CN114456558A - Flame-retardant modified nano calcium carbonate/polylactic acid composite material and preparation method thereof - Google Patents
Flame-retardant modified nano calcium carbonate/polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN114456558A CN114456558A CN202210091877.0A CN202210091877A CN114456558A CN 114456558 A CN114456558 A CN 114456558A CN 202210091877 A CN202210091877 A CN 202210091877A CN 114456558 A CN114456558 A CN 114456558A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention relates to the technical field of composite materials of nano modified bio-based resin, in particular to a flame-retardant modified nano calcium carbonate/polylactic acid composite material and a preparation method thereof. The preparation method specifically comprises the following steps: dissolving a flame-retardant nitrogen-containing compound in acetone, adding a Tris reagent for multi-stage reaction, and filtering, washing and drying to obtain a flame retardant; dissolving the flame retardant in acetone, heating, adding calcium carbonate, stirring for reaction, filtering, washing and drying to obtain the flame-retardant modified nano calcium carbonate; and uniformly mixing the flame-retardant modified nano calcium carbonate and the dried polylactic acid, extruding, and carrying out grain cutting and tabletting to obtain the flame-retardant modified nano calcium carbonate/polylactic acid composite material. The obtained composite material contains flame-retardant elements, has a good flame-retardant effect, and has a synergistic effect with calcium carbonate, so that the dispersibility of the calcium carbonate is improved, and the mechanical property of the material is improved.
Description
Technical Field
The invention relates to the technical field of composite materials of nano modified bio-based resin, in particular to a flame-retardant modified nano calcium carbonate/polylactic acid composite material and a preparation method thereof.
Background
Polylactic acid (PLA) is a degradable plastic polymer prepared from a series of renewable materials such as corn starch and the like, has become one of the most competitive green polymer materials recognized in the world after decades of development, and is approved by the food and drug administration in the United states as a biodegradable medical polymer material implantable into a human body. The composite material is often applied to industries such as degradable packaging materials, interior decoration fabrics, automobiles, electronic and electric appliances, cups, disposable tableware, sunshades and the like, and has the advantages of no toxicity, environmental friendliness, excellent mechanical property and the like. However, PLA is not suitable for use in high temperature environments because it is not flammable and is associated with a severe dripping phenomenon due to its poor flame retardant ability, and is prone to post combustion.
In order to meet flame retardant properties, it is common in the art to melt blend PLA with flame retardants to increase the flame retardant properties of PLA. For example, the chinese patent publication No. CN101260227B discloses a method for preparing a halogen-free flame-retardant polylactic acid, which comprises uniformly mixing a flame retardant with a flame-retardant auxiliary agent and an antioxidant to obtain a flame-retardant mixture, uniformly mixing polylactic acid, the flame-retardant mixture, a coupling agent and a compatibilizer, and then melt-blending to obtain a flame-retardant polylactic acid material, wherein the limited oxygen index of the material can reach 28%. And the Chinese patent publication No. CN103694657B discloses a ternary composite flame-retardant system polylactic acid material, wherein the polylactic acid, loaded nano-zinc oxide red horse and a phosphorus-containing flame retardant are mixed to be called, and the limiting oxygen index of the material can reach 31.2%. In view of the increasing requirements on the flame retardant property and mechanical property of the polylactic acid material in the current market, the flame retardant material of the polylactic acid needs to be further improved.
Disclosure of Invention
Aiming at the technical problems, in order to improve the flame retardant property and the mechanical property of the polylactic acid composite material, the flame retardant modified calcium carbonate is matched with the polylactic acid, so that the flame retardant property of the material is synergistically improved among the materials, and the mechanical property of the composite material is improved.
In view of the above, the embodiment of the present invention provides a preparation method of a flame-retardant modified nano calcium carbonate/polylactic acid composite material, which specifically includes the following steps:
s1, dissolving the flame-retardant nitrogen-containing compound in acetone, adding a Tris reagent for multi-stage reaction, and filtering, washing and drying to obtain the flame retardant;
s2, dissolving the flame retardant in acetone, heating, adding calcium carbonate, stirring for reaction, filtering, washing and drying to obtain the flame-retardant modified nano calcium carbonate;
and S3, uniformly mixing the flame-retardant modified nano calcium carbonate and the dried polylactic acid, extruding, and carrying out granulation and tabletting to obtain the flame-retardant modified nano calcium carbonate/polylactic acid composite material.
Further, in step S1, the flame retardant nitrogen-containing compound is any one of cyanuric chloride, melamine, and hexachlorocyclotriphosphazene.
Further, the molar ratio of the flame retardant nitrogen-containing compound to the Tris reagent in the step S1 is 1:1 to 1: 6.
Further, the multistage reaction in step S1 specifically includes:
reaction stage 1: the reaction temperature is 0-5 ℃, and the reaction time is 1-5 h;
reaction stage 2: the reaction temperature is between room temperature and 90 ℃, and the reaction time is 3 to 6 hours;
reaction stage 3: the reaction temperature is 60-120 ℃, and the reaction time is 3-6 h.
Further, in the step S2, the temperature is increased, calcium carbonate is added, and the reaction process is carried out at the temperature of 60-90 ℃ for 1-6 h;
further, the mass ratio of the flame retardant to the calcium carbonate is 1: 10-30.
Further, the temperature of the extrusion process in the step S3 is 160-.
The embodiment of the invention also provides a flame-retardant modified nano calcium carbonate/polylactic acid composite material prepared by the preparation method, wherein the composite material comprises the following raw materials in percentage by mass: 90-95% of polylactic acid and 5-10% of flame-retardant modified nano calcium carbonate;
the flame-retardant modified nano calcium carbonate is obtained by reacting a flame-retardant nitrogen-containing compound with a Tris reagent to obtain a flame retardant and then modifying calcium carbonate by adopting the flame retardant.
Has the advantages that:
(1) according to the invention, calcium carbonate is subjected to flame retardant modification to obtain the flame retardant modified calcium carbonate containing flame retardant elements/groups, so that the flame retardant modified calcium carbonate has a good flame retardant effect, and simultaneously has a synergistic effect with calcium carbonate, the dispersibility of the calcium carbonate is improved, and the mechanical property of the composite material is further improved.
(2) The flame-retardant modified nano calcium carbonate/polylactic acid composite material has the advantages that the oxygen index can reach 32.7 percent through a flame-retardant performance test, the performances such as tensile strength, elongation at break and the like are improved, the raw material source of the composite material is wide, the preparation process is simple, and the composite material is suitable for industrial production.
Drawings
FIG. 1 is a schematic infrared view of TRIS-TCT and its raw materials provided in example 1 of the present invention;
FIG. 2 is a schematic infrared diagram of TRIS-TCT @ CaCO3 and its raw material provided in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the technical content of the present invention, the detailed description is given herein with reference to specific examples and drawings, and it is obvious that the examples are only preferred embodiments of the technical solution, and other technical solutions that can be obviously derived by those skilled in the art from the technical content disclosed still belong to the protection scope of the present invention.
In the embodiment of the invention, the chemical reagents used are all analytical grade reagents, and are obtained by purchasing or preparing by an existing method.
Example 1
S1: dissolving 0.1mol of cyanuric chloride TCT in 50mL of acetone, stirring for 30min at the temperature of 0-5 ℃, slowly adding 0.3mol of Tris reagent into the solution, continuously reacting for 4 hours, heating to 60 ℃, continuously reacting for 6 hours, heating to 90 ℃, reacting for 3 hours, filtering, washing and drying to obtain the flame retardant TRIS-TCT. The reaction equation is as follows:
s2, dissolving 0.1g of flame retardant TRIS-TCT in 50mL of acetone, slowly adding 2g of CaCO3 at 90 ℃, uniformly stirring, reacting for 6 hours, filtering, washing and drying to obtain the flame-retardant modified nano calcium carbonate TRIS-TCT @ CaCO 3. The reaction equation is as follows:
s3: taking 90g of dried polylactic acid PLA (the raw material is from Nature works company, model: 4032D, PLA is the same as the PLA mentioned later) and 90g of flame-retardant modified nano calcium carbonate TRIS-TCT @ CaCO 310 g, uniformly mixing, adding into a double-screw extruder, and extruding, wherein the processing temperature of the double-screw extruder is respectively set to be 160 ℃ at the front section, 170 ℃ at the middle section and 180 ℃ at the rear end. And granulating and tabletting after extrusion.
The TRIS-TCT obtained in step S1 is subjected to infrared spectroscopy, and is specifically shown in FIG. 1. As can be seen from fig. 1: 3500-3000cm-1Characteristic peaks of N-H and O-H ascribed to Tris reagent, 1023cm-1C-O characteristic peaks ascribed to Tris reagents; 1562/1499/1470/812cm-1Framework group Peak assigned to TCT, 836cm-1C-Cl bond attributed to TCT; in the intermediate Tris-TCT, the skeleton group peak of TCT can still be found, such as 1588/1507/1467/811cm-1The vibration peak of the vibration sensor can be 1043cm-1The peak of C-O bond vibration was found to be 1117cm-1The newly formed C-N bond after reaction of Tris-NH 2 with TCT C-Cl. And the intermediate product Tris-TCT is 3500-3000cm-1A broad peak was formed between, again demonstrating that the amino group of the Tris reagent was reacted.
The TRIS-TCT @ CaCO obtained in the step S23Infrared spectroscopy was performed, as shown in detail in FIG. 2. As can be seen from fig. 2: 1454/872cm-1Is ascribed to CaCO3Characteristic peak. Relative to CaCO3,TRIS-TCT@CaCO3Except for CaCO3Characteristic peak at 1588/1118/1043/811cm-1The series of oscillation peaks of TRIS-TCT is found at 3500-3000cm-1Form a broad peak therebetween, and at the same time, TRIS-TCT @ CaCO3872cm of-1The characteristic peak intensity is also reduced to a certain extent, which indicates that TRIS-TCT @ CaCO3The preparation is successful.
Example 2
S1: dissolving 0.1mol of cyanuric chloride TCT in 50mL of acetone, stirring for 30min at the temperature of 0-5 ℃, slowly adding 0.3mol of Tris reagent into the solution, continuously reacting for 4 hours, heating to 60 ℃, continuously reacting for 6 hours, heating to 90 ℃, reacting for 3 hours, filtering, washing and drying to obtain the flame retardant TRIS-TCT.
S2, dissolving 0.1g of flame retardant TRIS-TCT in 50mL of acetone, slowly adding 2g of CaCO3 at 90 ℃, uniformly stirring, reacting for 6 hours, filtering, washing and drying to obtain the flame-retardant modified nano calcium carbonate TRIS-TCT @ CaCO3。
S3: taking dried PLA 95g and TRIS-TCT @ CaCO3And 5g, uniformly mixing, adding the mixture into a double-screw extruder, and extruding, wherein the processing temperature of the double-screw extruder is respectively set to be 160 ℃ at the front section, 170 ℃ at the middle section and 180 ℃ at the rear end. And then granulating and tabletting.
Comparative example 1
Taking dried PLA90g and CaCO3And 10g, uniformly mixing, adding the mixture into a double-screw extruder, extruding, wherein the processing temperature of the double-screw extruder is respectively set to be 160 ℃ at the front section, 170 ℃ at the middle section and 180 ℃ at the rear end, and then carrying out granulation and tabletting to obtain the composite material.
Comparative example 2
Preparing flame retardant TRIS-TCT according to the step 1 of the embodiment 1, uniformly mixing 90g of dried PLA and 10g of dried TRIS-TCT, adding the mixture into a double-screw extruder, extruding, wherein the processing temperature of the double-screw extruder is respectively set to be 160 ℃ at the front section, 170 ℃ at the middle section and 180 ℃ at the rear end, and then carrying out granulation and tabletting to obtain the composite material.
Comparative example 3
Pure PLA is added into a double-screw extruder for extrusion, wherein the processing temperature of the double-screw extruder is respectively set to be 160 ℃ at the front section, 170 ℃ at the middle section and 180 ℃ at the rear end. And then granulating and tabletting.
The materials obtained in examples 1-2 and comparative examples 1-3 were subjected to performance tests, respectively:
(1) and (3) testing mechanical properties: the measurement was carried out according to the test method disclosed in GB/T1040-2006 "measurement of tensile Properties of plastics".
(2) And (3) testing the flame retardant property: the measurement was carried out according to the test method disclosed in GB/T2406-1993 test method for Plastic Combustion Property oxygen index method.
The performance test results are shown in table 1:
TABLE 1 Material Property measurements
Oxygen index/% | Tensile strength/MPa | Elongation at break/% | |
Example 1 | 32.7 | 36.5 | 3.8 |
Example 2 | 25.1 | 41.3 | 4.9 |
Comparative example 1 | 21.3 | 32.5 | 3.2 |
Comparative example 2 | 27.9 | 33.0 | 3.3 |
Comparative example 3 | 19.8 | 48.5 | 6.0 |
The higher the oxygen index is, the better the flame retardant property of the material is, and from the result of the above performance test, compared with comparative examples 1-3, the composite material obtained in examples 1-2 has improved properties such as flame retardant property, tensile strength and elongation at break. Compared with comparative examples 1-2 in which nano calcium carbonate is added, the modified nano calcium carbonate adopted in example 1 endows the composite material with stronger flame retardant effect. Thus, in conjunction with the data from the performance test, it can be seen that: the flame retardant material modified nano calcium carbonate shows good synergistic flame retardant performance.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.
Claims (8)
1. The preparation method of the flame-retardant modified nano calcium carbonate/polylactic acid composite material is characterized by comprising the following steps:
s1, dissolving the flame-retardant nitrogen-containing compound in acetone, adding a Tris reagent for multi-stage reaction, and filtering, washing and drying to obtain the flame retardant;
s2, dissolving the flame retardant in acetone, heating, adding calcium carbonate, stirring for reaction, filtering, washing and drying to obtain the flame-retardant modified nano calcium carbonate;
and S3, uniformly mixing the flame-retardant modified nano calcium carbonate and the dried polylactic acid, extruding, and carrying out granulation and tabletting to obtain the flame-retardant modified nano calcium carbonate/polylactic acid composite material.
2. The preparation method of the flame-retardant modified nano calcium carbonate/polylactic acid composite material according to claim 1, wherein the flame-retardant nitrogen-containing compound in the step S1 is any one of cyanuric chloride, melamine and hexachlorocyclotriphosphazene.
3. The preparation method of the flame-retardant modified nano calcium carbonate/polylactic acid composite material as claimed in claim 1, wherein the molar ratio of the flame-retardant nitrogen-containing compound to the Tris reagent in step S1 is 1:1-1: 6.
4. The method for preparing the flame-retardant modified nano calcium carbonate/polylactic acid composite material according to claim 1, wherein the multi-stage reaction in the step S1 specifically comprises the following steps:
reaction stage 1: the reaction temperature is 0-5 ℃, and the reaction time is 1-5 h;
reaction stage 2: the reaction temperature is between room temperature and 90 ℃, and the reaction time is 3 to 6 hours;
reaction stage 3: the reaction temperature is 60-120 ℃, and the reaction time is 3-6 h.
5. The method for preparing the flame-retardant modified nano calcium carbonate/polylactic acid composite material according to claim 1, wherein the temperature of the reaction process of heating and adding calcium carbonate in the step S2 is 60-90 ℃, and the reaction time is 1-6 h.
6. The preparation method of the flame-retardant modified nano calcium carbonate/polylactic acid composite material according to claim 1, wherein the mass ratio of the flame retardant to the calcium carbonate is 1: 10-30.
7. The method for preparing the flame-retardant modified nano calcium carbonate/polylactic acid composite material as claimed in claim 1, wherein the temperature of the extrusion process in the step S3 is 160-180 ℃.
8. The flame-retardant modified nano calcium carbonate/polylactic acid composite material obtained by the preparation method according to any one of claims 1 to 7, which is characterized by comprising the following raw materials in percentage by mass: 90-95% of polylactic acid and 5-10% of flame-retardant modified nano calcium carbonate;
the flame-retardant modified nano calcium carbonate is obtained by reacting a flame-retardant nitrogen-containing compound with a Tris reagent to obtain a flame retardant and then modifying calcium carbonate by adopting the flame retardant.
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CN115304888A (en) * | 2022-09-15 | 2022-11-08 | 湖南金箭新材料科技有限公司 | Flame-retardant modified nano calcium carbonate/epoxy resin composite material and preparation method thereof |
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CN109776865A (en) * | 2019-03-11 | 2019-05-21 | 安徽理工大学 | A kind of toughening flame-proof lactic acid composite material and preparation method thereof |
CN113121885A (en) * | 2021-03-05 | 2021-07-16 | 浙江工业大学 | Flame retardant, flame-retardant PLA composite material and preparation method thereof |
CN113121916A (en) * | 2021-04-26 | 2021-07-16 | 杭州吉邦综合服务有限公司 | Production process of flame-retardant polypropylene |
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EP2774922A1 (en) * | 2013-03-04 | 2014-09-10 | Borealis Agrolinz Melamine GmbH | Method for obtaining a functionalized triazine compound and the triazine compound obtained by said method |
CN109776865A (en) * | 2019-03-11 | 2019-05-21 | 安徽理工大学 | A kind of toughening flame-proof lactic acid composite material and preparation method thereof |
CN113121885A (en) * | 2021-03-05 | 2021-07-16 | 浙江工业大学 | Flame retardant, flame-retardant PLA composite material and preparation method thereof |
CN113121916A (en) * | 2021-04-26 | 2021-07-16 | 杭州吉邦综合服务有限公司 | Production process of flame-retardant polypropylene |
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CN115304888A (en) * | 2022-09-15 | 2022-11-08 | 湖南金箭新材料科技有限公司 | Flame-retardant modified nano calcium carbonate/epoxy resin composite material and preparation method thereof |
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