CN111471217A - Modified nano cerium oxide and preparation method thereof, and modified nano cerium oxide flame-retardant polyformaldehyde and preparation method thereof - Google Patents
Modified nano cerium oxide and preparation method thereof, and modified nano cerium oxide flame-retardant polyformaldehyde and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified nano cerium oxide, which comprises a modifier, nano cerium oxide, deionized water and ethanol, wherein the modifier is any one or a combination of more of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH570, the mass of the modifier is 1-7% of that of the nano cerium oxide, and the unmodified nano cerium oxide has the characteristics of easy agglomeration, hydrophilicity and oleophobicity, poor compatibility with polymers such as polyformaldehyde and the like; the modified polyformaldehyde material has the advantages of obviously improving the dispersibility, obviously improving the compatibility with polyformaldehyde and improving the flame retardant property of polyformaldehyde.
Description
Technical Field
The invention belongs to the field of inorganic flame retardant modification and flame retardant application, and particularly relates to modified nano cerium oxide and a preparation method thereof, and modified nano cerium oxide flame retardant polyformaldehyde and a preparation method thereof.
Background
Polyformaldehyde is used as engineering plastic with excellent comprehensive performance, has high mechanical property, elastic modulus, rigidity and hardness, and is widely applied to the fields of electric appliances, automobiles and the like. However, the limit oxygen index of polyformaldehyde is only 15%, and the characteristics of easy combustion (Ma Xiao Feng. plastic industry, 2017,45(10): 113-. The flame retardant properties of polyoxymethylene are mainly achieved by the addition of various flame retardants (Zhang Qing et al. plastics science 2009,11: 31-33). However, the problems that various additive flame retardants are not matched with polyformaldehyde at present, toxic gas is released in the combustion process, whether a proper synergistic additive can be found or not and the like still exist.
Cerium oxide is an important rare earth product and is widely applied to the fields of metallurgy, energy, chemical industry, agriculture, materials and the like (Zhang Fu quan. Guangdong chemical industry 2014,41(19): 48-49). The invention patent with application publication number CN107759965A discloses that nano cerium oxide has a certain function of synergistic flame retardant polyformaldehyde. However, since the nano cerium oxide has fine particles, extremely high surface energy and extremely high surface activity, and is easy to agglomerate when doped into polyoxymethylene, as shown in fig. 4, fig. 4 is an electron microscope image of a polyoxymethylene composite material prepared from unmodified nano cerium oxide, and it can be seen from the image that the nano cerium oxide is not uniformly dispersed in a polyoxymethylene body, which results in interface defects and material performance degradation.
Disclosure of Invention
The invention aims to provide modified nano cerium oxide and a preparation method thereof, and modified nano cerium oxide flame-retardant polyformaldehyde and a preparation method thereof.
In order to solve the problems, the technical scheme of the invention is as follows:
a modified nano cerium oxide comprises a modifier, nano cerium oxide, deionized water and ethanol, wherein the modifier is any one or a combination of more of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH570, and the mass of the modifier is 1-7% of that of the nano cerium oxide.
Based on the same inventive concept, the invention also provides a preparation method of the modified nano cerium oxide, which comprises the following steps:
s1: mixing deionized water and ethanol in a certain proportion to prepare a solvent;
s2: weighing a certain amount of modifier, and dissolving the modifier in a certain amount of the solvent prepared in the step S1 to obtain a modifier solution, wherein the modifier is any one or a combination of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH 570;
s3: weighing a certain amount of nano cerium oxide, placing the nano cerium oxide in a certain amount of the solvent prepared in the step S1, heating in a water bath, and heating to 50-70 ℃ to obtain a nano cerium oxide solution;
s4: adding the modifier solution prepared in the step S2 into the nano cerium oxide solution prepared in the step S3 for reaction at the temperature of 50-70 ℃ for 1-2 hours, and performing vacuum filtration after the reaction is finished;
s5: and (5) drying the reaction product obtained in the step (S4) in a drying oven at the drying temperature of 50-70 ℃ for 6-10 h to obtain the modified nano cerium oxide.
Preferably, the ratio of the deionized water to the ethanol is 1: 1-2: 1.
based on the same inventive concept, the invention also provides modified nano cerium oxide flame-retardant polyformaldehyde, which comprises the modified nano cerium oxide and polyformaldehyde, wherein the mass of the modified nano cerium oxide is 0.5-10% of that of the polyformaldehyde.
Based on the same inventive concept, the invention also provides a preparation method of the modified nano cerium oxide flame-retardant polyformaldehyde, which comprises the following steps:
a1: weighing a certain amount of polyformaldehyde, putting the polyformaldehyde into an internal mixer for melt blending, wherein the melting temperature of the internal mixer is 185-195 ℃, the first melting time is 20-60 min, and the melt rotating speed is 20-40 r/min;
a2: weighing a certain amount of the modified nano cerium oxide, adding the modified nano cerium oxide into the polyformaldehyde prepared in the step A1, and continuously carrying out banburying melting blending, wherein the second melting time is 10-60 min;
a3: crushing the polyformaldehyde material prepared in the step A2 by using a crusher;
a4: and B, performing injection molding on the polyoxymethylene material crushed in the step A3 through an injection molding machine.
Preferably, the injection molding temperature in the step A4 is 180-200 ℃.
Preferably, the injection molding pressure in the step A4 is 0.6-1 MPa.
Preferably, the injection molding dwell time in the step A4 is 2-4 s.
Preferably, the step a1 specifically includes:
a11: weighing a certain amount of polyformaldehyde, and placing the polyformaldehyde in a drying oven for drying at the drying temperature of 50-70 ℃ for 6-10 hours;
a12: and B, placing the polyformaldehyde dried in the step A11 into an internal mixer for melt blending, wherein the melting temperature of the internal mixer is 185-195 ℃, the first melting time is 20-60 min, and the melt rotating speed is 20-40 r/min.
Preferably, in the step A1, the melting temperature of the internal mixer is 190 ℃, the first melting time is 40min, and the melt rotation speed is 30 r/min.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
1) the invention provides a modified nano cerium oxide, which comprises a modifier, nano cerium oxide, deionized water and ethanol, wherein the modifier is any one or a combination of more of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH570, the mass of the modifier is 1-7% of that of the nano cerium oxide, and the unmodified nano cerium oxide has the characteristics of easy agglomeration, hydrophilicity and oleophobicity, poor compatibility with polymers such as polyformaldehyde and the like; the modified polyformaldehyde material has the advantages of obviously improving the dispersibility, obviously improving the compatibility with polyformaldehyde and improving the flame retardant property of polyformaldehyde.
2) The invention also provides a preparation method of the modified nano cerium oxide, which comprises the steps of mixing deionized water and ethanol in a certain proportion to prepare a solvent; then weighing a certain amount of modifier, placing the modifier in a solvent, and heating to dissolve the modifier, wherein the modifier is any one or a combination of more of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH 570; weighing a certain amount of nano cerium oxide, placing the nano cerium oxide in the obtained solvent, carrying out water bath heating reaction at the temperature of 50-70 ℃ for 1-2 h, and carrying out vacuum filtration treatment after the reaction is finished; and finally, placing a reaction product obtained by the water-bath heating reaction in a drying oven for drying at the drying temperature of 50-70 ℃ for 6-10 h to obtain the modified nano cerium oxide, wherein the modified nano cerium oxide obtained by the preparation method has the advantages of obviously improved dispersity, obviously improved compatibility with polyformaldehyde and improved flame retardant property for polyformaldehyde.
3) The invention also provides a modified nano cerium oxide flame-retardant polyformaldehyde, which comprises the modified nano cerium oxide and polyformaldehyde, wherein the mass of the modified nano cerium oxide is 0.5-10% of that of the polyformaldehyde, and the flame-retardant property of the polyformaldehyde is obviously improved by the added modified nano cerium oxide.
Drawings
FIG. 1 is a flow chart of a method for preparing modified nano cerium oxide according to an embodiment of the present invention;
FIG. 2 is a flow chart of a preparation method of modified nano cerium oxide flame-retardant paraformaldehyde according to an embodiment of the present invention;
FIG. 3 is a detailed flowchart of step A1 in FIG. 2;
FIG. 4 is an electron microscope image of a polyoxymethylene composite prepared from unmodified nano cerium oxide;
FIG. 5 is an electron microscope image of modified nano-cerium oxide flame-retardant polyoxymethylene prepared in example V of the present invention;
FIG. 6 is an electron microscope image of modified nano-cerium oxide flame-retardant polyoxymethylene prepared in example six of the present invention;
FIG. 7 is an electron microscope image of modified nano-cerium oxide flame-retardant polyoxymethylene prepared in example VII of the present invention;
FIG. 8 is an electron microscope image of modified nano cerium oxide flame-retardant polyoxymethylene prepared in example eight of the present invention.
Description of reference numerals:
S1-S5: a step of; A1-A4: a step of; A11-A12: and (5) carrying out the following steps.
Detailed Description
The modified nano cerium oxide and the preparation method thereof, and the modified nano cerium oxide flame-retardant polyoxymethylene and the preparation method thereof proposed by the present invention are further described in detail below with reference to the accompanying drawings and specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims.
The test items and methods adopted by the invention are introduced as follows:
(1) modified nano cerium oxide activation index test
The method of putting the modified nano cerium oxide on the water surface evenly and freely sinking is adopted. The change of the polarity of the nano cerium oxide can generate huge surface tension and present the phenomenon of floating like an oil film. The activation index (g) of the floating part of the sample/the total mass (g) of the sample) is 100%, so as to characterize the polarity change degree of the modified nano cerium oxide.
(2) Oleophilic degree test of modified nano cerium oxide
1g of modified nano cerium oxide powder is placed on 50ml of water surface by adopting an oleophilic degree testing method, then methanol is dropwise added until the powder is completely wetted, and the adding amount V (ml) of the methanol is recorded, wherein the oleophilic degree is V/(50+ V) × 100%, and the parameter is used for representing the oleophilic degree of the modified cerium oxide.
(3) Determination of cross-sectional morphology characteristics of modified nano cerium oxide flame-retardant polyformaldehyde
The surface appearance of the section of the polyformaldehyde prepared by the modified nano cerium oxide is observed by adopting a field emission Scanning Electron Microscope (SEM), and the dispersibility and compatibility of the nano cerium oxide in the polyformaldehyde are represented.
(4) Determination of flame retardant property of modified nano cerium oxide flame retardant polyformaldehyde
And (3) determining the flame retardant property of the modified nano cerium oxide/polyformaldehyde composite material by adopting a limit oxygen index instrument and a vertical combustion experiment according to the national standard GB/T2406.1-2008.
(5) Determination of mechanical properties of modified nano cerium oxide flame-retardant polyformaldehyde
And (3) measuring the mechanical properties of the modified nano cerium oxide/polyformaldehyde composite material by using a universal tester according to the national standard GB/T1039-1992, and measuring the tensile strength.
Example one
The embodiment provides a modified nano cerium oxide, which comprises a modifier, nano cerium oxide, deionized water and ethanol, wherein the modifier is any one or a combination of several of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH570, and the mass of the modifier is 1-7% of that of the nano cerium oxide.
The unmodified nano cerium oxide has the characteristics of easy agglomeration, hydrophilicity and oleophobicity, and poor compatibility with polymers such as polyformaldehyde and the like; the modified nano cerium oxide provided by the embodiment is modified to obviously improve the dispersibility of the modified nano cerium oxide, obviously improve the compatibility of the modified nano cerium oxide with polyformaldehyde, and improve the flame retardant property of the modified nano cerium oxide to polyformaldehyde.
Example two
Referring to fig. 1, this example provides a method for preparing modified nano cerium oxide, including the following steps:
s1: mixing deionized water and ethanol in a certain proportion to prepare a solvent, wherein in the embodiment, the proportion of the deionized water to the ethanol is 1: 1-2: 1;
s2: weighing a certain amount of modifier, placing the modifier in a certain amount of solvent prepared in step S1, and dissolving to obtain a modifier solution, in this embodiment, fully stirring with a high-speed dispersion machine to fully dissolve the modifier, wherein the modifier is any one or a combination of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH 570;
s3: weighing a certain amount of nano cerium oxide, placing the nano cerium oxide in a certain amount of the solvent prepared in the step S1, heating in a water bath, and heating to 50-70 ℃ to obtain a nano cerium oxide solution;
in this embodiment, a certain amount of nano cerium oxide is weighed and placed in a drying oven for drying, then the dried nano cerium oxide powder is placed in a certain amount of the solvent prepared in step S1 for sufficient stirring, and the solution is placed in a three-neck flask and heated in a water bath to 60 ℃ to obtain a nano cerium oxide solution;
s4: adding the modifier solution prepared in the step S2 into the nano cerium oxide solution prepared in the step S3 for reaction at the temperature of 50-70 ℃ for 1-2 hours, and performing vacuum filtration after the reaction is finished;
in the embodiment, the modifier solution prepared in step S2 is slowly added into a three-neck flask, continuously stirred, heated at a constant temperature of 60 ℃ for 2 hours, filtered by a circulating water vacuum pump after the reaction is finished, and washed with deionized water for three times;
s5: and (5) drying the reaction product obtained in the step (S4) in a drying oven at the drying temperature of 50-70 ℃ for 6-10 h to obtain a light yellow solid, namely the modified nano cerium oxide, wherein the drying temperature is 60 ℃ and the drying time is 8h in the embodiment.
EXAMPLE III
The embodiment provides a modified nano cerium oxide flame-retardant polyformaldehyde, which comprises the modified nano cerium oxide and polyformaldehyde, wherein the mass of the modified nano cerium oxide is 0.5-10% of that of the polyformaldehyde. The embodiment obviously improves the flame retardant property of polyformaldehyde through the added modified nano cerium oxide.
Example four
Referring to fig. 2, this embodiment provides a preparation method of modified nano cerium oxide flame-retardant polyformaldehyde, which includes the following steps:
a1: weighing a certain amount of polyformaldehyde, putting the polyformaldehyde into an internal mixer for melt blending, wherein the melting temperature of the internal mixer is 185-195 ℃, the first melting time is 20-60 min, and the melt rotating speed is 20-40 r/min;
in this embodiment, referring to fig. 3, step a1 specifically includes:
a11: weighing a certain amount of polyformaldehyde, and placing the polyformaldehyde in a drying oven for drying at the drying temperature of 50-70 ℃ for 6-10 hours;
a12: b, placing the polyformaldehyde dried in the step A11 into an internal mixer for melt blending, wherein the melting temperature of the internal mixer is 185-195 ℃, the first melting time is 20-60 min, and the melt rotating speed is 20-40 r/min;
a2: weighing a certain amount of the modified nano cerium oxide, adding the modified nano cerium oxide into the polyformaldehyde prepared in the step A1, and continuously carrying out banburying melting blending, wherein the second melting time is 10-60 min;
a3: crushing the polyformaldehyde material prepared in the step A2 by using a crusher;
a4: the polyformaldehyde material crushed in the step A3 is subjected to injection molding through an injection molding machine, in the embodiment, the parameters of the injection molding machine are set as follows, and the temperature of an injection molding charging barrel is 180-200 ℃, preferably 190 ℃; the injection molding pressure is 0.6-1 MPa, preferably 0.8 MPa; the injection molding dwell time is 2-4 s, preferably 3 s.
Preferably, in the step A1, the melting temperature of the internal mixer is 190 ℃, the first melting time is 40min, and the melt rotation speed is 30 r/min.
EXAMPLE five
Weighing 20g of nano cerium oxide powder, and drying in a constant temperature drying oven at 60 ℃ for 8 h. Taking the solution with the ratio of the absolute ethyl alcohol to the deionized water of 1:1, uniformly stirring in a beaker, and compounding to obtain a mixed solvent for later use. And pouring a certain amount of the mixed solution of absolute ethyl alcohol and deionized water into the dried nano cerium oxide powder, and fully stirring. And taking 20ml of anhydrous ethanol and deionized water at a ratio of 1:1 to dissolve in a beaker, weighing 4g of KH570, and uniformly stirring by using a magnetic stirrer. Transferring the nano cerium oxide solution into a three-neck flask, heating the nano cerium oxide solution to 60 ℃ in a water bath, slowly adding the KH570 solution into the three-neck flask, and continuously stirring. Heating at a constant temperature of 60 ℃ for 2h, performing suction filtration by using a circulating water type vacuum pump after the reaction is finished, washing for three times by using deionized water, and then placing the reaction product in a constant-temperature drying oven at 60 ℃ for drying for 8h to obtain a light yellow solid, namely the nano cerium oxide powder modified by the modifier;
weighing 796g of polyformaldehyde, and placing in an electric heating constant-temperature air-blast drying oven at 60 ℃ for drying for 8 hours; using an experimental internal mixer to carry out internal mixing on the completely dried polyformaldehyde at the temperature of 190 ℃, and regulating the rotating speed to be 30 r/min; opening the vertical air pump after 20min, and adding 4g of nano cerium oxide powder modified by KH 570; closing the vertical air pump, continuously carrying out banburying for 20min, and taking out the polyformaldehyde material subjected to banburying; crushing the polyformaldehyde material by using a crusher, and filling into a sealing bag; the polyformaldehyde material is made into a sample strip by using an injection molding machine, and the parameters of the injection molding machine are set as follows: the temperature of the charging barrel is 190 ℃, the pressure is 0.8MPa, and the pressure maintaining time is 3 s; and standing the molded sample strip for 12h to obtain the required flame-retardant polyformaldehyde sample strip.
Referring to fig. 5, the nano cerium oxide added to the flame-retardant polyoxymethylene prepared in this example is modified by a modifier KH570, and the modified nano cerium oxide is distributed more uniformly in the composite material than the unmodified nano cerium oxide, so that the agglomeration phenomenon is significantly reduced, and the compatibility between the nano cerium oxide and the polyoxymethylene is also greater, which proves that the nano cerium oxide modified by the modifier has a better modification effect, reduces the agglomeration phenomenon in the material, and enhances the compatibility with the material.
Referring to table 1, the modified nano-cerium oxide and flame-retardant polyoxymethylene samples prepared in this example have the following test results through detection:
TABLE 1 test results of modified nano-cerium oxide and flame-retardant polyoxymethylene samples
Test items | Test results |
Activation index of modified cerium oxide | 89% |
Oleophilic degree of modified cerium oxide | 18.03% |
Oxygen index of flame-retardant polyoxymethylene | 19% |
Flame rating of flame retardant polyoxymethylene | V-2 |
Tensile strength/MPa of flame-retardant polyoxymethylene | 25.11 |
EXAMPLE six
Weighing 20g of nano cerium oxide powder, and drying in a constant temperature drying oven at 60 ℃ for 8 h. Taking the solution with the ratio of the absolute ethyl alcohol to the deionized water of 1:1, uniformly stirring in a beaker, and compounding to obtain a mixed solvent for later use. And pouring a certain amount of the mixed solution of absolute ethyl alcohol and deionized water into the dried nano cerium oxide powder, and fully stirring. And additionally taking 20ml of a solution with the ratio of the absolute ethyl alcohol to the deionized water being 1:1, dissolving 4g of stearic acid in the solution, and uniformly stirring the solution by using a magnetic stirrer. Transferring the nano cerium oxide solution into a three-neck flask, heating the three-neck flask to 60 ℃ in a water bath, slowly adding the stearic acid solution into the three-neck flask, and continuously stirring. Heating at a constant temperature of 60 ℃ for 2h, performing suction filtration by using a circulating water type vacuum pump after the reaction is finished, washing for three times by using deionized water, and then placing the reaction product in a constant-temperature drying oven at 60 ℃ for drying for 8h to obtain a light yellow solid, namely the nano cerium oxide powder modified by the modifier;
weighing 796g of polyformaldehyde, and placing in an electric heating constant-temperature air-blast drying oven at 60 ℃ for drying for 8 hours; using an experimental internal mixer to carry out internal mixing on the completely dried polyformaldehyde at the temperature of 190 ℃, and regulating the rotating speed to be 30 r/min; opening the vertical air pump after 20min, and adding 4g of stearic acid modified nano cerium oxide powder; closing the vertical air pump, continuously carrying out banburying for 20min, and taking out the polyformaldehyde material subjected to banburying; crushing the polyformaldehyde material by using a crusher, and filling into a sealing bag; the polyformaldehyde material is made into a sample strip by using an injection molding machine, and the parameters of the injection molding machine are set as follows: the temperature of the charging barrel is 190 ℃, the pressure is 0.8MPa, and the pressure maintaining time is 3 s; and standing the molded sample strip for 12h to obtain the required flame-retardant polyformaldehyde sample strip.
Referring to fig. 6, the nano cerium oxide added to the flame-retardant polyoxymethylene prepared in this embodiment is modified by the modifier stearic acid, and the modified nano cerium oxide is distributed more uniformly in the composite material than the unmodified nano cerium oxide, so that the agglomeration phenomenon is significantly reduced, and the compatibility between the nano cerium oxide and the polyoxymethylene is also greater, which proves that the nano cerium oxide modified by the modifier has a better modification effect, reduces the agglomeration phenomenon in the material, and enhances the compatibility with the material.
Referring to table 2, the modified nano-cerium oxide and flame-retardant polyoxymethylene samples prepared in this example have the following test results through detection:
TABLE 2 test results of modified nano-cerium oxide and flame-retardant polyoxymethylene samples
Test items | Test results |
Activation index of modified cerium oxide | 91% |
Oleophilic degree of modified cerium oxide | 19.35% |
Oxygen index of flame-retardant polyoxymethylene | 19% |
Flame rating of flame retardant polyoxymethylene | V-2 |
Tensile strength/MPa of flame-retardant polyoxymethylene | 25.59 |
EXAMPLE seven
Weighing 20g of nano cerium oxide powder, and drying in a constant temperature drying oven at 60 ℃ for 8 h. Taking anhydrous ethanol and deionized water according to the proportion of 3: the solution of 2 is evenly stirred in a beaker and is compounded into a mixed solvent for standby. And pouring a certain amount of the mixed solution of absolute ethyl alcohol and deionized water into the dried nano cerium oxide powder, and fully stirring. And taking anhydrous ethanol and deionized water according to the proportion of 3: 2 in a beaker, 4g of sodium dodecyl sulfate was weighed out and dissolved in the solution, and stirred uniformly by a magnetic stirrer. Transferring the nano cerium oxide solution into a three-neck flask, heating the three-neck flask to 60 ℃ in a water bath, slowly adding the sodium dodecyl sulfate solution into the three-neck flask, and continuously stirring. Heating at a constant temperature of 60 ℃ for 2h, performing suction filtration by using a circulating water type vacuum pump after the reaction is finished, washing for three times by using deionized water, and then placing the reaction product in a constant-temperature drying oven at 60 ℃ for drying for 8h to obtain a light yellow solid, namely the nano cerium oxide powder modified by the modifier;
weighing 796g of polyformaldehyde, and placing in an electric heating constant-temperature air-blast drying oven at 60 ℃ for drying for 8 hours; using an experimental internal mixer to carry out internal mixing on the completely dried polyformaldehyde at the temperature of 190 ℃, and regulating the rotating speed to be 30 r/min; opening the vertical air pump after 20min, and adding 4g of sodium dodecyl sulfate modified nanometer cerium oxide powder; closing the vertical air pump, continuously carrying out banburying for 20min, and taking out the polyformaldehyde material subjected to banburying; crushing the polyformaldehyde material by using a crusher, and filling into a sealing bag; the polyformaldehyde material is made into a sample strip by using an injection molding machine, and the parameters of the injection molding machine are set as follows: the temperature of the charging barrel is 190 ℃, the pressure is 0.8MPa, and the pressure maintaining time is 3 s; and standing the molded sample strip for 12h to obtain the required flame-retardant polyformaldehyde sample strip.
Referring to fig. 7, the nano cerium oxide added to the flame-retardant polyoxymethylene prepared in this example is modified by the modifier sodium dodecyl sulfate, and the modified nano cerium oxide is distributed more uniformly in the composite material than the unmodified nano cerium oxide, so that the agglomeration phenomenon is significantly reduced, and the compatibility between the nano cerium oxide and the polyoxymethylene is also greater, which proves that the nano cerium oxide modified by the modifier has a better modification effect, reduces the agglomeration phenomenon in the material, and enhances the compatibility with the material.
Referring to table 3, the modified nano-cerium oxide and flame-retardant polyoxymethylene samples prepared in this example have the following test results through detection:
TABLE 3 test results of modified nano-cerium oxide and flame-retardant polyoxymethylene samples
Test items | Test results |
Activation index of modified cerium oxide | 89% |
Oleophilic degree of modified cerium oxide | 18.7% |
Oxygen index of flame-retardant polyoxymethylene | 20% |
Flame rating of flame retardant polyoxymethylene | V-2 |
Tensile strength/MPa of flame-retardant polyoxymethylene | 28.62 |
Example eight
Weighing 20g of nano cerium oxide powder, and drying in a constant temperature drying oven at 60 ℃ for 8 h. Taking anhydrous ethanol and deionized water according to the proportion of 2: the solution of 1 is evenly stirred in a beaker and is compounded into a mixed solvent for standby. And pouring a certain amount of the mixed solution of absolute ethyl alcohol and deionized water into the dried nano cerium oxide powder, and fully stirring. And taking anhydrous ethanol and deionized water according to the proportion of 2: 1 in a beaker, 4g of sodium dodecyl sulfate was weighed out and dissolved in the solution, and stirred uniformly by a magnetic stirrer. Transferring the nano cerium oxide solution into a three-neck flask, heating the three-neck flask to 60 ℃ in a water bath, slowly adding the sodium dodecyl sulfate solution into the three-neck flask, and continuously stirring. Heating at a constant temperature of 60 ℃ for 2h, performing suction filtration by using a circulating water type vacuum pump after the reaction is finished, washing for three times by using deionized water, and then placing the reaction product in a constant-temperature drying oven at 60 ℃ for drying for 8h to obtain a light yellow solid, namely the nano cerium oxide powder modified by the modifier;
weighing 796g of polyformaldehyde, and placing in an electric heating constant-temperature air-blast drying oven at 60 ℃ for drying for 8 hours; using an experimental internal mixer to carry out internal mixing on the completely dried polyformaldehyde at the temperature of 190 ℃, and regulating the rotating speed to be 30 r/min; opening the vertical air pump after 20min, and adding 4g of sodium dodecyl sulfate modified nanometer cerium oxide powder; closing the vertical air pump, continuously carrying out banburying for 20min, and taking out the polyformaldehyde material subjected to banburying; crushing the polyformaldehyde material by using a crusher, and filling into a sealing bag; the polyformaldehyde material is made into a sample strip by using an injection molding machine, and the parameters of the injection molding machine are set as follows: the temperature of the charging barrel is 190 ℃, the pressure is 0.8MPa, and the pressure maintaining time is 3 s; and standing the molded sample strip for 12h to obtain the required flame-retardant polyformaldehyde sample strip.
Referring to fig. 8, the nano cerium oxide added to the flame-retardant polyoxymethylene prepared in this example is modified by the modifier sodium dodecyl sulfate, and the modified nano cerium oxide is distributed more uniformly in the composite material than the unmodified nano cerium oxide, so that the agglomeration phenomenon is significantly reduced, and the compatibility between the nano cerium oxide and the polyoxymethylene is also relatively high, which proves that the nano cerium oxide modified by the modifier has a relatively good modification effect, reduces the agglomeration phenomenon in the material, and enhances the compatibility with the material.
Referring to table 4, the modified nano-cerium oxide and flame-retardant polyoxymethylene samples prepared in this example have the following test results through detection:
TABLE 4 test results of modified nano-cerium oxide and flame-retardant polyoxymethylene samples
Test items | Test results |
Activation index of modified cerium oxide | 68% |
Oleophilic degree of modified cerium oxide | 10.71% |
Oxygen index of flame-retardant polyoxymethylene | 19% |
Flame rating of flame retardant polyoxymethylene | V-2 |
Tensile strength/MPa of flame-retardant polyoxymethylene | 27.47 |
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, it is still within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (10)
1. The modified nano cerium oxide is characterized by comprising a modifier, nano cerium oxide, deionized water and ethanol, wherein the modifier is any one or a combination of more of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH570, and the mass of the modifier is 1-7% of that of the nano cerium oxide.
2. A preparation method of modified nano cerium oxide is characterized by comprising the following steps:
s1: mixing deionized water and ethanol in a certain proportion to prepare a solvent;
s2: weighing a certain amount of modifier, and dissolving the modifier in a certain amount of the solvent prepared in the step S1 to obtain a modifier solution, wherein the modifier is any one or a combination of polyethylene glycol, stearic acid, sodium dodecyl sulfate, KH550 and KH 570;
s3: weighing a certain amount of nano cerium oxide, placing the nano cerium oxide in a certain amount of the solvent prepared in the step S1, heating in a water bath, and heating to 50-70 ℃ to obtain a nano cerium oxide solution;
s4: adding the modifier solution prepared in the step S2 into the nano cerium oxide solution prepared in the step S3 for reaction at the temperature of 50-70 ℃ for 1-2 hours, and performing vacuum filtration after the reaction is finished;
s5: and (5) drying the reaction product obtained in the step (S4) in a drying oven at the drying temperature of 50-70 ℃ for 6-10 h to obtain the modified nano cerium oxide.
3. The method for preparing modified nano cerium oxide according to claim 2, wherein the ratio of the deionized water to the ethanol is 1: 1-2: 1.
4. a modified nano cerium oxide flame-retardant polyformaldehyde is characterized by comprising the modified nano cerium oxide and polyformaldehyde of claim 1, wherein the mass of the modified nano cerium oxide is 0.5-10% of that of the polyformaldehyde.
5. A preparation method of modified nano cerium oxide flame-retardant polyformaldehyde is characterized by comprising the following steps:
a1: weighing a certain amount of polyformaldehyde, putting the polyformaldehyde into an internal mixer for melt blending, wherein the melting temperature of the internal mixer is 185-195 ℃, the first melting time is 20-60 min, and the melt rotating speed is 20-40 r/min;
a2: weighing a certain amount of the modified nano cerium oxide of claim 1, adding the weighed modified nano cerium oxide into the polyformaldehyde prepared in the step A1, and continuously carrying out banburying melt blending, wherein the second melting time is 10-60 min;
a3: crushing the polyformaldehyde material prepared in the step A2 by using a crusher;
a4: and B, performing injection molding on the polyoxymethylene material crushed in the step A3 through an injection molding machine.
6. The preparation method of the modified nano cerium oxide flame-retardant polyformaldehyde according to claim 5, wherein the injection molding temperature in the step A4 is 180-200 ℃.
7. The preparation method of the modified nano cerium oxide flame-retardant polyformaldehyde according to claim 5, wherein the injection molding pressure in the step A4 is 0.6-1 MPa.
8. The preparation method of the modified nano cerium oxide flame-retardant polyformaldehyde according to claim 7, wherein the injection molding dwell time in the step A4 is 2-4 s.
9. The preparation method of the modified nano cerium oxide flame-retardant polyformaldehyde according to claim 5, wherein the step A1 specifically comprises the following steps:
a11: weighing a certain amount of polyformaldehyde, and placing the polyformaldehyde in a drying oven for drying at the drying temperature of 50-70 ℃ for 6-10 hours;
a12: and B, placing the polyformaldehyde dried in the step A11 into an internal mixer for melt blending, wherein the melting temperature of the internal mixer is 185-195 ℃, the first melting time is 20-60 min, and the melt rotating speed is 20-40 r/min.
10. The preparation method of the modified nano cerium oxide flame-retardant paraformaldehyde according to claim 5, wherein in the step A1, the melting temperature of the internal mixer is 190 ℃, the first melting time is 40min, and the melt rotation speed is 30 r/min.
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