Summary of the invention
The object of the present invention is to provide Nitrogen-containing Phenolic Resins of a kind of modified by cardanol and preparation method thereof, the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention has higher resistance toheat.
The invention provides a kind of Nitrogen-containing Phenolic Resins of modified by cardanol, there is structure shown in formula I:
In formula I, n is polymerization, n > 2;
R is H or alkyl.
Preferably, n=5~20.
The invention provides a kind of method of preparing the Nitrogen-containing Phenolic Resins of modified by cardanol, comprise the following steps:
Cardanol, phenol compound, benzaldehyde compound and ammoniac compounds are mixed, carry out polycondensation, obtain the Nitrogen-containing Phenolic Resins of modified by cardanol.
Preferably, described ammoniac compounds comprises one or more in organic amine compound and ammoniacal liquor;
Described phenol compound is preferably phenol and/or ortho-cresol;
Described benzaldehyde compound is formaldehyde and/or paraformaldehyde.
Preferably, the mass ratio of described cardanol and described phenol compound is 1.0:(0.1~3.0);
Described cardanol is 1:(0.8~1.2 with the total amount of substance of described phenol compound with the ratio of described ammoniac compounds amount of substance);
Described cardanol is 1:(1.8~2.2 with the total amount of substance of described phenol compound with the ratio of described benzaldehyde compound amount of substance).
Preferably, described cardanol, phenol compound, benzaldehyde compound and ammoniac compounds mixed and be specially:
Cardanol, phenol compound and ammoniac compounds are mixed, obtain mixture;
In batches described benzaldehyde compound is added in described mixture.
Preferably, to add in described mixture batch be 3 times~5 times to described benzaldehyde compound.
Preferably, under the condition of 60 ℃~70 ℃, benzaldehyde compound is added in described mixture in batches;
It is 100min~150min that described benzaldehyde compound adds the time in described mixture.
Preferably, the temperature of described polycondensation is 70 ℃~80 ℃;
The time of described polycondensation is 100min~150min.
Preferably, after described polycondensation, also comprise:
The reaction solution dehydration that described polycondensation is obtained;
The viscosity of the reaction solution after dehydration is adjusted to 600cp/25 ℃~800cp/25 ℃.
The invention provides a kind of Nitrogen-containing Phenolic Resins with the modified by cardanol of structure shown in formula I, in the structure of resol provided by the invention, both comprised cardanol side group, contain again N element, thereby in the defect of fragility that has overcome the existence of prior art resol, improved the resistance to elevated temperatures of resol.Therefore, the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention, when having guaranteed the resistance to toughness of resol and mechanical property, has also improved flexibility and the shock resistance of resol.Experimental result shows, the flexural strength of the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention reaches 21.03MPa, and shock strength reaches 7.86KJ/m
2, thermogravimetric analysis shows that the Nitrogen-containing Phenolic Resins of described modified by cardanol has higher resistance to elevated temperatures.
Embodiment
The invention provides a kind of Nitrogen-containing Phenolic Resins of modified by cardanol, there is structure shown in formula I:
In formula I, n is the polymerization degree, n > 2; Preferably, n=5~20; Concrete, in an embodiment of the present invention, the number-average molecular weight of the Nitrogen-containing Phenolic Resins of described modified by cardanol is 601 or 596;
In the present invention, the molecular weight distribution of the Nitrogen-containing Phenolic Resins of described modified by cardanol is 2.0
In formula I, R is the alkyl that H, alkyl or hydroxyl replace, the hydroxyl substituted alkyl that the alkyl that to be preferably H, C atomicity be 1~22 or carbonatoms are 1~10, most preferably be H, the tertiary butyl or-CH
2cH
2oH.
In the structure of the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention, side group has been introduced cardanol group, has also introduced N element, thereby when having guaranteed the resistance to toughness of resol and mechanical property, has also improved flexibility and the shock resistance of resol.
The present invention also provides a kind of method of preparing the Nitrogen-containing Phenolic Resins of modified by cardanol, comprises following methods:
Cardanol, phenol compound, benzaldehyde compound and ammoniac compounds are mixed, carry out polycondensation, obtain the Nitrogen-containing Phenolic Resins of modified by cardanol.
The present invention mixes cardanol, phenol compound, benzaldehyde compound and ammoniac compounds, carries out polycondensation.The method that the present invention mixes described cardanol, phenol compound, benzaldehyde compound and ammoniac compounds does not have special restriction, adopts the technical scheme of mixing well known to those skilled in the art.The present invention is preferred:
Cardanol, phenol compound and ammoniac compounds are mixed, obtain mixture;
In batches described benzaldehyde compound is added in described mixture.
The present invention preferably mixes cardanol, phenol compound and ammoniac compounds, obtains mixture, then in described mixture, adds in batches benzaldehyde compound, carries out polycondensation.The present invention preferably, under the condition of 60 ℃~70 ℃, adds described benzaldehyde compound in described mixture, more preferably under the condition of 63 ℃~69 ℃, most preferably under the condition of 65 ℃~67 ℃; In the present invention, describedly add the time in described mixture to be preferably 100min~150min described benzaldehyde compound, more preferably 110min~140min, most preferably is 120min~130min; The present invention preferably divides 3 times~5 times described benzaldehyde compound is added in described mixture, and in an embodiment of the present invention, described benzaldehyde compound adds batch can be specially 3 times, 4 times or 5 times in described mixture.The present invention comes the amount of compound there is no special restriction to every batch of formaldehyde adding, and those skilled in the art can be divided into described benzaldehyde compound 3 equal portions~5 equal portions, are divided into 3 times~5 times and join in described mixture.
In the present invention, described phenol compound is preferably toluene and/or ortho-cresol.Described benzaldehyde compound is preferably formaldehyde and/or paraformaldehyde, more preferably paraformaldehyde.Described ammoniac compounds is preferably one or more in organic amine compound and ammoniacal liquor, and one or more in fat amine compound, alcamine compound and ammoniacal liquor most more preferably preferably are one or more in TERTIARY BUTYL AMINE, trolamine and ammoniacal liquor; The present invention does not have special restriction to the mass concentration of described ammoniacal liquor, adopt ammoniacal liquor well known to those skilled in the art, as adopted the commercial goods of ammoniacal liquor, the ammoniacal liquor that mass concentration is 20wt%~30wt%, can also adopt mass concentration is the ammoniacal liquor of 20wt%~25wt%.
In the present invention, the mass ratio of described cardanol and described phenol compound is preferably 1.0:(0.1~3.0), 1.0:(0.3~2.0 more preferably), most preferably be 1.0:(0.5~1.0); In the present invention, described cardanol and described phenol compound are generically and collectively referred to as phenolic compound; Described phenolic compound is preferably 1:(0.8~1.2 with the ratio of the amount of substance of described ammoniac compounds), 1:(0.9~1.1 more preferably), most preferably be 1:1.0; Described phenolic compound is preferably 1:(0.8~1.2 with the ratio of the amount of substance of described benzaldehyde compound), 1:(0.9~1.1 more preferably), most preferably be 1:1.0;
The present invention does not have special restriction to the source of described cardanol, phenol compound, benzaldehyde compound and ammoniac compounds, adopts the commercial goods of above-mentioned cardanol well known to those skilled in the art, phenol compound, benzaldehyde compound and ammoniac compounds.
After described cardanol, phenol compound, benzaldehyde compound and ammoniac compounds are mixed, carry out polycondensation, obtain the Nitrogen-containing Phenolic Resins of modified by cardanol.In the present invention, the temperature of described polycondensation is preferably 70 ℃~80 ℃, more preferably 73 ℃~78 ℃, most preferably is 75 ℃~77 ℃; In the present invention, described polycondensation is carried out under constant temperature.The time of described polycondensation is preferably 100min~150min, and more preferably 110min~140min, most preferably is 120min~130min.
The present invention preferably, adding after benzaldehyde compound in mixture described in technique scheme, rises to temperature the temperature of polycondensation in 20min~40min, more preferably, in 25min~35min, most preferably is in 30min.
Complete after described polycondensation the reaction solution dehydration that the present invention preferably obtains described polycondensation;
The viscosity of the reaction solution after dehydration is adjusted to 600cp/25 ℃~800cp/25 ℃, obtains the Nitrogen-containing Phenolic Resins of modified by cardanol.
The present invention does not have special restriction to the method for described dehydration, adopt the technical scheme of dehydration well known to those skilled in the art, as the method that can adopt underpressure distillation to as described in reaction solution dewater, concrete can be by the pressure distillation to 80 ℃ of described reaction solution;
Complete after the dehydration of described reaction solution, the present invention is preferably adjusted to 600cp/25 ℃~800cp/25 ℃ by the viscosity of the reaction solution after described dehydration, obtains the Nitrogen-containing Phenolic Resins of modified by cardanol, is more preferably adjusted to 650cp/25 ℃~750cp/25 ℃.The present invention preferably mixes the reaction solution after described dehydration with organic solvent, the viscosity that regulates the reaction solution after described dehydration is 600cp/25 ℃~800cp/25 ℃; In the present invention, described solvent is preferably ethyl acetate and/or methyl alcohol.
The invention provides a kind of Nitrogen-containing Phenolic Resins with the modified by cardanol of structure shown in formula I, in the structure of resol provided by the invention, both comprised cardanol side group, contain again N element, thereby in the defect of fragility that has overcome the existence of prior art resol, improved the resistance to elevated temperatures of resol.Therefore, the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention, when having guaranteed the resistance to toughness of resol and mechanical property, has also improved flexibility and the shock resistance of resol.Experimental result shows, the flexural strength of the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention reaches 21.03MPa, and shock strength reaches 7.86KJ/m
2, thermogravimetric analysis shows that the Nitrogen-containing Phenolic Resins of described modified by cardanol has higher resistance to elevated temperatures.
In order to further illustrate the present invention, below in conjunction with embodiment, Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as to limiting the scope of the present invention.
Embodiment 1
550g cardanol, 350g phenol and ammoniacal liquor 530g are put into there is thermometer, in the reaction vessel of whipping appts, reflux exchanger, heat to 65 ℃, then start minutes 4 batches and add paraformaldehyde, add in 1/4th, 2 hours of total paraformaldehyde at every turn and all add, and then be warmed up to 75 ℃, constant temperature 2 hours, finish reaction and carry out underpressure distillation, to temperature be 80 ℃, stop experiment.In the most backward reaction solution obtaining, add the mixed solvent adjusting viscosity of ethyl acetate and methyl alcohol to 700cp/25 ℃, obtain modified phenolic resins.
The present invention carries out gel permeation chromatography (GPC) by the modified phenolic resins obtaining and detects, the results are shown in Figure 1, Fig. 1 is the GPC spectrogram of the modified phenolic resins that obtains of the embodiment of the present invention 1, as seen from Figure 1, the number-average molecular weight of the modified phenolic resins that the present embodiment obtains is 601, and molecular weight distribution is 2.0;
The present invention carries out thermogravimetric analysis by the modified phenolic resins obtaining, result as shown in Figure 2, Fig. 2 is the thermogravimetric analysis collection of illustrative plates of modified phenolic resins in the embodiment of the present invention 1 and comparative example, the thermogravimetric analysis curve of the modified phenolic resins that wherein curve 2 obtains for the embodiment of the present invention 1, relatively can the finding out of curve 1 and curve 2 in Fig. 2, the modified phenolic resins that the present embodiment obtains has higher thermotolerance.
The present invention carries out infrared spectra detection by the modified phenolic resins obtaining, result as shown in Figure 3, Fig. 3 is the infrared spectrogram of modified phenolic resins in the embodiment of the present invention 1 and comparative example, wherein curve a is the infrared spectra curve of the modified phenolic resins that obtains of the embodiment of the present invention 1, by curve a, can be found out, at 2800cm
-1and 2900cm
-1there is larger absorption peak at place, is respectively the stretching vibration peak of methyl and methylene radical, illustrates that modified by cardanol has reached object; And by relatively can the finding out of curve a and curve b, in modification cardanol provided by the invention, contain N element; Modified phenolic resins provided by the invention is strong than the modified phenolic resins in comparative example in the vibration peak intensity of above-mentioned two wave numbers, thus in the resol of modification provided by the invention the content of cardanol than the height in the modified phenolic resins in comparative example.
The physical parameter of the modified phenolic resins that the present invention test obtains is measured, and result is as shown in table 1, the physical parameter of the modified phenolic resins that table 1 obtains for the embodiment of the present invention.
The present invention mixes 5min according to the component shown in table 2 in high-speed mixer, then the mixture obtaining is put into the mould that scribbles releasing agent, respectively at 160 ℃, under 20MPa, suppress 10min, the model obtaining is placed in baking oven, at 140 ℃, constant temperature is 2 hours, then the speed with 5 ℃/min is warming up to 160 ℃, constant temperature 2 hours, speed with 5 ℃/min is warming up to 180 ℃ again, constant temperature 2 hours, , prepare test sample plate, shock strength and the flexural strength of the test sample plate that test obtains, shock strength adopts XJ balance weight impact testing machine (development area, Chengde De Sheng test set company limited) to test, flexural strength adopts microcomputer controlled electro minor universal testing machine (the Jinan epoch ensaying trier WDW of company limited) to test, result is as shown in table 3, the mechanical experimental results of the modified phenolic resins that table 3 obtains for the embodiment of the present invention 1~2 and comparative example.
Embodiment 2
Cardanol 350g, phenol 220g and ammoniacal liquor 350g are put into there is thermometer, in the reaction vessel of whipping appts, reflux exchanger, heat to 65 ℃, then start to add in batches paraformaldehyde, in 2 hours, add, and then be warmed up to 75 ℃, constant temperature 2 hours, finish reaction and carry out underpressure distillation, to temperature be 80 ℃, stop experiment, finally add ethyl acetate adjusting viscosity to 770cp/25 ℃, obtain the Nitrogen-containing Phenolic Resins of modified by cardanol.
The present invention carries out GPC detection by the gained modified phenolic resins obtaining, result as shown in Figure 4, Fig. 4 is the gpc chromatogram of the modified phenolic resins that obtains of the embodiment of the present invention 2, as seen from Figure 4, the number-average molecular weight of the modified phenolic resins that the present embodiment prepares is 596, and molecular weight distribution is 2.0.
The present invention is according to the preparation method of embodiment 1 test sample plate, the modified phenolic resins that the present embodiment of take obtains prepares test sample plate as raw material, shock strength and the flexural strength of the test sample plate that test obtains, result is as shown in table 3, the mechanical experimental results of the modified phenolic resins that table 3 obtains for the embodiment of the present invention 1~2 and comparative example.
Comparative example
With the resol of commercially available common modified by cardanol sample in contrast, the present invention carries out thermogravimetric analysis by described control sample, result as shown in Figure 2, Fig. 2 is the thermogravimetric analysis collection of illustrative plates of modified phenolic resins in the embodiment of the present invention 1 and comparative example, wherein curve 1 is the thermogravimetric analysis curve of common Cardanol Modified PF Resin in comparative example, by relatively can finding out of curve in Fig. 21 and curve 2, modified phenolic resins provided by the invention has higher thermotolerance;
The present invention carries out infrared spectra detection by control sample, result as shown in Figure 3, Fig. 3 is the infrared spectrogram of modified phenolic resins in the embodiment of the present invention 1 and comparative example, wherein curve b is the infrared spectra curve of modified phenolic resins in comparative example of the present invention, by relatively can finding out of curve a in Fig. 3 and curve b, with commercially available common modified by cardanol resin-phase ratio, in modified phenolic resins provided by the invention, contain N element.
The present invention is according to the preparation method of embodiment 1 test sample plate, the control sample of take in this comparative example prepares test sample plate as raw material, shock strength and the flexural strength of the test sample plate that test obtains, result is as shown in table 3, the mechanical experimental results of the modified phenolic resins that table 3 obtains for the embodiment of the present invention 1~2 and comparative example.
The physical parameter of the modified phenolic resins that table 1 embodiment of the present invention 1~2 obtains
? |
Embodiment 1 |
Embodiment 2 |
Number-average molecular weight M
n |
601 |
596 |
Weight-average molecular weight M
w |
1517 |
1510 |
Gu containing (%) |
79.78 |
77.14 |
Free phenol (%) |
6.89 |
7.45 |
The component of test sample plate in table 2 embodiment of the present invention 1~2 and comparative example
The mechanical experimental results of the modified phenolic resins that table 3 embodiment of the present invention 1~2 and comparative example obtain
? |
Shock strength (KJ/m
2)
|
Flexural strength (MPa) |
Embodiment 1 |
7.84 |
21.03 |
Embodiment 2 |
7.86 |
20.69 |
Comparative example |
7.37 |
19.92 |
As can be seen from Table 3, the modified phenolic resins that the present embodiment obtains has higher shock strength and flexural strength.
Embodiment 3
The present invention prepares the Nitrogen-containing Phenolic Resins of modified by cardanol according to the technical scheme of embodiment 1, different, and the present embodiment adopts tertiary butyl ammonia to replace the ammoniacal liquor in embodiment 1.
The present invention carries out thermogravimetric analysis and Mechanics Performance Testing by the Nitrogen-containing Phenolic Resins of the modified by cardanol obtaining, and result shows, the Nitrogen-containing Phenolic Resins of the modified by cardanol that the present embodiment prepares has higher resistance toheat, shock strength and flexural strength.
As seen from the above embodiment, the invention provides a kind of Nitrogen-containing Phenolic Resins with the modified by cardanol of structure shown in formula I, in the structure of resol provided by the invention, both comprised cardanol side group, contain again N element, thereby in the defect of fragility that has overcome the existence of prior art resol, improved the resistance to elevated temperatures of resol.Therefore, the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention, when having guaranteed the resistance to toughness of resol and mechanical property, has also improved flexibility and the shock resistance of resol.Experimental result shows, the flexural strength of the Nitrogen-containing Phenolic Resins of modified by cardanol provided by the invention reaches 21.03MPa, and shock strength reaches 7.86KJ/m
2, thermogravimetric analysis shows that the Nitrogen-containing Phenolic Resins of described modified by cardanol has higher resistance to elevated temperatures.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.