CN110156946A - A kind of shape memory phenolic resin and preparation method thereof - Google Patents
A kind of shape memory phenolic resin and preparation method thereof Download PDFInfo
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- CN110156946A CN110156946A CN201910461525.8A CN201910461525A CN110156946A CN 110156946 A CN110156946 A CN 110156946A CN 201910461525 A CN201910461525 A CN 201910461525A CN 110156946 A CN110156946 A CN 110156946A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The present invention provides a kind of shape memory phenolic resin and preparation method thereof, the shape memory phenolic resin by weight, including 100 parts of resols, 5~15 parts of isocyano group base polyurethane prepolymer for use as, 1~15 part of curing agent.Shape memory phenolic resin provided by the invention, by introducing polyurethane flexible segment on phenyl ring, using longer polyurethane flexible segment molecule segment to phenolic resin modified, reduce the crosslink density of phenolic resin, increase the length of molecule segment between crosslinking points, the molecular structure of shape memory phenolic resin is set there are two kinds of molecule segment structures of hard section and soft section, improve the toughness of phenolic resin, so that shape memory phenolic resin has shape memory effect performance, it is made to be applied in more areas.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of shape memory phenolic resin and its system
Preparation Method.
Background technique
Shape-memory polymer (shape memory polymer, SMP) is a kind of novel intelligent high molecular material.Relatively
For marmem and shape memory ceramics, it has, and density is small, deflection is big, figuration is easy, response temperature is adjustable
The features such as.When this kind of material is by environmental stimulus such as temperature, light, electric field, solvent, magnetic fields, corresponding response can be made, thus
It is restored to preset shape.Not only deflection is big for shape-memory polymer, figuration is easy, shape response temperature is convenient for tune
It is whole, and have many advantages, such as heat preservation, good insulation preformance, do not corrode, easy coloring, can print, is light inexpensive, in aerospace, letter
The fields such as breath, medical treatment, flexible electronic, photovoltaic have broad application prospects.
For phenolic resin as one of three big resins for universal use, phenolic resin has excellent mechanics because of phenoplasts made from it
Performance, electrical insulation capability, ablation resistance and higher heat resistance and good water resistance, resistance to chemical corrosion are wide
It is general to be applied to production machinery, electrical component and anti-corrosion, product of resistance to ablation etc..But since phenolic resin has, brittleness is big, resistance
The problems such as shape ability is poor limits the further development of phenolic resin.
Summary of the invention
Problems solved by the invention is: how to improve the toughness of phenolic resin, it is made to be applied in more areas.
To solve the above problems, the present invention provides a kind of shape memory phenolic resin, the shape memory phenolic resin
Structural formula are as follows:
Wherein, R is
R1 is Or,-(CH3)6-;
R2 is-(CH2)n, 2≤n≤20.
Optionally, the shape memory phenolic resin is by weight, comprising: 100 parts of resols, 5~15 parts
Isocyano group base polyurethane prepolymer for use as, 1~15 part of curing agent.
Optionally, the molecular weight of the isocyano group base polyurethane prepolymer for use as be 1000~20000, and isocyanide group account for it is described different
Cyano polyurethane prepolymer weight is 1%~8%.
Optionally, the curing agent includes that amine curing agent, imidazole curing agent, acid anhydride type curing agent or synthetic resin are low
One of polymers curing agent.
Optionally, the resol is that phenolic compound and aldehyde compound occur under basic catalyst effect
The product that addition reaction obtains.
Optionally, the phenolic compound includes: phenol, fluorophenol, cresols, mixed phenol, nonyl phenol, octyl phenol, diformazan
One of phenol, anacardol, aralkyl phenol or bisphenol-A are a variety of;The aldehyde compound includes: formaldehyde, paraformaldehyde, chaff
One of aldehyde or acetaldehyde are a variety of.
Another object of the present invention is to provide a kind of preparation method of shape memory phenolic resin as described above, packets
Include following steps:
S1, basic catalyst is added into the phenolic compound of melting, stirs evenly, add aldehyde compound, heat
It is condensed back, dehydration is vacuumized after being cooled to room temperature, resol is made;
Isocyano group base polyurethane prepolymer for use as, curing agent are sequentially added in S2, Xiang Suoshu resol, are stirred evenly, and
It injects the mixture into preset die, is heating and curing in vacuum furnace;
S3, demoulding obtain the shape memory phenolic resin.
Optionally, in the step S1, the phenolic compound, the aldehyde compound and the basic catalyst rub
You are than being 1:(1.5-2): (0.02-0.04).
Optionally, the basic catalyst include: one of ammonium hydroxide, sodium hydroxide, barium hydroxide or aluminium hydroxide or
It is a variety of.
Optionally, in the step S2, the solidification temperature being heating and curing is 60~90 DEG C, and curing time is 7~9h.
Compared with the existing technology, photo-thermal Joule heat collaboration membrane component of the present invention has the advantage that
(1) shape memory phenolic resin provided by the invention, by phenyl ring introduce polyurethane flexible segment, using compared with
Long polyurethane flexible molecule segment reduces the crosslink density of phenolic resin to phenolic resin modified, increases between crosslinking points
The length of molecule segment makes the molecular structure of shape memory phenolic resin have two kinds of molecule segment structures of hard section and soft section,
The toughness of phenolic resin is improved, shape memory phenolic resin has shape memory effect performance, obtains it in more areas
Using.
(2) preparation method of shape memory phenolic resin provided by the invention, simple process, raw material are easy to get, and prepare
Shape memory phenolic resin thermal response time is short, and recovery of shape rate is fast.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the preparation flow figure of shape memory phenolic resin of the present invention;
Fig. 2 is one of the infrared spectrogram of the shape memory phenolic resin prepared under different solidification temperatures;
Fig. 3 is the two of the infrared spectrogram of the shape memory phenolic resin prepared under different solidification temperatures;
Fig. 4 is the deformation recovery process schematic of shape memory phenolic resin of the present invention.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment in the present invention can be combined with each other.Art
Language "comprising", " comprising ", " containing ", " having " meaning be non-limiting, the other steps for influencing result can be added not
With other ingredients.Terms above cover term " by ... form " and " substantially by ... form ".Unless otherwise specified, material
Material, equipment, reagent are commercially available.
To make the above purposes, features and advantages of the invention more obvious and understandable, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.
Thermosetting phenolic resin crosslink density with higher, higher mechanical property, high-temperature resistant grade, good weatherability,
The features such as moulding processability is good.Exactly because the molecular structure of thermosetting resin is highly cross-linked reticular structure, adjacent friendship
Molecule segment between connection point is shorter, so the brittleness of resin is larger, deformability is weaker.With aerospace field technology
Development, proposes higher requirement to material, and this requires phenolic resin not only to have preferable mechanical property, simultaneously also
It needs with shape memory function, it can autonomous unfolding mechanism, deformation spacecraft, morphing aircraft etc. in space flight large size convenient for applying
Aerospace field.
The embodiment of the invention provides a kind of shape memory phenolic resin, the structural formula of the shape memory phenolic resin
Are as follows:
Wherein, R is
R1 is Or,-(CH3)6-;R2 is-(CH2)n, 2≤n≤20.
Wherein, by weight, including 100 parts of resols, 5~15 parts of isocyano groups are poly- for shape memory phenolic resin
Urethane performed polymer, 1~15 part of curing agent.
The molecular weight of isocyano group base polyurethane prepolymer for use as is 1000~20000, and isocyanide group accounts for the isocyanide based polyurethanes
Prepolymer mass is 1%~8%.
Curing agent includes: amine curing agent, imidazole curing agent, acid anhydride type curing agent or synthetic resin oligomer curing agent
One of.
Resol is that the generation addition reaction under basic catalyst effect of phenolic compound and aldehyde compound obtains
The product obtained.Wherein, phenolic compound includes: phenol, fluorophenol, cresols, mixed phenol, nonyl phenol, octyl phenol, xylenol, waist
One of fruit phenol, aralkyl phenol or bisphenol-A are a variety of;Aldehyde compound includes: in formaldehyde, paraformaldehyde, furfural or acetaldehyde
It is one or more.
By introducing polyurethane flexible segment on phenyl ring, using longer polyurethane flexible segment molecule segment to phenolic aldehyde
Resin modified reduces the crosslink density of phenolic resin, increases the length of molecule segment between crosslinking points, makes shape memory phenolic aldehyde
The molecular structure of resin has a hard section and soft two kinds of molecule segment structures of section, and soft section as resin can anti-phase, raising
The deformability of resin, so that shape memory phenolic resin has shape memory effect performance.
The preparation method of above-mentioned shape memory phenolic resin, comprising the following steps:
S1, basic catalyst is added into the phenolic compound of melting, stirs evenly, add aldehyde compound, heat
It is condensed back, finally vacuumizes dehydration, resol is made;
Isocyano group base polyurethane prepolymer for use as, curing agent are sequentially added in S2, Xiang Suoshu resol, are stirred evenly, and
It injects the mixture into preset die, is heating and curing in vacuum furnace;
S3, it is cooled to room temperature and demoulds, obtain the shape memory phenolic resin.
Specifically, in step sl, by taking phenolic compound is phenol, aldehyde compound is formaldehyde as an example, the chemistry of reaction
Reaction equation are as follows:
In step sl, basic catalyst include: one of ammonium hydroxide, sodium hydroxide, barium hydroxide or aluminium hydroxide or
It is a variety of.Wherein, the molar ratio of phenol, formalin and basic catalyst is 1:(1.5-2): (0.02-0.04), temperature when stirring
Degree is 50-60 DEG C;Heating is condensed back and specifically includes: keeping the temperature 30min after reaction solution is heated to 70 DEG C, is further continued for being warming up to 98
30min is condensed back at DEG C;70 DEG C are finally cooled to hereinafter, and carrying out vacuumizing dehydration.
It is understood that phenolic compound can also be fluorophenol, cresols, mixed phenol, nonyl phenol, octyl phenol, diformazan
One of phenol, anacardol, aralkyl phenol or bisphenol-A are a variety of;Aldehyde compound can also be paraformaldehyde, furfural or acetaldehyde
One of or it is a variety of, as long as realize be made resol.
The chemical equation of step S2 are as follows:
R1 is Or,-(CH3)6-;R2 is-(CH2)n, 2≤n≤20.
It is understood that R1 is the trunk segment of the diisocyanate molecules of synthesis of polyurethane performed polymer, R2 is synthesis
The trunk segment of the dihydric alcohol molecule of base polyurethane prepolymer for use as.
In step s 2, the solidification temperature being heating and curing is 60~90 DEG C, and curing time is 7~9h;Resol
The weight fraction ratio of isocyano group base polyurethane prepolymer for use as and curing agent is 100:(5-15): (1-15).Wherein, isocyanide based polyurethanes are pre-
The molecular weight of aggressiveness is 1000~20000, and it is 1%~8% that isocyanide group, which accounts for the isocyano group polyurethane prepolymer weight,.
Isocyanide group can react with more active hydrogen, therefore the hydrogen on the methylol in resol may
It is the polyurethane prepolymer precursor reactant of isocyano group with end group, phenolic resin and isocyano group base polyurethane prepolymer for use as in the curing process can be with
Crosslinking well forms inierpeneirating network structure, makes to introduce flexible fabulous polyurethane chain in the molecular structure of phenolic resin rigidity
Section.Two kinds of soft section of hard section and polyurethane molecular chain formation that entire molecular structure just has resol to be cross-linked to form
Chain structure improves the mechanical property of phenolic resin, especially so that shape memory phenolic resin has shape memory function
Toughness, can be used as intelligent deformation aircraft, space flight can autonomous unfolding mechanism composite material resin matrix.
It is understood that phenolic resin the degree of cross linking it is excessively high will lead to that its is hard and crisp, and heating is difficult to the excipient that softens,
It is unfavorable for the embodiment of shape-memory properties, therefore, in the heat curing process of step S2, needs to control shape memory phenolic aldehyde tree
The solidification degree of cross linking of rouge.In an embodiment of the present invention, the solidification process using low temperature for a long time or between high temperature, short time, is dropped with this
The degree of cross linking for the hard section that low resol is formed.To guarantee that the shape memory phenolic resin of preparation of the embodiment of the present invention has
Good toughness, it is preferred that the soft section that polyurethane molecular chain is formed accounts for entire shape memory phenolic resin molecular network structure
5%~20%.
Fig. 2, Fig. 3 be reacting material ratio, two kinds of phenolic resin that reaction process is identical but solidification temperature is different it is red
Outer test chart spectrum, i.e. polyurethane prepolymer of the two kinds of phenolic resin by identical resol through identical deal are modifies solid again
Change preparation, prepare the raw material proportioning of the resol are as follows: the molar ratio of phenol, formalin and basic catalyst is 1:
1.8:0.02;The mass ratio of resol and base polyurethane prepolymer for use as is 5:1, and solidification duration is 8h, and solidification temperature is then divided
It is not 80 DEG C and 140 DEG C.With the infrared test map of the shape memory phenolic resin of different solidification temperatures preparation.It can be with from figure
Find out, in 1644cm-1The absorption peak at place is the stretching vibration of C=O, in 1611cm-1The absorption peak at place is that phenyl ring C=C skeleton is stretched
Contracting vibration, in 1512cm-1The absorption peak at place is amide II key (N-H) deformation vibration, in 1214cm-1The absorption peak at place is polyester
C-O stretches or OH deformation vibration, in 1014cm-1The absorption peak at place is the absorption peak of methylol.In 2260cm-1Place is without isocyanic acid
Root absorption peak, illustrate isocyano in base polyurethane prepolymer for use as in resol water or phenolic hydroxyl group reacted.
1611cm-1、1512cm-1And 1214cm-1The methylol that the characteristic peak at place is shown in isocyano and phenolic resin has occurred instead
It answers, base polyurethane prepolymer for use as has been introduced into phenolic resin cross linked molecular structures;In 1014cm-1At absorption peak, 140 DEG C of solidification temperatures
The characteristic peak of the shape memory phenolic resin of lower preparation is markedly less than the shape memory phenolic resin prepared under 80 DEG C of solidification temperatures,
Show that the methylol of the shape memory phenolic resin prepared under 140 DEG C of solidification temperatures is less, resol is formed hard
The degree of cross linking of section is larger.That is, the shape memory phenolic resin prepared under 140 DEG C of solidification temperatures is difficult excipient after the heating, it is difficult
To show shape-memory properties.The shape memory phenolic resin prepared under 80 DEG C of solidification temperatures has apparent shape memory
Energy.
Therefore, to guarantee that shape memory phenolic resin provided in an embodiment of the present invention has excellent in shape memory performance, compared with
Good toughness, solidification temperature range in step s 2 are 60-90 DEG C, and preferred solidification temperature is 80 DEG C.
Fig. 4 is that the shape memory phenolic resin resin for preparing is in 170 DEG C of drying boxes under above-mentioned 80 DEG C of solidification temperatures, deformation
Recovery Process schematic diagram.Using the DMA analysis tester of model TA Q800, the shape memory phenol is measured under stretch mode
The glass transition temperature of urea formaldehyde is 161 DEG C.For the deformation recovery ability for testing shape memory phenolic resin obtained, first
Excipient is carried out to shape memory phenolic resin under its glass transition temperature, makes it from flat transformation in bending, then
Shape memory phenolic resin after excipient is placed in 170 DEG C of drying boxes, its recoil state is observed and changes with time relationship.
Figure 4, it is seen that shape memory phenolic resin is bending shape, curved after 35s under original state (0s)
Folding degree becomes smaller, and the deformation nature of base polyurethane prepolymer for use as embodies as time increases, and shape memory phenolic resin only has after 60s
Curved edge, after 86s, being returned to original-shape by shape memory phenolic resin bending shape lasts 86s.This explanation, is compared
In conventional phenolic resin, shape memory phenolic resin provided in an embodiment of the present invention has shape memory function, has cracking
Turnaround time.And shape memory phenolic resin in secondary figuration temperature range have high tenacity, heat resistance be not added with
The shape memory phenolic resin of the respective type of isocyano group base polyurethane prepolymer for use as is not much different, and is not likely to produce cracking, destroys
Phenomenon has biggish value in terms of the engineer application of phenolic resin composite.
Illustrate the specific preparation method of shape memory phenolic resin with different embodiments below:
Embodiment 1
This example provides a kind of preparation method of shape memory phenolic resin, specifically follows the steps below:
1) take be in melting state phenol, be added three-necked flask in, the pre- thermal agitation in 55 DEG C of oil bath pan;To three mouthfuls
Instill ammonium hydroxide in flask, the molar ratio of ammonium hydroxide and phenol is 0.05:1, stirs 5min under the conditions of 55 DEG C;It is slowly burnt again to three mouthfuls
Formalin is added in bottle, and the molar ratio of formalin and phenol is 1:1.6, continues to stir, keep the temperature after then heating to 70 DEG C
30min, then be warming up to 98 DEG C of condensing reflux 30min, last natural cooling be cooled to 70 DEG C hereinafter, and vacuumize dehydration, be made
Resol.
2) prepared by step 1) 100 parts of resol are taken, 5 parts of isocyano group base polyurethane prepolymer for use as are uniformly mixed, stirring
2 parts of curing agent are added after 30min, is uniformly mixed.It is then injected into preprepared mold, it is complete in 80 DEG C of vacuum furnaces
At solidification.
Embodiment 2
The difference of the present embodiment and above-described embodiment is, a kind of preparation for shape memory phenolic resin that this example provides
Method specifically follows the steps below:
1) take be in melting state phenol, be added three-necked flask in, the pre- thermal agitation in 55 DEG C of oil bath pan;To three mouthfuls
Instill ammonium hydroxide in flask, the molar ratio of ammonium hydroxide and phenol is 0.05:1, stirs 5min under the conditions of 55 DEG C;It is slowly burnt again to three mouthfuls
Formalin is added in bottle, and the molar ratio of formalin and phenol is 1:2, continues to stir, keep the temperature after then heating to 70 DEG C
30min, then be warming up to 98 DEG C of condensing reflux 30min, last natural cooling be cooled to 70 DEG C hereinafter, and vacuumize dehydration, be made
Resol.
2) prepared by step 1) 100 parts of resol are taken, 5 parts of isocyano group base polyurethane prepolymer for use as are uniformly mixed, stirring
2 parts of curing agent are added after 30min, is uniformly mixed.It is then injected into preprepared mold, it is complete in 80 DEG C of vacuum furnaces
At solidification.
Embodiment 3
The difference of the present embodiment and above-described embodiment is, a kind of preparation for shape memory phenolic resin that this example provides
Method specifically follows the steps below:
1) take be in melting state phenol, be added three-necked flask in, the pre- thermal agitation in 55 DEG C of oil bath pan;To three mouthfuls
Instill ammonium hydroxide in flask, the molar ratio of ammonium hydroxide and phenol is 0.05:1, stirs 5min under the conditions of 55 DEG C;It is slowly burnt again to three mouthfuls
Formalin is added in bottle, and the molar ratio of formalin and phenol is 1:2, continues to stir, keep the temperature after then heating to 70 DEG C
30min, then be warming up to 98 DEG C of condensing reflux 30min, last natural cooling be cooled to 70 DEG C hereinafter, and vacuumize dehydration, be made
Resol.
2) prepared by step 1) 100 parts of resol are taken, 6 parts of isocyano group base polyurethane prepolymer for use as are uniformly mixed, stirring
4 parts of curing agent are added after 30min, is uniformly mixed.It is then injected into preprepared mold, it is complete in 80 DEG C of vacuum furnaces
At solidification.
Embodiment 4
The difference of the present embodiment and above-described embodiment is, a kind of preparation for shape memory phenolic resin that this example provides
Method specifically follows the steps below:
1) take be in melting state phenol, be added three-necked flask in, the pre- thermal agitation in 55 DEG C of oil bath pan;To three mouthfuls
Instill ammonium hydroxide in flask, the molar ratio of ammonium hydroxide and phenol is 0.05:1, stirs 5min under the conditions of 55 DEG C;It is slowly burnt again to three mouthfuls
Formalin is added in bottle, and the molar ratio of formalin and phenol is 1:2, continues to stir, keep the temperature after then heating to 70 DEG C
30min, then be warming up to 98 DEG C of condensing reflux 30min, last natural cooling be cooled to 70 DEG C hereinafter, and vacuumize dehydration, be made
Resol.
2) prepared by step 1) 100 parts of resol are taken, 10 parts of isocyano group base polyurethane prepolymer for use as are uniformly mixed, stirring
9 parts of curing agent are added after 30min, is uniformly mixed.It is then injected into preprepared mold, it is complete in 80 DEG C of vacuum furnaces
At solidification.
Embodiment 5
The difference of the present embodiment and above-described embodiment is, a kind of preparation for shape memory phenolic resin that this example provides
Method specifically follows the steps below:
1) take be in melting state phenol, be added three-necked flask in, the pre- thermal agitation in 55 DEG C of oil bath pan;To three mouthfuls
Instill ammonium hydroxide in flask, the molar ratio of ammonium hydroxide and phenol is 0.05:1, stirs 5min under the conditions of 55 DEG C;It is slowly burnt again to three mouthfuls
Formalin is added in bottle, and the molar ratio of formalin and phenol is 1:2, continues to stir, keep the temperature after then heating to 70 DEG C
30min, then be warming up to 98 DEG C of condensing reflux 30min, last natural cooling be cooled to 70 DEG C hereinafter, and vacuumize dehydration, be made
Resol.
2) prepared by step 1) 100 parts of resol are taken, 15 parts of isocyano group base polyurethane prepolymer for use as are uniformly mixed, stirring
15 parts of curing agent are added after 30min, is uniformly mixed.It is then injected into preprepared mold, in 80 DEG C of vacuum furnaces
Complete solidification.
Although the disclosure discloses as above, the protection scope of the disclosure is not limited only to this.Those skilled in the art, not
Under the premise of being detached from spirit and scope of the present disclosure, it can make various changes and modify, these changes will fall into this with modification
The protection scope of invention.
Claims (10)
1. a kind of shape memory phenolic resin, which is characterized in that the structural formula of the shape memory phenolic resin are as follows:
Wherein, R is
R1 is Or,-(CH3)6-;
R2 is-(CH2)n, 2≤n≤20.
2. shape memory phenolic resin according to claim 1, which is characterized in that the shape memory phenolic resin is by weight
Measure part meter, comprising: 100 parts of resols, 5~15 parts of isocyano group base polyurethane prepolymer for use as, 1~15 part of curing agent.
3. shape memory phenolic resin according to claim 2, which is characterized in that the isocyano group base polyurethane prepolymer for use as
Molecular weight is 1000~20000, and isocyanide group accounts for the 1%~8% of the isocyano group polyurethane prepolymer weight.
4. shape memory phenolic resin according to claim 2, which is characterized in that the curing agent includes amine-type cure
One of agent, imidazole curing agent, acid anhydride type curing agent or synthetic resin oligomer curing agent.
5. shape memory phenolic resin according to claim 2, which is characterized in that the resol is phenol generalization
It closes object and aldehyde compound and the product that addition reaction obtains occurs under basic catalyst effect.
6. shape memory phenolic resin according to claim 5, which is characterized in that the phenolic compound include: phenol,
One of fluorophenol, cresols, mixed phenol, nonyl phenol, octyl phenol, xylenol, anacardol, aralkyl phenol or bisphenol-A are a variety of;
The aldehyde compound includes: one of formaldehyde, paraformaldehyde, furfural or acetaldehyde or a variety of.
7. a kind of preparation method of shape memory phenolic resin of any of claims 1-6, which is characterized in that including
Following steps:
S1, basic catalyst is added into the phenolic compound of melting, stirs evenly, add aldehyde compound, heating condensation
Reflux vacuumizes dehydration after cooling, and resol is made;
Isocyano group base polyurethane prepolymer for use as, curing agent are sequentially added in S2, Xiang Suoshu resol, is stirred evenly, and will be mixed
It closes in object injection preset die, is heating and curing in vacuum furnace;
S3, demoulding obtain the shape memory phenolic resin.
8. the preparation method of shape memory phenolic resin according to claim 7, which is characterized in that in the 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)。
9. the preparation method of shape memory phenolic resin according to claim 7, which is characterized in that the basic catalyst
It include: one of ammonium hydroxide, sodium hydroxide, barium hydroxide or aluminium hydroxide or a variety of.
10. the preparation method of shape memory phenolic resin according to claim 7, which is characterized in that in the step S2,
The solidification temperature being heating and curing is 60~90 DEG C, and curing time is 7~9h.
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CN113637130A (en) * | 2021-08-18 | 2021-11-12 | 四川东树新材料有限公司 | Modified polyurethane for wind power blade pultrusion plate |
CN114702633A (en) * | 2022-03-16 | 2022-07-05 | 陕西科技大学 | Modified resol and preparation method thereof |
CN114752180A (en) * | 2022-05-13 | 2022-07-15 | 哈尔滨工业大学 | Shape memory phenolic foam and preparation method thereof |
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WU,HD ET AL: "Pultruded fiber-reinforced polyurethane-toughened phenolic resin .1. Reactivity and morphology", 《ANGEWANDTE MAKROMOLEKULARE CHEMIE》 * |
Cited By (6)
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CN111647118A (en) * | 2020-06-24 | 2020-09-11 | 苏州兴业材料科技南通有限公司 | Toughened flame-retardant phenolic resin and preparation method thereof |
CN113637130A (en) * | 2021-08-18 | 2021-11-12 | 四川东树新材料有限公司 | Modified polyurethane for wind power blade pultrusion plate |
CN113637130B (en) * | 2021-08-18 | 2024-04-30 | 四川东树新材料有限公司 | Modified polyurethane for wind power blade pultrusion plate |
CN114702633A (en) * | 2022-03-16 | 2022-07-05 | 陕西科技大学 | Modified resol and preparation method thereof |
CN114702633B (en) * | 2022-03-16 | 2023-10-31 | 晶瓷(北京)新材料科技有限公司 | Modified resol resin and preparation method thereof |
CN114752180A (en) * | 2022-05-13 | 2022-07-15 | 哈尔滨工业大学 | Shape memory phenolic foam and preparation method thereof |
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