CN110156946B - Shape memory phenolic resin and preparation method thereof - Google Patents
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Abstract
The invention provides a shape memory phenolic resin and a preparation method thereof, wherein the shape memory phenolic resin comprises, by weight, 100 parts of resol, 5-15 parts of isocyano polyurethane prepolymer and 1-15 parts of curing agent. According to the shape memory phenolic resin provided by the invention, the polyurethane flexible chain segment is introduced on the benzene ring, and the phenolic resin is modified by using the longer polyurethane flexible chain segment molecular chain segment, so that the cross-linking density of the phenolic resin is reduced, the length of the molecular chain segment between cross-linking points is increased, the molecular structure of the shape memory phenolic resin has two molecular chain segment structures of a hard segment and a soft segment, the toughness of the phenolic resin is improved, the shape memory phenolic resin has the shape memory effect performance, and the shape memory phenolic resin is applied to more fields.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to shape memory phenolic resin and a preparation method thereof.
Background
Shape Memory Polymers (SMP) are a new class of intelligent polymeric materials. Compared with shape memory alloy and shape memory ceramic, it has the features of small density, great deformation, easy forming, adjustable response temperature, etc. When the material is subjected to environmental stimuli such as temperature, light, an electric field, a solvent, a magnetic field and the like, the material can respond correspondingly so as to recover to a preset shape. The shape memory polymer has the advantages of large deformation, easy shaping, convenient adjustment of shape response temperature, heat preservation, good insulating property, corrosion resistance, easy coloring, printing, light weight, low price and the like, and has wide application prospect in the fields of aerospace, information, medical treatment, flexible electronics, photoelectric products and the like.
Phenolic resin is one of three general-purpose resins, and phenolic plastics prepared from the phenolic resin have excellent mechanical property, electrical insulation property, ablation resistance, higher heat resistance, good water resistance and good chemical corrosion resistance, so that the phenolic resin is widely applied to manufacturing of machinery and electrical appliance parts, corrosion-resistant products and ablation-resistant products and the like. However, the phenolic resin has the problems of high brittleness, poor deformation resistance and the like, so that the further development of the phenolic resin is limited.
Disclosure of Invention
The invention solves the problems that: how to improve the toughness of the phenolic resin and enable the phenolic resin to be applied in more fields.
In order to solve the above problems, the present invention provides a shape memory phenolic resin, the structural formula of which is:
wherein R is
；
R1 is
、
、
、
R2 is- (CH)2)n-，2≤n≤20。
Optionally, the shape memory phenolic resin comprises, by weight: 100 parts of resol, 5-15 parts of isocyano polyurethane prepolymer and 1-15 parts of curing agent.
Optionally, the molecular weight of the isocyano-based polyurethane prepolymer is 1000-20000, and the weight of the isocyano group in the isocyano-based polyurethane prepolymer is 1% -8%.
Optionally, the curing agent includes one of an amine curing agent, an imidazole curing agent, an anhydride curing agent, or a synthetic resin oligomer curing agent.
Optionally, the resol is a product obtained by an addition reaction of a phenolic compound and an aldehyde compound under the action of an alkaline catalyst.
Optionally, the phenolic compound comprises: one or more of phenol, fluorophenol, cresol, nonylphenol, octylphenol, xylenol, cardanol, aralkylphenol, or bisphenol a; the aldehyde compounds include: one or more of formaldehyde, paraformaldehyde, furfural, or acetaldehyde.
Another object of the present invention is to provide a method for preparing the shape memory phenolic resin, which comprises the following steps:
s1, adding an alkaline catalyst into the molten phenolic compound, uniformly stirring, adding an aldehyde compound, heating, condensing, refluxing, cooling to room temperature, and then vacuumizing and dehydrating to obtain the resol;
s2, sequentially adding an isocyano polyurethane prepolymer and a curing agent into the resol, uniformly stirring, injecting the mixture into a preset mold, and heating and curing in a vacuum heating furnace;
and S3, demolding to obtain the shape memory phenolic resin.
Optionally, in step S1, the molar ratio of the phenolic compound, the aldehyde compound, and the basic catalyst is 1: (1.5-2):(0.02-0.04).
Optionally, the basic catalyst comprises: one or more of ammonia, sodium hydroxide, barium hydroxide or aluminum hydroxide.
Optionally, in the step S2, the curing temperature of the heating curing is 60 to 90 ℃, and the curing time is 7 to 9 hours.
Compared with the prior art, the photo-thermal joule heat synergistic membrane distillation assembly has the following advantages:
(1) according to the shape memory phenolic resin provided by the invention, the polyurethane flexible chain segment is introduced on the benzene ring, and the phenolic resin is modified by using the longer polyurethane flexible molecular chain segment, so that the cross-linking density of the phenolic resin is reduced, the length of the molecular chain segment between cross-linking points is increased, the molecular structure of the shape memory phenolic resin has two molecular chain segment structures of a hard segment and a soft segment, the toughness of the phenolic resin is improved, and the shape memory phenolic resin has the shape memory effect performance, so that the shape memory phenolic resin can be applied in more fields.
(2) The preparation method of the shape memory phenolic resin provided by the invention has the advantages of simple process, easily obtained raw materials, short thermal response time and high shape recovery rate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of the preparation of the shape memory phenolic resin of the present invention;
FIG. 2 is one of the infrared spectra of shape memory phenolic resins prepared at different curing temperatures;
FIG. 3 is a second infrared spectrum of a shape memory phenolic resin prepared at different curing temperatures;
FIG. 4 is a schematic diagram of the deformation recovery process of the shape memory phenolic resin of the present invention.
Detailed Description
It should be noted that the features in the embodiments of the present invention may be combined with each other without conflict. The terms "comprising," "including," "containing," and "having" are intended to be inclusive, i.e., that additional steps and other ingredients may be added without affecting the result. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment and reagents are commercially available unless otherwise specified.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The thermosetting phenolic resin has the characteristics of higher crosslinking density, higher mechanical property, high temperature resistance level, good weather resistance, good molding processability and the like. Just because the molecular structure of the thermosetting resin is a highly cross-linked network structure, and the molecular chain segment between adjacent cross-linking points is short, the resin has high brittleness and low deformability. With the development of the technology in the aerospace field, higher use requirements are put forward on materials, so that the phenolic resin is required to have better mechanical property and shape memory function, and is convenient to apply to the aerospace fields such as large aerospace autonomously deployable mechanisms, deformable spacecrafts, variant aircrafts and the like.
The embodiment of the invention provides shape memory phenolic resin, which has a structural formula as follows:
wherein R is
；
R1 is
、
、
、
Or, - (CH)3)6-; r2 is- (CH)2)n-，2≤n≤20。
The shape memory phenolic resin comprises, by weight, 100 parts of resol, 5-15 parts of an isocyanated polyurethane prepolymer and 1-15 parts of a curing agent.
The molecular weight of the isocyano-based polyurethane prepolymer is 1000-20000, and the weight of the isocyano group in the isocyano-based polyurethane prepolymer is 1% -8%.
The curing agent comprises: amine curing agent, imidazole curing agent, anhydride curing agent or synthetic resin oligomer curing agent.
The resol is a product obtained by the addition reaction of a phenolic compound and an aldehyde compound under the action of an alkaline catalyst. Wherein the phenolic compounds include: one or more of phenol, fluorophenol, cresol, nonylphenol, octylphenol, xylenol, cardanol, aralkylphenol, or bisphenol a; the aldehyde compounds include: one or more of formaldehyde, paraformaldehyde, furfural, or acetaldehyde.
The polyurethane flexible chain segment is introduced to the benzene ring, and the phenolic resin is modified by using the longer polyurethane flexible chain segment molecular chain segment, so that the cross-linking density of the phenolic resin is reduced, the length of the molecular chain segment between cross-linking points is increased, the molecular structure of the shape memory phenolic resin has two molecular chain segment structures of a hard segment and a soft segment, and the soft segment is used as a reversible phase of the resin, so that the deformability of the resin is improved, and the shape memory phenolic resin has the shape memory effect performance.
The preparation method of the shape memory phenolic resin comprises the following steps:
s1, adding an alkaline catalyst into the molten phenolic compound, uniformly stirring, adding an aldehyde compound, heating, condensing, refluxing, and finally vacuumizing and dehydrating to obtain the resol;
s2, sequentially adding an isocyano polyurethane prepolymer and a curing agent into the resol, uniformly stirring, injecting the mixture into a preset mold, and heating and curing in a vacuum heating furnace;
and S3, cooling to room temperature and demolding to obtain the shape memory phenolic resin.
Specifically, in step S1, taking the phenolic compound as phenol and the aldehyde compound as formaldehyde, the chemical reaction formula of the reaction is:
in step S1, the basic catalyst includes: one or more of ammonia, sodium hydroxide, barium hydroxide or aluminum hydroxide. Wherein the molar ratio of the phenol to the formaldehyde solution to the basic catalyst is 1: (1.5-2) and (0.02-0.04), wherein the temperature is 50-60 ℃ during stirring; the heating condensation reflux specifically comprises: heating the reaction solution to 70 ℃, preserving heat for 30min, continuously heating to 98 ℃, and condensing and refluxing for 30 min; finally, the temperature is reduced to below 70 ℃, and the vacuum-pumping dehydration is carried out.
It will be appreciated that the phenolic compound may also be one or more of fluorophenol, cresol, nonylphenol, octylphenol, xylenol, cardanol, aralkylphenol, or bisphenol a; the aldehyde compound may also be one or more of polyformaldehyde, furfural or acetaldehyde, as long as the preparation of the resol is achieved.
The chemical reaction formula of step S2 is:
r1 is
、
、
， 
Or, - (CH)3)6-; r2 is- (CH)2)n-，2≤n≤20。
It is understood that R1 is the main chain segment of the diisocyanate molecule of the synthetic polyurethane prepolymer and R2 is the main chain segment of the diol molecule of the synthetic polyurethane prepolymer.
In step S2, the curing temperature of heating and curing is 60-90 ℃, and the curing time is 7-9 h; the weight percentage ratio of the phenolic resole isocyano polyurethane prepolymer to the curing agent is 100 (5-15) to (1-15). The molecular weight of the isocyano-based polyurethane prepolymer is 1000-20000, and the weight of the isocyano group in the isocyano-based polyurethane prepolymer is 1% -8%.
The isocyano group can react with active hydrogen, so that the hydrogen on hydroxymethyl in the resol can react with the isocyano-terminated polyurethane prepolymer, and the phenolic resin and the isocyano-terminated polyurethane prepolymer can be well crosslinked in the curing process to form an interpenetrating network structure, so that a polyurethane chain segment with excellent flexibility is introduced into a rigid molecular structure of the phenolic resin. The whole molecular structure has two chain structures of a hard section formed by the cross-linking of the resol and a soft section formed by the molecular chain of polyurethane, so that the shape memory phenolic resin has the shape memory function, the mechanical property, particularly the toughness, of the phenolic resin is improved, and the composite material can be used as a resin matrix of a composite material for intelligent deformable aircrafts and aerospace self-deployable mechanisms.
It is understood that, in the case where the degree of crosslinking of the phenolic resin is too high, the phenolic resin is hard and brittle, and is hard to soften and form under heating, which is not favorable for the shape memory performance, therefore, it is necessary to control the degree of crosslinking of the phenolic resin during the heat curing process of step S2. In the embodiment of the invention, a curing process with a low temperature for a long time or a high temperature for a short time is adopted, so that the crosslinking degree of the hard segment formed by the resol is reduced. In order to ensure that the shape memory phenolic resin prepared by the embodiment of the invention has good toughness, preferably, the soft segment formed by the polyurethane molecular chain accounts for 5-20% of the whole shape memory phenolic resin molecular network structure.
Fig. 2 and 3 are infrared test spectra of two phenolic resins with the same material ratio and the same reaction process but different curing temperatures, that is, the two phenolic resins are prepared by modifying and curing the same resol with the same amount of polyurethane prepolymer, and the resol is prepared from the following raw materials in proportion: the molar ratio of the phenol to the formaldehyde solution to the basic catalyst is 1:1.8: 0.02; the mass ratio of the resol to the polyurethane prepolymer is 5:1, the curing time is 8 hours, and the curing temperatures are 80 ℃ and 140 ℃ respectively. And infrared test patterns of the shape memory phenolic resin prepared at different curing temperatures. As can be seen in the figure, at 1644cm-1Has an absorption peak of C = O, at 1611 cm-1The absorption peak is the stretching vibration of the C = C skeleton of the benzene ring, and is 1512cm-1The absorption peak is the deformation vibration of the amide II bond (N-H), and is 1214cm-1The absorption peak is the C-O stretching or OH deformation vibration of the polyester and is 1014cm-1The absorption peak at (A) is the absorption peak of the hydroxymethyl group. At 2260cm-1The isocyanate group absorption peak is not generated, which shows that the isocyanate group in the polyurethane prepolymer reacts with the water or phenolic hydroxyl group in the resol. 1611cm-1、1512cm-1And 1214cm-1The characteristic peak shows that isocyanic acid radical reacts with hydroxymethyl in the phenolic resin, and the polyurethane prepolymer is introduced into a phenolic resin cross-linking molecular structure; at 1014cm-1At the absorption peak, the characteristic peak of the shape memory phenolic resin prepared at the curing temperature of 140 ℃ is obviously weaker than that of the shape memory phenolic resin prepared at the curing temperature of 80 ℃, which shows that the shape memory phenolic resin prepared at the curing temperature of 140 ℃ has less hydroxymethyl and the hard segment formed by the resol has larger crosslinking degree. That is, the shape memory phenolic resin prepared at the curing temperature of 140 ℃ is difficult to shape after being heated, and is difficult to show the shape memory performance. The shape memory phenolic resin prepared at the curing temperature of 80 ℃ has obvious shape memory performance.
Therefore, in order to ensure that the shape memory phenolic resin provided by the embodiment of the invention has good shape memory performance and better toughness, the curing temperature in the step S2 is in the range of 60-90 ℃, and the preferred curing temperature is 80 ℃.
FIG. 4 is a schematic diagram of the deformation recovery process of the shape memory phenolic resin prepared at the curing temperature of 80 ℃ in a drying oven at 170 ℃. The glass transition temperature of the shape memory phenolic resin was measured to be 161 ℃ in tensile mode using a DMA analytical tester model TA Q800. In order to test the deformation recovery capability of the prepared shape memory phenolic resin, the shape memory phenolic resin is firstly shaped at the glass transition temperature of the shape memory phenolic resin to be converted from a straight shape into a bent shape, then the shaped shape memory phenolic resin is placed in a drying oven at 170 ℃, and the change relation of the recovery state along with time is observed.
As can be seen from fig. 4, in the initial state (0 s), the shape memory phenolic resin is in a bent shape, after 35s, the degree of bending becomes small, and the deformation performance of the polyurethane prepolymer is expressed with the increase of time, after 60s, the shape memory phenolic resin is only bent at the edge, and after 86s, the bent shape of the shape memory phenolic resin is restored to the original shape for 86 s. This shows that the shape memory phenolic resin provided by the embodiment of the invention has a shape memory function and a quick recovery time compared with the conventional phenolic resin. The shape memory phenolic resin has high toughness in a secondary forming temperature range, has a small difference in heat resistance compared with the corresponding type of shape memory phenolic resin without the isocyano polyurethane prepolymer, is not easy to crack and destroy, and has a great value in the aspect of engineering application of phenolic resin composite materials.
The following different examples illustrate the specific preparation of the shape memory phenolic resin:
example 1
The example provides a preparation method of a shape memory phenolic resin, which comprises the following steps:
1) adding melted phenol into a three-neck flask, and preheating and stirring in an oil bath kettle at 55 ℃; dropwise adding ammonia water into a three-neck flask, wherein the mol ratio of the ammonia water to the phenol is 0.05:1, and stirring for 5min at the temperature of 55 ℃; slowly adding a formaldehyde solution into the three-neck flask, keeping the molar ratio of the formaldehyde solution to the phenol at 1:1.6, continuously stirring, heating to 70 ℃, keeping the temperature for 30min, heating to 98 ℃, condensing and refluxing for 30min, naturally cooling to below 70 ℃, and vacuumizing for dehydration to obtain the resol.
2) Uniformly mixing 100 parts of the resol prepared in the step 1) and 5 parts of the isocyano polyurethane prepolymer, stirring for 30min, adding 2 parts of the curing agent, and uniformly mixing. Then, the mixture was poured into a mold prepared in advance, and curing was completed in a vacuum heating furnace at 80 ℃.
Example 2
The present embodiment is different from the above embodiments in that the method for preparing the shape memory phenolic resin provided by the present embodiment specifically comprises the following steps:
1) adding melted phenol into a three-neck flask, and preheating and stirring in an oil bath kettle at 55 ℃; dropwise adding ammonia water into a three-neck flask, wherein the mol ratio of the ammonia water to the phenol is 0.05:1, and stirring for 5min at the temperature of 55 ℃; slowly adding a formaldehyde solution into the three-neck flask, keeping the molar ratio of the formaldehyde solution to the phenol at 1:2, continuously stirring, heating to 70 ℃, keeping the temperature for 30min, heating to 98 ℃, condensing and refluxing for 30min, naturally cooling to below 70 ℃, and vacuumizing for dehydration to obtain the resol.
2) Uniformly mixing 100 parts of the resol prepared in the step 1) and 5 parts of the isocyano polyurethane prepolymer, stirring for 30min, adding 2 parts of the curing agent, and uniformly mixing. Then, the mixture was poured into a mold prepared in advance, and curing was completed in a vacuum heating furnace at 80 ℃.
Example 3
The present embodiment is different from the above embodiments in that the method for preparing the shape memory phenolic resin provided by the present embodiment specifically comprises the following steps:
1) adding melted phenol into a three-neck flask, and preheating and stirring in an oil bath kettle at 55 ℃; dropwise adding ammonia water into a three-neck flask, wherein the mol ratio of the ammonia water to the phenol is 0.05:1, and stirring for 5min at the temperature of 55 ℃; slowly adding a formaldehyde solution into the three-neck flask, keeping the molar ratio of the formaldehyde solution to the phenol at 1:2, continuously stirring, heating to 70 ℃, keeping the temperature for 30min, heating to 98 ℃, condensing and refluxing for 30min, naturally cooling to below 70 ℃, and vacuumizing for dehydration to obtain the resol.
2) Uniformly mixing 100 parts of the resol prepared in the step 1) and 6 parts of the isocyano polyurethane prepolymer, stirring for 30min, adding 4 parts of the curing agent, and uniformly mixing. Then, the mixture was poured into a mold prepared in advance, and curing was completed in a vacuum heating furnace at 80 ℃.
Example 4
The present embodiment is different from the above embodiments in that the method for preparing the shape memory phenolic resin provided by the present embodiment specifically comprises the following steps:
1) adding melted phenol into a three-neck flask, and preheating and stirring in an oil bath kettle at 55 ℃; dropwise adding ammonia water into a three-neck flask, wherein the mol ratio of the ammonia water to the phenol is 0.05:1, and stirring for 5min at the temperature of 55 ℃; slowly adding a formaldehyde solution into the three-neck flask, keeping the molar ratio of the formaldehyde solution to the phenol at 1:2, continuously stirring, heating to 70 ℃, keeping the temperature for 30min, heating to 98 ℃, condensing and refluxing for 30min, naturally cooling to below 70 ℃, and vacuumizing for dehydration to obtain the resol.
2) Uniformly mixing 100 parts of the resol prepared in the step 1) and 10 parts of the isocyano polyurethane prepolymer, stirring for 30min, adding 9 parts of the curing agent, and uniformly mixing. Then, the mixture was poured into a mold prepared in advance, and curing was completed in a vacuum heating furnace at 80 ℃.
Example 5
The present embodiment is different from the above embodiments in that the method for preparing the shape memory phenolic resin provided by the present embodiment specifically comprises the following steps:
1) adding melted phenol into a three-neck flask, and preheating and stirring in an oil bath kettle at 55 ℃; dropwise adding ammonia water into a three-neck flask, wherein the mol ratio of the ammonia water to the phenol is 0.05:1, and stirring for 5min at the temperature of 55 ℃; slowly adding a formaldehyde solution into the three-neck flask, keeping the molar ratio of the formaldehyde solution to the phenol at 1:2, continuously stirring, heating to 70 ℃, keeping the temperature for 30min, heating to 98 ℃, condensing and refluxing for 30min, naturally cooling to below 70 ℃, and vacuumizing for dehydration to obtain the resol.
2) Uniformly mixing 100 parts of the resol prepared in the step 1) and 15 parts of the isocyano polyurethane prepolymer, stirring for 30min, adding 15 parts of the curing agent, and uniformly mixing. Then, the mixture was poured into a mold prepared in advance, and curing was completed in a vacuum heating furnace at 80 ℃.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.
Claims (9)
1. The shape memory phenolic resin is characterized by comprising the following components in parts by weight: 100 parts of resol, 5-15 parts of isocyanate-terminated polyurethane prepolymer and 1-15 parts of curing agent;
the preparation method of the shape memory phenolic resin comprises the following steps:
s1, adding an alkaline catalyst into the molten phenolic compound, uniformly stirring, adding an aldehyde compound, heating, condensing, refluxing, cooling, and then vacuumizing and dehydrating to obtain the resol, wherein the molar ratio of the phenolic compound to the aldehyde compound to the alkaline catalyst is 1 (1.5-2) to 0.02-0.04;
s2, sequentially adding the isocyanate-terminated polyurethane prepolymer and the curing agent into the resol, uniformly stirring, injecting the mixture into a preset mold, and heating and curing in a vacuum heating furnace, wherein the heating and curing temperature is 60-90 ℃, and the curing time is 7-9 hours;
and S3, demolding to obtain the shape memory phenolic resin.
2. The shape memory phenolic resin as claimed in claim 1, wherein the molecular weight of the isocyanate-terminated polyurethane prepolymer is 1000-20000, and the isocyanate group accounts for 1-8% of the mass of the isocyanate-terminated polyurethane prepolymer.
3. The shape memory phenolic resin of claim 1, wherein the curing agent comprises one of an amine curing agent, an imidazole curing agent, an anhydride curing agent, or a synthetic resin oligomer curing agent.
4. The shape memory phenolic resin according to claim 1, wherein the phenolic resole resin is a product obtained by an addition reaction of a phenolic compound and an aldehyde compound under the action of a basic catalyst.
5. The shape memory phenolic resin of claim 4, wherein the phenolic compound comprises: one or more of phenol, fluorophenol, cresol, nonylphenol, octylphenol, xylenol, cardanol, aralkylphenol, or bisphenol a; the aldehyde compounds include: one or more of formaldehyde, paraformaldehyde, furfural, or acetaldehyde.
6. A method of preparing a shape memory phenolic resin according to any of claims 1 to 5, comprising the steps of:
s1, adding an alkaline catalyst into the molten phenolic compound, uniformly stirring, adding an aldehyde compound, heating, condensing, refluxing, cooling, and then vacuumizing and dehydrating to obtain the resol;
s2, sequentially adding the isocyanate-terminated polyurethane prepolymer and the curing agent into the resol, uniformly stirring, injecting the mixture into a preset mold, and heating and curing in a vacuum heating furnace;
and S3, demolding to obtain the shape memory phenolic resin.
7. The method for preparing a shape memory phenolic resin according to claim 6, wherein in the step S1, the molar ratio of the phenolic compound, the aldehyde compound and the basic catalyst is 1 (1.5-2) to 0.02-0.04.
8. The method of claim 6, wherein the basic catalyst comprises: one or more of ammonia, sodium hydroxide, barium hydroxide or aluminum hydroxide.
9. The method for preparing the shape memory phenolic resin according to claim 6, wherein in the step S2, the curing temperature of the heating curing is 60-90 ℃, and the curing time is 7-9 h.
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