CN107641313A - A kind of high abrasion TPU materials available for 3D printings and preparation method thereof - Google Patents
A kind of high abrasion TPU materials available for 3D printings and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high abrasion TPU materials available for 3D printings and preparation method thereof, the raw material of the TPU materials includes following components：The parts by weight of TPU particles 60 80, the parts by weight of ABS resin 10 20, the parts by weight of polyvinyl alcohol 15 25, the parts by weight of graphene nanometer sheet 3 10, the parts by weight of nano silicon 15 20, the parts by weight of nm-class boron nitride 58, the parts by weight of silane coupler 15.High abrasion TPU material wear abilities of the present invention available for 3D printings are good, and smooth, no interim card is printed in printing process.
Description
Technical field
The invention belongs to 3D print fields, are related to a kind of high abrasion TPU materials available for 3D printings and preparation method thereof.
Background technology
3D prints, and is called stereosopic printing, generally use is that a kind of human eye spacing of simulating can produce the principle of space parallax, will
Different angle, the pixel record of different levels are on photosensitive material, then by the compound of grating material, in the plan of two dimension
As the upper stereoeffect that three-dimensional is presented or even virtual reality are directly passed through by this approach, people without any instrument
Eye observation can experience to clear and definite the marvellous enjoyment of stereoscopic picture plane.
3D printings are generally used in Rapid Product prototype, mould generation and master mold generation；3D printing technologies are considered as
It is adding technology, because it, which is related to combination, applies continuous material layer, this puts removes material so as to generate with being often relied on
The tradition machinery processing technology of final object is different.The material used in 3D printings often needs to solidify or fuse, for some
Completed for material using the extrusion or sintering of heat auxiliary.
Usual 3D printings mainly realize three-dimensional stereo effect by print thickness, and thickness mainly passes through print pass or thing
Reason, chemical blowing process realize that this general corner angle of 3D effect are clearly demarcated, feel can be touched；But it can produce in use big
The abrasion of amount, impact effect；Also, interim card occurs for the 3D printing materials used at present occasional in printing process, and printing is not
Smooth phenomenon, can so influence the 3D effect finally showed.Therefore, the high abrasion material that can be used in 3D printing technologies is found
The problems such as expecting and reducing the interim card in printing process is badly in need of solving.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides it is a kind of available for 3D printing high abrasion TPU materials and its
Preparation method.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the invention provides a kind of TPU materials available for 3D printings, the raw materials of the TPU materials include with
Lower component：
TPU materials provided by the invention include nano silicon and nm-class boron nitride, and the two can be homogeneously dispersed in
Graphene film interlayer, the two synergy, as far as possible graphene nanometer sheet can be avoided to reunite, avoid influenceing the globality of material
Energy.Graphene nanometer sheet is added in TP U materials provided by the invention, can have TPU materials of the present invention good
Antistatic property, and can improve TPU materials of the present invention printing when fluency, make it easier for printing,
Avoid influenceing last 3D printing effects because of printing not smooth.
In the present invention, the parts by weight of the TPU particles are 60-80 parts by weight, such as 60 parts by weight, 65 parts by weight, 70
Parts by weight, 75 parts by weight, 80 parts by weight etc..
In the present invention, the parts by weight of the ABS resin are 10-20 parts by weight, such as 10 parts by weight, 12 parts by weight, 15
Parts by weight, 17 parts by weight, 20 parts by weight etc..
In the present invention, the parts by weight of the polyvinyl alcohol are 15-25 parts by weight, such as 15 parts by weight, 17 parts by weight, 20
Parts by weight, 22 parts by weight, 25 parts by weight etc..
Include polyvinyl alcohol in the high abrasion TPU materials of the present invention available for 3D printings, polyvinyl alcohol can be with
Increase the compatibility of nano silicon, nm-class boron nitride and graphene nanometer sheet and polymer organic composition, to greatest extent
The agglomeration for preventing each component, so as to improve the wearability of material；Also, polyvinyl alcohol also has good antistatic behaviour,
Increase the antistatic behaviour of TPU materials with graphene collective effect.
In the present invention, the parts by weight of the graphene nanometer sheet are 3-10 parts by weight, such as 3 parts by weight, 5 parts by weight, 7
Parts by weight, 9 parts by weight, 10 parts by weight etc..
Graphene nanometer sheet is added in TPU materials of the present invention, on the one hand can increase the wearability of material, separately
One side graphene has good antistatic behaviour, and graphene is added in TPU materials can increase the antistatic behaviour of material, and
The fluency in printing can be improved, avoids influenceing last 3D printing effects because of phenomena such as interim card.
In the present invention, the parts by weight of the nano silicon are 15-20 parts by weight, such as 15 parts by weight, 17 weight
Part, 20 parts by weight etc..
Preferably, the particle diameter of the nano silicon is 100-200 nanometers, such as 100-120 nanometers, 120-140 receive
Rice, 140-160 nanometers, 160-180 nanometers, 180-200 nanometers etc..
In the present invention, the parts by weight of the nm-class boron nitride are 5-8 parts by weight, such as 5 parts by weight, 6 parts by weight, 7 weights
Measure part, 8 parts by weight etc..
Preferably, the particle diameter of the nm-class boron nitride is 10-30 nanometers, such as 10-20 nanometers, 20-30 nanometers etc..
High abrasion TPU materials provided by the invention available for 3D printings include nano silicon and nano silicon nitride
Boron, the two Synergistic, graphene film interlayer on the one hand can be uniformly filled to, avoid graphene because of the work between lamella
Agglomeration firmly occurs, on the other hand, polyvinyl alcohol can increase nano silicon, nm-class boron nitride and graphene nano
The compatibility of piece and polymeric matrix, and then increase the wearability of material.
In the present invention, the parts by weight of the silane coupler are 1-5 parts by weight, such as 1 parts by weight, 2.5 parts by weight, 3
Parts by weight, 4 parts by weight, 5 parts by weight etc..
Preferably, the silane coupler is isobutyl triethoxy silane and/or VTES.
In the present invention, silane coupler is used cooperatively with polyethylene glycol, can play increase nano silicon, nanometer
Compatibility between boron nitride and graphene nanometer sheet and polymeric matrix, and then improve the wearability of material.
On the other hand, the invention provides a kind of preparation method of the TPU materials as described above available for 3D printings, institute
The method of stating comprises the following steps：
(1) nano silicon is well mixed with nm-class boron nitride, and graphene nanometer sheet is added in backward mixture,
It is well mixed；
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), is well mixed；
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), is well mixed, is squeezed using twin-screw
Go out machine to extrude to obtain the TPU materials available for 3D printings.
The preparation method of TPU materials as described above available for 3D printings provided by the invention is simple for process, and
And the TPU material wear abilities as described above available for 3D printings prepared by such a method are good, in printing without interim card.
In the present invention, the order of addition of each component can not arbitrarily change in the preparation method, in step (1), add
Entering order can not overturn, and nano silicon and nm-class boron nitride could be blended after being sufficiently mixed with graphene nanometer sheet, so
Nano silicon can be caused to be substantially filled to graphene nanometer sheet piece interlayer with nm-class boron nitride, make graphene be not easy to roll into a ball
It is poly-；If filling and less efficient dispersal can be caused if exchanging addition sequence, and then the resistance to of material is influenceed in subsequent process
Mill property and printing fluency.
Preferably, the stir speed (S.S.) that step (1) is described when mixing twice independently is 50-80r/min, such as 50r/min,
60r/min, 65r/min, 70r/min, 75r/min, 80r/min etc..
Preferably, stir speed (S.S.) during step (2) described mixing is 300-550r/min, such as 300r/min, 350r/
Min, 400r/min, 450r/min, 500r/min, 550r/min etc..
Preferably, stir speed (S.S.) during step (3) described mixing is 500-800r/min, such as 500r/min, 550r/
Min, 650r/min, 700r/min, 750r/min, 800r/min etc..
Preferably, the feeding section temperature of step (3) described double screw extruder be 120-140 DEG C (such as 120 DEG C, 130
DEG C, 140 DEG C etc.), mixing section temperature is 150-170 DEG C (such as 150 DEG C, 160 DEG C, 170 DEG C etc.), and extruding zone temperature is 180-
200 DEG C (such as 180 DEG C, 190 DEG C, 200 DEG C), head temperature are 160-170 DEG C (such as 160 DEG C, 165 DEG C, 170 DEG C etc.).
As optimal technical scheme, the described method comprises the following steps：
(1) nano silicon is well mixed under 50-80r/min stir speed (S.S.) with nm-class boron nitride, and it is backward
Graphene nanometer sheet is added in mixture, is well mixed under 50-80r/min stir speed (S.S.)；
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in stirring for 300-550r/min
Mix and be well mixed under speed；
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), in 500-800r/min stirring speed
It is well mixed under rate, is extruded using double screw extruder, the feeding section temperature of the double screw extruder is 120-140 DEG C, is mixed
It is 150-170 DEG C to close section temperature, and extruding zone temperature is 180-200 DEG C, and head temperature is 160-170 DEG C, obtains can be used for 3D to print
The TPU materials of brush.
Relative to prior art, the invention has the advantages that：
High abrasion TPU materials of the present invention available for 3D printings include nano silicon and nm-class boron nitride,
The two can be homogeneously dispersed in graphene film interlayer, Synergistic, avoid graphene from reuniting as far as possible, avoid influenceing the whole of material
Body performance.Graphene nanometer sheet is added in TPU materials of the present invention, can have TPU materials of the present invention
Good antistatic property, and fluency of the TPU materials of the present invention in printing can be improved, make it easier for printing
Brush, avoid influenceing last 3D effect because of printing not smooth.TPU materials of the present invention also include polyvinyl alcohol and silicon
Alkane coupling agent, on the one hand, polyvinyl alcohol has good antistatic behaviour, can be cooperated with graphene nanometer sheet, increases material
Antistatic behaviour, on the other hand, the addition of polyvinyl alcohol and silane coupler can help nano silicon as described above,
Nm-class boron nitride and graphene nanometer sheet are preferably compatible with polymeric matrix, so as to improve the wear-resisting of final TPU materials
Property.Mutual cooperation between TPU material uses component of the present invention so that the wearability of material is less than 0.032 Akron,
Tensile strength is 50.8-52.4MPa, and elongation at break has good printing fluency between 409-433%.
The preparation method of TPU materials as described above available for 3D printings provided by the invention is simple for process, and
And the TPU material wear abilities as described above available for 3D printings prepared by such a method are good, in printing without interim card.
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 raw material for the TPU materials that the present embodiment provides includes following components：
Wherein, the particle diameter of nano silicon is 100-120 nanometers, and the particle diameter of nm-class boron nitride is 10-20 nanometers, silane
Coupling agent is isobutyl triethoxy silane.
Preparation method is as follows：
(1) nano silicon is well mixed under 50r/min stir speed (S.S.) with nm-class boron nitride, and mixed backward
Graphene nanometer sheet is added in thing, is well mixed under 80r/min stir speed (S.S.).
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in 400r/min stirring speed
It is well mixed under rate.
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), under 800r/min stir speed (S.S.)
It is well mixed, extruded using double screw extruder, the feeding section temperature of the double screw extruder is 140 DEG C, mixing section temperature
For 170 DEG C, extruding zone temperature is 190 DEG C, and head temperature is 165 DEG C, obtains the TPU materials that can be used for 3D printings.
Embodiment 2
The raw material for the TPU materials that the present embodiment provides includes following components：
Wherein, the particle diameter of nano silicon is 180-200 nanometers, and the particle diameter of nm-class boron nitride is 10-20 nanometers, silane
Coupling agent is VTES.
Preparation method is as follows：
(1) nano silicon is well mixed under 80r/min stir speed (S.S.) with nm-class boron nitride, and mixed backward
Graphene nanometer sheet is added in thing, is well mixed under 50r/min stir speed (S.S.).
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in 550r/min stirring speed
It is well mixed under rate.
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), under 500r/min stir speed (S.S.)
It is well mixed, extruded using double screw extruder, the feeding section temperature of the double screw extruder is 120 DEG C, mixing section temperature
For 150 DEG C, extruding zone temperature is 180 DEG C, and head temperature is 160 DEG C, obtains the TPU materials that can be used for 3D printings.
Embodiment 3
The raw material for the TPU materials that the present embodiment provides includes following components：
Wherein, the particle diameter of nano silicon is 140-160 nanometers, and the particle diameter of nm-class boron nitride is 20-30 nanometers, silane
Coupling agent is isobutyl triethoxy silane.
Preparation method is as follows：
(1) nano silicon is well mixed under 60r/min stir speed (S.S.) with nm-class boron nitride, and mixed backward
Graphene nanometer sheet is added in thing, is well mixed under 70r/min stir speed (S.S.).
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in 300r/min stirring speed
It is well mixed under rate.
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), under 600r/min stir speed (S.S.)
It is well mixed, extruded using double screw extruder, the feeding section temperature of the double screw extruder is 130 DEG C, mixing section temperature
For 155 DEG C, extruding zone temperature is 185 DEG C, and head temperature is 162 DEG C, obtains the TPU materials that can be used for 3D printings.
Embodiment 4
The raw material for the TPU materials that the present embodiment provides includes following components：
Wherein, the particle diameter of nano silicon is 120-140 nanometers, and the particle diameter of nm-class boron nitride is 10-20 nanometers, silane
Coupling agent is isobutyl triethoxy silane.
Preparation method is as follows：
(1) nano silicon is well mixed under 70r/min stir speed (S.S.) with nm-class boron nitride, and mixed backward
Graphene nanometer sheet is added in thing, is well mixed under 60r/min stir speed (S.S.).
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in 500r/min stirring speed
It is well mixed under rate.
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), under 700r/min stir speed (S.S.)
It is well mixed, extruded using double screw extruder, the feeding section temperature of the double screw extruder is 135 DEG C, mixing section temperature
For 165 DEG C, extruding zone temperature is 195 DEG C, and head temperature is 170 DEG C, obtains the TPU materials that can be used for 3D printings.
Embodiment 5
The raw material for the TPU materials that the present embodiment provides includes following components：
Wherein, the particle diameter of nano silicon is 160-180 nanometers, and the particle diameter of nm-class boron nitride is 20-30 nanometers, silane
Coupling agent is VTES.
Preparation method is as follows：
(1) nano silicon is well mixed under 60r/min stir speed (S.S.) with nm-class boron nitride, and mixed backward
Graphene nanometer sheet is added in thing, is well mixed under 70r/min stir speed (S.S.).
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in 450r/min stirring speed
It is well mixed under rate.
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), under 650r/min stir speed (S.S.)
It is well mixed, extruded using double screw extruder, the feeding section temperature of the double screw extruder is 125 DEG C, mixing section temperature
For 160 DEG C, extruding zone temperature is 200 DEG C, and head temperature is 167 DEG C, obtains the TPU materials that can be used for 3D printings.
Comparative example 1
The TPU particle weights part added in TPU materials that differs only in embodiment 1 is 50 parts by weight, remaining raw material
It is same as Example 1 with raw material dosage and preparation method and condition.
Comparative example 2
The TPU particle weights part added in TPU materials that differs only in embodiment 1 is 90 parts by weight, remaining raw material
It is same as Example 1 with raw material dosage and preparation method and condition.
Comparative example 3
The ABS resin parts by weight added in TPU materials that differ only in embodiment 1 are 1 parts by weight, remaining raw material and
Raw material dosage and preparation method and condition are same as Example 1.
Comparative example 4
The ABS resin parts by weight added in TPU materials that differ only in embodiment 1 are 30 parts by weight, remaining raw material
It is same as Example 1 with raw material dosage and preparation method and condition.
Comparative example 5
The polyvinyl alcohol weight part added in TPU materials that differs only in embodiment 1 is 5 parts by weight, remaining raw material
It is same as Example 1 with raw material dosage and preparation method and condition.
Comparative example 6
The polyvinyl alcohol weight part added in TPU materials that differs only in embodiment 1 is 35 parts by weight, remaining raw material
It is same as Example 1 with raw material dosage and preparation method and condition.
Comparative example 7
The graphene nanometer sheet parts by weight added in TPU materials that differ only in embodiment 1 are 0.1 parts by weight, its
Remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 8
The graphene nanometer sheet parts by weight added in TPU materials that differ only in embodiment 1 are 20 parts by weight, remaining
Raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 9
Nano silicon is not added in TPU materials with differing only in for embodiment 1, and the addition of nm-class boron nitride
The addition sum for nano silicon in embodiment 1 and nm-class boron nitride is measured, i.e. the addition of nm-class boron nitride is 23 weights
Measure part；Remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 10
Nm-class boron nitride is not added in TPU materials with differing only in for embodiment 1, and the addition of nano silicon
The addition sum for nano silicon in embodiment 1 and nm-class boron nitride is measured, i.e. the addition of nano silicon is 23
Parts by weight；Remaining raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 11
The nano silicon parts by weight added in TPU materials that differ only in embodiment 1 are 5 parts by weight, remaining
Raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 12
The nano silicon parts by weight added in TPU materials that differ only in embodiment 1 are 30 parts by weight, remaining
Raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 13
The nm-class boron nitride parts by weight added in TPU materials that differ only in embodiment 1 are 1 parts by weight, and remaining is former
Material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 14
The nm-class boron nitride parts by weight added in TPU materials that differ only in embodiment 1 are 20 parts by weight, and remaining is former
Material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 15
The silane coupler parts by weight added in TPU materials that differ only in embodiment 1 are 0.1 parts by weight, remaining
Raw material and raw material dosage and preparation method and condition are same as Example 1.
Comparative example 16
The silane coupler parts by weight added in TPU materials that differ only in embodiment 1 are 15 parts by weight, and remaining is former
Material and raw material dosage and preparation method and condition are same as Example 1.
The performance of the embodiment 1-5 TPU materials prepared and comparative example 1-16 the TPU materials prepared is measured, surveyed
It is as shown in table 1 to determine result.
Table 1
As seen from the results in Table 1, the tensile strength of the high abrasion TPU materials available for 3D printings provided by the invention can
To reach 50.8-52.4MPa, elongation at break has good toughness between 409-433%；And abrasion resistance index is then less than
0.032 Akron, and without Caton phenomenon in printing process.The TPU material combination properties provided in embodiment 1-5 are best.
Although the TPU material parts performance provided in comparative example 1-16 is better than the TPU materials that embodiment 1 provides, such as right
Ratio 8-9 tensile strength is better than embodiment 1, but can be seen that Caton phenomenon, or even Caton phenomenon from printing fluency
Than more serious, decline from the point of view of the overall performance of material, it is therefore, provided by the invention available for the high resistance to of 3D printings
The technical scheme for grinding TPU materials is optimal case, the performance in the face that can coordinate all quarters concerned, overall performance is reached optimal.
The present invention by above-described embodiment come illustrate the present invention it is a kind of available for 3D printing high abrasion TPU materials and its
Preparation 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 ability
Implement.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, to each raw material of product of the present invention etc.
Effect replacement and the addition of auxiliary element, the selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of TPU materials available for 3D printings, it is characterised in that the raw material of the TPU materials includes following components：
2. the TPU materials according to claim 1 available for 3D printings, it is characterised in that the nano silicon
Particle diameter is 100-200 nanometers.
3. the TPU materials according to claim 1 or 2 available for 3D printings, it is characterised in that the nm-class boron nitride
Particle diameter is 10-30 nanometers.
4. the TPU materials that can be used for 3D printings according to any one of claim 1-3, it is characterised in that the silane
Coupling agent is isobutyl triethoxy silane and/or VTES.
5. the preparation method of the TPU materials that can be used for 3D printings according to any one of claim 1-4, its feature exist
In the described method comprises the following steps：
(1) nano silicon is well mixed with nm-class boron nitride, and graphene nanometer sheet is added in backward mixture, mixed
Uniformly；
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), is well mixed；
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), is well mixed, utilizes double screw extruder
Extrusion obtains the TPU materials that can be used for 3D printings.
6. preparation method according to claim 5, it is characterised in that stir speed (S.S.) when being mixed twice described in step (1)
It independently is 50-80r/min.
7. the preparation method according to claim 5 or 6, it is characterised in that stir speed (S.S.) during step (2) described mixing is
300-550r/min。
8. according to the preparation method any one of claim 5-7, it is characterised in that stirring during step (3) described mixing
It is 500-800r/min to mix speed.
9. according to the preparation method any one of claim 5-8, it is characterised in that step (3) described twin-screw extrusion
The feeding section temperature of machine is 120-140 DEG C, and mixing section temperature is 150-170 DEG C, and extruding zone temperature is 180-200 DEG C, head temperature
Spend for 160-170 DEG C.
10. according to the preparation method any one of claim 5-9, it is characterised in that the described method comprises the following steps：
(1) nano silicon is well mixed under 50-80r/min stir speed (S.S.) with nm-class boron nitride, and mixed backward
Graphene nanometer sheet is added in thing, is well mixed under 50-80r/min stir speed (S.S.)；
(2) polyvinyl alcohol and silane coupler are added in the mixture obtained to step (1), in 300-550r/min stirring speed
It is well mixed under rate；
(3) TPU particles and ABS resin are added in the mixture obtained to step (2), under 500-800r/min stir speed (S.S.)
It is well mixed, extruded using double screw extruder, the feeding section temperature of the double screw extruder is 120-140 DEG C, mixing section
Temperature is 150-170 DEG C, and extruding zone temperature is 180-200 DEG C, and head temperature is 160-170 DEG C, obtains can be used for 3D printings
TPU materials.
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| CN109679324A (en) * | 2018-12-26 | 2019-04-26 | 山东一诺威聚氨酯股份有限公司 | Low temperature resistant wear-resisting TPU composite material and preparation method for nailed climbing boots |
| CN109836802A (en) * | 2019-02-22 | 2019-06-04 | 福鼎市肯普聚氨酯科技发展有限公司 | A kind of composition, impact resistance polymer composite and preparation method thereof |
| CN110240796A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | Soft consumptive material composition of 3D printing and the preparation method and application thereof |
| CN112745657A (en) * | 2021-01-26 | 2021-05-04 | 福州大学 | Anti-slip thermoplastic polyurethane composite material and preparation method thereof |
| WO2021212901A1 (en) * | 2020-04-21 | 2021-10-28 | He Jianxiong | Tpu thin film for express packaging and preparation method therefor |
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| CN108329679A (en) * | 2018-02-02 | 2018-07-27 | 江苏洛基木业有限公司 | A kind of preparation method of solvent-free graphene electric-heating thin film |
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| CN109679324A (en) * | 2018-12-26 | 2019-04-26 | 山东一诺威聚氨酯股份有限公司 | Low temperature resistant wear-resisting TPU composite material and preparation method for nailed climbing boots |
| CN109836802A (en) * | 2019-02-22 | 2019-06-04 | 福鼎市肯普聚氨酯科技发展有限公司 | A kind of composition, impact resistance polymer composite and preparation method thereof |
| WO2021212901A1 (en) * | 2020-04-21 | 2021-10-28 | He Jianxiong | Tpu thin film for express packaging and preparation method therefor |
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