CN107974071A - A kind of protection of high intensity TPU alloy materials and preparation method thereof - Google Patents
A kind of protection of high intensity TPU alloy materials and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- B29C2948/92504—Controlled parameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention provides a kind of protection of high intensity TPU alloy materials and preparation method thereof, the preparing raw material of the TPU alloy materials includes the component of following parts by weight：50 70 parts by weight of TPU particles, 10 20 parts by weight of carbon fiber, 5 10 parts by weight of graphene oxide, 10 20 parts by weight of graphene, 58 parts by weight of polyester containing phosphonitrile, 14 parts by weight of antioxidant.Carbon fiber, graphene oxide, graphene and the polyester containing phosphonitrile cooperate and TPU alloys provided by the invention is had the characteristics that high intensity, can be used as protective materials application.Preparation method provided by the invention is simple and practicable.
Description
Technical field
The invention belongs to field of alloy material, is related to a kind of TPU alloy materials and preparation method thereof, more particularly to a kind of high
The protection of intensity TPU alloy materials and preparation method thereof.
Background technology
The entitled thermoplastic polyurethane elastomer rubber of TPU, its molecular structure are anti-by diisocyanate and chain extender
The hard block and diisocyanate that should be obtained replace what is formed with the soft segment that macromolecular polyol reacts, and are one
The new organic polymer synthetic material of kind, can substitute rubber or soft polyvinyl chloride material, its good wearability, rebound
Property is superior to conventional polyurethanes, and ageing-resistant performance is better than rubber, it may be said that and TPU possesses the rigidity of plastics and the high resiliency of rubber,
It is known as novel polymer material in the world；And processing method is diversified, vulcanization reaction is not required in its production process, it is overall
With short production cycle, the characteristics of rubber such as recoverable leftover pieces does not possess, the performance of TPU brilliances determines the extensive of application
Property；Again because TPU has good mechanical property, by adjusting to match somebody with somebody the hardness of product can be made to change in very large range, and
And there is excellent tearing strength and damping capacity, TPU is widely used to health care, electronic apparatus and sports goods etc.
Aspect.
Although TPU has been used widely, TPU as protective materials in application, there are still insufficient strength is high
The defects of, need to develop a kind of new TPU materials at present to extend applications of the TPU in terms of protective materials.
The content of the invention
In order to solve the above technical problem, the present invention provides a kind of TPU alloy materials and preparation method thereof, particularly one
Protection TPU alloy materials and preparation method thereof of kind high intensity.
For this purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of TPU alloy materials, the preparing raw material of the TPU alloy materials is including following
The component of parts by weight：
TPU alloys provided by the invention include carbon fiber, graphene oxide and graphene, and carbon fiber can increase material
Be filled in the piece interlayer of graphene and graphene oxide while intensity, form the structure for interting interlayer each other, avoid graphene,
While graphene oxide is assembled and it can assign material excellent antistatic property；And the addition of graphene oxide and graphene
The unit mass of lightening material to a certain extent while can increasing the strength of materials；TPU alloys provided by the invention also wrap
The polyester containing phosphonitrile is included, on the one hand material can be influenced to avoid inorganic combustion inhibitor is added by adding the polyester containing phosphonitrile in the alloy
Between compatibility, on the other hand the polyester containing phosphonitrile can increase the intensity of material；Carbon fiber, graphene oxide, graphene
Cooperating with the polyester containing phosphonitrile makes TPU alloys provided by the invention have the characteristics that high intensity, can be used as protective materials
Using.
In the present invention, the parts by weight of the TPU particles are 50-70 parts by weight, such as 50 parts by weight, 55 parts by weight, 60
Parts by weight, 65 parts by weight, 70 parts by weight etc..
Preferably, the TPU particles are mass ratio 1:The mixing of the polyether-type TPU particles and polyester-type TPU particles of (1-5)
Thing, described 1:(1-5) can be 1:1、1:2、1:3、1:4、1:5 etc..
When polyester-type TPU granule contents are too many, although TPU alloys still have the characteristics that high intensity, TPU alloys
Pliability can be deteriorated；And when polyethers TPU granule contents are too many, still intensity can lose the increase of TPU alloys pliability.
In the present invention, the parts by weight of the carbon fiber are 10-20 parts by weight, such as 10 parts by weight, 12 parts by weight, 15 weights
Measure part, 17 parts by weight, 20 parts by weight etc..
In the present invention, the parts by weight of the graphene oxide are 5-10 parts by weight, such as 5 parts by weight, 6 parts by weight, 7 weights
Measure part, 8 parts by weight, 9 parts by weight, 10 parts by weight etc..
In the present invention, the parts by weight of the graphene are 10-20 parts by weight, such as 10 parts by weight, 12 parts by weight, 15 weights
Measure part, 17 parts by weight, 20 parts by weight etc..
In the present invention, the parts by weight of the polyester containing phosphonitrile are 5-8 parts by weight, such as 5 parts by weight, 6 parts by weight, 7
Parts by weight, 8 parts by weight etc..
Preferably, the polyester containing phosphonitrile has such as lower structure：
Wherein n is 1-10, such as 1,3,5,7,9,10 etc..
In the present invention, the parts by weight of the antioxidant are 1-4 parts by weight, for example, 1 parts by weight, 2 parts by weight, 3 parts by weight,
4 parts by weight etc..
Preferably, the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 264, antioxidant TPP or antioxidant
In TNP any one or at least two mixture.
On the other hand, the present invention provides the preparation method of TPU alloy materials as described above, the preparation method to include
Following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide, obtains mixture；
(2) mixture that step (1) obtains is uniformly mixed with TPU particles, the polyester containing phosphonitrile and antioxidant, obtained
Mixture；
(3) it is kneaded 10-30 minutes at 80-100 DEG C after the mixture drying obtained step (2)；Described 80-100 DEG C can
To be 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C etc., described 10-30 minutes can be 10 minutes, 15 minutes, 20 minutes, 25 points
Clock, 30 minutes etc..
(4) product after step (3) is kneaded continues to be kneaded 5-10 minutes at 140-180 DEG C；Described 140-180 DEG C can be with
140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C etc., described 5-10 minutes can be 5 minutes, 7 minutes, 8 minutes, 9 minutes,
10 minutes etc..
(5) product after step (4) is kneaded continues to be kneaded 10-20 minutes at 100-120 DEG C, then extrudes described in obtaining
TPU alloy materials；Described 100-120 DEG C can be 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C etc., 10-20 minutes described
It can be 10 minutes, 12 minutes, 15 minutes, 17 minutes, 20 minutes etc..
Preparation method provided by the invention is simple and practicable, and the TPU being prepared using preparation method provided by the invention is closed
Gold utensil has intensity high, and the excellent properties of good toughness, can meet the requirement of protective materials completely.And in system provided by the invention
, it is necessary to which stepwise Co-mixturing interts interlayer each other to ensure that carbon fiber is constituted with graphene and graphene oxide well in Preparation Method
Structure, the intensity of TPU alloys and antistatic is improved on the basis of the dispersiveness of graphene oxide and graphene is improved
Property；And three-level mixing is also required in mixing process to be used cooperatively, can just obtain high intensity TPU alloys.
Preferably, mixing speed during step (1) described mixing is 50-80r/min, such as 50r/min, 55r/min,
60r/min, 65r/min, 70r/min, 75r/min, 80r/min etc..
Preferably, the mixing speed of step (2) described mixing is 100-200r/min, such as 100r/min, 125r/min,
150r/min, 175r/min, 200r/min etc..
Preferably, temperature when step (3) is described dry is 50-70 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C
Deng.
Preferably, step (5) extrusion is extruded using double screw extruder, the feeding Duan Wen of the double screw extruder
Spend for 110-120 DEG C (such as 110 DEG C, 115 DEG C, 120 DEG C etc.), mixing section temperature for 140-160 DEG C (such as 140 DEG C, 145 DEG C,
150 DEG C, 155 DEG C, 160 DEG C etc.), extruding zone temperature is 180-200 DEG C (such as 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C
Deng), head temperature is 160-170 DEG C (such as 160 DEG C, 165 DEG C, 170 DEG C etc.).
As optimal technical scheme, the preparation method comprises the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 50-80r/min, is mixed
Thing；
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 100-200r/min, obtains mixture；
(3) after the mixture for obtaining step (2) is dry at 50-70 DEG C, it is kneaded 10-30 minutes at 80-100 DEG C；
(4) product after step (3) is kneaded continues to be kneaded 5-10 minutes at 140-180 DEG C；
(5) product after step (4) is kneaded continues to be kneaded 10-20 minutes at 100-120 DEG C, is then squeezed using twin-screw
Go out machine extrusion, the feeding section temperature of the double screw extruder is 110-120 DEG C, and mixing section temperature is 140-160 DEG C, extruding zone
Temperature is 180-200 DEG C, and head temperature is 160-170 DEG C, obtains the TPU alloy materials.
Relative to the prior art, the invention has the advantages that：
TPU alloys provided by the invention include carbon fiber, graphene oxide and graphene, and carbon fiber can increase material
Be filled in the piece interlayer of graphene and graphene oxide while intensity, form the structure for interting interlayer each other, avoid graphene,
While graphene oxide is assembled and it can assign material excellent antistatic property；And TPU alloys provided by the invention are also
Including the polyester containing phosphonitrile, on the one hand material can be influenced to avoid inorganic combustion inhibitor is added by adding the polyester containing phosphonitrile in the alloy
Compatibility between material, on the other hand the polyester containing phosphonitrile can increase the intensity of material.Carbon fiber, graphene oxide, graphite
Alkene and polyester containing phosphonitrile cooperate and TPU alloys provided by the invention is had the characteristics that high intensity, can be used as and protect material
Material application.Preparation method provided by the invention is simple and practicable.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art should be bright
, the embodiment be only to aid in understand the present invention, be not construed as to the present invention concrete restriction.
Embodiment 1
The preparing raw material of TPU alloys provided in this embodiment includes the component of following parts by weight：
Wherein, TPU particles are mass ratio 1:1 polyether-type TPU particles and the mixture of polyester-type TPU particles；Containing phosphonitrile
Polyester have such as lower structure：
Wherein n is 5；Antioxidant is antioxidant 1010.
Preparation method includes the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 60r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 150r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 60 DEG C, it is kneaded 20 minutes at 90 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 8 minutes at 160 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 15 minutes at 110 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is 190 DEG C, head temperature
Spend for 165 DEG C, obtain TPU alloy materials.
Embodiment 2
The preparing raw material of TPU alloys provided in this embodiment includes the component of following parts by weight：
Wherein, TPU particles are mass ratio 1:5 polyether-type TPU particles and the mixture of polyester-type TPU particles；Containing phosphonitrile
Polyester have such as lower structure：
Wherein n is 1；Antioxidant is antioxidant 1076 and the mixture of antioxidant 264.
Preparation method includes the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 80r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 100r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 70 DEG C, it is kneaded 10 minutes at 100 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 10 minutes at 140 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 20 minutes at 100 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 120 DEG C, and mixing section temperature is 160 DEG C, and extruding zone temperature is 200 DEG C, head temperature
Spend for 170 DEG C, obtain TPU alloy materials.
Embodiment 3
The preparing raw material of TPU alloys provided in this embodiment includes the component of following parts by weight：
Wherein, TPU particles are mass ratio 1:3 polyether-type TPU particles and the mixture of polyester-type TPU particles；Containing phosphonitrile
Polyester have such as lower structure：
Wherein n is 10；Antioxidant is antioxidant TPP.
Preparation method includes the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 50r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 200r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 50 DEG C, it is kneaded 30 minutes at 80 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 5 minutes at 180 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 10 minutes at 120 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 110 DEG C, and mixing section temperature is 140 DEG C, and extruding zone temperature is 180 DEG C, head temperature
Spend for 160 DEG C, obtain TPU alloy materials.
Embodiment 4
The preparing raw material of TPU alloys provided in this embodiment includes the component of following parts by weight：
Wherein, TPU particles are mass ratio 1:2 polyether-type TPU particles and the mixture of polyester-type TPU particles；Containing phosphonitrile
Polyester have such as lower structure：
Wherein n is 7；Antioxidant is antioxidant 1010.
Preparation method includes the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 70r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 125r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 65 DEG C, it is kneaded 25 minutes at 85 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 9 minutes at 150 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 12 minutes at 115 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 117 DEG C, and mixing section temperature is 155 DEG C, and extruding zone temperature is 195 DEG C, head temperature
Spend for 167 DEG C, obtain TPU alloy materials.
Embodiment 5
The preparing raw material of TPU alloys provided in this embodiment includes the component of following parts by weight：
Wherein, TPU particles are mass ratio 1:4 polyether-type TPU particles and the mixture of polyester-type TPU particles；Containing phosphonitrile
Polyester have such as lower structure：
Wherein n is 3；Antioxidant is the composition of antioxidant 1010, antioxidant 264 and antioxidant TNP.
Preparation method includes the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 55r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 175r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 55 DEG C, it is kneaded 15 minutes at 95 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 6 minutes at 170 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 17 minutes at 105 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 112 DEG C, and mixing section temperature is 145 DEG C, and extruding zone temperature is 185 DEG C, head temperature
Spend for 162 DEG C, obtain TPU alloy materials.
Comparative example 1
With differing only in for embodiment 1, the carbon fiber parts by weight of this comparative example addition are 1 parts by weight.
Comparative example 2
With differing only in for embodiment 1, the carbon fiber parts by weight of this comparative example addition are 30 parts by weight.
Comparative example 3
With differing only in for embodiment 1, TPU particles are mass ratio 1 in this comparative example:10 polyether-type TPU particles and
The mixture of polyester-type TPU particles.
Comparative example 4
With differing only in for embodiment 1, TPU particles are mass ratio 10 in this comparative example:1 polyether-type TPU particles and
The mixture of polyester-type TPU particles.
Comparative example 5
With differing only in for embodiment 1, the preparation method that this comparative example prepares TPU alloys is as follows：
(1) by TPU particles, carbon fiber, graphene, graphene oxide, the polyester containing phosphonitrile and antioxidant in 150r/
It is uniformly mixed under min, obtains mixture.
(2) after the mixture for obtaining step (1) is dry at 60 DEG C, it is kneaded 20 minutes at 90 DEG C.
(3) product after step (2) is kneaded continues to be kneaded 8 minutes at 160 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 15 minutes at 110 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is 190 DEG C, head temperature
Spend for 165 DEG C, obtain TPU alloy materials.
Comparative example 6
With differing only in for embodiment 1, the preparation method that this comparative example prepares TPU alloys is as follows：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 60r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 150r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 60 DEG C, it is kneaded 20 minutes at 90 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 15 minutes at 110 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 8 minutes at 160 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is 190 DEG C, head temperature
Spend for 165 DEG C, obtain TPU alloy materials.
Comparative example 7
With differing only in for embodiment 1, the preparation method that this comparative example prepares TPU alloys is as follows：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 60r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 150r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 60 DEG C, it is kneaded 8 minutes at 160 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 15 minutes at 110 DEG C.
(5) product after step (4) is kneaded continues to be kneaded 20 minutes at 90 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is 190 DEG C, head temperature
Spend for 165 DEG C, obtain TPU alloy materials.
Comparative example 8
With differing only in for embodiment 1, the preparation method that this comparative example prepares TPU alloys is as follows：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 60r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 150r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 60 DEG C, it is kneaded 20 minutes at 90 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 23 minutes at 110 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is 190 DEG C, head temperature
Spend for 165 DEG C, obtain TPU alloy materials.
Comparative example 9
With differing only in for embodiment 1, the preparation method that this comparative example prepares TPU alloys is as follows：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 60r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 150r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 60 DEG C, it is kneaded 20 minutes at 90 DEG C.
(4) product after step (3) is kneaded continues to be kneaded 23 minutes at 160 DEG C, is then squeezed using double screw extruder
Go out, the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is 190 DEG C, head temperature
Spend for 165 DEG C, obtain TPU alloy materials.
Comparative example 10
With differing only in for embodiment 1, the preparation method that this comparative example prepares TPU alloys is as follows：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 60r/min, obtains mixture.
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed
It is uniformly mixed under 150r/min, obtains mixture.
(3) after the mixture for obtaining step (2) is dry at 60 DEG C, continues to be kneaded 43 minutes at 110 DEG C, then utilize
Double screw extruder is extruded, and the feeding section temperature of double screw extruder is 115 DEG C, and mixing section temperature is 150 DEG C, extruding zone temperature
For 190 DEG C, head temperature is 165 DEG C, obtains TPU alloy materials.
Performance characterization is carried out to the TPU alloys that embodiment 1-5 and comparative example 1-10 is provided, the results are shown in Table 1：
Table 1
From the contrast of embodiment 1-5 and comparative example 1-10, matched using TPU alloy compositions provided by the invention and
The tensile strengths of the TPU alloys that the preparation method of TPU alloys is prepared, bending strength and impact strength are higher, and comprehensive
Performance reaches optimal；And from the contrast of embodiment 1 and comparative example 1-2, the dosage for adding carbon fiber is excessive or too small can
The performance of TPU alloys is influenced, and the TPU alloys that comparative example 1 provides substantially show component skewness on apparent form
Phenomenon, thus it is speculated that when carbon fiber additive amount is too small, cause graphene oxide, graphene the phenomenon reunited occur and cause material
The decline of performance；From the contrast of embodiment 1 and comparative example 3-4, the quality of polyether-type TPU particles and polyester-type TPU particles
Than not in the framework of the present definition when, although TPU alloys can still act as protective materials use, compared to implementation
The TPU alloys that example 1-5 is provided, comprehensive performance are simultaneously not up to optimal；From the contrast of embodiment 1 and comparative example 5-10, if not
Using preparation method provided by the invention, although TPU alloys still can be used with protective materials, system provided by the invention is used
The TPU alloy properties that Preparation Method is prepared can reach optimal.
The present invention illustrates protection TPU alloy materials and its preparation side of the high intensity of the present invention by above-described embodiment
Method, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention has to rely on above-described embodiment and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of each raw material of product of the present invention
And the addition of auxiliary element, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of TPU alloy materials, it is characterised in that the preparing raw material of the TPU alloy materials includes the group of following parts by weight
Point：
2. TPU alloy materials according to claim 1, it is characterised in that the TPU particles are mass ratio 1:(1-5's)
The mixture of polyether-type TPU particles and polyester-type TPU particles.
3. TPU alloy materials according to claim 1 or 2, it is characterised in that the polyester containing phosphonitrile has following knot
Structure：Wherein n is 1-10.
4. TPU alloy materials according to any one of claim 1-3, it is characterised in that the antioxidant is antioxidant
1010th, any one in antioxidant 1076, antioxidant 264, antioxidant TPP or antioxidant TNP or at least two mixture.
5. the preparation method of the TPU alloy materials according to any one of claim 1-4, it is characterised in that the preparation
Method comprises the following steps：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide, obtains mixture；
(2) mixture that step (1) obtains is uniformly mixed with TPU particles, the polyester containing phosphonitrile and antioxidant, is mixed
Thing；
(3) it is kneaded 10-30 minutes at 80-100 DEG C after the mixture drying obtained step (2)；
(4) product after step (3) is kneaded continues to be kneaded 5-10 minutes at 140-180 DEG C；
(5) product after step (4) is kneaded continues to be kneaded 10-20 minutes at 100-120 DEG C, then extrudes and obtains the TPU
Alloy material.
6. preparation method according to claim 5, it is characterised in that mixing speed during step (1) described mixing is 50-
80r/min。
7. the preparation method according to claim 5 or 6, it is characterised in that the mixing speed of step (2) described mixing is
100-200r/min。
8. according to the preparation method any one of claim 5-7, it is characterised in that temperature when step (3) is described dry
Spend for 50-70 DEG C.
9. according to the preparation method any one of claim 5-8, it is characterised in that step (5) extrusion utilizes double
Screw extruder is extruded, and the feeding section temperature of the double screw extruder is 110-120 DEG C, and mixing section temperature is 140-160 DEG C,
Extruding zone temperature is 180-200 DEG C, and head temperature is 160-170 DEG C.
10. according to the preparation method any one of claim 5-9, it is characterised in that the preparation method includes following
Step：
(1) carbon fiber is uniformly mixed with graphene, graphene oxide low whipping speed 50-80r/min, obtains mixture；
(2) mixture for obtaining step (1) and TPU particles, the polyester containing phosphonitrile and antioxidant low whipping speed 100-
It is uniformly mixed under 200r/min, obtains mixture；
(3) after the mixture for obtaining step (2) is dry at 50-70 DEG C, it is kneaded 10-30 minutes at 80-100 DEG C；
(4) product after step (3) is kneaded continues to be kneaded 5-10 minutes at 140-180 DEG C；
(5) product after step (4) is kneaded continues to be kneaded 10-20 minutes at 100-120 DEG C, then utilizes double screw extruder
Extrusion, the feeding section temperature of the double screw extruder is 110-120 DEG C, and mixing section temperature is 140-160 DEG C, extruding zone temperature
For 180-200 DEG C, head temperature is 160-170 DEG C, obtains the TPU alloy materials.
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| US10793695B2 (en) | 2017-10-25 | 2020-10-06 | Case Western Reserve University | Thermoplastic polyurethane graphene oxide nanocomposites with enhanced mechanical behavior |
| CN113652018A (en) * | 2021-06-22 | 2021-11-16 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
| CN118440488A (en) * | 2024-05-16 | 2024-08-06 | 连云港神鹰碳纤维自行车有限公司 | Low-water-absorption water ripple appearance composite material and preparation method thereof |
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