CN109943071A - A kind of polysiloxane-modified cyanate resin base shape-memory material and preparation method thereof with high glass-transition temperature - Google Patents
A kind of polysiloxane-modified cyanate resin base shape-memory material and preparation method thereof with high glass-transition temperature Download PDFInfo
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- CN109943071A CN109943071A CN201910248570.5A CN201910248570A CN109943071A CN 109943071 A CN109943071 A CN 109943071A CN 201910248570 A CN201910248570 A CN 201910248570A CN 109943071 A CN109943071 A CN 109943071A
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Abstract
The invention discloses a kind of polysiloxane-modified cyanate resin base shape-memory material and preparation method thereof with high glass-transition temperature, shape-memory material is obtained by hydroxyl-terminated injecting two methyl siloxane, epoxy resin, silane coupling agent, cyanate etc. by heat cure；The shape-memory material intensity of preparation is high, modulus is high, shape-memory properties are excellent, and glass transition temperature with higher, can adapt to compared with elevated operating temperature environment, preparation process is simple and convenient to operate, and is conducive to industrialized production.
Description
Technical field
The present invention relates to a kind of shape-memory material, in particular to a kind of cyanate resin base using polysiloxane toughening
Shape-memory material, which is able to maintain higher mechanical strength under the high temperature conditions, with higher to use temperature,
Good application prospect is all had in biomedical, weaving, packaging, aerospace field, belongs to shape-memory polymer function
Field of material technology.
Background technique
Shape-memory polymer (SMP) is a kind of novel intelligent material with broad prospect of application.In biomedical, spinning
Knit, pack, aerospace field all has good application prospect, especially cause extensive concern in aerospace field.
In aerospace field, shape-memory material is mainly used in the detection load of satellite, such as antenna, stretching, extension arm configuration, truss
Deployable structure.Shape-memory polymer is mainly polynorbornene, polyurethane, styrene-butadiene copolymer, epoxy at present
Resin etc..Its glass transition temperature is lower, when setting operating temperature and glass transition temperature is close, in use
It makes mistakes vulnerable to such environmental effects and is unfolded or is unfolded in advance, it is difficult to it is higher to be applied to shape-memory properties precise requirements
In structure.Heat-resistant polymer is the direction of hi tech and new material development, and the application especially on aerospace industry has weight
Big realistic meaning.The shape-memory polymer studied at present is using temperature generally within the scope of 50 DEG C~120 DEG C.Such as Publication No.
(CN104744893A) Chinese patent (shape memory epoxy resin and preparation method thereof) discloses a kind of hyper-branched polyester and changes
The epoxy resin-matrix shape-memory material of property.The heat distortion temperature of the shape-memory material is 80 DEG C~140 DEG C, working environment
Temperature is lower, can not use in high-temperature work environment.Therefore, needing design has with one kind is prepared compared with high glass transition temperature
The good shape-memory material of degree, high temperature resistance still has accurately shape memory under higher working temperature environment
Energy.
Cyclic trimerization reaction can occur under heating or catalyst action for cyanate ester resin, generate a large amount of triazine ring knots
Structure.Triazine ring cross-linked structure has high steric hindrance, and there are the rigid structures such as a large amount of aromatic rings to solidify cyanate in system
Object has high glass transition temperature (240 DEG C~290 DEG C), high-fire resistance, excellent tensile strength, impact strength, low Jie
Electric constant, low hydroscopicity and thermal expansion coefficient etc. have broad application prospects in fields such as aerospace, adhesives.But
The triazine ring rigid structure generated after ethylene rhodanate resin curing makes that system crystallinity is high, solidfied material is more crisp, toughness is poor, deformation
The disadvantages of small is measured, the toughness reguirements for making it be difficult to meet distressed structure material.
Summary of the invention
The problems such as low using temperature for current shape-memory polymer, the first purpose of this invention is to be to provide one
Kind by dimethyl silicone polymer, epoxy resin and cyanate ester resin tri compound it is modified obtain have high glass transition temperature,
The good polysiloxane-modified cyanate resin base shape-memory material of high temperature resistance.
Another object of the present invention is to be to provide a kind of polysiloxane-modified cyanate resin base shape-memory material
Preparation method, this method is simple, at low cost, is conducive to industrialized production.
In order to achieve the above technical purposes, the present invention provides a kind of polysiloxanes with high glass-transition temperature to change
Property cyanate resin base shape-memory material, is obtained by following content of component raw material by heat cure: the poly- diformazan of terminal hydroxy group
Radical siloxane 16~25%；Epoxy resin 13~20%；Silane coupling agent 3~5%；Cyanate 50~67%；Catalyst 0.1~
0.3%.
Preferred scheme, the molecular weight of the hydroxyl-terminated injecting two methyl siloxane are 500~1000.Molecular weight is bigger, material
The viscosity of material is bigger, and the functional group reacted under equal quality is fewer, and hydroxyl-terminated injecting two methyl siloxane is reunited in resin matrix
The rubber phase particle of formation may be bigger, will affect the mechanical property of material, it is compound in preferred molecular weight ranges can be with
Obtain preferable comprehensive performance.
Preferred scheme, the epoxy resin are selected from the AL-3040 epoxy resin that epoxide number is 0.41~0.44.Preferably
Unsaturated bond is free of in AL-3040 epoxy molecule structure, there is good heat resistance and weatherability, viscosity is low, processability
Can be good, other opposite epoxy resin have a clear superiority.
Preferred scheme, the silane coupling agent include at least one of KH-550, KH-560, KH-570, KH-590.
Most preferred silane coupling agent is KH-550 silane coupling agent.
Preferred scheme, the cyanate include bisphenol E-type cyanate and/or bisphenol A cyanate ester.Most preferred cyanic acid
Ester is bisphenol E-type cyanate, is in a liquid state at room temperature, be can purchase in Hubei Ju Sheng Science and Technology Ltd..
Preferred scheme, the catalyst include di lauric dibutyl transition metal complex and/or acetylacetone,2,4-pentanedione mistake
Cross metal complex.Most preferably dibutyl tin dilaurate.
The polysiloxane-modified cyanate resin base shape with high glass-transition temperature that the present invention also provides a kind of
The preparation method of memory material, this method are by hydroxyl-terminated injecting two methyl siloxane, epoxy resin, silane coupling agent and catalysis
Agent, heating stirring reaction, obtains expanding material；The expanding material and cyanate carry out prepolymerization, obtain pouring building body；It is described to pour
Building body by vacuum defoamation, pour and heat cure to get.
Preferred scheme, the temperature being stirred to react are 90~100 DEG C, and the time is 2~3 hours.
Preferred scheme, the temperature of prepolymerization are 90~100 DEG C, and the time is 0.5~1 hour.
Preferred scheme, the thermosetting turn to temperature programming solidification: at 120~125 DEG C, keeping the temperature 3~4h；150~
155 DEG C, keep the temperature 1~2h；At 170~175 DEG C, 1~2h is kept the temperature.Most preferred curing process are as follows: 120 DEG C/4h+150 DEG C/
2h+170℃/2h。
There are excellent mechanics, heat-resisting, environmental resistance, but three generated after hardening for existing cyanate ester resin
Piperazine ring rigid structure makes system crystallinity height, solidfied material compared with crisp, toughness is poor, deformation quantity is small, it is difficult to meet distressed structure material
The problems such as toughness reguirements of material.Present invention firstly provides using dimethyl silicone polymer as improving cyanate ester resin toughness, weather-proof
Property and high temperature resistance material be used for cyanate ester resin carry out composite modified, Si- in dimethyl silicone polymer molecular structure
O-Si segment has good flexibility, and main chain Si-O key bond energy is higher, has good high-temperature stability, flexibility, resistance to
Hou Xing is a kind of ideal cyanate resin modifier material.But polydimethylsiloxanebackbone backbone is inorganic siloxanes, with cyanogen
Acid ester resin has that compatibility is poor, and there are apparent laminations for the two.The present invention passes through terminal hydroxy group poly- two first
Methylsiloxane, epoxy resin and silane coupling agent obtain a kind of new expanding material by pre- copolyreaction, will be gathered by pre-polymerization
Dimethyl siloxane uniformly introduces epoxy resin, then compound so as to utilizing by the solidification between epoxy resin and cyanate
Epoxy resin improves the compatibility between dimethyl silicone polymer and cyanate ester resin, to obtain a kind of ideal tri compound shape
Shape memory material.Si-O-Si segment flexible is introduced in cyanate ester resin system by polydimethylsiloxane--modified, greatly
Greatly cyanate ester resin toughness, weatherability and high temperature resistance are improved, obtained a kind of with higher glass transition temperature
Polysiloxane-modified cyanate resin base shape-memory material.The tri compound shape-memory material remains cyanate ester resin height
Intensity, while the toughness and shape-memory properties of cyanate ester resin are improved, and glass transition temperature is at 152 DEG C~186 DEG C
Between, there is preferable heat resistance, applied at elevated temperature performance, excellent shape-memory properties, high tensile and impact flexibility etc..
Polysiloxane-modified cyanate resin base shape-memory material of the invention using cyanate ester resin as matrix resin,
Using dibutyl tin dilaurate as catalyst, pass through epoxy resin, hydroxyl-terminated injecting two methyl siloxane, silane coupling agent pre-polymerization
Conjunction prepares expanding material, is used for toughening cyanate ester resin.It adequately embodies cyanate ester resin and dimethyl silicone polymer is compound
Advantage.The introducing of dimethyl silicone polymer significantly improves the toughness of cyanate ester resin system, and the shape-memory properties of material obtain
Great raising has been arrived, mechanical property, the application requirement of shape-memory properties are met.
The specific preparation method of polysiloxane-modified cyanate resin base shape-memory material of the invention: by AL-3040
Epoxy resin 50g, hydroxyl-terminated injecting two methyl siloxane 60g, KH-550 silane coupling agent 10g, are stirred after being heated to 100 DEG C
Uniformly.Catalyst dibutyltin dilaurylate 0.5g is then added, continues to be stirred to react 2h obtaining expanding material.According to expanding material with
The ratio of cyanate ester resin is separately added into 120g, 180 g or 240g bisphenol E-type cyanates, continues to be stirred to react 1h.By gained
Prepreg vacuum extract bubble, subsequent normal pressure is poured into mold, finally according to 120 DEG C/4h+150 DEG C/2h of curing process
+ 170 DEG C/2h solidifies to obtain cyanate resin base shape-memory material.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1) polysiloxane-modified cyanate resin base shape-memory material glass transition temperature with higher of the invention, glass
Glass transition temperature is between 152 DEG C~186 DEG C.Compared with existing epoxy resin-matrix shape-memory material, it is suitable for temperature
Higher environment is not easy influenced by ambient temperature.
2) polysiloxane-modified cyanate resin base shape-memory material excellent in mechanical performance of the invention, it is with higher
Intensity and modulus, and there are excellent shape-memory properties, shape fixed rate and shape recovery rate are 95% or more.
3) polysiloxane-modified cyanate resin base shape-memory material preparation method of the invention is simple, at low cost, has
Conducive to industrialized production.
Detailed description of the invention
[Fig. 1] is that polysiloxane-modified cyanate resin base shape-memory material solidification front and back is red in the embodiment of the present invention 1
External spectrum figure.
[Fig. 2] is the embodiment of the present invention 1, embodiment 2, embodiment 3, compares the stress-strain curve diagram for applying example group.
[Fig. 3] is the thermogravimetric analysis figure that example group is applied in the embodiment of the present invention 1 and control.
[Fig. 4] is polysiloxane-modified cyanate resin base shape-memory material shape memory in the embodiment of the present invention 1
Energy test record figure, a 0s, b 18s, c 41s, d 54s, the deformed state of material when e is 65s.
Specific embodiment
Below in conjunction with Figure of description and specific preferred example, the invention will be further described, but is not so limited this
Invention scope of protection of the claims.
Equipment and instrument employed in implementing below are commercially available.
Polysiloxane-modified cyanate resin base shape-memory material is by following mass percent component in following embodiment
Raw material composition: hydroxyl-terminated injecting two methyl siloxane 16%~25%；AL-3040 epoxy resin 13%~20%；KH-550 silane
Coupling agent 3%~5%；Bisphenol E-type cyanate 50%~67%；Dibutyltin dilaurate catalyst 0.1%~0.3%.
In following implementation, hydroxyl-terminated injecting two methyl siloxane comes from Jiashan Jiangnan textile material Co., Ltd, molecular weight
600, the trade mark: M30-203.Bisphenol E-type cyanate comes from Hubei Ju Sheng Science and Technology Ltd.；AL-3040 epoxy resin comes from cigarette
Tai Aolifu Chemical Co., Ltd., epoxide number 0.4.
Embodiment 1
Polysiloxane-modified cyanate resin base shape-memory material the preparation method comprises the following steps: being weighed according to above-mentioned mass fraction
AL-3040 epoxy resin 100g, hydroxyl-terminated injecting two methyl siloxane 120g, KH-550 silane coupling agent 20g, are heated to 100 DEG C
After be uniformly mixed.Catalyst dibutyltin dilaurylate 1g is then added, continues to be stirred to react 2h obtaining expanding material.Then
Bisphenol E-type cyanate 240g is added, continues to be stirred to react 1h.Resulting prepreg vacuum is extracted into bubble, subsequent normal pressure pours
To in mold, finally solidify to obtain terminal hydroxy group poly dimethyl silicon according to 120 DEG C/4h+150 DEG C/2h+170 DEG C/2h of curing process
Oxygen alkane toughening cyanate resin base shape-memory material.
Expanding material is prepared by hydroxyl-terminated injecting two methyl siloxane, KH-550 silane coupling agent and AL-3040 epoxy resin.
Using AL-3040 epoxy resin and the good compatibility of bisphenol E-type cyanate resin, improves hydroxyl-terminated injecting two methyl siloxane and exist
Dispersibility in bisphenol E-type cyanate resin matrix.Pass through two fourth of epoxy group and catalyst dibutyltin cinnamic acid in epoxy resin
Ji Xi solidifies bisphenol E-type cyanate resin.From figure 1 it appears that 2238cm-1Place is the absorption peak of cyano (- CN).Cyanogen
In the infrared spectrogram of acid esters, 2970 cm-1The peak of left and right is the stretching vibration peak of methyl, methylene.Positioned at 2270cm-1With
2238cm-1The strong absworption peak at place is belonging respectively to the absorption peak of cyanic acid ester group (- OCN) and cyano (- CN).With adding for expanding material
Enter, the infrared peak of cyanic acid ester group (- OCN) and cyano (- CN) disappears, and after bisphenol E-type cyanate solidification, cyanate generates triazine
Ring structure, in 1570cm-1、1370cm-1There is new peak in place, respectively corresponds C-N the and C=N structure in triazine ring.
The cyanate ester resin base shape memory of the hydroxyl-terminated injecting two methyl siloxane toughening modifying as made from the embodiment
Compatibilizer Content is 50% in material, and the glass transition temperature of material is 152 DEG C, and material shows good toughness, is had preferable
Good mechanical property and excellent shape-memory properties.Its impact strength is 19.7 kJ/m2, elongation at break is
8.8%, tensile strength about 32MPa, Young's modulus about 519MPa.Fig. 3 can be seen that hydroxyl-terminated injecting two methyl siloxane was modified
Cyanate resin base shape-memory material has good heat resistance, under 800 DEG C of hot environments, terminal hydroxy group poly dimethyl silicon
The residual heavy rate of siloxane modified cyanate resin base shape-memory material is 37.8%, and the residual heavy rate of cyanate ester resin is 6.5%.
The shape fixed rate of the cyanate resin base shape-memory material of obtained hydroxyl-terminated injecting two methyl siloxane toughening modifying is about
96%, shape recovery rate about 99%.Figure 4, it is seen that shape memory recovery of shape-memory material completion is made to obtain
Take around 65s.
Embodiment 2
Polysiloxane-modified cyanate resin base shape-memory material the preparation method comprises the following steps: being weighed according to above-mentioned mass fraction
AL-3040 epoxy resin 66.7g, hydroxyl-terminated injecting two methyl siloxane 80g, KH-550 silane coupling agent 13.3g, are heated to 100
It is uniformly mixed after DEG C.0.67 g of catalyst dibutyltin dilaurylate is then added, continues to be stirred to react 2h obtaining increase-volume
Agent.Bisphenol E-type cyanate 240g is then added, continues to be stirred to react 1h.Resulting prepreg vacuum is extracted into bubble, then often
Pressure is poured into mold, finally solidifies to obtain terminal hydroxy group poly- two according to 120 DEG C/4h+150 DEG C/2h+170 DEG C/2h of curing process
Methylsiloxane toughening cyanate resin base shape-memory material.
The cyanate resin base shape of the hydroxyl-terminated injecting two methyl siloxane toughening modifying as made from the embodiment is remembered
Recalling in material Compatibilizer Content is 40%, and the glass transition temperature of material is 172 DEG C, and material shows preferable toughness, have compared with
Good good mechanical property and excellent shape-memory properties.Its impact strength is 19.1 kJ/m2, elongation at break is
7.5%, tensile strength about 39MPa, Young's modulus about 637MPa, shape fixed rate about 96%, shape recovery rate about 98%.
Embodiment 3
Polysiloxane-modified cyanate resin base shape-memory material the preparation method comprises the following steps: being weighed according to above-mentioned mass fraction
AL-3040 epoxy resin 50g, hydroxyl-terminated injecting two methyl siloxane 60g, KH-550 silane coupling agent 10g, after being heated to 100 DEG C
It is uniformly mixed.Catalyst dibutyltin dilaurylate 0.5g is then added, continues to be stirred to react 2h obtaining expanding material.Then
Bisphenol E-type cyanate 240g is added, continues to be stirred to react 1h.Resulting prepreg vacuum is extracted into bubble, subsequent normal pressure pours
To in mold, finally solidify to obtain terminal hydroxy group poly dimethyl silicon according to 120 DEG C/4h+150 DEG C/2h+170 DEG C/2h of curing process
Oxygen alkane toughening cyanate resin base shape-memory material.
The cyanate resin base shape of the hydroxyl-terminated injecting two methyl siloxane toughening modifying as made from the embodiment is remembered
Recalling in material Compatibilizer Content is 33%, and the glass transition temperature of material is 186 DEG C, and material shows preferable toughness, have compared with
Good good mechanical property and excellent shape-memory properties.Its impact strength is 16.6 kJ/m2, elongation at break is
5.8%, tensile strength about 42MPa, Young's modulus about 670MPa, shape fixed rate about 98%, shape recovery rate about 96%.
Comparative examples group:
For shape-memory material, the soft segment in system is in the ability for assigning material memory original-shape.Not add
Add the bisphenol E-type cyanate resin control group of expanding material.Bisphenol E-type cyanate resin 120g is weighed, catalyst two is then added
Dibutyl tin laurate 0.5g, 100 DEG C are stirred to react prepreg vacuum abstraction bubble after 1h, and normal pressure is poured into mold,
Finally solidify to obtain bisphenol E-type cyanate resin according to 120 DEG C/4h+150 DEG C/2h+170 DEG C/2h of curing process.Obtained cyanogen
Acid ester resin glass transition temperature is up to 258 DEG C, is triazine ring rigid structure in system, and material is more crisp, is not suitable for use in shape note
Recall material.
Claims (10)
1. a kind of polysiloxane-modified cyanate resin base shape-memory material with high glass-transition temperature, feature exist
In: it is obtained by following mass percent component raw material by heat cure:
Hydroxyl-terminated injecting two methyl siloxane 16~25%；
Epoxy resin 13~20%；
Silane coupling agent 3~5%；
Cyanate 50~67%；
Catalyst 0.1~0.3%.
2. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 1
Shape memory material, it is characterised in that: the molecular weight of the hydroxyl-terminated injecting two methyl siloxane is 500~1000.
3. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 1
Shape memory material, it is characterised in that: the epoxy resin is selected from the AL-3040 epoxy resin that epoxide number is 0.41~0.44.
4. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 1
Shape memory material, it is characterised in that: the silane coupling agent includes at least one in KH-550, KH-560, KH-570, KH-590
Kind.
5. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 1
Shape memory material, it is characterised in that: the cyanate includes bisphenol E-type cyanate and/or bisphenol A cyanate ester.
6. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 1
Shape memory material, it is characterised in that: the catalyst includes di lauric dibutyl transition metal complex and/or diacetyl third
Ketone transition metal complex.
7. a kind of described in any item polysiloxane-modified cyanate resins with high glass-transition temperature of claim 1~6
The preparation method of aliphatic radical shape-memory material, it is characterised in that: hydroxyl-terminated injecting two methyl siloxane, epoxy resin, silane is even
Join agent and catalyst, heating stirring reaction obtains expanding material；The expanding material and cyanate carry out prepolymerization, are poured
Building body；It is described pour building body by vacuum defoamation, pour and heat cure to get.
8. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 7
The preparation method of shape memory material, it is characterised in that: the temperature being stirred to react is 90~100 DEG C, and the time is 2~3 hours.
9. a kind of polysiloxane-modified cyanate resin base shape with high glass-transition temperature according to claim 7
The preparation method of shape memory material, it is characterised in that: the temperature of prepolymerization is 90~100 DEG C, and the time is 0.5~1 hour.
10. a kind of polysiloxane-modified cyanate resin base with high glass-transition temperature according to claim 7
The preparation method of shape-memory material, it is characterised in that: the thermosetting turns to temperature programming solidification: at 120~125 DEG C, heat preservation 3
~4h；At 150~155 DEG C, 1~2h is kept the temperature；At 170~175 DEG C, 1~2h is kept the temperature.
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