CN114752115B - Flame-retardant modified cellulose and polylactic acid based composite material and preparation method thereof - Google Patents
Flame-retardant modified cellulose and polylactic acid based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant modified cellulose and polylactic acid based composite material and a preparation method thereof; the cellulose modification method comprises the following steps: adding cellulose to Ti 3 C 2 Ultrasonically dispersing in a nano sheet water solution, and then reacting at 20-80 ℃ to obtain Ti 3 C 2 A coated cellulose; mixing Ti 3 C 2 Adding the coated cellulose into a mixed solution of water and ethanol for ultrasonic dispersion, then adding a silane coupling agent containing active sulfydryl, and reacting for 0.5-12 h at the temperature of 0-60 ℃ to obtain cellulose modified by the silane coupling agent; adding the cellulose modified by the silane coupling agent into a toluene solution containing an acid binding agent for ultrasonic dispersion, then dropwise adding CDPP under the protection of nitrogen, and reacting for 0.5-12 h at 0-60 ℃ after dropwise adding is finished to obtain the flame-retardant modified cellulose. The flame-retardant modified cellulose has excellent flame-retardant property and interface compatibility.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a flame-retardant modified cellulose and polylactic acid based composite material and a preparation method thereof.
Background
Polylactic acid (PLA) is a nontoxic, completely biodegradable thermoplastic linear aliphatic polymer, has good mechanical properties, and is widely applied to the related fields of biomedicine, textile clothing, packaging materials, electronic and electric appliances and the like. However, the flame retardant has poor thermal stability, is inflammable (the limiting oxygen index is only about 20 percent), has only UL-94HB flame retardant performance, and is accompanied with serious dripping phenomenon during combustion. Therefore, improving the flame retardant property of PLA is of great significance to expand its practical applications. The blending modification with the flame-retardant filler is the simplest and most effective method for improving the flame-retardant property of the PLA. Common flame-retardant fillers include halogen-based, metal hydroxide, phosphorus/nitrogen/silicon-based, intumescent, natural polymer and other flame retardants. Among them, natural polymer flame retardants (chitosan, starch, cellulose, etc.) have received increasing attention due to their advantages of being biodegradable, environmentally friendly, etc. Cellulose is a renewable biodegradable natural polymer material with excellent mechanical strength, but the low flame retardant property limits the large-scale application of cellulose as a flame retardant additive in composite materials.
Patent document CN112521662A discloses a nitrogen and phosphorus element containing modified cellulose flame retardant, which improves the flame retardant property of polymer and the interfacial compatibility between the substrate and the flame retardant, but has the problems of limited improvement of flame retardant effect, high addition amount, etc. In addition, in order to improve the flame retardant performance of cellulose, patent document No. CN112521662A discloses that a cellulose stock solution and inorganic Ti are mixed 3 C 2 The flame retardant is blended and spun to prepare the composite cellulose flame retardant, but the composite cellulose flame retardant is embedded in the cellulose to ensure that Ti is contained 3 C 2 The flame retardant effect is inhibited to a certain extent, and the preparation process of the composite cellulose is complex and has poor interface compatibility with a polymer matrix.
Disclosure of Invention
Based on the defects in the prior art, the invention provides a flame-retardant modified cellulose/polylactic acid composite material and a preparation method thereof.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of flame-retardant modified cellulose comprises the following steps:
(1) Adding cellulose to Ti 3 C 2 Ultrasonically dispersing in a nanosheet aqueous solution, then reacting for 0.5-12 h at 20-80 ℃, and after the reaction is finished, carrying out vacuum filtration and drying to obtain Ti 3 C 2 A coated cellulose;
(2) Mixing Ti 3 C 2 Adding the coated cellulose into a mixed solution of water and ethanol for ultrasonic dispersion, then adding a silane coupling agent containing active sulfydryl, reacting for 0.5-12 h at 0-60 ℃, and after the reaction is finished, carrying out vacuum filtration and drying to obtain the cellulose modified by the silane coupling agent;
(3) Adding the cellulose modified by the silane coupling agent into a toluene solution containing an acid binding agent for ultrasonic dispersion, then dropwise adding CDPP under the protection of nitrogen, reacting at 0-60 ℃ for 0.5-12 h after dropwise adding, and performing vacuum filtration and drying after the reaction is finished to obtain the flame-retardant modified cellulose.
Preferably, the Ti is 3 C 2 In the coated cellulose, ti 3 C 2 The coating amount of the nano sheet on the cellulose is 1-5 wt%.
Preferably, the modification amount of the reactive mercapto group-containing silane coupling agent is Ti 3 C 2 0.1-10% of the content of the nano sheet.
Preferably, the molar ratio of the CDPP to the silane coupling agent containing a reactive mercapto group is 1:1.
Preferably, the silane coupling agent containing an active mercapto group is at least one of KH580, KH590, TESPD and TESPT.
Preferably, in the step (2), the volume ratio of water to ethanol is 1: (0.5-10).
Preferably, the acid-binding agent is at least one of sodium acetate, sodium carbonate, potassium carbonate, triethylamine, diisopropylethylamine and pyridine.
The invention also provides the flame-retardant modified cellulose prepared by the preparation method in any one of the above schemes.
The invention also provides a preparation method of the polylactic acid-based composite material, which comprises the following steps:
uniformly mixing the dried polylactic acid and the flame-retardant modified cellulose according to the scheme, and then extruding to obtain a polylactic acid-based composite material;
wherein the extrusion is carried out by adopting a double-screw extruder, and the extrusion temperature is set to be 150-170-185-180 ℃.
The invention also provides a polylactic acid-based composite material prepared by the preparation method, wherein the content of the flame-retardant modified cellulose in the polylactic acid-based composite material is 1-30 wt%.
Compared with the prior art, the invention has the beneficial effects that:
the flame-retardant modified cellulose of the invention firstly utilizes flame-retardant Ti 3 C 2 The nano-sheet coats cellulose, and then Ti is sequentially coated by using a mercaptosilane coupling agent and CDPP 3 C 2 Carrying out surface modification to obtain flame-retardant modified cellulose; the flame-retardant modified cellulose contains inorganic flame-retardant Ti 3 C 2 The flame retardant is rich in silicon-sulfur-phosphorus flame retardant elements with organic flame retardant cellulose, and can exert the flame retardant effect synergistically; in addition, the mercapto silane coupling agent and the CDPP surface modification endow the flame-retardant modified cellulose and a polymer matrix with better interface compatibility, the flame retardance and the enhancement are integrated, and after the flame-retardant modified cellulose and the polylactic acid are fused and blended, the obtained polylactic acid-based composite material can obtain better flame retardance and mechanical properties.
The preparation process of the flame-retardant modified cellulose is simple and mild, and the raw materials are wide in source; the polylactic acid-based composite material has low cost and excellent comprehensive performance.
Drawings
Fig. 1 shows SEM photographs (a, C) before and after coating of cellulose in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following specific examples.
Example 1:
the preparation method of the flame-retardant modified cellulose comprises the following steps:
1) 5g of cellulose was added to 100mL of a solution having a concentration of 2 mg. Multidot.mL -1 Ti 3 C 2 Ultrasonically dispersing for 30min in a nanosheet aqueous solution, then reacting for 3h at 60 ℃, and after the reaction is finished, carrying out vacuum filtration and drying to obtain Ti 3 C 2 A coated cellulose; as shown in FIG. 1, ti was confirmed 3 C 2 The nanosheets were successfully coated onto the surface of the cellulose.
2) 2g of the cellulose obtained in step 1) was added to 40mL of a mixed solution of water and ethanol (water: alcohol volume ratio =1: 4) And (3) ultrasonically dispersing for 30min, then dropwise adding 0.5mL KH580 silane coupling agent into the dispersion liquid, reacting for 6h at 30 ℃, and after the reaction is finished, carrying out vacuum filtration and drying to obtain the cellulose modified by the silane coupling agent.
3) Adding 2g of the cellulose obtained in the step 2) into a toluene solution containing triethylamine, performing ultrasonic dispersion, then dropwise adding CDPP under the condition of nitrogen protection, reacting at 30 ℃ for 6 hours after dropwise adding, and performing vacuum filtration and drying after the reaction to obtain the flame-retardant modified cellulose.
The preparation method of the polylactic acid-based composite material of the embodiment comprises the following steps:
firstly, drying polylactic acid in an oven for 24 hours;
then, the flame-retardant modified cellulose of the embodiment and the dried polylactic acid are mixed uniformly;
finally, extruding the mixture of the flame-retardant modified cellulose and the polylactic acid by using a double-screw extruder, wherein the extrusion temperature is 150-170-185-180 ℃, and the screw rotation speed is 25rpm; after repeating the extrusion 3 times, the polylactic acid-based composite material obtained was obtained.
Wherein the mass fraction of the flame-retardant modified cellulose in the polylactic acid-based composite material is 10%.
The polylactic acid-based composite material of the present example was injection molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 1:
this comparative example differs from example 1 in that: mixing cellulose and Ti 3 C 2 KH580 and CDCarrying out physical blending on PP to obtain blended modified cellulose; then, the blended modified cellulose is used for replacing the flame-retardant modified cellulose in the example 1 to prepare the polylactic acid-based composite material;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 2:
this comparative example differs from example 1 in that:
in the process of step 1), the cellulose is mixed with Ti 3 C 2 The powder is physically blended until uniform to obtain Ti 3 C 2 A mixture of cellulose;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 3:
this comparative example differs from example 1 in that:
mixing Ti 3 C 2 Physically blending the coated cellulose with KH580 and CDPP to modify the cellulose;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 4:
this comparative example differs from example 1 in that:
the silane coupling agent adopts KH550 for surface modification reaction, and the KH550 does not contain sulfydryl;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 5:
this comparative example differs from example 1 in that:
directly physically blending the cellulose modified by the silane coupling agent with CDPP to obtain blended modified cellulose;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 6:
the comparative example differs from example 1 in that:
commercial Al (OH) is adopted 3 The flame retardant replaced the flame retardant modified cellulose in example 1;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
Comparative example 7:
this comparative example differs from example 1 in that:
commercial dimethyl methylphosphonate flame retardant was used in place of the flame retardant modified cellulose in example 1;
the other steps and process conditions were the same as in example 1.
The polylactic acid-based composite material of the present comparative example was injection-molded into a standard sample to test the flame retardant property and mechanical properties of the composite material.
The polylactic acid-based composite materials of example 1 and comparative examples 1 to 7 and the pure polylactic acid material were subjected to a limiting oxygen index test (LOI) and a vertical burning (UL 94) test, and the specific test results are shown in table 1.
TABLE 1 flame retardancy of the samples of the examples and comparative examples
The results of example 1 and comparative example 1 show that the Ti content is higher than that of the other 3 C 2 KH580, CDPP chemically modified cellulose and polylactic acid are blended to obtain the composite material with the flame retardant effect far higher than that of Ti 3 C 2 KH580, CDPP and lactic acid;
comparative example 2 shows that Ti 3 C 2 Coating cellulose surface area ratio Ti 3 C 2 The flame retardant is directly blended with cellulose, so that the flame retardant effect is better;
comparative example 3 shows that KH580 and CDPP are chemically attached to Ti 3 C 2 The surface ratio of the coated cellulose is KH580, CDPP and Ti 3 C 2 The coated cellulose has better flame retardant effect by blending;
comparative example 4 shows that after the cellulose is modified, the modified cellulose has better flame retardant and lifting effects compared with the modified cellulose without the S element;
comparative example 5 shows that chemical attachment of CDPP to the cellulose surface can enhance the flame retardant effect of the polylactic acid composite;
comparative examples 6 and 7 show that, at the same addition ratio, the modified cellulose is more than commercial Al (OH) 3 Has better flame retardant effect with dimethyl methylphosphonate flame retardant.
In addition, the polylactic acid-based composite materials and the pure polylactic acid materials in example 1 and comparative examples 1 to 7 were also subjected to mechanical property tests, and the specific test results are shown in table 2.
TABLE 2 mechanical properties of the samples of the examples and comparative examples
The results of example 1 and comparative example 1 show that the Ti content is higher than that of the other 3 C 2 KH580, CDPP chemically modified cellulose and polylactic acid are blended to obtain the composite material with mechanical property far higher than that of Ti 3 C 2 KH580, CDPP and lactic acid;
comparative example 2 shows that Ti 3 C 2 Coating cellulose surface area ratio Ti 3 C 2 The cellulose is directly blended with the cellulose, so that a better mechanical enhancement effect is achieved;
comparative example 3 shows that KH580 is chemically attached to Ti with CDPP 3 C 2 Coated cellulose surface ratio KH580, CDPP and Ti 3 C 2 The coated cellulose has better mechanical enhancement effect by blending;
comparative example 4 shows that the existence of the S element in the modified cellulose has no obvious influence on the mechanical property of the polylactic acid composite material;
comparative example 5 shows that the CDPP on the surface of the modified cellulose has no obvious influence on the mechanical property of the polylactic acid composite material;
comparative examples 6 and 7 show that, at the same addition ratio, al (OH) is used commercially 3 The mechanical property of the polylactic acid composite material is reduced by the flame retardant of dimethyl methylphosphonate; the modified cellulose can obviously improve the mechanical property of the polylactic acid composite material.
The chemical modification principle of the flame-retardant modified cellulose is as follows:
1. ti 3 C 2 The abundant hydroxyl on the surface of the nanosheet is connected with the hydroxyl on the surface of the cellulose in a reaction way to obtain Ti 3 C 2 Cellulose coated with nanosheets; wherein, ti 3 C 2 Has flame retardant effect;
2. the siloxane groups on the silane coupling agent containing reactive mercapto groups are hydrolyzed to hydroxyl groups, and Ti 3 C 2 Connecting the hydroxyl on the surface of the nanosheet; si and S elements contained in the mercapto-coupling agent can resist flame;
3. reacting the P-Cl bond on the CDPP with the active S of the coupling agent to obtain the flame-retardant modified cellulose; wherein, CDPP is phosphorus flame retardant molecule, its P element can be flame retardant.
In view of numerous embodiments of the scheme of the invention, all components, component contents and process parameters can be determined in corresponding ranges according to application requirements, and experimental data of each embodiment is huge and numerous and is not suitable for being enumerated and explained one by one, but the contents to be verified and the final conclusion obtained by each embodiment are approximate.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. The preparation method of the flame-retardant modified cellulose is characterized by comprising the following steps of:
(1) Adding cellulose to Ti 3 C 2 Ultrasonically dispersing in a nanosheet aqueous solution, then reacting for 0.5-12 h at 20-80 ℃, and after the reaction is finished, carrying out vacuum filtration and drying to obtain Ti 3 C 2 A coated cellulose;
(2) Mixing Ti 3 C 2 Adding the coated cellulose into a mixed solution of water and ethanol for ultrasonic dispersion, then adding a silane coupling agent containing active sulfydryl, reacting for 0.5-12 h at 0-60 ℃, and after the reaction is finished, carrying out vacuum filtration and drying to obtain the cellulose modified by the silane coupling agent;
(3) Adding the cellulose modified by the silane coupling agent into a toluene solution containing an acid binding agent for ultrasonic dispersion, then dropwise adding CDPP under the protection of nitrogen, reacting at 0-60 ℃ for 0.5-12 h after dropwise adding, and performing vacuum filtration and drying after the reaction is finished to obtain the flame-retardant modified cellulose.
2. The method for preparing flame-retardant modified cellulose according to claim 1, wherein the Ti is Ti 3 C 2 In the coated cellulose, ti 3 C 2 The coating amount of the nano sheet on the cellulose is 1-5 wt%.
3. A flame retardant modification according to claim 2The preparation method of cellulose is characterized in that the modification amount of the silane coupling agent containing active sulfydryl is Ti 3 C 2 0.1-10% of the content of the nano sheet.
4. The method of claim 3, wherein the molar ratio of CDPP to silane coupling agent containing reactive mercapto group is 1:1.
5. the method for preparing the flame-retardant modified cellulose according to any one of claims 1 to 4, wherein the silane coupling agent containing the active mercapto group is at least one of KH580, KH590, TESPD and TESPT.
6. The method for preparing the flame-retardant modified cellulose according to any one of claims 1 to 4, wherein in the step (2), the volume ratio of water to ethanol is 1: (0.5-10).
7. The method for preparing the flame-retardant modified cellulose according to any one of claims 1 to 4, wherein the acid-binding agent is at least one of sodium acetate, sodium carbonate, potassium carbonate, triethylamine, diisopropylethylamine and pyridine.
8. A flame-retardant modified cellulose obtained by the production method according to any one of claims 1 to 7.
9. A method for preparing a polylactic acid-based composite material, which is characterized by comprising the following steps:
uniformly mixing the dried polylactic acid and the flame-retardant modified cellulose as defined in claim 8, and then extruding to obtain a polylactic acid-based composite material;
wherein the extrusion is carried out by adopting a double-screw extruder, and the extrusion temperature is set to be 150-170-185-180 ℃.
10. The polylactic acid-based composite material according to the preparation method of claim 9, wherein the flame retardant modified cellulose is contained in the polylactic acid-based composite material in an amount of 1 to 30wt%.
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