CN109851755A - A kind of carrying/deformation integrated polymer based composites and preparation method thereof - Google Patents
A kind of carrying/deformation integrated polymer based composites and preparation method thereof Download PDFInfo
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- CN109851755A CN109851755A CN201910018224.8A CN201910018224A CN109851755A CN 109851755 A CN109851755 A CN 109851755A CN 201910018224 A CN201910018224 A CN 201910018224A CN 109851755 A CN109851755 A CN 109851755A
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- based composites
- polymer based
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Abstract
The present invention relates to a kind of carrying/deformation integrated polymer based composites and preparation method thereof, and hydroxy-end capped polycaprolactone, the inorganic material of hydroxyl modification and isocyanates are dispersed in super dry n,N-Dimethylformamide first in glove box；Room temperature is stirred to react 8-24h in glove box；Again by four -3-thiopropionate of pentaerythrite and catalyst 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene is added in the dispersion liquid, and dispersion liquid is added in closed mold, it is statically placed in 60-150 DEG C of vacuum drying oven and reacts 12-24h to get target product is arrived.The present invention introduces the function that ester exchange reaction obtains multiple plastotype with the intensity of inorganic material-modified polymer, preparation take into account with high intensity, variation rigidity, can multiple plastotype function polymer matrix composite, realize that carrying/deformation is integrated.
Description
Technical field
The invention belongs to functional polymer technical field of composite materials, more particularly, are related to a kind of carrying/deformation one
Body fluidized polymer based composites and preparation method thereof.
Background technique
Shape-memory polymer can not only show high elastic modulus small deformation, but also can show as the big change of low elastic modulus
Shape is a kind of high molecular material of variation rigidity.However conventional shape-memory polymer, the mechanics such as its own modulus, intensity and
Thermodynamic property is poor, causes material deformation-recovery power output smaller, and kinetic stability and reliability are poor, and creep and relaxation are existing
As more serious, its use as loading material has been seriously affected；In addition, general shape-memory polymer is limited only to one kind
Deformation, it is difficult to the function of realizing heating for multiple times plastotype, the environment for making it may not apply to that there are a variety of deformation.If passing through technique
It is modified, prepare it is a kind of have variation rigidity, high intensity, can multiple plastotype polymer matrix composite, it can be achieved that carrying/deformation one
The function of body.
By retrieval, the patent document of following near field is given.
A kind of preparation method of high performance polymer base composite material and products thereof (CN109021493A).This method packet
It includes: obtaining reactable and carbon nanometer with good solvent dispersibility by carrying out functional modification to carbon nanomaterial surface
Material, and it is uniformly mixed with high molecular polymer, chemical bonded refractory is obtained using electrostatic powder coating and heat pressure forming process
Carbon nanomaterial-high molecular polymer of conjunction-fabric high-performance composite materials product.The present invention passes through in hot forming mistake
Cheng Zhong enables and the end position active function groups in functionalized carbon nano material and occurs between high molecular polymer and fabric
Cross-linking reaction forms dimensional network structure, and the chemical bonds between three can significantly improve the mechanical performance of composite material,
Solve the problems, such as that carbon nanomaterial is easy to gather, is difficult evenly dispersed in a polymer matrix and carbon nanomaterial, polymerization
The small problem of interaction force between object and fabric.
A method of polymer matrix composite thermal expansion coefficient is caused based on free-radical contents prediction spoke
(CN108333212A), it belongs to the assessment technique field of the dimensional stability of composite material, and the present invention solves spacecraft and exists
During rail is run, due to being limited by experiment condition and appointed condition, to the heat of complicated polymer matrix composite
The time that the measurement of the coefficient of expansion needs is longer, and measures the higher problem of difficulty.The present invention utilizes polymer matrix composite
As laboratory sample, under the conditions of vacuum degree is less than 1Pa, irradiation experiment is carried out to laboratory sample, show that the polymer matrix is compound
The free-radical contents of material are as the changing rule and thermal expansion coefficient of irradiation fluence or dosage are with irradiation fluence or dosage
Changing rule is consistent, therefore, in orbit period, can measure free-radical contents only to predict the heat of polymer matrix composite
The coefficient of expansion.Present invention could apply to the assessment technique field of the dimensional stability of composite material use.
A kind of polymer matrix composite (CN108570200A), the polymer matrix composite include following parts by weight
Several following component: 400 parts of polymeric matrix；5-600 parts of filler, wherein the filler is heterojunction structure particle, described heterogeneous
Structure particles be two or more raw material with forbidden band difference made of crystal grain, the raw material be semiconductor and/
Or insulator.
By comparison, the technology contents of present patent application, specific preparation method and preparation effect and documents phase
Than there are biggish differences.
Summary of the invention
It is an object of the invention to overcome extensive electric car access adverse effect caused by power grid, one kind is provided and is held
Load/deformation integrated polymer based composites and preparation method thereof, using the intensity of inorganic material-modified polymer, and utilize
Ester exchange reaction obtains the function of multiple plastotype, obtain take into account high intensity, variation rigidity, can multiple plastotype polymer matrix composite wood
Material realizes carrying/deformation integration.
The present invention solves its technical problem and adopts the following technical solutions to achieve:
A kind of carrying/deformation integrated polymer based composites, by hydroxy-end capped polycaprolactone, isocyanates, season
The inorganic material of penta four -3-thiopropionate of tetrol and hydroxyl modification is prepared.
Moreover, the number-average molecular weight of the hydroxy-end capped polycaprolactone be 10000-500, isocyanates 2,4 or 2,
6- toluene di-isocyanate(TDI), hexamethylene diisocyanate or 1, one of 5- naphthalene diisocyanate, hydroxyl modification it is inorganic
Material is one of carbon nanotube or nano silica.
Moreover, the molar feed ratio of the isocyanates and hydroxy-end capped polycaprolactone is 10-1:1；The isocyanic acid
The molar feed ratio of ester and four -3-thiopropionate of pentaerythrite is 5-1:1；The content of the inorganic material of the hydroxyl modification is
The weight 0.5-10wt% of all reactants.(molar ratio and weight ratio in embodiment do not cover in claims
End value, there are the possibility to reduce the scope in examination reports)
Moreover, the draw ratio of the carbon nanotube is 2-20:1, the partial size of nano silica is 20-500nm.
Above-mentioned carrying/deformation integrated polymer based composites preparation method is hydroxy-end capped polycaprolactone, hydroxyl
The modified inorganic material of base first reacts to form uniform dispersion liquid with isocyanates, adds four -3- mercaptopropionic acid of pentaerythrite
Ester.
Moreover, the hydroxy-end capped polycaprolactone, the inorganic material of hydroxyl modification and reacting in gloves for isocyanates
It is carried out in case, used reagent is super dry n,N-Dimethylformamide.
Moreover, the hydroxy-end capped polycaprolactone, the inorganic material of hydroxyl modification and the reaction time of isocyanates are
8-24h, reaction temperature are room temperature.
Moreover, that there are transesterifications between the four -3-thiopropionate of pentaerythrite and the polycaprolactone of hydroxyl modification is anti-
It answers, the temperature that ester exchange reaction carries out is 60-150 DEG C, reaction time 12-24h.
Moreover, ester exchange reaction is carried out under the action of 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene catalyst
's.
Moreover, the dosage of catalyst is the 1-3wt% of four -3-thiopropionate of pentaerythrite.
The advantages and positive effects of the present invention are:
Compared with prior art, the present invention intensity of the present invention using inorganic material enhancing polymer, by complex
Ester exchange reaction is introduced in system makes material have the function of heating for multiple times plastotype, obtains the integrated polymer matrix of carrying/deformation
Composite material.
Detailed description of the invention
Fig. 1 is the preparation flow figure of heretofore described composite material；
Fig. 2 is a kind of load-deformation curve of sample of the invention at different temperatures；
Fig. 3 is a kind of tensile strength curve of sample of the invention under different carbon fiber contents.
Specific embodiment
Below such as Fig. 1 preparation route, above content of the invention is described in further detail in conjunction with the embodiments.Hydroxyl changes
Property polycaprolactone, isocyanates be purchased from Beijing lark prestige Science and Technology Ltd., 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5-
Alkene purchase has in uncommon love (Shanghai) the chemical conversion industry Development Co., Ltd of ladder, carbon nanotube purchase in Nanjing Xian Feng nano material science and technology
Limit company, nano silica purchase in Shanghai carat Ma Er Reagent Company, the purchase of four -3-thiopropionate of pentaerythrite in
Sigma-Aldrich。
Embodiment 1
(1) in glove box, the molar feed ratio for weighing the polycaprolactone of isocyanates and hydroxyl modification is 10:1, inorganic
The weight ratio of material is the raw material of 10wt%, i.e. 5g hexamethylene diisocyanate, the hydroxyl that 5.9g number-average molecular weight is 2000
Modified polycaprolactone, 1.6g draw ratio are the carbon nanotube of 20:1, are then dispersed in the super dry n,N-Dimethylformamide of 10mL
In, obtain uniform dispersion liquid；
(2) in glove box, step (1) resulting dispersion is placed in room temperature, obtains the first step after being stirred to react 8h
The dispersion liquid of product；
(3) pentaerythrite for being 1:5 with the molar feed ratio of isocyanates is added in the dispersion liquid that step (2) obtains
Four -3-thiopropionates, 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene that mass fraction is 3wt%, i.e. 2.9g Ji Wusi
Four -3-thiopropionate of alcohol, tri- azacyclo- of 0.09g 1,5,7- two ring [4.4.0] last of the ten Heavenly stems 5- alkene, is placed in closed die after evenly mixing
In tool, the heating reaction 20h in 60 DEG C of vacuum drying ovens is after reaction dried sample in vacuum drying oven to get target is arrived
Product.
Embodiment 2
(1) in glove box, the molar feed ratio for weighing the polycaprolactone of isocyanates and hydroxyl modification is 1:1, inorganic
The weight ratio of material is the raw material of 0.5wt%, i.e. 1g 2,6- toluene di-isocyanate(TDI), 57.4g number-average molecular weight is 10000
The polycaprolactone of hydroxyl modification, 0.3g draw ratio are the carbon nanotube of 2:1, are then dispersed in the super dry N of 10mL, N- dimethyl formyl
In amine, uniform dispersion liquid is obtained；
(2) in glove box, step (1) resulting dispersion is placed in room temperature, is stirred to react and obtains the first step afterwards for 24 hours
The dispersion liquid of product；
(3) pentaerythrite for being 1:1 with the molar feed ratio of isocyanates is added in the dispersion liquid that step (2) obtains
Four -3-thiopropionates, 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene that mass fraction is 1wt%, i.e. 2.8g Ji Wusi
Four -3-thiopropionate of alcohol, tri- azacyclo- of 0.03g 1,5,7- two ring [4.4.0] last of the ten Heavenly stems 5- alkene, is placed in closed die after evenly mixing
In tool, the heating reaction 12h in 150 DEG C of vacuum drying ovens is after reaction dried sample in vacuum drying oven to get target is arrived
Product.
Embodiment 3
(1) in glove box, the molar feed ratio for weighing the polycaprolactone of isocyanates and hydroxyl modification is 5:1, inorganic
The weight ratio of material is the raw material of 3wt%, i.e. 5g 1,5- naphthalene diisocyanate, the hydroxyl modification that 38g number-average molecular weight is 8000
Polycaprolactone, 1.45g partial size be 20nm nano silica, be then dispersed in the super dry n,N-Dimethylformamide of 10mL
In, obtain uniform dispersion liquid；
(2) in glove box, step (1) resulting dispersion is placed in room temperature, obtains the first step after being stirred to react 12h
The dispersion liquid of product；
(3) pentaerythrite for being 1:3 with the molar feed ratio of isocyanates is added in the dispersion liquid that step (2) obtains
Four -3-thiopropionates, 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene that mass fraction is 3wt%, i.e. 3.8g Ji Wusi
Four -3-thiopropionate of alcohol, tri- azacyclo- of 0.12g 1,5,7- two ring [4.4.0] last of the ten Heavenly stems 5- alkene, is placed in closed die after evenly mixing
In tool, heating reaction for 24 hours, after reaction dries sample to get target is arrived in vacuum drying oven in 70 DEG C of vacuum drying ovens
Product.
Embodiment 4
(1) in glove box, the molar feed ratio for weighing the polycaprolactone of isocyanates and hydroxyl modification is 2:1, inorganic
Raw material of the weight ratio of material for 8wt%, i.e. 6g 1,5- naphthalene diisocyanate, the hydroxyl that 28.5g number-average molecular weight is 2000 change
Property polycaprolactone, 3.4g partial size be 500nm nano silica, be then dispersed in the super dry n,N-Dimethylformamide of 10mL
In, obtain uniform dispersion liquid；
(2) in glove box, step (1) resulting dispersion is placed in room temperature, obtains the first step after being stirred to react 20h
The dispersion liquid of product；
(3) pentaerythrite for being 1:3 with the molar feed ratio of isocyanates is added in the dispersion liquid that step (2) obtains
Four -3-thiopropionates, 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene that mass fraction is 2wt%, i.e. 4.6g Ji Wusi
Four -3-thiopropionate of alcohol, tri- azacyclo- of 0.09g 1,5,7- two ring [4.4.0] last of the ten Heavenly stems 5- alkene, is placed in closed die after evenly mixing
In tool, the heating reaction 18h in 90 DEG C of vacuum drying ovens is after reaction dried sample in vacuum drying oven to get target is arrived
Product.
Load-deformation curve and tensile strength are tested: using electronics sound state universal testing machine (Britain Instron
Company) test, rate of extension 50mm/min.
Load-deformation curve measurement result is as shown in Figure 2.As can be known from Fig. 2, at different temperatures, sample display goes out not
Same mechanical performance, this just illustrates that polymer matrix composite prepared by the present invention has the property of variation rigidity.
It is as shown in Figure 3 that tensile strength tests structure.As can be known from Fig. 3, the tensile strength of material increases with carbon fiber content
And increase, this just illustrates that the method proposed by the present invention for improving polymer machinery intensity has feasibility, and it is high-intensitive to be expected to preparation
Polymer matrix composite.
Application scheme citing: the integrated polymer matrix composite of carrying/deformation of the invention can be realized certain
At a temperature of high intensity, change temperature be able to achieve variation rigidity and deformation again, can be used as morphing aircraft skin material, and can
To be applicable in the morphing aircraft of different deformation.
Content carries out the adjustment of preparation technology parameter according to the present invention, and Inventive polymers based composites system can be achieved
It is standby, and show the performance almost the same with embodiment.Illustrative description has been done to the present invention above, it should explanation,
In the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art can not
The equivalent replacement of creative work is spent to each fall within protection scope of the present invention.
Claims (10)
1. a kind of carrying/deformation integrated polymer based composites, which is characterized in that by hydroxy-end capped polycaprolactone, different
The inorganic material of cyanate, four -3-thiopropionate of pentaerythrite and hydroxyl modification is prepared.
2. a kind of carrying according to claim 1/deformation integrated polymer based composites, which is characterized in that described
The number-average molecular weight of hydroxy-end capped polycaprolactone be 10000-500, isocyanates 2,4 or 2,6- toluene di-isocyanate(TDI),
Hexamethylene diisocyanate or 1, one of 5- naphthalene diisocyanate, the inorganic material of hydroxyl modification are carbon nanotube or receive
One of rice silica.
3. a kind of carrying according to claim 1/deformation integrated polymer based composites, which is characterized in that described
The molar feed ratio of isocyanates and hydroxy-end capped polycaprolactone is 10-1:1；The isocyanates and four -3- of pentaerythrite
The molar feed ratio of mercaptopropionic acid ester is 5-1:1；The content of the inorganic material of the hydroxyl modification is the weight of all reactants
0.5-10wt%.(molar ratio and weight ratio in embodiment do not cover the end value in claims, and there are examination reports
In the possibility that reduces the scope).
4. a kind of carrying according to claim 2/deformation integrated polymer based composites, which is characterized in that described
The draw ratio of carbon nanotube is 2-20:1, and the partial size of nano silica is 20-500nm.
5. a kind of prepare a kind of method of carrying/deformation integrated polymer based composites as described in claim 1, spy
Sign is, the hydroxy-end capped polycaprolactone, hydroxyl modification inorganic material uniform point of formation is first reacted with isocyanates
Dispersion liquid adds four -3-thiopropionate of pentaerythrite.
6. a kind of carrying according to claim 5/deformation integrated polymer based composites preparation method, feature
Be, the hydroxy-end capped polycaprolactone, hydroxyl modification inorganic material carried out in glove box with reacting for isocyanates,
Used reagent is super dry n,N-Dimethylformamide.
7. a kind of carrying according to claim 5/deformation integrated polymer based composites preparation method, feature
It is, the reaction time of the hydroxy-end capped polycaprolactone, the inorganic material of hydroxyl modification and isocyanates is 8-24h, instead
Answering temperature is room temperature.
8. a kind of carrying according to claim 5/deformation integrated polymer based composites preparation method, feature
It is, there are ester exchange reaction, transesterifications between the four -3-thiopropionate of pentaerythrite and the polycaprolactone of hydroxyl modification
The temperature that reaction carries out is 60-150 DEG C, reaction time 12-24h.
9. a kind of carrying according to claim 8/deformation integrated polymer based composites preparation method, feature
It is, ester exchange reaction is carried out under the action of 1,5,7- tri- azacyclo-, two ring [4.4.0] last of the ten Heavenly stems 5- alkene catalyst.
10. a kind of carrying according to claim 9/deformation integrated polymer based composites preparation method, special
Sign is that the dosage of catalyst is the 1-3wt% of four -3-thiopropionate of pentaerythrite.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558828A (en) * | 2011-12-29 | 2012-07-11 | 华南理工大学 | Method for preparing polyurethane hybridization material for hydroxyl-containing filler |
| EP2570441A2 (en) * | 2008-10-15 | 2013-03-20 | Covidien LP | Bioabsorbable surgical composition |
| CN105037702A (en) * | 2015-07-23 | 2015-11-11 | 浙江大学 | Application method of plasticity shape memory polymer based on ester exchange |
| CN105238034A (en) * | 2015-10-09 | 2016-01-13 | 滁州环球聚氨酯科技有限公司 | Carbon nanotube modified polyurethane composite material |
| CN105733493A (en) * | 2016-05-11 | 2016-07-06 | 烟台德邦科技有限公司 | Ultraviolet light curing glue with low volatile content |
-
2019
- 2019-01-09 CN CN201910018224.8A patent/CN109851755A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2570441A2 (en) * | 2008-10-15 | 2013-03-20 | Covidien LP | Bioabsorbable surgical composition |
| CN102558828A (en) * | 2011-12-29 | 2012-07-11 | 华南理工大学 | Method for preparing polyurethane hybridization material for hydroxyl-containing filler |
| CN105037702A (en) * | 2015-07-23 | 2015-11-11 | 浙江大学 | Application method of plasticity shape memory polymer based on ester exchange |
| CN105238034A (en) * | 2015-10-09 | 2016-01-13 | 滁州环球聚氨酯科技有限公司 | Carbon nanotube modified polyurethane composite material |
| CN105733493A (en) * | 2016-05-11 | 2016-07-06 | 烟台德邦科技有限公司 | Ultraviolet light curing glue with low volatile content |
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Application publication date: 20190607 |