low, and the method is economical and practical; the material processing technology is simple, no toxic substance is generated in the processing process, the raw material is green and degradable, and the prepared polylactic acid composite material is a bio-based environment-friendly material.
Description
Technical Field
The invention relates to a heat-resistant composite material and a preparation method thereof, in particular to polylactic acid/Zn+A heat-resistant composite material and a preparation method thereof, belonging to the technical field of composite material modification.
Background
The traditional high molecular materials mostly use non-renewable petrochemical resources as raw materials, and along with the increasing exhaustion of petroleum resources, the traditional high molecular materials are not only difficult to degrade, but also bring huge damage to the environment. Polylactic acid (PLA) is a biodegradable green environment-friendly high polymer material as an aliphatic thermoplastic polyester, has good environmental friendliness, biocompatibility, processability and energy economy, and is widely applied to industrial products. In addition, polylactic acid has excellent mechanical properties, such as: high modulus and high strength. It is therefore considered to be one of the most potential plastic varieties to replace traditional petroleum-based polymers.
However, polylactic acid still has some disadvantages, such as: low glass transition temperature, slow crystallization rate, poor toughness, poor heat resistance and the like. Therefore, the method has great significance for improving the crystallization property and the heat resistance of the polylactic acid, expanding the application range of the polylactic acid and enabling the polylactic acid to replace part of the existing engineering plastics.
Polylactic acid is a semi-crystalline polymer, the heat resistance temperature is around 60 ℃, and the heat resistance of polylactic acid depends on the crystallinity and the crystallization behavior thereof. In order to improve the heat resistance of polylactic acid, the modification methods at home and abroad are mainly divided into two categories: firstly, the nucleating agent is added, the processing technology is improved, and the crystallization performance of the polylactic acid is improved, so that the heat resistance is improved. And secondly, the heat resistance is improved by blending with other heat-resistant high polymer materials and inorganic nano materials.
At present, various polylactic acid nucleating agents are reported, such as talcum powder, carbon nano tubes and metal nano particles, and researches show that Ag-Cu and ZnO nano particles can improve the crystallinity of the polylactic acid/polyethylene glycol composite material, the material strength is also improved, and the nano particles have good dispersibility in the composite material. In addition, it has been reported that the heat resistance of polylactic acid can be improved by blending modification of polyoxymethylene, polycarbonate, nylon, ABS, and the like. A binary blend of PLA and Polycaprolactone (PCL) is prepared by research, and the existence of the PCL obviously reduces the crystallization temperature of the PLA and slightly increases the crystallinity of the PLA. Although many documents are reported, the overall effect is not satisfactory.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide polylactic acid/Zn+A heat-resistant composite material and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions:
polylactic acid/Zn+Heat resistant composite material comprising polylactic acid and Zn+。
Preferably, Zn+The content is 0.2-1%.
Preferably, Zn+Is one of zinc chloride, zinc stearate or zinc acetate.
Polylactic acid/Zn+The preparation method of the heat-resistant composite material comprises the following steps:
the method comprises the following steps: mixing polylactic acid and Zn+Drying the raw materials in a vacuum drying oven;
step two: mixing the polylactic acid dried in the step one with Zn+Melt blending, and banburying in a torque rheometer;
step three: and D, compression molding the mixture subjected to internal mixing in the step two in a vacuum film pressing machine.
Preferably, the drying condition in the step one is drying at 40 ℃ for 12 h.
Preferably, the banburying conditions in the second step are banburying at 190 ℃ for 10 min.
Preferably, the compression molding temperature in the third step is 180 ℃.
The invention has the advantages that:
(1) adding a small amount of Zn+The crystallinity and the Vicat softening temperature of the polylactic acid can be simultaneously improved, the use temperature of the material is improved, and the application range of the polylactic acid material is widened;
(2)Zn+as a polylactic acid modifier, the polylactic acid modifier has low price, is economical and practical and has wide application prospect in industry;
(3) the material processing technology is simple, no toxic substance is generated in the processing process, the raw material is green and degradable, and the prepared polylactic acid composite material is a bio-based environment-friendly material.
Drawings
FIG. 1 is a thermogravimetric analysis curve of a polylactic acid composite material with different zinc chloride contents in specific example 1 of the present invention;
FIG. 2 is a bar graph of Vicat softening points of the polylactic acid composite material under different zinc chloride contents in example 1 of the present invention;
FIG. 3 is a thermogravimetric analysis curve of the polylactic acid composite material with different zinc stearate contents in the embodiment 2 of the present invention;
FIG. 4 is a thermogravimetric analysis curve of the polylactic acid composite material with different zinc acetate contents in the embodiment 3 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
Example 1
Taking 100 parts of polylactic acid, wherein zinc chloride is respectively 0%, 0.2%, 0.4%, 0.6%, 0.8% and 1% of the mass of the polylactic acid, drying the polylactic acid in a vacuum drying oven at 40 ℃ for 12 hours, melting and blending the polylactic acid and the zinc chloride in a torque rheometer at 190 ℃ for 10 minutes, and then carrying out compression molding at 180 ℃ to obtain the polylactic acid/zinc chloride heat-resistant composite material, wherein the first table describes the corresponding relationship between the zinc chloride content of the embodiment and the glass transition temperature Tg, the cold crystallization temperature Tc, the melting enthalpy △ Hm, the crystallization enthalpy △ Hcc and the crystallinity of the polylactic acid/zinc chloride composite material, and the table shows that when the zinc chloride content reaches 0.8%, the crystallinity of the polymer is improved to 7.23%, thus the adding of the zinc chloride effectively improves the crystallinity of the polymer2The temperature of the atmosphere is increased from room temperature to 450 ℃ at a rate of 10 ℃/min to obtain a thermal weight loss curve, as shown in figure 1, and figure 1 shows that the degradation temperature of the composite material is gradually reduced along with the increase of the content of zinc chloride. Figure 2 shows that the vicat softening temperature increased from 68 ℃ to 79 ℃ when the zinc chloride content reached 0.4%, indicating an increase in the service temperature of the composite.
Watch 1
Example 2
Taking 100 parts of polylactic acid, wherein the mass of zinc stearate is respectively 0%, 0.2%, 0.4%, 0.6%, 0.8% and 1% of that of the polylactic acid, drying the polylactic acid for 12 hours in a vacuum drying oven at 40 ℃, melting and blending the polylactic acid and the zinc stearate for 10 minutes at 190 ℃ in a torque rheometer, and then carrying out compression molding at 180 ℃ to obtain the polylactic acid/zinc stearate heat-resistant composite material, Table II describes the corresponding relationship among the zinc chloride content and the glass transition temperature Tg, the cold crystallization temperature Tc, the melting enthalpy △ Hm, the crystallization enthalpy △ Hcc and the crystallinity of the polylactic acid/zinc stearate composite material, and shows that when the zinc stearate content reaches 0.4%, the polymer crystallinity is improved to 11.76%, and the polylactic acid/zinc stearate heat-resistant composite material is subjected to N, the polymer crystallinity is improved to 11.76%, and the polylactic acid/2The temperature is increased from room temperature to 450 ℃ at the rate of 10 ℃/min in the atmosphere to obtain a thermal weight loss curve, as shown in fig. 3, fig. 3 shows that the degradation temperature of the composite material is gradually reduced along with the increase of the content of zinc stearate, but the degradation temperature of the zinc stearate composite material with the content of 0.4% has an inflection point, but is higher than that of the zinc stearate composite material with the content of 0.2%, because the thermal stability of the composite material is improved due to the improvement of the crystallinity, the addition of zinc stearate is illustrated, and the crystallinity and the thermal stability of the composite material are effectively improved.
Watch two
| Zinc stearate content/%) | Tg/℃ | Tc/℃ | △Hm/(J*g-1) | △Hcc/(J*g-1) | Degree of crystallization/%) |
| 0 | 59.39 | 103.02 | 22.05 | 16.58 | 5.88 |
| 0.2 | 56.02 | 91.90 | 19.89 | 14.40 | 5.92 |
| 0.4 | 56.29 | 92.42 | 27.13 | 16.24 | 11.76 |
| 0.6 | 54.23 | 91.69 | 20.14 | 14.40 | 6.21 |
| 0.8 | 55.14 | 93.87 | 32.67 | 24.77 | 8.56 |
| 1 | 52.59 | 89.82 | 32.42 | 23.39 | 9.81 |
Example 3
Taking 100 parts of polylactic acid, wherein the zinc acetate accounts for 0%, 0.2%, 0.4%, 0.6%, 0.8% and 1% of the mass of the polylactic acid, drying the polylactic acid in a vacuum drying oven at 40 ℃ for 12 hours, melting and blending the polylactic acid and the zinc acetate in a torque rheometer at 190 ℃ for 10min, and then performing compression molding at 180 ℃ to obtain the polylactic acid/zinc acetate heat-resistant composite material, the third table describes the corresponding relationship among the content of zinc chloride in the embodiment, the glass transition temperature Tg, the cold crystallization temperature Tc, the melting enthalpy △ Hm, the crystallization enthalpy △ Hcc and the crystallinity of the polylactic acid/zinc acetate composite material, and the table 3 shows that when the content of zinc acetate reaches 0.4%, the crystallinity of the polymer is improved to 20.91%, and the polylactic acid/zinc acetate heat-resistant composite material is subjected to N, and then the polymer is subjected2The temperature was increased from room temperature to 450 c at a rate of 10 c/min under the atmosphere to obtain a thermogravimetric curve, as shown in fig. 4, and fig. 4 shows that the degradation temperature of the composite material gradually decreased with increasing zinc acetate content.
Watch III
| Zinc acetate content/%) | Tg/℃ | Tc/℃ | △Hm/(J*g-1) | △Hcc/(J*g-1) | Degree of crystallization/%) |
| 0 | 59.39 | 103.02 | 22.05 | 16.58 | 5.88 |
| 0.2 | 49.20 | 83.21 | 15.98 | 1.89 | 15.15 |
| 0.4 | 48.18 | 82.89 | 22.23 | 2.78 | 20.91 |
| 0.6 | 48.84 | 82.54 | 18.79 | 4.62 | 15.23 |
| 0.8 | 41.49 | 82.17 | 19.96 | 3.71 | 17.47 |
| 1 | 47.59 | 81.04 | 20.17 | 9.36 | 11.62 |
It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.
Claims (7)
1. Polylactic acid/Zn+A heat-resistant composite material characterized by comprising polylactic acid and Zn+。
2. Polylactic acid/Zn according to claim 1+Heat-resistant composite material, characterised in that Zn+The content is 0.2-1%.
3. Polylactic acid/Zn according to claim 1+Heat-resistant composite material, characterised in that Zn+Is one of zinc chloride, zinc stearate or zinc acetate.
4. Polylactic acid/Zn according to any one of claims 1 to 3+The preparation method of the heat-resistant composite material is characterized by comprising the following steps:
the method comprises the following steps: mixing polylactic acid and Zn+Drying the raw materials in a vacuum drying oven;
step two: drying in the step oneFormed polylactic acid and Zn+Melt blending, and banburying in a torque rheometer;
step three: and D, compression molding the mixture subjected to internal mixing in the step two in a vacuum film pressing machine.
5. Polylactic acid/Zn according to claim 4+The preparation method of the heat-resistant composite material is characterized in that in the step one, the drying condition is drying for 12 hours at 40 ℃.
6. Polylactic acid/Zn according to claim 4+The preparation method of the heat-resistant composite material is characterized in that the banburying condition in the second step is banburying at 190 ℃ for 10 min.
7. Polylactic acid/Zn according to claim 4+The preparation method of the heat-resistant composite material is characterized in that the compression molding temperature in the third step is 180 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3988619B2 (en) * | 2002-10-31 | 2007-10-10 | 東レ株式会社 | Polylactic acid resin composition and molded article comprising the same |
| KR100979635B1 (en) * | 2008-01-31 | 2010-09-01 | 금오공과대학교 산학협력단 | PLA/POSS-PLA including POSS-PLA and method for preparing the same |
| CN103554856A (en) * | 2013-10-22 | 2014-02-05 | 山西省化工研究所（有限公司） | Polylactic acid nucleating agent composition and application thereof |
| CN107805373A (en) * | 2017-11-06 | 2018-03-16 | 丽水市莲都区君正模具厂 | A kind of therapeutic medical lactic acid composite material and its disposable syringe of preparation |
| CN108359087A (en) * | 2018-02-12 | 2018-08-03 | 贵州大学 | Low melting point branched polylactic acid and preparation method thereof |
| CN109608690A (en) * | 2018-12-12 | 2019-04-12 | 贵州大学 | The method of fast degradation polylactic acid |
-
2020
- 2020-04-24 CN CN202010329594.6A patent/CN111303600B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3988619B2 (en) * | 2002-10-31 | 2007-10-10 | 東レ株式会社 | Polylactic acid resin composition and molded article comprising the same |
| KR100979635B1 (en) * | 2008-01-31 | 2010-09-01 | 금오공과대학교 산학협력단 | PLA/POSS-PLA including POSS-PLA and method for preparing the same |
| CN103554856A (en) * | 2013-10-22 | 2014-02-05 | 山西省化工研究所（有限公司） | Polylactic acid nucleating agent composition and application thereof |
| CN107805373A (en) * | 2017-11-06 | 2018-03-16 | 丽水市莲都区君正模具厂 | A kind of therapeutic medical lactic acid composite material and its disposable syringe of preparation |
| CN108359087A (en) * | 2018-02-12 | 2018-08-03 | 贵州大学 | Low melting point branched polylactic acid and preparation method thereof |
| CN109608690A (en) * | 2018-12-12 | 2019-04-12 | 贵州大学 | The method of fast degradation polylactic acid |
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