CN110903491A - Flame retardant, modified polylactic acid and preparation method thereof - Google Patents
Flame retardant, modified polylactic acid and preparation method thereof Download PDFInfo
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- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- 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
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention relates to a flame retardant, modified polylactic acid and a preparation method thereof. The flame retardant is prepared from the raw materials including urea and/or melamine, orthosilicic acid and modified lignin, wherein the modified lignin is hydroxymethylated lignin obtained by reacting alkaline lignin with formaldehyde, and hydroxyl can react with hydroxyl in polylactic acid molecules, so that the compatibility with polylactic acid can be improved; when the flame retardant formed by urea or melamine, orthosilicic acid and modified lignin is used for polylactic acid, a compact and high-temperature-resistant Si-C layer can be formed on the surface of the polylactic acid under the combustion condition, the external oxygen is isolated from entering, meanwhile, the urea and the melamine are combusted to release nitrogen, and a large number of air holes are formed in the modified polylactic acid, so that a nitrogen layer which does not support combustion is formed in the air holes of the modified polylactic acid, the flame retardance of the polylactic acid can be improved, and meanwhile, the thermal stability and the mechanical property of the polylactic acid can be improved.
Description
Technical Field
The invention relates to the field of modified polymers, and particularly relates to a flame retardant, modified polylactic acid and a preparation method thereof.
Background
Polylactic acid (PLLA) is a biodegradable plastic with wide application prospect, but the flame retardance and heat resistance of the PLLA are poor, so that the practical application of the PLLA is greatly limited, and in order to further expand the practical application range of the PLLA, how to improve the performances of the PLLA in various aspects including the flame retardance, the heat resistance and the like is a key point. At present, flame retardant is mainly added into PLLA resin to improve the flame retardant performance, however, the compatibility of the traditional nucleating agent and flame retardant with polylactic acid is poor, the physical performance and the mechanical performance of the polylactic acid are reduced, the cost is high, and the large-scale application is not facilitated.
Disclosure of Invention
Based on the flame retardant, the invention provides the flame retardant, the modified polylactic acid and the preparation method thereof.
The technical scheme of the invention is as follows.
The invention provides a flame retardant, which comprises the following raw materials in parts by weight:
1 part of urea and/or melamine;
0.5 to 2 portions of orthosilicic acid; and
1-2 parts of modified lignin;
the modified lignin is prepared by the following method: mixing alkali lignin, formaldehyde and a solvent, and then heating and refluxing for reaction to obtain the modified lignin.
In the flame retardant, the mass ratio of the urea and/or melamine to the orthosilicic acid to the modified lignin is 1: 1: (1-2).
In the flame retardant, the mass ratio of the alkali lignin to the formaldehyde in the raw material for preparing the modified lignin is 1 (0.1-0.3).
In the flame retardant, the charging ratio of the alkali lignin to the solvent is 1g (4 mL-6 mL).
In the flame retardant, the solvent is at least one selected from alcohols and ethers having 1 to 10 carbon atoms.
Further, the invention also provides a preparation method of the flame retardant, which comprises the following steps:
mixing alkali lignin, formaldehyde and a solvent, and then heating and refluxing for reaction to obtain modified lignin;
mixing urea and/or melamine, orthosilicic acid and the modified lignin, and reacting at 80-100 ℃ to obtain a prepolymer;
and calcining the prepolymer at 220-240 ℃ for 2-3 h to obtain the flame retardant.
The invention further provides the application of the flame retardant or the flame retardant prepared by the preparation method in the preparation of polylactic acid.
The invention also provides modified polylactic acid, which comprises the following raw materials in parts by weight:
1 part of polylactic acid;
0.1 to 0.3 portion of fire retardant.
Wherein the flame retardant is the flame retardant or the flame retardant prepared by the preparation method.
The invention further provides a preparation method of the modified polylactic acid, which comprises the following steps:
providing the flame retardant;
mixing the flame retardant and polylactic acid to obtain a primary mixed material;
and melting and extruding the initial mixture to obtain the modified polylactic acid.
In the preparation method, the operation of melt extrusion of the initial mixture is as follows: and melting and extruding the initial mixture by a double-screw extruder, wherein the temperature of a machine barrel of the double-screw extruder from a feed end to a discharge end is gradually increased from 110 ℃ to 115 ℃, and the temperature of a machine head is 165-110 ℃.
Advantageous effects
The flame retardant is prepared from urea and/or melamine, modified lignin prepared from alkali lignin and formaldehyde and orthosilicic acid. On one hand, the hydroxymethylated lignin is obtained by the reaction of the alkali lignin and formaldehyde, wherein hydroxyl can react with hydroxyl in polylactic acid molecules, so that the compatibility with polylactic acid can be improved, and the alkali lignin also contains rigid benzene rings, so that the heat resistance can be improved; on the other hand, when the flame retardant formed by urea and/or melamine, modified lignin and orthosilicic acid is used for modifying polylactic acid, a compact and high-temperature-resistant Si-C layer can be formed on the surface of the polylactic acid under the combustion condition, the external oxygen is isolated from entering, meanwhile, the urea and the melamine are combusted to release nitrogen, and a large number of air holes are formed in the modified polylactic acid, so that a nitrogen layer which does not support combustion is formed in the air holes of the modified polylactic acid. Furthermore, the flame retardant contains a large number of benzene ring groups with stable structures, so that the thermal stability and the mechanical property of the polylactic acid can be greatly improved; under the synergistic effect of the components, the modified polylactic acid can obtain excellent flame retardant effect, and meanwhile, the thermal stability and the mechanical property of the modified polylactic acid are also improved. In addition, the alkali lignin for preparing the modified lignin comes from papermaking industrial waste, so that the cost is greatly reduced.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the invention provides a flame retardant, which comprises the following raw materials in parts by weight:
1 part of urea and/or melamine;
0.5 to 2 portions of orthosilicic acid; and
1-2 parts of modified lignin;
the modified lignin is prepared by the following method: mixing alkali lignin, formaldehyde and a solvent, and then heating and refluxing for reaction to obtain the modified lignin.
In the flame retardant, the mass ratio of the urea and/or melamine to the orthosilicic acid to the modified lignin is 1: 1: (1-2).
In the flame retardant, the mass ratio of the alkali lignin to the formaldehyde in the raw material for preparing the modified lignin is 1 (0.1-0.3).
In the flame retardant, the charging ratio of the alkali lignin to the solvent is 1g (4 mL-6 mL).
In the flame retardant, the solvent is at least one selected from alcohols and ethers having 1 to 10 carbon atoms.
In one embodiment, the solvent is ethanol, and the feed ratio of ethanol to alkali lignin is 4mL:1 g.
It is understood that the above-mentioned solvents are different, and the heating temperature is different, and the temperature can be reached to make the reaction system implement reflux reaction.
On the one hand, in the flame retardant comprising urea and/or melamine, modified lignin and ortho-silicic acid, the modified lignin is hydroxymethylated lignin obtained by reacting alkaline lignin with formaldehyde, and hydroxyl groups can react with hydroxyl groups at the ends of polylactic acid molecules, so that the compatibility with polylactic acid can be improved.
On the other hand, when the flame retardant formed by urea and/or melamine, modified lignin and orthosilicic acid is used for modifying polylactic acid, a compact and high-temperature-resistant Si-C layer can be formed on the surface of the polylactic acid under the combustion condition, the external oxygen is isolated from entering, meanwhile, the urea and the melamine are combusted to release nitrogen, and a large number of air holes are formed in the modified polylactic acid, so that a nitrogen layer which does not support combustion is formed in the air holes of the modified polylactic acid. Furthermore, the flame retardant contains a large number of benzene ring groups with stable structures, so that the thermal stability and the mechanical property of the polylactic acid can be greatly improved, the flame retardance and the heat resistance of the polylactic acid are greatly improved under the synergistic effect of all the components, meanwhile, the mechanical property of the polylactic acid is also improved, and the alkali lignin for preparing the modified lignin is derived from paper-making industrial wastes, so that the cost is greatly reduced.
Further, an embodiment of the present invention provides a method for preparing the above flame retardant, including the following steps S1-S3.
S1, mixing alkali lignin, formaldehyde and a solvent, and heating and refluxing for reaction to obtain the modified lignin.
In one embodiment, the alkali lignin, formaldehyde and solvent are mixed thoroughly in a high speed mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
In one embodiment, the solvent is ethanol, and the feed ratio of ethanol to alkali lignin is 4mL:1 g.
It is understood that the above-mentioned solvents are different, and the heating temperature is different, and the temperature can be reached to make the reaction system implement reflux reaction.
S2, mixing urea and/or melamine, ortho-silicic acid and the modified lignin obtained in the step S1, and reacting at 80-100 ℃ to obtain a prepolymer.
In one embodiment, urea and/or melamine, ortho-silicic acid and modified lignin are mixed and reacted at 80-100 ℃ until a large amount of bubbles are generated in the reaction system to obtain the prepolymer.
In one embodiment, the raw materials are added into a reactor in proportion, and the temperature is raised to 80-100 ℃ according to the temperature raising rate of 20 ℃/mi2 while stirring.
In the above operation of carrying out the reaction at a temperature of 80 to 100 ℃ until bubbles are generated, the number of bubbles is not limited, and the reaction may be carried out until a small amount or a large amount of bubbles are generated.
S3, calcining the prepolymer obtained in the step S2 at 220-240 ℃ for 2-3 h to obtain the flame retardant.
The embodiment of the invention also provides application of the flame retardant or the flame retardant prepared by the preparation method in preparation of polylactic acid.
The invention also provides modified polylactic acid, which comprises the following raw materials in parts by weight:
1 part of polylactic acid;
0.1 to 0.3 portion of flame retardant;
wherein the flame retardant is the flame retardant or the flame retardant prepared by the preparation method.
The modified polylactic acid prepared by the flame retardant has high mechanical strength, good heat resistance and good flame retardant effect, greatly reduces the cost and is more favorable for further expanding the actual application range of the polylactic acid.
The invention further provides a preparation method of the modified polylactic acid, which comprises the following steps of S10-S30.
S10, providing the flame retardant.
And S20, mixing the polylactic acid and the flame retardant to obtain a primary mixed material.
In one embodiment, the polylactic acid and the flame retardant are mixed thoroughly in a high-speed mixer.
It will be appreciated that the mixing process described above may also be carried out in other mixing devices, as long as adequate mixing of the materials is achieved.
S30, carrying out melt extrusion on the initial mixture to obtain the modified polylactic acid.
In one embodiment, the melt extrusion temperature is 110 ℃ to 110 ℃.
In one embodiment, the melt extrusion of the initial mixture is performed by: and melting and extruding the initial mixture by a double-screw extruder, wherein the temperature of a machine barrel of the double-screw extruder from a feed end to a discharge end is gradually increased from 110 ℃ to 115 ℃, and the temperature of a machine head is 165-110 ℃.
Preferably, the temperature of the die is less than the temperature of the discharge end of the barrel. Normally, the temperature of the head is set according to the temperature required for the product, but since the molten material in the twin-screw extruder flows from the barrel to the head, the temperature of the molten material coincides with the temperature of the discharge end of the barrel when the molten material flows to the discharge end of the barrel. The molten material then continues to flow forward to the head where it brings the previous temperature to the head causing the temperature to build up. Therefore, in the technical scheme of the preparation method of the modified polylactic acid, the temperature of the machine head is preferably lower than that of the discharge end of the machine barrel, and the temperature of the machine head is set to be slightly lower than the temperature required by a product, so that the phenomenon that the material performance is damaged due to the temperature aggregation of the machine head can be avoided.
The modified polylactic acid prepared by the preparation method has high mechanical strength, good heat resistance and good flame retardant effect, greatly reduces the cost and is more favorable for further expanding the actual application range of the polylactic acid.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Here, the flame retardant, the modified polylactic acid and the method for producing the same according to the present invention are exemplified, but the present invention is not limited to the following examples.
Example 1
1) Fully mixing 100g of alkali lignin, 25g of formaldehyde and 400mL of ethanol in a high-speed mixer, reacting for 1h at 10 ℃, filtering, and drying filter residues to obtain the modified lignin.
2) Adding 40g of melamine, 40g of orthosilicic acid and 60g of modified lignin obtained in the step 1) into a reactor for mixing, and heating to 100 ℃ for reaction at a heating rate of 20 ℃/mi2 while stirring until a large amount of bubbles are generated in a reaction system to obtain a prepolymer.
And pouring the prepolymer into a porcelain container, and placing the porcelain container into a constant temperature furnace at 240 ℃ to continue reacting for 2 hours to obtain the flame retardant.
3) And fully mixing 100g of polylactic acid and 20g of the flame retardant obtained in the step 2) in a high-speed mixer to obtain a primary mixed material.
And (3) carrying out melt extrusion granulation on the initial mixture through a double-screw extruder, wherein the double-screw extruder comprises a machine barrel and a machine head, and during extrusion granulation, the temperature of the machine barrel from a feed end to a discharge end is increased from 110 ℃ to 115 ℃, and the temperature of the machine head is 110 ℃ to obtain the modified polylactic acid.
Example 2
1) Fully mixing 100g of alkali lignin, 25g of formaldehyde and 400mL of ethanol in a high-speed mixer, reacting for 1h at 10 ℃, filtering, and drying filter residues to obtain the modified lignin.
2) Adding 40g of melamine, 40g of orthosilicic acid and 40g of modified lignin obtained in the step 1) into a reactor for mixing, and heating to 80 ℃ for reaction at a heating rate of 20 ℃/mi2 while stirring until a large amount of bubbles are generated in a reaction system to obtain a prepolymer.
And pouring the prepolymer into a porcelain container, and placing the porcelain container into a constant temperature furnace at 220 ℃ to continue reacting for 2.5 hours to obtain the flame retardant.
3) And fully mixing 100g of polylactic acid and 30g of the flame retardant obtained in the step 2) in a high-speed mixer to obtain a primary mixed material.
And (3) carrying out melt extrusion granulation on the initial mixture through a double-screw extruder, wherein the double-screw extruder comprises a machine barrel and a machine head, and during extrusion granulation, the temperature of the machine barrel from a feed end to a discharge end is increased from 110 ℃ to 115 ℃, and the temperature of the machine head is 110 ℃ to obtain the modified polylactic acid.
Example 3
1) Fully mixing 100g of alkali lignin, 30g of formaldehyde and 400mL of ethanol in a high-speed mixer, reacting for 0.5h at 80 ℃, filtering, and drying filter residues to obtain the modified lignin.
2) Adding 20g of melamine, 20g of urea, 80g of orthosilicic acid and 60g of the modified lignin obtained in the step 1) into a reactor for mixing, and heating to 100 ℃ for reaction at a heating rate of 20 ℃/mi2 while stirring until a large amount of bubbles are generated in a reaction system to obtain a prepolymer.
And pouring the prepolymer into a porcelain container, and placing the porcelain container into a constant temperature furnace at 240 ℃ to continue reacting for 2 hours to obtain the flame retardant.
3) And fully mixing 100g of polylactic acid and 25g of the flame retardant obtained in the step 2) in a high-speed mixer to obtain a primary mixed material.
And (3) carrying out melt extrusion granulation on the initial mixture through a double-screw extruder, wherein the double-screw extruder comprises a machine barrel and a machine head, and during extrusion granulation, the temperature of the machine barrel from a feed end to a discharge end is increased from 110 ℃ to 115 ℃, and the temperature of the machine head is 110 ℃ to obtain the modified polylactic acid.
Example 4
1) Fully mixing 100g of alkali lignin, 20g of formaldehyde and 400mL of ethanol in a high-speed mixer, reacting for 0.5h at 10 ℃, filtering, and drying filter residues to obtain the modified lignin.
2) Adding 40g of urea, 20g of orthosilicic acid and 80g of modified lignin obtained in the step 1) into a reactor for mixing, and heating to 90 ℃ for reaction at a heating rate of 20 ℃/mi2 while stirring until a large amount of bubbles are generated in a reaction system to obtain a prepolymer.
And pouring the prepolymer into a porcelain container, and placing the porcelain container into a constant temperature furnace at 220 ℃ to continue reacting for 2.5 hours to obtain the flame retardant.
3) And fully mixing 100g of polylactic acid and 10g of the flame retardant obtained in the step 2) in a high-speed mixer to obtain a primary mixed material.
And (3) carrying out melt extrusion granulation on the initial mixture through a double-screw extruder, wherein the double-screw extruder comprises a machine barrel and a machine head, and during extrusion granulation, the temperature of the machine barrel from a feed end to a discharge end is increased from 110 ℃ to 115 ℃, and the temperature of the machine head is 110 ℃ to obtain the modified polylactic acid.
Comparative example 1
1) Fully mixing 100g of alkali lignin, 25g of formaldehyde and 400mL of ethanol in a high-speed mixer, reacting for 1h at 10 ℃, filtering, and drying filter residues to obtain the modified lignin.
2) Adding 40g of melamine, 40g of orthosilicic acid and 20g of modified lignin obtained in the step 1) into a reactor for mixing, and heating to 100 ℃ for reaction at a heating rate of 20 ℃/mi2 while stirring until a large amount of bubbles are generated in a reaction system to obtain a prepolymer.
And pouring the prepolymer into a porcelain container, and placing the porcelain container into a constant temperature furnace at 240 ℃ to continue reacting for 2 hours to obtain the flame retardant.
3) And fully mixing 100g of polylactic acid and 20g of the flame retardant obtained in the step 2) in a high-speed mixer to obtain a primary mixed material.
And (3) carrying out melt extrusion granulation on the initial mixture through a double-screw extruder, wherein the double-screw extruder comprises a machine barrel and a machine head, and during extrusion granulation, the temperature of the machine barrel from a feed end to a discharge end is increased from 110 ℃ to 115 ℃, and the temperature of the machine head is 110 ℃ to obtain the modified polylactic acid.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that orthosilicic acid is replaced with phosphoric acid of equal mass.
Performance testing
1) The oxygen indexes of the modified polylactic acids prepared in examples 1 to 4 and comparative examples 1 to 2 were measured according to the GJBJ5231-2003, and the results are shown in Table 1.
2) Tensile strength tests were performed on the modified polylactic acids obtained in examples 1 to 4 and comparative examples 1 to 2: the results are shown in Table 1, performed according to the standard GB/T1040-2006.
3) Modified polylactic acids obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to Thermogravimetric analysis (TGA) under an oxygen atmosphere at a temperature rise rate of 5 ℃/mi2, respectively, and the initial decomposition temperatures were 5% of the polymer weight loss and are shown in table 1.
TABLE 1 flame retardancy, mechanical Properties, Heat resistance of modified polylactic acid
As can be seen from the results in Table 1, the oxygen index of the modified polylactic acids of examples 1 to 4 is larger than that of the modified polylactic acids of comparative examples 1 to 2, indicating that the modified polylactic acids of examples 1 to 4 have good flame retardancy.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The flame retardant is characterized by comprising the following preparation raw materials in parts by weight:
1 part of urea and/or melamine;
0.5 to 2 portions of orthosilicic acid; and
1-2 parts of modified lignin;
the modified lignin is prepared by the following method: mixing alkali lignin, formaldehyde and a solvent, and then heating and refluxing for reaction to obtain the modified lignin.
2. Flame retardant according to claim 1, characterized in that the mass ratio of urea and/or melamine, orthosilicic acid and modified lignin is 1: 1: (1-2).
3. The flame retardant according to claim 1, wherein the mass ratio of the alkali lignin to the formaldehyde in the raw material for producing the modified lignin is 1 (0.1 to 0.3).
4. The flame retardant of claim 3, wherein the dosage ratio of the alkali lignin to the solvent is 1g (4 mL-6 mL).
5. The flame retardant according to any one of claims 1 to 4, wherein the solvent is at least one selected from the group consisting of alcohols and ethers having 1 to 10 carbon atoms.
6. The method for preparing the flame retardant according to any one of claims 1 to 5, comprising the steps of:
mixing alkali lignin, formaldehyde and a solvent, and then heating and refluxing for reaction to obtain modified lignin;
mixing urea and/or melamine, orthosilicic acid and the modified lignin, and reacting at 80-100 ℃ to obtain a prepolymer;
and calcining the prepolymer at 220-240 ℃ for 2-3 h to obtain the flame retardant.
7. Use of the flame retardant according to any one of claims 1 to 5 or the flame retardant prepared by the preparation method according to claim 6 in the preparation of modified polylactic acid.
8. The modified polylactic acid is characterized by comprising the following raw materials in parts by weight:
1 part of polylactic acid;
0.1 to 0.3 portion of flame retardant;
wherein the flame retardant is the flame retardant of any one of claims 1 to 5 or the flame retardant prepared by the preparation method of claim 6.
9. The method for producing a modified polylactic acid according to claim 8, comprising the steps of:
providing said flame retardant;
mixing the flame retardant and polylactic acid to obtain a primary mixed material;
and melting and extruding the initial mixture to obtain the modified polylactic acid.
10. A method of making as set forth in claim 9 wherein melt extruding the initial mix is by: and melting and extruding the initial mixed material in a double-screw extruder, wherein the temperature of a machine barrel of the double-screw extruder from a feed end to a discharge end is gradually increased from 110 ℃ to 175 ℃, and the temperature of a machine head of the double-screw extruder is 165-170 ℃.
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| CN112625356A (en) * | 2020-12-21 | 2021-04-09 | 东北师范大学 | Lignin-based melamine phosphorus-containing flame retardant, and preparation method and application thereof |
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