CN109608669A - A kind of PP type composite material and preparation method of carbon nanotube enhancing - Google Patents
A kind of PP type composite material and preparation method of carbon nanotube enhancing Download PDFInfo
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- CN109608669A CN109608669A CN201811552484.5A CN201811552484A CN109608669A CN 109608669 A CN109608669 A CN 109608669A CN 201811552484 A CN201811552484 A CN 201811552484A CN 109608669 A CN109608669 A CN 109608669A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a kind of PP type composite material and preparation methods of carbon nanotube enhancing; wherein; the method includes the steps: carbon nano pipe array and polypropylene-based resin M1 are placed in protective gas atmosphere and carry out treatment with ultraviolet light; so that graft polymerization reaction occurs for PP type and carbon nano pipe array, modified carbon nano-tube is obtained；The modified carbon nano-tube and polypropylene-based resin M2 are placed in melt in protective gas atmosphere and are kneaded, the PP type composite material of carbon nanotube enhancing is made.The present invention solves the problems, such as that the mechanical property of PP type composite material in the prior art is bad.
Description
Technical field
The PP type enhanced the present invention relates to polypropylene-based resin technical field more particularly to a kind of carbon nanotube is compound
Material and preparation method thereof.
Background technique
Polypropylene-based resin is a kind of raw material easily processed into type, while weight and mechanical performance be than high, often quilt
In various daily necessities and industrial part.And the mechanical strength and heat resistance of polypropylene-based resin are unsatisfactory, in industry
In polypropylene-based resin used in component, generally require to add the inorfils such as talcum powder, mica powder, glass fibre thereto
Enhance its mechanical property, but effect is undesirable.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of PP types of carbon nanotube enhancing
Composite material and preparation method, it is intended to solve the problems, such as that the mechanical property of PP type composite material in the prior art is bad.
Technical scheme is as follows:
A kind of preparation method of the PP type composite material of carbon nanotube enhancing, wherein comprising steps of
Carbon nano pipe array and polypropylene-based resin M1 are placed in protective gas atmosphere and carry out treatment with ultraviolet light, so that polypropylene
Graft polymerization reaction occurs for class and carbon nano pipe array, obtains modified carbon nano-tube;
The modified carbon nano-tube and polypropylene-based resin M2 are placed in melt in protective gas atmosphere and are kneaded, carbon nanotube is made
The PP type composite material of enhancing.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein the treatment with ultraviolet light
Wavelength is 216nm.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein carrying out treatment with ultraviolet light
When, protective gas constant flow is controlled, and polypropylene-based resin M1 is set and is located at uptake position.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein the protective gas is nitrogen
Gas or inert gas.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein the polypropylene-based resin
M1 is unmodified polypropylene resinoid, and the polypropylene-based resin M2 is the modified PP type of unsaturated carboxylic acid or derivatives thereof
Resin.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein in polypropylene-based resin M2
Acid amount be converted into maleic anhydride after account for the 0.004 ~ 0.05% of sour modified polypropylene resin M2 gross mass.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein by the modified carbon nano tube
Pipe is mixed by the mass ratio of 25 ~ 50:50 ~ 75 with sour modified polypropylene resin and melts mixing.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein the polypropylene-based resin
For polyacrylic polymer, ethylene/propene copolymer or propylene/alpha olefin copolymer；
The unsaturated carboxylic acid includes one of maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid or a variety of；
The derivative of the unsaturated carboxylic acid includes the acid anhydrides of unsaturated carboxylic acid, esters of unsaturated carboxylic acids, unsaturated carboxylic acid amide, no
One of metal salt of saturated carboxylic acid is a variety of.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein modified carbon nano-tube is put down
Equal length is 0.8 ~ 8mm, and the diameter of carbon nanotube is 10 ~ 50nm.
The preparation method of the PP type composite material of the carbon nanotube enhancing, wherein the melting temperature is 250
~300℃。
A kind of PP type composite material of carbon nanotube enhancing, wherein prepared by as above any preparation method
It forms.
The utility model has the advantages that the present invention is handled in protective gas gas by ultraviolet light, make polypropylene and carbon nanotube
Graft polymerization reaction occurs, to be grafted upper polypropylene molecule in carbon nano tube surface, forms modified carbon nano-tube, changes described
Property carbon nanotube mixing is mixed and melted with polypropylene, it is modified so that the PP type composite material of carbon nanotube enhancing be made
The presence of the polypropylene molecule of carbon nano tube surface can overcome the boundary strength between carbon nanotube and acrylic resin, so that
The modified carbon nano-tube and acrylic resin have a good compatibility and mechanics transfer performance, and the modified carbon nano-tube of addition can be with
The mechanical strength for increasing acrylic resin, to enhance the mechanical property of material entirety.
Detailed description of the invention
Fig. 1 is the preparation method preferred embodiment process of the PP type composite material of carbon nanotube of the present invention enhancing
Schematic diagram.
Specific embodiment
The present invention provides a kind of PP type composite material and preparation method of carbon nanotube enhancing, of the invention to make
Purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that this place is retouched
The specific embodiment stated is only used to explain the present invention, is not intended to limit the present invention.
The preparation method of the PP type composite material of carbon nanotube enhancing of the present invention, as shown in Figure 1, including step
It is rapid:
S1, it carbon nano pipe array and polypropylene-based resin M1 is placed in protective gas atmosphere carries out treatment with ultraviolet light, so that poly-
Graft polymerization reaction occurs for propylene class and carbon nano pipe array, obtains modified carbon nano-tube；
S2, the modified carbon nano-tube and polypropylene-based resin M2 are placed in protective gas atmosphere and melt mixing, obtained carbon is received
The PP type composite material of mitron enhancing.
Carbon nanotube is a kind of monodimension nanometer material with special construction, and radial dimension is nanometer scale, axial ruler
Very little is micron dimension, and pipe both ends are substantially all sealing.Carbon nanotube mainly constitutes several layers by the carbon atom of hexagonal arrangement
To tens of layers of coaxial round tube, there are the spies such as the distance being kept fixed between layers, light-weight, hexagonal structure connection perfection
Point, so that the manufacture craft and cost of carbon nanotube are all far superior to carbon fiber, while its mechanical property and to composite material
Performance is better than carbon fiber, and match ratio is relatively low.But since carbon nano tube surface is excessively smooth, and polypropylene-based resin it
Between mechanics transmitting, compatibility it is bad so that its boundary strength between polypropylene-based resin is excessively high, if by carbon nanotube
If the molding of polypropylene-based resin direct die press, although being easy to cause pressing mold moulded products that there is very high tensile strength,
Impact strength is lower.Therefore in the present invention, need to first pass through step S1 and carbon nanotube is modified.
In the step S1, need first to provide carbon nano pipe array and polypropylene-based resin M1, then by carbon nano-pipe array
Column and polypropylene-based resin M1 are placed side by side after tiling respectively to be placed in protective gas atmosphere, and treatment with ultraviolet light is then carried out,
The radiation of ultraviolet light is conducive to provide the fuel factor of reaction system, so that system is that temperature is increased to PP type polymerization
Object forms gaseous state, and surface and the carbon nano pipe array of carbon nano pipe array are moved under the action of protective gas air-flow
Graft polymerization reaction occurs, meanwhile, ultraviolet light can make C=C double bond of carbon nano tube surface open to generate vacantly
Key can also make polypropylene based polymers generate portion fractures and form free radical, when the dangling bonds of free radical and carbon nano tube surface
After contact, can bonding so that polypropylene based polymers are further grafted to carbon nano tube surface obtain modified carbon nano tube
Pipe, the modified carbon nano-tube activate through ultraviolet irradiation, are conducive in conjunction with polypropylene based polymers；Meanwhile modified carbon nano-tube
One layer polypropylene class molecular structure of surface grafting, further provides more bound sites for it in conjunction with PP type molecule
Point can combine more PP type molecules.
Wherein, the polypropylene-based resin M1 is unmodified polypropylene resinoid, including object, second is polymerized alone in polypropylene
Alkene/propylene copolymer, propylene/alpha olefin copolymer etc..The melt flow rate (MFR) (MFR) of the unmodified polypropylene resinoid M1
Preferably 5 ~ 70g/10min, more preferably 30 ~ 60g/10min, when more than above-mentioned lower limit value, mouldability is preferable, and
When below above-mentioned upper limit value, impact strength is higher.Wherein, MFR is 230 DEG C of loads under the standard of JIS K 7210
Measurement obtains in the case where 2.16kg.
In preferably, carbon nano pipe array and polypropylene-based resin powder M1 are tiled be placed in protective gas atmosphere respectively
Treatment with ultraviolet light is carried out, in order to ultraviolet light uniform activation polypropylene-based resin.
Protective gas in the step S1 is nitrogen or inert gas, and when carrying out treatment with ultraviolet light, control is protected
Gas constant flow is protected, and polypropylene-based resin is set and is located at uptake, the protective gas of constant flow can accelerate polypropylene
Resinoid is moved to surface and the carbon nano pipe array of carbon nano pipe array, makes the two that graft polymerization reaction occur.
Preferably, the wavelength for the treatment of with ultraviolet light is 216nm in the step S1, and wavelength is too long can not effective activation carbon nanometer
Pipe and polypropylene-based resin, wavelength is too short, is easily destroyed this body structure of carbon nano pipe array, carbon nanotube is caused to damage.
Wherein, the power of the treatment with ultraviolet light is 40 ~ 50mW, and the time is 40 ~ 60mins.Preferably, the ultraviolet light
The power of processing is 45mW, time 50mins, and processing overlong time will lead to the degradation of polypropylene-based resin.
The average length of modified carbon nano-tube in step S1 be 0.8 ~ 8mm because carbon nanotube itself have it is high
The mechanical strength of itself preferably can be carried out mechanics transmitting, made by mechanical property only in the sufficiently long situation of length
The intensity for obtaining composite material entirety is enhanced, while the appearance of end product is also preferable, but being averaged when modified carbon nano-tube
Length is too long, and the dispersibility of modified carbon nano-tube can be made bad.Preferably, the average length of carbon nano pipe array be 1mm ~
6mm, more preferably 1.2mm ~ 5mm.
The diameter of carbon nanotube is 10 ~ 50nm, in more preferably 12 ~ 20nm.Within this range, it can guarantee carbon nanometer
Draw ratio with higher is managed, so that its surface area is larger, to increase the interface between entire carbon nanotube and resin material
Intensity.
In the step S1, carbon nano-pipe array is classified as many walls nanotube array, and average length is 0.8 ~ 10mm, carbon nanotube
Diameter be 12 ~ 15nm.Wherein, the preparation step of the carbon nano pipe array includes: the cobalt in deposition on substrate 20 ~ 50nm thickness
Alloy nickel catalysis oxidant layer is placed in chemical vapour deposition reactor furnace and is passed through protective gas (such as hydrogen), it is warming up to 750 ~
900 DEG C, then it is passed through carbon-source gas, flow control reacts 20 ~ 60min in 1 ~ 2L/min, to generate carbon nanometer on substrate
Pipe array.Wherein, the carbon-source gas by volume, including 25 ~ 40% ethylene, 10 ~ 15% hexane and as the nitrogen of surplus
Gas.
The specific steps of the step S1 are as follows:
By the first substrate and evenly laid out the second base for having unmodified polypropylene resinoid powder with carbon nano pipe array
Piece is placed side by side in the reaction chamber with high-strength ultraviolet lamp, and edge and the unmodified polypropylene class tree of carbon nano pipe array is arranged
The EDGE CONTACT of cosmetics last layer, and the uptake that unmodified polypropylene resinoid powder bed is in reaction chamber is set；Capping
The air inlet of chamber and gas outlet, and vacuumize process is carried out to reaction chamber, so that the air pressure in reaction chamber is down to 10-6Torr hereinafter,
Pure nitrogen gas is passed through into reaction chamber by air inlet again, until reach normal atmosphere (An), opens gas outlet, it is not open close enter nitrogen
Keep the flowing of intracavity gas, flow velocity 2L/min；High-strength ultraviolet lamp is opened, the wavelength of irradiation power 45mW, ultraviolet light are
The distance of 216nm, the first substrate of ultraviolet source distance and the second substrate is 3mm, and irradiation maintains 50min, and obtaining surface grafting has
The modified carbon nano-tube of polypropylene molecule.
Preferably, it before step S2, further comprises the steps of: and modified carbon nano-tube is spun to 6 ~ 20 μm of diameter of carbon nanometer
Pipe fiber, to enhance the overall mechanical properties of carbon nanotube.Specific step is as follows: above-mentioned generation is had to the base of carbon nano pipe array
Piece is fixed, and by spinning tool, is clamped carbon nano pipe array and is carried out spinning, it is fine that the carbon nanotube that average diameter is 6 ~ 20 μm is made
Dimension；By cutting implement, carbon nano-tube fibre is cut into the carbon nanotube staple fiber of different length.The average fibre of the number of staple fiber
Dimension is long preferably within the scope of 2.7 ~ 8.9mm.When several average fiber lengths are in 2.7mm or less, to the machinery of entire composite material
There is no positive effects for the promotion of intensity；As several average fiber length 8.9mm or more, when manufacturing composite material, will cause
Dispersibility decline of the staple fiber in matrix, or even fall off.
In the step S2, the modified carbon nano-tube is placed in protective gas atmosphere with polypropylene-based resin M2 and is melted
And be kneaded at a temperature of 250 ~ 300 DEG C, there is PP type molecule by modified carbon nano-tube surface grafting and whole by ultraviolet
Photoactivation can be bonded together with polypropylene-based resin M2, form stable structure, the carbon nanotube enhancing of excellent in mechanical performance
PP type composite material.Protective gas therein is nitrogen or inert gas.
Preferably, the polypropylene-based resin M2 is the modified polypropylene-based resin of unsaturated carboxylic acid or derivatives thereof, and
Its acid amount accounts for 0.004 ~ 0.050% after being converted into anhydrous maleic acid acid anhydride for the total weight of polypropylene-based resin, unsaturation
The presence of carboxylic acid can provide more strong binding sites for the PP type molecule and modified carbon nano tube in polypropylene-based resin M2
PP type molecule and carbon nanotube in pipe are firmly bonded together.It, cannot when the acid amount of polypropylene-based resin M2 is too low
Enough unsaturated carboxyls are provided, and will affect PP type molecule itself in polypropylene-based resin M2 if acid is excessively high and impact
Intensity.Preferably, the acid amount of polypropylene-based resin M2 is best in 0.005 ~ 0.025%.Correspondingly, the carbon modified is received
Mitron is mixed by the mass ratio of 25 ~ 50:50 ~ 75 and is melted mixing with sour modified polypropylene resin, can access mechanical property
The modified material that energy is ideal and appearance is relatively good.I.e. further preferred modified carbon nano-tube and sour modified polypropylene resin quality
Than for 25 ~ 50:55 ~ 70, most preferably 25 ~ 50:57 ~ 68.When the additional amount of polypropylene-based resin M2 within the above range when, it is whole
The yield of a product is higher.
Wherein, the polypropylene-based resin in the polypropylene-based resin M2 equally include polypropylene be polymerized alone object, ethylene/
Propylene copolymer, propylene/alhpa olefin copolymer etc., and polypropylene-based resin M2 includes by polypropylene-based resin and unsaturated carboxylic
Acid or derivatives thereof carry out graft copolymerization obtain polymer, by propylene and unsaturated carboxylic acid or derivatives thereof progress random copolymerization
Obtained polymer, the polymer for obtaining propylene and unsaturated carboxylic acid or derivatives thereof progress block copolymerization or will be above-mentioned
Random copolymer or block copolymer carry out the obtained polymer of graft copolymerization with unsaturated carboxylic acid or derivatives thereof again.Institute
State unsaturated carboxylic acid, including maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid etc..The unsaturated carboxylic acid spreads out
Biology includes the acid anhydrides (such as anhydrous maleic acid, anhydrous itaconic acid) of unsaturated carboxylic acid, esters of unsaturated carboxylic acids (such as acrylic acid first
Ester, methyl methacrylate etc.), unsaturated carboxylic acid amide (such as maleic acid diamides, itaconic acid diamides, acrylic acid amides, first
Base acrylic acid amides etc.), the metal salt (such as Sodium methacrylate) of unsaturated carboxylic acid etc..
In above-mentioned unsaturated carboxylic acid or derivatives thereof, preferably acrylic acid, methacrylic acid, maleic anhydride.
Preferably, polymer polypropylene-based resin and maleic anhydride progress graft copolymerization obtained is as M2, or incites somebody to action
The copolymer that propylene and acrylic acid, methacrylic acid or maleic anhydride are copolymerized is as M2.
Under the premise of controlling the acid amount of polypropylene-based resin M2 within the above range, acid amount, which can be directly used, is
0.004 ~ 0.050% sour modified polypropylene resin, can also as the polypropylene-based resin M2 with modified carbon nano tube tube reaction
Sour modified polypropylene resin (M2-1) and unmodified polypropylene resinoid (M2-2) are carried out the quality by 0.1 ~ 4:50 ~ 75
Than being quantitatively used in mixed way, wherein the acid amount of sour modified polypropylene resin (M2-1) is converted into after maleic anhydride and preferably accounts for acid and change
The 0.4 ~ 8% of property polypropylene-based resin (M2-1) gross mass.When acid is measured within the above range, sour modified polypropylene resin
(M2-1) boundary strength between carbon nano-tube fibre is higher, so that the tensile strength for the product being finally press-formed is mentioned
It rises.The unmodified polypropylene resinoid (M2-2), can be using pointed in above-mentioned sour modified polypropylene resin (M2-1)
All kinds of polypropylene-based resins.Among these, the block copolymer of more preferred ethylene/propene and polyacrylic it is polymerized alone
Object.
Preferably, additive can also be added before mixing, the additive is antioxidant, fluorescent whitening agent, pigment, combustion
Material, carbon black, filler material, release agent, ultraviolet absorbing agent, antistatic agent, rubber, softening agent, wetting agent (atoleine, epoxy
Change soybean oil etc.), fire retardant, additives and the anti-drip polyflon such as organic metal salt or impact resistance it is poly-
Styrene, ABS, AES, AAS, AS, acrylic, polyamide, polyethylene terephthalate, polybutylene terephthalate,
The resins such as polyarylate, polysulfones resinoid and polyphenylene sulfide.
Based on the above method, the present patent application additionally provides a kind of PP type composite material of carbon nanotube enhancing,
In, it is prepared by preparation method as described above.
Below by embodiment, the present invention is described in detail.
Test and characterizing method:
A. tension test
According to 527 standard of ISO, using wide 10mm, the dumbbell shaped experiment slice of thick 4mm, a length of 80mm of parallel section are tested.
B. cantilever impact experiment
According to 179 standard of ISO, which is carried out to the sample for being cut into scratch.
C. gravity test
According to 1183 standard of ISO, it is measured using Archimedes method.
D. crooked experiment
Using wide 10mm, the short strip shape experiment slice of thick 4mm, long 80mm carry out 3 crooked experiments on the basis of ISO 178.
Raw material
M2-1: (Sanyo's chemical conversion, YOUMEX1001, acid amount is 2.3%) for sour modified polypropylene resin
M2-2: unmodified polypropylene resinoid (Japan Polypropylene Corporation product), propylene is polymerized alone
Body, MFR 40g/10min.
Embodiment 1
(1) it prepares carbon nano pipe array: in the cobalt-nickel alloy catalyst layer of the first deposition on substrate 20nm thickness, being placed in chemical gas
In phase deposition reaction furnace and it is passed through hydrogen shield gas, is warming up to 800 DEG C, then be passed through carbon-source gas and (wherein, by volume, contain
30% ethylene, 15% hexane and remaining as nitrogen), flow control reacts 40min, thus in the first substrate in 1.5L/min
It is upper to generate the carbon nano pipe array that average length is 0.8 ~ 10mm；
(2) it prepares modified carbon nano-tube: the first substrate with carbon nano pipe array is had into unmodified polypropylene with evenly laid out
Second substrate of resinoid powder is placed side by side in the reaction chamber with high-strength ultraviolet lamp, and the edge of carbon nano pipe array is arranged
With the EDGE CONTACT of unmodified polypropylene resinoid powder bed, and unmodified polypropylene resinoid powder bed is set and is in reaction chamber
Uptake；The air inlet of capping chamber and gas outlet, and vacuumize process is carried out to reaction chamber, make the air pressure in reaction chamber
It is down to 10-6Torr is hereinafter, be passed through pure nitrogen gas into reaction chamber by air inlet again, up to reaching normal atmosphere (An), opening outlet
Mouthful, it is not open close enter nitrogen keep intracavity gas flowing, flow velocity 2L/min；High-strength ultraviolet lamp is opened, irradiation power is
45mW, the wavelength of ultraviolet light are 216nm, and the distance of the first substrate of ultraviolet source distance and the second substrate is 3mm, and irradiation maintains
50min obtains the modified carbon nano-tube that surface grafting has polypropylene molecule；
(3) the PP type composite material of carbon nanotube enhancing:, in parts by mass, will be sour under the protective gas environment of nitrogen
0.45 part of modified polypropylene resin (M2-1), 69.55 parts of unmodified polypropylene resinoid (M2-2) are uniformly mixed to prepare
Polypropylene-based resin M2 after being heated to 280 DEG C of meltings, keeps that 30 parts of modified carbon nano-tube are added at this temperature, with 120rpm's
Speed is stirred 1.5h, obtains composite material (X-1) after standing cooling.
Embodiment 2
(1) carbon nano pipe array is prepared: referring to embodiment 1；
(2) modified carbon nano-tube is prepared: referring to embodiment 1；
(3) the PP type composite material of carbon nanotube enhancing:, in parts by mass, will be sour under the protective gas environment of nitrogen
0.65 part of modified polypropylene resin (M2-1), 69.35 parts of unmodified polypropylene resinoid (M2-2) are uniformly mixed poly- third
Vinyl resin M2 after being heated to 280 DEG C of meltings, keeps that 30 parts of modified carbon nano-tube are added at this temperature, with the speed of 120rpm
It is stirred 1.5h, obtains composite material (X-2) after standing cooling.
Embodiment 3
(1) carbon nano pipe array is prepared: referring to embodiment 1；
(2) modified carbon nano-tube is prepared: referring to embodiment 1；
(3) the PP type composite material of carbon nanotube enhancing:, in parts by mass, will not under the protective gas environment of nitrogen
After 70 parts of modified polypropylene resin (M2-2) are heated to 280 DEG C of meltings directly as polypropylene-based resin M2, the temperature is kept
Lower 30 parts of addition modified carbon nano-tube, 1.5h is stirred with the speed of 120rpm, obtains composite material (X- after standing cooling
3).
Embodiment 4
(1) carbon nano pipe array is prepared: referring to embodiment 1；
(2) modified carbon nano-tube is prepared: referring to embodiment 1；
(3) the PP type composite material of carbon nanotube enhancing:, in parts by mass, will be sour under the protective gas environment of nitrogen
1.4 parts of modified polypropylene resin (M2-1), 68.6 parts of unmodified polypropylene resinoid (M2-2) progress are uniformly mixed as poly-
Propylene resin M2 after being heated to 280 DEG C of meltings, keeps that 30 parts of modified carbon nano-tube are added at this temperature, with the speed of 120rpm
Degree is stirred 1.5h, obtains composite material (X-4) after standing cooling.
By product (X-1), product (X-2), product (X-3), product (X-4) by temperature in 230 DEG C of temperature cylinder, mold
Extrusion molding in the environment of 80 DEG C, after carry out tension test, cantilever impact experiment, gravity test and crooked experiment respectively, tie
Fruit is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Composite material | X-1 | X-2 | X-3 | X-4 |
| The weight ratio of polypropylene-based resin (M2) | 70 | 70 | 70 | 70 |
| The weight ratio of modified carbon nano-tube fiber | 30 | 30 | 30 | 30 |
| (M2) acid amount % | 0.014 | 0.022 | 0.000 | 0.045 |
| The average length (mm) of modified carbon nano-tube fiber | 3.5 | 3.5 | 3.5 | 3.5 |
| The weight ratio % of (M2-1) in M2 | 6.4 | 9.3 | 0.0 | 2.0 |
| The weight ratio % of (M2-2) in M2 | 93.6 | 90.7 | 100.0 | 98.0 |
| Tensile strength GPa | 0.75 | 1.18 | 0.45 | 1.12 |
| Cantilever impact strength kJ/m2 | 88 | 80 | 92 | 61 |
| Specific gravity | 1.10 | 1.10 | 1.08 | 1.09 |
| Bending strength MPa | 432 | 478 | 383 | 627 |
By above table as it can be seen that using embodiment 1 and embodiment 2 scheme, its tensile strength of obtained product and impact strength
Good balance is all obtained.Relatively, in embodiment 3, since the acid amount of polypropylene-based resin M2 is optimal lower than embodiment
Range, obtained product tensile strength are lower；In example 4, since the acid amount of polypropylene-based resin M2 is higher than embodiment
Optimized scope, obtained product impact strength are lower.
In conclusion the preparation method of the PP type composite material of carbon nanotube enhancing provided by the present invention, is being protected
It protects in gas gas and is handled by ultraviolet light, make polypropylene and carbon nanotube that graft polymerization reaction occur, to receive in carbon
Nanotube surface is grafted upper polypropylene molecule, forms modified carbon nano-tube, the modified carbon nano-tube is mixed and melted with polypropylene
Change and is kneaded, so that the PP type composite material of carbon nanotube enhancing is made, the polypropylene molecule of modified carbon nano tube pipe surface
In the presence of the boundary strength that can be overcome between carbon nanotube and acrylic resin, so that the modified carbon nano-tube and acrylic resin
There are good compatibility and mechanics transfer performance, the modified carbon nano-tube of addition can increase the mechanical strength of acrylic resin,
To enhance the mechanical property of material entirety.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of the PP type composite material of carbon nanotube enhancing, which is characterized in that comprising steps of
Carbon nano pipe array and polypropylene-based resin M1 are placed in protective gas atmosphere and carry out treatment with ultraviolet light, so that polypropylene
Graft polymerization reaction occurs for class and carbon nano pipe array, obtains modified carbon nano-tube;
The modified carbon nano-tube and polypropylene-based resin M2 are placed in melt in protective gas atmosphere and are kneaded, carbon nanotube is made
The PP type composite material of enhancing.
2. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 1, which is characterized in that
The wavelength of the treatment with ultraviolet light is 216nm.
3. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 1, which is characterized in that
When carrying out treatment with ultraviolet light, protective gas constant flow is controlled, and polypropylene-based resin M1 is set and is located at uptake position.
4. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 1, which is characterized in that
The polypropylene-based resin M1 is unmodified polypropylene resinoid, and the polypropylene-based resin M2 is unsaturated carboxylic acid or its derivative
The modified polypropylene-based resin of object.
5. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 4, which is characterized in that
Acid amount in polypropylene-based resin M2 be converted into account for after maleic anhydride sour modified polypropylene resin M2 gross mass 0.004 ~
0.05%。
6. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 4, which is characterized in that
The modified carbon nano-tube is mixed with sour modified polypropylene resin by the mass ratio of 25 ~ 50:50 ~ 75 and melts mixing.
7. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 4, which is characterized in that
The polypropylene-based resin is polyacrylic polymer, ethylene/propene copolymer or propylene/alpha olefin copolymer；
The unsaturated carboxylic acid includes one of maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid or a variety of；
The derivative of the unsaturated carboxylic acid includes the acid anhydrides of unsaturated carboxylic acid, esters of unsaturated carboxylic acids, unsaturated carboxylic acid amide, no
One of metal salt of saturated carboxylic acid is a variety of.
8. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 1, which is characterized in that
The average length of modified carbon nano-tube is 0.8 ~ 8mm, and the diameter of carbon nanotube is 10 ~ 50nm.
9. the preparation method of the PP type composite material of carbon nanotube enhancing according to claim 1, which is characterized in that
The melting temperature is 250 ~ 300 DEG C.
10. a kind of PP type composite material of carbon nanotube enhancing, which is characterized in that by as described in claim 1 ~ 9 is any
Preparation method be prepared.
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| CN117024873A (en) * | 2023-06-15 | 2023-11-10 | 广州力合新材料科技有限公司 | Preparation method of modified polypropylene plastic |
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