CN115975359B - A bio-based flame retardant and degradable composition and preparation method thereof - Google Patents
A bio-based flame retardant and degradable composition and preparation method thereof Download PDFInfo
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Abstract
本发明涉及阻燃可降解领域，特别涉及一种生物基阻燃可降解组合物及其制备方法。其中，所述一种生物基阻燃可降解组合物包括以下制备原料：PCL树脂、PLA树脂、变性淀粉、生物基阻燃剂、相容剂、增韧剂、抗氧化剂，与现有技术相比，本发明通过利用竹纤维素微晶独特的棒状纳米材料，通过表面改性和负载相结合处理方法，制备竹纤维素微晶负载苯基磷酸‑牛磺酸(PHPA‑PA)，形成高效阻燃酸源，同时，通过对淀粉进行变性处理，解决传统淀粉粘度高、亲水能力强、容易糊化等缺点，以变性淀粉作为碳源，竹纤维素微晶负载苯基磷酸‑牛磺酸(PHPA‑PA)作为酸源，复配PCL、PLA树脂及其他加工助剂，开发出一种生物基阻燃可降解组合物，解决传统的生物基材料阻燃性能不佳，而阻燃剂不可再生且不可降解相矛盾问题，拓宽可降解材料应用领域。
The present invention relates to the flame retardant and degradable field, and particularly to a bio-based flame retardant and degradable composition and a preparation method thereof. Wherein, the bio-based flame retardant and degradable composition includes the following raw materials for preparation: PCL resin, PLA resin, modified starch, bio-based flame retardant, compatibilizer, toughening agent, antioxidant, compared with the prior art, the present invention uses the unique rod-shaped nanomaterials of bamboo cellulose microcrystals, and combines surface modification and loading to prepare bamboo cellulose microcrystals loaded with phenyl phospho-taurine (PHPA-PA), forming an efficient flame retardant acid source, and at the same time, by modifying starch, the shortcomings of high viscosity, strong hydrophilicity, and easy gelatinization of traditional starch are solved, modified starch is used as a carbon source, bamboo cellulose microcrystals loaded with phenyl phospho-taurine (PHPA-PA) are used as an acid source, PCL, PLA resin and other processing aids are compounded, and a bio-based flame retardant and degradable composition is developed, which solves the poor flame retardancy of traditional bio-based materials, and the contradiction between non-renewable and non-degradable flame retardants, and broadens the application field of degradable materials.
Description
Technical Field
The invention relates to the field of flame retardance and degradability, in particular to a bio-based flame retardance and degradability composition and a preparation method thereof.
Background
In daily life, plastics exist on the aspect of our life, and various convenience is brought to us. Due to the consumption of petroleum resources and the problem of biodegradation of petroleum-based polymers in recent years, there is an increasing demand for biobased materials as degradable and renewable materials.
The bio-based polymer material is a polymer material with renewable and degradable characteristics. The modified polypropylene has good biocompatibility and processability, can be widely applied to the fields of automobile industry, electronic products and the like, and is an ideal petroleum-based polymer substitute material. However, the bio-based polymer material is very easy to burn as the conventional petroleum-based polymer material, and the application field is limited to a great extent, so that a flame retardant needs to be added to improve the flame retardant property. Most of the current flame retardants are not renewable and not degradable, which contradicts the renewable and degradable advantages of the bio-based polymer materials.
Disclosure of Invention
In order to solve the contradiction between flame retardance and degradability in the background art, the invention aims to develop a bio-based flame retardance degradable composition which comprises the following preparation raw materials of PCL resin, PLA resin, modified starch, bio-based flame retardant, compatilizer, toughening agent and antioxidant. The flame retardant material has the advantages of being renewable and degradable while improving the flame retardant purpose of the material, and the application field is widened.
Based on the scheme, the material further comprises the following raw materials in parts by weight:
Based on the scheme, the preparation method of the bio-based flame retardant is as follows:
(1) Preparing a phenyl phosphoric acid-taurine (PHPA-PA) solution with the concentration of 1-2 mol/L, and adding an alkaline regulator to adjust the acid-base value of the solution to about 7-7.5 to obtain a solution A;
(2) Adding surface modified bamboo cellulose microcrystals into the solution A, stirring and heating to 50-70 ℃ to enable the surface modified bamboo cellulose microcrystals to fully react for 12-24 hours, and obtaining a product B after the reaction is completed;
(3) And (3) centrifuging, drying and grinding the product B to obtain the bio-based flame retardant.
Based on the scheme, the preparation method of the phenyl phosphate-taurine (PHPA-PA) solution comprises the following steps:
(1) Adding 20g of 60% phenylphosphoric acid solution into a flask filled with 100mL of deionized water, and adding ammonia water to adjust the pH value of the solution to 4-5 to obtain solution A;
(2) Weighing 3g of taurine, adding the taurine into the solution A, heating to 80-100 ℃, and fully stirring and reacting for 6-12 hours to obtain a reaction liquid B;
(3) And removing deionized water from the reaction liquid by using a rotary evaporator at the temperature of 80-100 ℃, cooling the concentrated reaction liquid to room temperature, adding the cooled reaction liquid into 300-500 mL of ethanol, and separating out a product in the ethanol in a precipitation form. Filtering, washing with ethanol for 3-5 times, and then drying in a vacuum oven at 60-80 ℃ for 24-48 hours to obtain phenyl phosphoric acid-taurine (PHPA-PA) solution with the yield of 78.2%.
Based on the scheme, the preparation method of the surface modified bamboo cellulose microcrystal further comprises the following steps:
(1) Preparing an ethanol solution with the ratio of ethanol to purified water of 70/30 (mass fraction) in a beaker, adding a coupling agent into the ethanol water solution, and slowly adding acetic acid to adjust the pH value of the solution to 4-6 to obtain a solution A;
(2) Adding bamboo cellulose microcrystal into the solution A, reacting for 1-5 h at 50-65 ℃, centrifuging for 20-60 min by a centrifuge after the reaction is finished, and obtaining a surface modified bamboo cellulose microcrystal primary product at a centrifugal speed of 2000-4000 r/min;
(3) And (3) drying the primary product of the surface modified bamboo cellulose microcrystal, cleaning with deionized water and absolute ethyl alcohol for 3-5 times, and finally drying in vacuum to obtain the surface modified bamboo cellulose microcrystal.
On the basis of the above scheme, further, in the step (2), the coupling agent is at least one of silane coupling agents KH-550, KH-560 and KH-570.
Based on the scheme, the PCL resin is polycaprolactone resin, the melt flow rate (160 ℃ per 2.16 kg) is 5-7 g/10min, the PLA resin is polylactic acid resin, and the melt flow rate (190 ℃ per 2.16 kg) is 15-30 g/10min.
On the basis of the scheme, the preparation method of the modified starch comprises the steps of weighing a certain amount of starch and water, adding the starch and the water into a reaction container, stirring, heating to 40-60 ℃ while stirring, sequentially adding acetic anhydride and toluene-4-sulfonic acid for reaction, adding pH regulating solution to regulate the pH value to 7-8, finally adding a cross-linking agent for reaction, regulating the pH value to be neutral, and washing, drying and crushing to obtain the modified starch.
Based on the scheme, the compatilizer is at least one of POE-g-MAH, EAA-g-MAH and EVA-g-MAH, the toughening agent is at least one of POE, EVA and EAA, and the weight ratio of the antioxidants 168 and 1010 is 1 (1-5).
The invention provides a preparation method of the bio-based flame retardant degradable composition, which comprises the following steps:
step one, mixing and discharging PCL resin, PLA resin, modified starch, a bio-based flame retardant, a compatilizer, a toughening agent and an antioxidant to obtain a bio-based flame retardant degradable composition mixture;
and secondly, carrying out melt extrusion on the bio-based flame-retardant degradable composition mixture through a double-screw extruder to obtain a bio-based flame-retardant degradable composition modified material.
Based on the scheme, in the second step, the working parameters of the twin-screw extruder are that the temperature of the first area is 45-60 ℃, the temperature of the second area is 110-150 ℃, the temperature of the third area is 150-170 ℃, the temperature of the fourth area is 170-190 ℃, the temperature of the fifth area is 160-180 ℃, the temperature of the die head is 110-130 ℃, the feeding speed is 100-200 r/min, and the screw rotating speed is 200-300 r/min.
Compared with the prior art, the bio-based flame-retardant degradable composition and the preparation method thereof provided by the invention have the following technical principles and beneficial effects:
The traditional flame retardant is prepared by complex reaction of chemical raw materials, and has better flame retardant effect, but the preparation process usually involves a large amount of non-renewable chemical raw materials, even a large amount of organic solvents, is not renewable and degradable biomass in the full sense, and cannot truly realize renewable and degradable sustainable development, while most of the current bio-based flame retardants are derived from nature, but are required to be subjected to complex post-treatment, purification and other processing processes, have the problems of high production cost, poor heat stability and the like, are easy to degrade and blacken in the polymer processing process, influence the practical application value,
According to the invention, the unique rod-shaped nano material of the bamboo cellulose microcrystal is utilized, the characteristics of high specific surface area, strong adsorption capacity, high reactivity, large Young modulus and the like are utilized, the bamboo cellulose microcrystal is prepared by a surface modification and load combined treatment method, so that an efficient flame-retardant acid source is formed, meanwhile, the starch is subjected to denaturation treatment, acetic anhydride is adopted to carry out substitution reaction on starch hydroxyl groups, so that the intermolecular hydrogen bonding effect of the starch is weakened, the melting temperature of the starch is reduced, the thermoplasticity and hydrophobicity of the starch and hot melting processability are improved, the defects of high viscosity, strong hydrophilicity, easy gelatinization and the like of the traditional starch are overcome, the modified starch is used as a carbon source, and the PCL, PLA resin and other processing aids are compounded, so that the bio-based flame-retardant degradable composition is developed, the problems of poor flame retardant property, irreproducible and undegradable contradiction of the flame retardant are solved, and the application field of the degradable material is widened.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is an SEM image of a bio-based flame retardant provided by the present invention;
FIG. 2 is a TEM image of a bio-based flame retardant provided by the invention;
FIG. 3 is an SEM image of a combustion carbon layer of a bio-based flame retardant degradable composition provided by the invention;
fig. 4 is an SEM image of a combustion char layer of a degradable composition without the addition of a bio-based flame retardant.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention also provides the following embodiments:
in the following examples and comparative examples, the following preparation materials were used for each raw material:
PCL resin, polycaprolactone resin, model 6500, melt flow rate (160 ℃ C./2.16 kg) 5-7 g/10min, selected from Sweden Ingevity;
PLA resin, namely polylactic acid resin, wherein the model is LX575, and the melt flow rate (190 ℃ C./2.16 kg) is 15-30 g/10Min, and is selected from Taylor Dall;
The modified starch is BEST-2 with water content less than or equal to 10% and is selected from Sanming Baishida starch Co., ltd;
the compatilizer is POE-g-MAH, EAA-g-MAH and EVA-g-MAH which are all commercial products;
POE, EVA, EAA are all commercial products;
Antioxidants a mixture of antioxidants 168 and 1010, both commercially available products selected from the company Yantai chemical Co., guangzhou.
Examples 1-5 and comparative examples 1-4:
table 1 list of the components and proportions of examples 1-5 and comparative examples 1-4
The preparation method comprises the following steps:
The preparation method of the bio-based flame retardant comprises the following steps:
(1) Preparing a phenyl phosphoric acid-taurine (PHPA-PA) solution with the concentration of 1.5mol/L, and adding an alkaline regulator to adjust the pH value of the solution to about 7.5 to obtain a solution A;
(2) Adding surface modified bamboo cellulose microcrystal into the solution A, stirring and heating to 60 ℃ to fully react for 18 hours, and obtaining a product B after the reaction is completed;
(3) And (3) centrifuging, drying and grinding the product B to obtain the bio-based flame retardant. SEM and TEM images of the prepared bio-based flame retardant are shown in fig. 1.
In the scheme, the preparation method of the phenyl phosphate-taurine (PHPA-PA) solution comprises the following steps:
(1) Adding 20g of 60% phenylphosphoric acid solution into a flask filled with 100mL of deionized water, and adding ammonia water to adjust the pH value of the solution to 5 to obtain solution A;
(2) Weighing 3g of taurine, adding the taurine into the solution A, heating to 80 ℃, and fully stirring and reacting for 10 hours to obtain a reaction liquid B;
(3) The reaction liquid was freed from deionized water by rotary evaporator at a temperature of 90℃and, after cooling the concentrated reaction liquid to room temperature, taken into 350mL of ethanol, the product was precipitated in ethanol as a precipitate. Filtering, washing with ethanol for 5 times, and drying in a vacuum oven at 70 ℃ for 30 hours to obtain phenyl phosphoric acid-taurine (PHPA-PA) solution with the yield of 78.2%.
In the scheme, the preparation method of the surface modified bamboo cellulose microcrystal comprises the following steps:
(1) Preparing an ethanol solution with the ratio of ethanol to purified water of 70/30 (mass fraction) in a beaker, adding a coupling agent into the ethanol water solution, and slowly adding acetic acid to adjust the pH value of the solution to 6 to obtain a solution A;
(2) Adding bamboo cellulose microcrystal into the solution A, reacting for 4 hours at the temperature of 60 ℃, centrifuging for 50 minutes by a centrifuge after the reaction is finished, and obtaining a surface modified bamboo cellulose microcrystal primary product at the centrifugal speed of 3500 r/min;
(3) And (3) drying the primary product of the surface modified bamboo cellulose microcrystal, cleaning the primary product of the surface modified bamboo cellulose microcrystal with deionized water and absolute ethyl alcohol for 4 times, and finally drying the primary product of the surface modified bamboo cellulose microcrystal in vacuum to obtain the surface modified bamboo cellulose microcrystal.
The modified starch is prepared through the steps of weighing starch and water, stirring in a reaction container, heating to 50 deg.c while stirring, adding acetic anhydride and toluene-4-sulfonic acid to react, adding pH regulator to regulate pH value to 7.5, adding cross-linking agent to react, regulating pH value to neutrality, washing, stoving and crushing.
A method of preparing a bio-based flame retardant degradable composition comprising the steps of:
step one, mixing and discharging PCL resin, PLA resin, modified starch, a bio-based flame retardant, a compatilizer, a toughening agent and an antioxidant to obtain a bio-based flame retardant degradable composition mixture;
And secondly, carrying out melt extrusion on the bio-based flame-retardant degradable composition mixture through a double-screw extruder to obtain a bio-based flame-retardant degradable composition modified material. The working parameters of the double-screw extruder are that the temperature of the first area is 55 ℃, the temperature of the second area is 115 ℃, the temperature of the third area is 155 ℃, the temperature of the fourth area is 180 ℃, the temperature of the fifth area is 175 ℃, the temperature of the die head is 125 ℃, the feeding speed is 150r/min, and the rotating speed of the screw is 250r/min. The SEM image of the prepared bio-based flame retardant degradable composition combustion carbon layer is shown in figure 2, the SEM image of the non-bio-based flame retardant degradable composition combustion carbon layer is shown in figure 3, and the comparison of the SEM images can obviously show that the prepared bio-based flame retardant degradable composition combustion carbon layer is more compact and has better flame retardant effect than the non-bio-based flame retardant degradable composition combustion carbon layer.
Specific performance tests and results were evaluated as follows:
The samples obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to a vertical burning rating test according to GB/T2408-2021 "horizontal and vertical method for determination of Plastic burning Properties", a limiting oxygen index test according to "oxygen index for Plastic determination of burning behavior section 2: room temperature test", a 180d biodegradation rate was subjected to a Performance test according to ISO14855-1-2012 ", and the test results are shown in Table 2.
TABLE 2 test results for examples 1-5 and comparative examples 1-4
As can be seen from the results in Table 2, the addition of the bio-based flame retardant in examples 1 to 5 and comparative examples 1 to 4 can effectively improve the flame retardant property of the degradable material, the material of comparative example 1 is not added with the bio-based flame retardant, the material of comparative example 1 basically has no flame retardant property, and the flame retardant effect of comparative example 2 is obviously inferior to that of the modified starch compound bio-based flame retardant by using the common starch instead of the modified starch, which means that the bio-based flame retardant has good synergistic effect with the modified starch. And the comparative examples 3-4 are respectively that the bio-based flame retardant and the modified starch are not added and the bio-based flame retardant is not added alone, and the flame retardant effect is far less than that of the material by compounding the bio-based flame retardant with the modified starch. Therefore, the flame retardant performance of the PCL/PLA biodegradable material can be effectively improved by adopting the bio-based flame retardant to compound modified starch, and the bio-based flame retardant is green and degradable. According to the technical scheme, the unique rod-shaped nano material of the bamboo cellulose microcrystal is utilized, the surface modification and load combined treatment method is utilized to prepare the bamboo cellulose microcrystal loaded phenyl phosphate-taurine (PHPA-PA) as an acid source, and meanwhile, the modified starch is used as a carbon source to compound PCL, PLA resin and other processing aids, so that the bio-based flame-retardant degradable composition is developed, the problems that the traditional bio-based material is poor in flame retardant performance, and the flame retardant is not renewable and not degradable are contradictory are solved, and the application field of the degradable material is widened.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (4)
1. The bio-based flame-retardant degradable composition is characterized by comprising the following components in parts by weight:
20-30 parts of PCL resin;
20-35 parts of PLA resin;
5-15 parts of modified starch;
5-10 parts of a bio-based flame retardant;
2-6 parts of a compatilizer;
5-15 parts of a toughening agent;
0.2-1 parts of an antioxidant;
the preparation method of the bio-based flame retardant comprises the following steps:
(1) Preparing a phenyl phosphoric acid-taurine PHPA-PA solution with the concentration of 1-2 mol/L, and adding an alkaline regulator to adjust the acid-base value of the solution to about 7-7.5 to obtain a solution A;
(2) Adding surface modified bamboo cellulose microcrystals into the solution A, stirring and heating to 50-70 ℃ to enable the surface modified bamboo cellulose microcrystals to fully react for 12-24 hours, and obtaining a product B after the reaction is completed;
(3) Centrifuging, drying and grinding the product B to obtain a bio-based flame retardant;
the preparation method of the phenylphosphoric acid-taurine PHPA-PA solution comprises the following steps:
(1) Adding a 60% phenylphosphoric acid solution of 20 g into a flask filled with 100mL deionized water, and adding ammonia water to adjust the pH value of the solution to 4-5 to obtain a solution C;
(2) Weighing 3g of taurine, adding the taurine into the solution C, heating to 80-100 ℃, and fully stirring and reacting for 6-12 hours to obtain a reaction liquid D;
(3) Removing deionized water from the reaction liquid D by using a rotary evaporator at the temperature of 80-100 ℃, cooling the concentrated reaction liquid to room temperature, adding the reaction liquid into 300-500 mL of ethanol, separating out a product in the ethanol in a precipitation form, filtering, washing the product with ethanol for 3-5 times, and then placing the product in a vacuum oven at 60-80 ℃ for drying for 24-48 hours to obtain a PHPA-PA solution with the yield of 78.2%;
The preparation method of the modified starch comprises the steps of weighing a certain amount of starch and water, adding the starch and the water into a reaction container, stirring, heating to 40-60 ℃ while stirring, sequentially adding acetic anhydride and toluene-4-sulfonic acid for reaction, adding pH regulating solution to regulate the pH value to 7-8, finally adding a cross-linking agent for reaction, regulating the pH value to be neutral, and washing, drying and crushing to obtain the modified starch.
2. The bio-based flame retardant degradable composition of claim 1, wherein the preparation method of the surface modified bamboo cellulose microcrystals is as follows:
(1) Preparing an ethanol solution with the mass fraction ratio of ethanol to pure water of 70/30 in a beaker, adding a coupling agent into the ethanol water solution, and slowly adding acetic acid to adjust the pH value of the solution to 4-6 to obtain a solution E;
(2) Adding the bamboo cellulose microcrystal into the solution E, reacting for 1-5 hours at the temperature of 50-65 ℃, and centrifuging for 20-60 minutes by a centrifuge after the reaction is finished, wherein the centrifugal speed is 2000-4000 r/min, so as to obtain a surface modified bamboo cellulose microcrystal primary product;
(3) Drying the primary product of the surface modified bamboo cellulose microcrystal, cleaning the primary product of the surface modified bamboo cellulose microcrystal with deionized water and absolute ethyl alcohol for 3-5 times, and finally drying the primary product of the surface modified bamboo cellulose microcrystal in vacuum to obtain the surface modified bamboo cellulose microcrystal;
the coupling agent in the step (1) is at least one of silane coupling agents KH-550, KH-560 and KH-570.
3. The bio-based flame retardant degradable composition of claim 1, wherein the compatilizer is at least one of POE-g-MAH, EAA-g-MAH and EVA-g-MAH, the toughening agent is at least one of POE, EVA and EAA, and the weight ratio of the antioxidants 168 and 1010 is 1 (1-5).
4. A method of preparing a bio-based flame retardant degradable composition according to any of claims 1-3, comprising the steps of:
step one, mixing and discharging PCL resin, PLA resin, modified starch, a bio-based flame retardant, a compatilizer, a toughening agent and an antioxidant to obtain a bio-based flame retardant degradable composition mixture;
and secondly, carrying out melt extrusion on the mixture of the bio-based flame-retardant degradable composition through a double-screw extruder to obtain the bio-based flame-retardant degradable composition.
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| CN1832951A (en) * | 2003-06-09 | 2006-09-13 | 大八化学工业株式会社 | Organophosphorus compound having phosphate-phosphonate bond, flame-retardant polyester fiber using same, and flame-retardant polyurethane resin composition |
| CN109517188A (en) * | 2018-10-17 | 2019-03-26 | 广东省测试分析研究所（中国广州分析测试中心） | A kind of biology base composite flame-retardant agent and its application |
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| CN1832951A (en) * | 2003-06-09 | 2006-09-13 | 大八化学工业株式会社 | Organophosphorus compound having phosphate-phosphonate bond, flame-retardant polyester fiber using same, and flame-retardant polyurethane resin composition |
| CN109517188A (en) * | 2018-10-17 | 2019-03-26 | 广东省测试分析研究所（中国广州分析测试中心） | A kind of biology base composite flame-retardant agent and its application |
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