CN109263079A - High tensile plastic film and its preparation process - Google Patents
High tensile plastic film and its preparation process Download PDFInfo
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Abstract
The invention discloses high tensile plastic film, each component including following parts by weight: 43-52 parts of grafting carbon nanotube, 14-16 parts of trifluoroacetic anhydride, 27-33 parts of vinyltrimethoxysilane, 75-82 parts of ether, 31-34 parts of azodiisobutyronitrile, 3-5 parts of polyethylene glycol stearate diester, 2-4 parts of plasticizer, 100 parts of water.Resin produced by the present invention is with carbon nanotube for neutral supporter, then in several branches of the surface grafting of carbon nanotube, it can be realized resin ageing-resistant performance containing several fluorine elements on each branch, pass through the super collateralization of polymerization reaction in one end of branch simultaneously, realization polymerize several polymer branches on branch, it can be improved the intensity and toughness of resin by super collateralization, since polymer is polymerized by vinyltrimethoxysilane, so that being evenly equipped with several alkoxies on the resin over-expense chain of preparation, so that resin intensity with higher and water resistance, and since the presence of alkoxy makes resin have certain fire retardancy.
Description
Technical field
The invention belongs to plastic film field, it is related to a kind of high tensile plastic film and its preparation process.
Background technique
Existing plastic film polyvinyl chloride, polyethylene, polypropylene, polystyrene and other resins are made, and are used for
Packaging and it is used as coating layer, shared share is increasing on the market for plastics package and plastic packet product, especially multiple
Plastic flexible package is closed, the fields such as food, medicine, chemical industry are had been widely used for.
Existing plastic film directly passes through polyvinyl chloride, polyethylene, polypropylene, polystyrene and the addition of other resins
Function additive realizes different performances, and the plastic film used for vinyl house is needed due to being subjected to exposing to the weather for a long time
It supports, it is therefore necessary to which tensile strength with higher and ageing resistance, existing polyvinyl chloride film are with higher resistance to
Photosensitiveness and resistance to ag(e)ing, and there is relatively good tearing-resistant performance, but intensity is not high, still holds under biggish pulling force effect
It is tearable, and the irradiation for being subjected to high temperature sunlight for a long time not only be easy to cause the aging of plastic film, and since plastics are thin
The heat-insulating capability of film is poor, and plastic film is easy melting deformation under high temperature.
Summary of the invention
The purpose of the present invention is to provide a kind of high tensile plastic film and its preparation processes, directly on the carbon nanotubes
After graft crosslinking, then it polymerize the polyurethane resin of generation, the plastic film of preparation is directly added into polyurethane with by carbon nanotube
The plastic film generated in resin is compared, and tensile strength is higher, and tensile strength reaches 43.86MPa, due to connecing on the carbon nanotubes
The resin of branch preparation is, by the supporting role of carbon nanotube, to realize the raising of tensile strength, simultaneously centered on carbon nanotube
After filling alpha-cyclodextrin in carbon nanotube, since alpha-cyclodextrin is cavity structure, and the cavity inside diameter of alpha-cyclodextrin is less than
The internal diameter of carbon nanotube, while the cavity surface of alpha-cyclodextrin is hydrophilic, cavity inside is hydrophobic, and the cavity inside of carbon nanotube is close
Water, therefore alpha-cyclodextrin enters in carbon nanotube under the peptizaiton of lauryl sodium sulfate, so that the inside of carbon nanotube
Alpha-cyclodextrin is filled, so that the plastic film intensity of preparation further increases, while by receiving in carbon in resin preparation process
One end of nanotube surface branch is by the super collateralization of polymerization reaction, and realization polymerize several polymer branches on branch, by super
Collateralization can be improved the intensity and toughness of resin, and it is not high to solve existing plastic film intensity, under biggish pulling force effect
Still the problem of being easy to tear.
The present invention directly prepares resin in carbon nano tube surface grafting, so that the walled thickness of carbon nanotube increases, and
Due to the cellular structure of carbon nanotube itself, so that the heat-insulating capability of carbon nanotube improves, while passing through carbon nanotube chamber and interior
The heat-proof quality of carbon nanotube can be improved in the effect of two layers of cavity of alpha-cyclodextrin chamber in portion, so improve plastic film every
The problem of thermal energy power, the existing plastic film of effective solution is easy melting deformation under high temperature irradiation.
Resin produced by the present invention is with carbon nanotube for neutral supporter, then several in the surface grafting of carbon nanotube
Branch can be realized resin ageing-resistant performance containing several fluorine elements on each branch, since polymer is by vinyl three
Methoxy silane is polymerized so that preparation resin over-expense chain on be evenly equipped with several alkoxies so that resin have compared with
High intensity and water resistance, and since the presence of alkoxy makes resin have certain fire retardancy.
The purpose of the present invention can be achieved through the following technical solutions:
High tensile plastic film, each component including following parts by weight:
43-52 parts of grafting carbon nanotube, 14-16 parts of trifluoroacetic anhydride, 27-33 parts of vinyltrimethoxysilane, ether
75-82 parts, 31-34 parts of azodiisobutyronitrile, 3-5 parts of polyethylene glycol stearate diester, 2-4 parts of plasticizer, 100 parts of water；
Wherein the specific preparation process of grafting carbon nanotube is as follows:
Step 1: it weighs a certain amount of carbon nanotube and is added in the mixed solution of concentrated nitric acid and the concentrated sulfuric acid, ultrasonic disperse
After 30min, solution is poured into reaction flask, 70 DEG C of isothermal reaction 2h is heated to, is then filtered washing, is dried to obtain oxygen
Carbon nano tube contains a large amount of carboxy functional group at this time on the outer wall of carbon nanotube；Dense nitre is added in every gram of carbon nanotube
The volume of acid and the concentrated sulfuric acid is respectively 1mL and 3mL；
Step 2: the oxide/carbon nanometer tube prepared in step 1 and thionyl chloride being added in reaction vessel, are warming up to 60 DEG C
3h is reacted, washing is then filtered, obtains acyl chlorides carbon nano tube, specific reaction structure formula is as follows；Wherein every gram of carbonoxide
Thionyl chloride 12-13mL is added in nanotube；
Step 3: acyl chlorides carbon nano tube prepared by step 2 is added to the water, and alpha-cyclodextrin is added thereto, while to
Lauryl sodium sulfate is wherein added, then heats to 80 DEG C of stirring 40-50min, filters while hot, obtain filling perforation carbon nanotube,
Since alpha-cyclodextrin is cavity structure, and the cavity inside diameter of alpha-cyclodextrin is less than the internal diameter of carbon nanotube, while alpha-cyclodextrin
Cavity surface it is hydrophilic, cavity inside is hydrophobic, and the cavity inside of carbon nanotube is hydrophilic, therefore alpha-cyclodextrin is in dodecyl sulphur
Enter in carbon nanotube under the peptizaiton of sour sodium, so that alpha-cyclodextrin is filled in the inside of carbon nanotube, carbon not only can be improved
The intensity of nanotube, while carbon nanometer can be improved by the effect of carbon nanotube chamber and internal two layers of cavity of alpha-cyclodextrin chamber
The heat-proof quality of pipe, and alpha-cyclodextrin is easy to precipitate crystal at normal temperature, and water is then dissolved in high-temperature-hot-water, passes through high temperature mistake
Filter is so that the alpha-cyclodextrin not entered into carbon nanotube filters out；Every gram of acyl chlorides carbon nano tube is added in 7-8mL water, simultaneously
Alpha-cyclodextrin 0.75-0.79g is added in every gram of acyl chlorides carbon nano tube, lauryl sodium sulfate 0.8-0.9g is added；
Step 4: a certain amount of filling perforation carbon nanotube being added to the water, while formalin being added thereto, is warming up to 60
DEG C it is stirred to react 5h, is then filtered washing drying, due to being filled with alpha-cyclodextrin in filling perforation carbon nanotube, alpha-cyclodextrin
Contain secondary alcohol groups on the outside of cavity, the secondary alcohol groups between adjacent alpha-cyclodextrin can be crosslinked by fixation by the crosslinked action of formaldehyde,
So that the mutual hinge of alpha-cyclodextrin inside carbon nanotube is fixed, so that filling carbon nano-pipe property is stablized；Wherein
Formalin 3.6-4.3mL is added in every gram of filling perforation carbon nanotube；
Step 5: the product prepared in step 4 being added to the water, melamine is added after being warming up to 80 DEG C thereto, is stirred
3h is reacted, amide carbon nano tube is obtained, wherein last amino is introduced on each carboxyl of carbon nanotube side-wall, so that two
Graft reaction can occur for amino, and reaction structure formula is as follows；Melamine 4.2- is added in the product of every gram of step 4 preparation
4.8g；
Step 6: a certain amount of amide carbon nano tube being added to the water, acrylamide is then added thereto and stirs evenly
Afterwards, hexamethylene diisocyanate is added thereto, grafting carbon nanotube is obtained by filtration after then reacting 2h, wherein carbon nanotube
Several chain allyls are grafted on surface, reaction structure formula is as follows；Water 12-14mL is added in every gram of amide carbon nano tube,
Acrylamide 0.42-0.48g is added, hexamethylene diisocyanate 0.72-0.75g is added；
The preparation process of high tensile plastic film, specific preparation process are as follows:
Grafting carbon nanotube is added in ether the first step, and trifluoroacetic anhydride is then added dropwise thereto, and side, which is added dropwise, becomes violent
Stirring, control rate of addition are 6-7mL per minute, react 30-40min at normal temperature after being added dropwise completely, are then filtered and wash
It washs, obtains ageing-resistant grafting carbon nanotube；It is a large amount of hot due to being generated in trifluoroacetic anhydride reaction process, it is easy to cause explosion,
So by control rate of addition and be vigorously stirred and prevent heat build-up from exploding, due on grafting carbon nanotube containing it is a large amount of-
NH- functional group, can with trifluoroacetic acid anhydride reactant, so that be grafted multiple three flutolanils functional groups on grafting carbon nanotube,
So that containing a large amount of fluorine element in the product finally prepared, wherein being grafted the carbon nanotube after three flutolanil functional groups
Structural formula it is as follows；
The ageing-resistant grafting carbon nanotube prepared in the first step is added to the water and stirs evenly, then thereto by second step
Azodiisobutyronitrile is added, is warming up to 90 DEG C after mixing, and vinyltrimethoxysilane is added dropwise into reaction vessel,
110 DEG C of reaction 5h are warming up to after being added dropwise completely, obtain carbon nano-tube modification polyamide, wherein the structural formula of the resin is such as
Under；It, can be with vinyltrimethoxysilane since end alkenyl is contained in the branch one end being grafted on ageing-resistant grafting carbon nanotube
Carry out polymerization reaction so that vinyltrimethoxysilane is incorporated on the branch of carbon nano tube surface, resin obtained be with
Carbon nanotube is neutral supporter, and several fluorine are then contained on several branches of the surface grafting of carbon nanotube, each branch
Element can be realized resin ageing-resistant performance, while be realized on branch in one end of branch by the super collateralization of polymerization reaction
It polymerize several polymer branches, can be improved the intensity and toughness of resin by super collateralization, since polymer is by vinyl
Trimethoxy silane is polymerized, so that several alkoxies are evenly equipped on the resin over-expense chain of preparation, so that resin has
Higher intensity and water resistance, and since the presence of alkoxy makes resin have certain fire retardancy；
Third step the resin prepared in second step is added in kneading machine, in 180 DEG C of refining 3-5min, then to mixing
It is squeezed out after polyethylene glycol stearate diester and plasticizer melting 8-10min is added in machine, then is stretched to obtain with stretching-machine
High tensile plastic film.
Beneficial effects of the present invention:
The present invention directly on the carbon nanotubes after graft crosslinking, then polymerize the polyurethane resin of generation, the plastics of preparation
Film, compared with carbon nanotube to be directly added into the plastic film generated in polyurethane resin, tensile strength is higher, tensile strength
Reach 43.86MPa, the resin due to being grafted preparation on the carbon nanotubes is to pass through carbon nanotube centered on carbon nanotube
The raising of tensile strength is realized in supporting role, while in carbon nanotube after filling alpha-cyclodextrin, since alpha-cyclodextrin is cavity
Structure, and the cavity inside diameter of alpha-cyclodextrin is less than the internal diameter of carbon nanotube, while the cavity surface of alpha-cyclodextrin is hydrophilic, cavity
Inner hydrophobic, and the cavity inside of carbon nanotube is hydrophilic, thus alpha-cyclodextrin under the peptizaiton of lauryl sodium sulfate into
Enter in carbon nanotube, so that alpha-cyclodextrin is filled in the inside of carbon nanotube, so that the plastic film intensity of preparation further increases,
Simultaneously by the way that in one end of carbon nano tube surface branch, by the super collateralization of polymerization reaction, realization is being propped up in resin preparation process
It polymerize several polymer branches on chain, can be improved the intensity and toughness of resin by super collateralization, it is thin to solve existing plastics
The problem of film-strength is not high, is still easy to tear under biggish pulling force effect.
The present invention directly prepares resin in carbon nano tube surface grafting, so that the walled thickness of carbon nanotube increases, and
Due to the cellular structure of carbon nanotube itself, so that the heat-insulating capability of carbon nanotube improves, while passing through carbon nanotube chamber and interior
The heat-proof quality of carbon nanotube can be improved in the effect of two layers of cavity of alpha-cyclodextrin chamber in portion, so improve plastic film every
The problem of thermal energy power, the existing plastic film of effective solution is easy melting deformation under high temperature irradiation.
Resin produced by the present invention is with carbon nanotube for neutral supporter, then several in the surface grafting of carbon nanotube
Branch can be realized resin ageing-resistant performance containing several fluorine elements on each branch, since polymer is by vinyl three
Methoxy silane is polymerized so that preparation resin over-expense chain on be evenly equipped with several alkoxies so that resin have compared with
High intensity and water resistance, and since the presence of alkoxy makes resin have certain fire retardancy.
Detailed description of the invention
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is acyl chlorides carbon nano tube reaction structure formula of the present invention；
Fig. 2 is amide carbon nano tube reaction structure formula of the present invention；
Fig. 3 is the reaction structure formula of grafting carbon nanotube of the present invention；
Fig. 4 is the ageing-resistant grafting carbon nanotube structural formula of the present invention；
Fig. 5 is carbon nano-tube modification polyamide structural formula of the present invention.
Specific embodiment
It is described in detail in conjunction with Fig. 1, Fig. 2, Fig. 3, Fig. 4 and Fig. 5 by following examples；
Embodiment 1:
The specific preparation process of grafting carbon nanotube is as follows:
Step 1: it weighs 1kg carbon nanotube and is added in the mixed solution of 1L concentrated nitric acid and the 3L concentrated sulfuric acid, ultrasonic disperse 30min
Afterwards, solution is poured into reaction flask, is heated to 70 DEG C of isothermal reaction 2h, is then filtered washing, is dried to obtain carbonoxide
Nanotube；
Step 2: the 1kg oxide/carbon nanometer tube prepared in step 1 and 12L thionyl chloride being added in reaction vessel, heating
To 60 DEG C of reaction 3h, it is then filtered washing, obtains acyl chlorides carbon nano tube；
Step 3: 1kg acyl chlorides carbon nano tube prepared by step 2 is added in 7L water, and 750g α-ring paste is added thereto
Essence, while 800g lauryl sodium sulfate being added thereto, 80 DEG C of stirring 40-50min are then heated to, filters, obtains while hot
Filling perforation carbon nanotube；
Step 4: 1kg filling perforation carbon nanotube being added in 1L water, while 3.6L formalin being added thereto, is warming up to 60
DEG C it is stirred to react 5h, is then filtered washing drying；
Step 5: the product prepared in step 4 being added in 1L water, is warming up to after 80 DEG C and 4.2kg melamine is added thereto
Amine is stirred to react 3h, obtains amide carbon nano tube；
Step 6: 1kg amide carbon nano tube being added in 12L water, it is equal that the stirring of 420g acrylamide is then added thereto
After even, 720g hexamethylene diisocyanate is added thereto, grafting carbon nanotube is obtained by filtration after then reacting 2h.
Embodiment 2:
The specific preparation process of grafting carbon nanotube is as follows:
Step 1: it weighs 1kg carbon nanotube and is added in the mixed solution of 1L concentrated nitric acid and the 3L concentrated sulfuric acid, ultrasonic disperse 30min
Afterwards, solution is poured into reaction flask, is heated to 70 DEG C of isothermal reaction 2h, is then filtered washing, is dried to obtain carbonoxide
Nanotube；
Step 2: the 1kg oxide/carbon nanometer tube prepared in step 1 and 13L thionyl chloride being added in reaction vessel, heating
To 60 DEG C of reaction 3h, it is then filtered washing, obtains acyl chlorides carbon nano tube；
Step 3: 1kg acyl chlorides carbon nano tube prepared by step 2 is added in 7L water, and 790g α-ring paste is added thereto
Essence, while 900g lauryl sodium sulfate being added thereto, 80 DEG C of stirring 40-50min are then heated to, filters, obtains while hot
Filling perforation carbon nanotube；
Step 4: 1kg filling perforation carbon nanotube being added in 1L water, while 4.3L formalin being added thereto, is warming up to 60
DEG C it is stirred to react 5h, is then filtered washing drying；
Step 5: the product prepared in step 4 being added in 1L water, is warming up to after 80 DEG C and 4.8kg melamine is added thereto
Amine is stirred to react 3h, obtains amide carbon nano tube；
Step 6: 1kg amide carbon nano tube being added in 14L water, it is equal that the stirring of 480g acrylamide is then added thereto
After even, 750g hexamethylene diisocyanate is added thereto, grafting carbon nanotube is obtained by filtration after then reacting 2h.
Embodiment 3:
The specific preparation process of grafting carbon nanotube is as follows:
Step 1: it weighs 1kg carbon nanotube and is added in the mixed solution of 1L concentrated nitric acid and the 3L concentrated sulfuric acid, ultrasonic disperse 30min
Afterwards, solution is poured into reaction flask, is heated to 70 DEG C of isothermal reaction 2h, is then filtered washing, is dried to obtain carbonoxide
Nanotube；
Step 2: the 1kg oxide/carbon nanometer tube prepared in step 1 and 12L thionyl chloride being added in reaction vessel, heating
To 60 DEG C of reaction 3h, it is then filtered washing, obtains acyl chlorides carbon nano tube；
Step 3: 1kg acyl chlorides carbon nano tube prepared by step 2 is added in 7L water, and 750g α-ring paste is added thereto
Essence, while 800g lauryl sodium sulfate being added thereto, 80 DEG C of stirring 40-50min are then heated to, filters, obtains while hot
Filling perforation carbon nanotube；
Step 4: the product prepared in step 4 being added in 1L water, is warming up to after 80 DEG C and 4.2kg melamine is added thereto
Amine is stirred to react 3h, obtains amide carbon nano tube；
Step 5: 1kg amide carbon nano tube being added in 12L water, it is equal that the stirring of 420g acrylamide is then added thereto
After even, 720g hexamethylene diisocyanate is added thereto, grafting carbon nanotube is obtained by filtration after then reacting 2h.
Embodiment 4:
The specific preparation process of grafting carbon nanotube is as follows:
Step 1: it weighs 1kg carbon nanotube and is added in the mixed solution of 1L concentrated nitric acid and the 3L concentrated sulfuric acid, ultrasonic disperse 30min
Afterwards, solution is poured into reaction flask, is heated to 70 DEG C of isothermal reaction 2h, is then filtered washing, is dried to obtain carbonoxide
Nanotube；
Step 2: the 1kg oxide/carbon nanometer tube prepared in step 1 and 12L thionyl chloride being added in reaction vessel, heating
To 60 DEG C of reaction 3h, it is then filtered washing, obtains acyl chlorides carbon nano tube；
Step 3: the product prepared in step 2 being added in 1L water, is warming up to after 80 DEG C and 4.2kg melamine is added thereto
Amine is stirred to react 3h, obtains amide carbon nano tube；
Step 4: 1kg amide carbon nano tube being added in 12L water, it is equal that the stirring of 420g acrylamide is then added thereto
After even, 720g hexamethylene diisocyanate is added thereto, grafting carbon nanotube is obtained by filtration after then reacting 2h.
Embodiment 5:
The preparation process of high tensile plastic film, specific preparation process are as follows:
The first step, grafting carbon nanotube prepared by 4.3kg embodiment 1 are added in ether, and 1.4kg is then added dropwise thereto
Trifluoroacetic anhydride, side are added dropwise to become and be vigorously stirred, and control rate of addition is 6-7mL per minute, react at normal temperature after being added dropwise completely
Then 30-40min is filtered washing, obtain ageing-resistant grafting carbon nanotube；
The ageing-resistant grafting carbon nanotube prepared in the first step is added in 10L water and stirs evenly, then to it by second step
Middle addition 3.1kg azodiisobutyronitrile, is warming up to 90 DEG C after mixing, and 2.7kg vinyl is added dropwise into reaction vessel
Trimethoxy silane is warming up to 110 DEG C of reaction 5h after being added dropwise completely, obtains carbon nano-tube modification polyamide；
Third step the resin prepared in second step is added in kneading machine, in 180 DEG C of refining 3-5min, then to mixing
Squeezed out after 0.3kg polyethylene glycol stearate diester and 0.2kg plasticizer melting 8-10min is added in machine, then with stretching-machine into
Row stretches and obtains high tensile plastic film.
Embodiment 6:
The preparation process of high tensile plastic film, specific preparation process are as follows:
The first step, grafting carbon nanotube prepared by 5.2kg embodiment 2 are added in ether, and 1.6kg is then added dropwise thereto
Trifluoroacetic anhydride, side are added dropwise to become and be vigorously stirred, and control rate of addition is 6-7mL per minute, react at normal temperature after being added dropwise completely
Then 30-40min is filtered washing, obtain ageing-resistant grafting carbon nanotube；
The ageing-resistant grafting carbon nanotube prepared in the first step is added in 10L water and stirs evenly, then to it by second step
Middle addition 3.4kg azodiisobutyronitrile, is warming up to 90 DEG C after mixing, and 3.3kg vinyl is added dropwise into reaction vessel
Trimethoxy silane is warming up to 110 DEG C of reaction 5h after being added dropwise completely, obtains carbon nano-tube modification polyamide；
Third step the resin prepared in second step is added in kneading machine, in 180 DEG C of refining 3-5min, then to mixing
Squeezed out after 0.5kg polyethylene glycol stearate diester and 0.4kg plasticizer melting 8-10min is added in machine, then with stretching-machine into
Row stretches and obtains high tensile plastic film.
Embodiment 7:
The preparation process of high tensile plastic film, specific preparation process are as follows:
The first step, grafting carbon nanotube prepared by 5.2kg embodiment 3 are added in ether, and 1.6kg is then added dropwise thereto
Trifluoroacetic anhydride, side are added dropwise to become and be vigorously stirred, and control rate of addition is 6-7mL per minute, react at normal temperature after being added dropwise completely
Then 30-40min is filtered washing, obtain ageing-resistant grafting carbon nanotube；
The ageing-resistant grafting carbon nanotube prepared in the first step is added in 10L water and stirs evenly, then to it by second step
Middle addition 3.4kg azodiisobutyronitrile, is warming up to 90 DEG C after mixing, and 3.3kg vinyl is added dropwise into reaction vessel
Trimethoxy silane is warming up to 110 DEG C of reaction 5h after being added dropwise completely, obtains carbon nano-tube modification polyamide；
Third step the resin prepared in second step is added in kneading machine, in 180 DEG C of refining 3-5min, then to mixing
Squeezed out after 0.5kg polyethylene glycol stearate diester and 0.4kg plasticizer melting 8-10min is added in machine, then with stretching-machine into
Row stretches and obtains high tensile plastic film.
Embodiment 8:
The preparation process of high tensile plastic film, specific preparation process are as follows:
The first step, grafting carbon nanotube prepared by 5.2kg embodiment 4 are added in ether, and 1.6kg is then added dropwise thereto
Trifluoroacetic anhydride, side are added dropwise to become and be vigorously stirred, and control rate of addition is 6-7mL per minute, react at normal temperature after being added dropwise completely
Then 30-40min is filtered washing, obtain ageing-resistant grafting carbon nanotube；
The ageing-resistant grafting carbon nanotube prepared in the first step is added in 10L water and stirs evenly, then to it by second step
Middle addition 3.4kg azodiisobutyronitrile, is warming up to 90 DEG C after mixing, and 3.3kg vinyl is added dropwise into reaction vessel
Trimethoxy silane is warming up to 110 DEG C of reaction 5h after being added dropwise completely, obtains carbon nano-tube modification polyamide；
Third step the resin prepared in second step is added in kneading machine, in 180 DEG C of refining 3-5min, then to mixing
Squeezed out after 0.5kg polyethylene glycol stearate diester and 0.4kg plasticizer melting 8-10min is added in machine, then with stretching-machine into
Row stretches and obtains high tensile plastic film.
Embodiment 9
The preparation process of high tensile plastic film, specific preparation process are as follows:
Polyurethane resin is added in kneading machine, in 180 DEG C of refining 3-5min, carbon nanometer is then added into kneading machine
It squeezes out after pipe, 0.5kg polyethylene glycol stearate diester and 0.4kg plasticizer melting 8-10min, is then stretched with stretching-machine
Obtain high tensile plastic film.
Embodiment 10:
The measurement of performance is carried out to the high tensile plastic film of embodiment 5-9 preparation, it is specific to measure structure such as 1 institute of table
Show:
Table 1: the high tensile plastic film of embodiment 5-9 preparation carries out the measurement result of performance
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Tensile strength (MPa) | 43.72 | 43.86 | 38.21 | 28.93 | 20.13 |
| Elongation at break % | 252.38 | 251.49 | 219.28 | 193.65 | 112.11 |
| Thermal coefficient (W/m.K) | 0.057 | 0.056 | 0.058 | 0.121 | 0.283 |
As shown in Table 1, directly then it polymerize the polyurethane resin of generation on the carbon nanotubes after graft crosslinking, preparation
Plastic film, compared with carbon nanotube to be directly added into the plastic film generated in polyurethane resin, tensile strength is higher, stretches
Intensity reaches 43.86MPa, and the resin due to being grafted preparation on the carbon nanotubes is to pass through carbon nanometer centered on carbon nanotube
The supporting role of pipe realizes the raising of tensile strength, and directly prepares resin in carbon nano tube surface grafting, so that carbon nanometer
The walled thickness of pipe increases, and due to the cellular structure of carbon nanotube itself, so that the heat-insulating capability of carbon nanotube improves；Together
When fill alpha-cyclodextrin in carbon nanotube after, since alpha-cyclodextrin is cavity structure, and the cavity inside diameter of alpha-cyclodextrin is small
In the internal diameter of carbon nanotube, while the cavity surface of alpha-cyclodextrin is hydrophilic, and cavity inside is hydrophobic, and the cavity inside of carbon nanotube
It is hydrophilic, therefore alpha-cyclodextrin enters in carbon nanotube under the peptizaiton of lauryl sodium sulfate, so that carbon nanotube is interior
Alpha-cyclodextrin is filled in portion, the intensity of carbon nanotube not only can be improved, while passing through carbon nanotube chamber and internal alpha-cyclodextrin
The heat-proof quality of carbon nanotube can be improved in the effect of two layers of cavity of chamber.
Embodiment 11:
By the high tensile plastic film prepared in embodiment 5-9 under the irradiation of fluorescent ultraviolet lamp, respectively act on 0h,
60h, 120h, 250h, 500h, then measurement acts on the tensile strength of different time high tensile plastic film, as a result such as 2 institute of table
Show:
Table 2: tensile strength (MPa) of the high tensile plastic film prepared in embodiment 5-9 under different time illumination
| Time | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| 0h | 43.82 | 43.81 | 38.21 | 28.93 | 20.13 |
| 60h | 43.78 | 43.86 | 38.23 | 28.91 | 18.36 |
| 120h | 43.69 | 43.76 | 38.15 | 28.76 | 16.52 |
| 250h | 43.72 | 43.77 | 37.92 | 28.83 | 13.19 |
| 500h | 42.45 | 42.69 | 37.83 | 28.72 | 8.36 |
As shown in Table 2, by passing through the carbon nanometer of grafting fluorine element after carbon nano tube surface is grafted a large amount of fluorine element
The standby resin of control prepares plastic film to produce time illumination condition Tensile strength almost unchanged, without being grafted fluorine element
Resin is easy aging under long-time illumination condition, causes the reduction of tensile strength.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (8)
1. high tensile plastic film, which is characterized in that each component including following parts by weight:
43-52 parts of grafting carbon nanotube, 14-16 parts of trifluoroacetic anhydride, 27-33 parts of vinyltrimethoxysilane, ether 75-82
Part, 31-34 parts of azodiisobutyronitrile, 3-5 parts of polyethylene glycol stearate diester, 2-4 parts of plasticizer, 100 parts of water；
Wherein the specific preparation process of grafting carbon nanotube is as follows:
Step 1: it weighs a certain amount of carbon nanotube and is added in the mixed solution of concentrated nitric acid and the concentrated sulfuric acid, after ultrasonic disperse 30min,
Solution is poured into reaction flask, 70 DEG C of isothermal reaction 2h is heated to, is then filtered washing, be dried to obtain carbonoxide nanometer
Pipe；
Step 2: the oxide/carbon nanometer tube prepared in step 1 and thionyl chloride being added in reaction vessel, 60 DEG C of reactions are warming up to
Then 3h is filtered washing, obtain acyl chlorides carbon nano tube；
Step 3: acyl chlorides carbon nano tube prepared by step 2 being added to the water, and alpha-cyclodextrin is added thereto, while thereto
Lauryl sodium sulfate is added, then heats to 80 DEG C of stirring 40-50min, filters while hot, obtain filling perforation carbon nanotube；
Step 4: a certain amount of filling perforation carbon nanotube being added to the water, while formalin being added thereto, then heats to 60
DEG C it is stirred to react 5h, is then filtered washing drying；
Step 5: the product prepared in step 4 being added to the water, melamine is added thereto after being warming up to 80 DEG C, is stirred to react
3h obtains amide carbon nano tube；
Step 6: a certain amount of amide carbon nano tube is added to the water, acrylamide then is added after mixing evenly thereto,
Hexamethylene diisocyanate is added thereto, grafting carbon nanotube is obtained by filtration after then reacting 2h.
2. high tensile plastic film according to claim 1, which is characterized in that add in every gram of carbon nanotube in step 1
The volume for entering concentrated nitric acid and the concentrated sulfuric acid is respectively 1mL and 3mL.
3. high tensile plastic film according to claim 1, which is characterized in that every gram of oxide/carbon nanometer tube in step 2
Middle addition thionyl chloride 12-13mL.
4. high tensile plastic film according to claim 1, which is characterized in that every gram of chloride carbon nanometer in step 3
Pipe is added in 7-8mL water, while alpha-cyclodextrin 0.75-0.79g being added in every gram of acyl chlorides carbon nano tube, and dodecyl sulphur is added
Sour sodium 0.8-0.9g.
5. high tensile plastic film according to claim 1, which is characterized in that every gram of filling perforation carbon nanotube in step 4
Middle addition formalin 3.6-4.3mL.
6. high tensile plastic film according to claim 1, which is characterized in that the production that in step 5 prepared by every gram of step 4
Melamine 4.2-4.8g is added in object.
7. high tensile plastic film according to claim 1, which is characterized in that every gram of amidation carbon nanometer in step 6
Water 12-14mL is added in pipe, acrylamide 0.42-0.48g is added, hexamethylene diisocyanate 0.72-0.75g is added.
8. the preparation process of high tensile plastic film, which is characterized in that specific preparation process is as follows:
Grafting carbon nanotube is added in ether the first step, and trifluoroacetic anhydride is then added dropwise thereto, and side is added dropwise to become and acutely stir
It mixes, control rate of addition is 6-7mL per minute, 30-40min reacted at normal temperature after being added dropwise completely, is then filtered washing,
Obtain ageing-resistant grafting carbon nanotube；
The ageing-resistant grafting carbon nanotube prepared in the first step is added to the water and stirs evenly, is then added thereto by second step
Azodiisobutyronitrile is warming up to 90 DEG C after mixing, and vinyltrimethoxysilane is added dropwise into reaction vessel, is added dropwise
110 DEG C of reaction 5h are warming up to after completely, obtain carbon nano-tube modification polyamide；
Third step the resin prepared in second step is added in kneading machine, in 180 DEG C of refining 3-5min, then into kneading machine
Polyethylene glycol stearate diester and plasticizer is added, is squeezed out after melting 8-10min, is then stretched to obtain highly resistance with stretching-machine
Drawing plastic film.
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