CN106479036A - A kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof - Google Patents
A kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof Download PDFInfo
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- CN106479036A CN106479036A CN201510530624.9A CN201510530624A CN106479036A CN 106479036 A CN106479036 A CN 106479036A CN 201510530624 A CN201510530624 A CN 201510530624A CN 106479036 A CN106479036 A CN 106479036A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention provides a kind of composite polyolefine material for melting lamination rapid shaping and preparation method thereof, it is prepared from by 5～45 parts of resin matrix 100 part, nanometer nitrile rubber, 1～5 part of compatilizer, 0.1～0.5 part of antioxidant, 0.1～0.5 part of heat stabilizer and 0.5～5 part of lubricant.The composite polyolefine material of present invention preparation has the features such as mechanical strength is high, wearability is good and shaping speed is fast, drastically increases the lower temperature resistance of composite simultaneously.In addition composite material preparation process according to the present invention is simple, can push directly on the application in rapid shaping field for the polyolefine material.
Description
Technical field
The invention belongs to composite polyolefine material rapid shaping technical field of modification is and in particular to a kind of be applied to melt the composite polyolefine material in lamination rapid shaping field and preparation method thereof.
Background technology
Melted extrusion modeling also known as melt-out spinning molding, be a kind of with filamentary material as raw material, by the use of heat energy as the molding energy, the quick shaping process realized by the heating melting of raw material.The operation principle of melted extrusion modeling comprises computer controls heater strip by links such as raw material heating melting, raw material cooling shaping thin layer and the three-dimensional movements of workbench, and wire stock is shaped to the three dimensional articles having stereochemical structure and having certain function the most at last.This kind of quick shaping process technology relatively easy it is easy to operation, in forming process no noxious substance or gas release, can be directly used for office etc. environment.
It is engineering plastics, industry oil wax and synthetic rubber etc. that melted extrusion modeling commonly uses raw material, wherein engineering plastics class material mostly is virgin resin raw material, therefore in the aspect Shortcomings such as mechanical strength, environmental resistance and shaping speed, when preparing large-scale product in addition, need supporting construction and post processing work.
Content of the invention
It is an object of the invention to improving melted extrusion modeling to commonly use the deficiency at aspects such as mechanical strength, environmental resistance and shaping speeds for the raw material, there is provided a kind of have the features such as mechanical strength is big, low-temperature impact is high, wearability good and shaping speed is fast for melting be laminated composite polyolefine material and preparation method thereof of rapid shaping.
For achieving the above object, the present invention employs the following technical solutions：
A kind of composite polyolefine material for melting lamination rapid shaping, is prepared from by weight by following components：
100 parts of resin matrix,
5～45 parts of nitrile rubber of nanometer,
1～5 part of compatilizer,
0.1～0.5 part of antioxidant,
0.1～0.5 part of heat stabilizer,
0.5～5 part of lubricant.
Scheme further, described resin matrix is HOPP or polyethylene.
Described nanometer nitrile rubber is the pale yellow powder of a diameter of 50～100nm.
Described compatilizer is maleic anhydride inoculated polypropylene or maleic anhydride grafted polyethylene.
Described antioxidant be four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] pentaerythritol ester, two kinds in the double octadecyl of three [2.4- di-tert-butyl-phenyl] phosphite esters or thio-2 acid.
Described heat stabilizer is calcium stearate or barium stearate.
Described lubricant is ethylidine bis-stearamides or pentaerythritol stearate.
Another goal of the invention of the present invention is the preparation method providing said polyolefins composite, and it comprises the steps of：
（1）By proportioning, by 5～45 parts of resin matrix 100 part, nanometer nitrile rubber, 1～5 part of compatilizer, 0.1～0.5 part of antioxidant, 0.1～0.5 part of heat stabilizer and 0.5～5 part of lubricant, it is placed in high-speed mixer and disperses 10～30 minutes；
（2）Raw material after dispersion is passed through in extruder, after melting, plasticizing, extrusion, traction, composite polyolefine material for melting lamination rapid shaping is obtained.
Then the composite polyolefine material of preparation is shaped to required product through melt extrusion processes.
The composite polyolefine material of present invention preparation has the features such as mechanical strength is high, wearability is good and shaping speed is fast, drastically increases the lower temperature resistance of composite simultaneously.In addition the composite polyolefine material preparation process is simple of the present invention, can push directly on the application in rapid shaping field for the polyolefine material.
Beneficial effects of the present invention have：
1st, the present invention is with polypropylene or poly- Class B alkene as matrix, and using nanometer nitrile rubber, matrix is modified, and has been obtained and a kind of can be used for melting the composite polyolefine material in lamination rapid shaping field.
2nd, due to the introducing of nanometer nitrile rubber, thus increasing bulk density during melt molding for the composite polyolefine material, reduce forming defect it is possible to significantly improve the mechanical property of composite；
3rd, the nanometer nitrile rubber adding in matrix material can serve as energy-absorbing unit when material occurs and destroys, and reduce generation and the development of crazing, can significantly improve the impact property of composite, especially low temperature impact properties；
4th, because the rubber grain of the Nano grade in nanometer nitrile rubber is dispersed in composite system, friction process can provide buffering and energy-absorbing function, thus significantly improving the wearability of composite；
5th, during composite polyolefine material cooling shaping, nanometer nitrile rubber can serve as crystalline temperature, accelerate composite material solidification and shape, shaping speed is greatly improved.
Specific implementation method
With reference to specific embodiment, present invention is further detailed; but described embodiment is not the simple restriction to true spirit, any all should be belonged within scope of the present invention based on the simple change done by true spirit or equivalent.
After the sample of preparation is adjusted under 23 DEG C, 50% humidity environment in embodiment, it is respectively adopted ASTM D790, ASTM D6110 and ASTM D1242 detects bending strength, low temperature impact strength and the wearability of composite, and record the speed of its melted extrusion modeling.
The specific embodiment of the present invention is as follows：
Embodiment 1
（1）It is equipped with raw material in the following proportions：
100 parts of HOPP resin matrix,
5 parts of nitrile rubber of nanometer,
1 part of compatilizer maleic anhydride inoculated polypropylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.04 part of pentaerythritol ester,
0.06 part of antioxidant three [2.4- di-tert-butyl-phenyl] phosphite ester,
0.1 part of heat stabilizer calcium stearate,
0.5 part of lubricant ethylidine bis-stearamides.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 10 minutes；
（2）Raw material after dispersion is passed through in extruder, after melting, plasticizing, extrusion, traction, composite polyolefine material for melting lamination rapid shaping is obtained.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects its performance.
The acrylonitrile butadiene rubber modified Properties of Polypropylene Composite of prepared nanometer is shown in Table one.
Embodiment 2
（1）It is equipped with raw material in the following proportions：
100 parts of HOPP resin matrix,
15 parts of nitrile rubber of nanometer,
2 parts of compatilizer maleic anhydride inoculated polypropylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.08 part of pentaerythritol ester,
0.12 part of antioxidant three [2.4- di-tert-butyl-phenyl] phosphite ester,
0.2 part of heat stabilizer calcium stearate,
1.5 parts of lubricant ethylidine bis-stearamides.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 15 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified Properties of Polypropylene Composite of prepared nanometer is shown in Table one.
Embodiment 3
（1）It is equipped with raw material in the following proportions：
100 parts of HOPP resin matrix,
25 parts of nitrile rubber of nanometer,
3 parts of compatilizer maleic anhydride inoculated polypropylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.12 part of pentaerythritol ester,
0.18 part of antioxidant three [2.4- di-tert-butyl-phenyl] phosphite ester,
0.3 part of heat stabilizer calcium stearate,
2.5 parts of lubricant ethylidine bis-stearamides.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 20 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified Properties of Polypropylene Composite of prepared nanometer is shown in Table one.
Embodiment 4
（1）It is equipped with raw material in the following proportions：
100 parts of HOPP resin matrix,
35 parts of nitrile rubber of nanometer,
4 parts of compatilizer maleic anhydride inoculated polypropylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.16 part of pentaerythritol ester,
0.24 part of antioxidant three [2.4- di-tert-butyl-phenyl] phosphite ester,
0.4 part of heat stabilizer calcium stearate,
3.5 parts of lubricant ethylidine bis-stearamides.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 25 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified Properties of Polypropylene Composite of prepared nanometer is shown in Table one.
Embodiment 5
（1）It is equipped with raw material in the following proportions：
100 parts of HOPP resin matrix,
45 parts of nitrile rubber of nanometer,
5 parts of compatilizer maleic anhydride inoculated polypropylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.2 part of pentaerythritol ester,
0.3 part of antioxidant three [2.4- di-tert-butyl-phenyl] phosphite ester,
0.5 part of heat stabilizer calcium stearate,
5 parts of lubricant ethylidine bis-stearamides.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 30 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified Properties of Polypropylene Composite of prepared nanometer is shown in Table one.
Embodiment 6
（1）It is equipped with raw material in the following proportions：
100 parts of polyvinyl resin matrix,
5 parts of nitrile rubber of nanometer,
1 part of compatilizer maleic anhydride grafted polyethylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.04 part of pentaerythritol ester,
Double 0.06 part of the octadecyl of antioxidant thio-2 acid,
0.1 part of heat stabilizer barium stearate,
0.5 part of lubricant pentaerythritol stearate.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 10 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified composite polyethylene material performance of prepared nanometer is shown in Table one.
Embodiment 7
（1）It is equipped with raw material in the following proportions：
100 parts of polyvinyl resin matrix,
15 parts of nitrile rubber of nanometer,
2 parts of compatilizer maleic anhydride grafted polyethylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.08 part of pentaerythritol ester,
Double 0.12 part of the octadecyl of antioxidant thio-2 acid,
0.2 part of heat stabilizer barium stearate,
1.5 parts of lubricant pentaerythritol stearate.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 15 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified composite polyethylene material performance of prepared nanometer is shown in Table one.
Embodiment 8
（1）It is equipped with raw material in the following proportions：
100 parts of polyvinyl resin matrix,
25 parts of nitrile rubber of nanometer,
3 parts of compatilizer maleic anhydride grafted polyethylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.12 part of pentaerythritol ester,
Double 0.18 part of the octadecyl of antioxidant thio-2 acid,
0.3 part of heat stabilizer barium stearate,
2.5 parts of lubricant pentaerythritol stearate.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 20 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified composite polyethylene material performance of prepared nanometer is shown in Table one.
Embodiment 9
（1）It is equipped with raw material in the following proportions：
100 parts of polyvinyl resin matrix,
35 parts of nitrile rubber of nanometer,
4 parts of compatilizer maleic anhydride grafted polyethylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.16 part of pentaerythritol ester,
Double 0.24 part of the octadecyl of antioxidant thio-2 acid,
0.4 part of heat stabilizer barium stearate,
3.5 parts of lubricant pentaerythritol stearate.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 25 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified composite polyethylene material performance of prepared nanometer is shown in Table one.
Embodiment 1
0
（1）It is equipped with raw material in the following proportions：
100 parts of polyvinyl resin matrix,
45 parts of nitrile rubber of nanometer,
5 parts of compatilizer maleic anhydride grafted polyethylene,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.2 part of pentaerythritol ester,
Double 0.3 part of the octadecyl of antioxidant thio-2 acid,
0.5 part of heat stabilizer barium stearate,
5 parts of lubricant pentaerythritol stearate.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 30 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
The acrylonitrile butadiene rubber modified composite polyethylene material performance of prepared nanometer is shown in Table one.
Comparative examples 1
（1）It is equipped with raw material in the following proportions：
100 parts of HOPP resin matrix,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.04 part of pentaerythritol ester,
0.06 part of antioxidant three [2.4- di-tert-butyl-phenyl] phosphite ester,
0.1 part of heat stabilizer calcium stearate,
0.5 part of lubricant ethylidine bis-stearamides.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 10 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects performance.
Prepared Properties of Polypropylene Composite is shown in Table one.
Comparative examples 2
（1）It is equipped with raw material in the following proportions：
100 parts of polyvinyl resin matrix,
Antioxidant four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] 0.04 part of pentaerythritol ester,
Double 0.06 part of the octadecyl of antioxidant thio-2 acid,
0.1 part of heat stabilizer barium stearate,
0.5 part of lubricant pentaerythritol stearate.
It is placed in high-speed mixer after above material is uniformly mixed to disperse 10 minutes；
（2）Raw material after dispersion is passed through extruder, raw material, after melting, plasticizing, extrusion, traction, is obtained the composite polyolefine material for melting lamination rapid shaping.
（3）The composite polyolefine material of preparation is shaped to required product through melt extrusion processes, and detects its performance.
Prepared composite polyethylene material performance is shown in Table one.
Table one：
| Performance | Bending strength（MPa） | Impact strength（KJ/m2-20℃） | Taber Abrasion（Mg/1000 time） | Shaping speed (cm3/h) |
| Embodiment 1 | 42 | 7.9 | 62 | 39 |
| Embodiment 2 | 44 | 8.1 | 61 | 41 |
| Embodiment 3 | 56 | 8.2 | 60 | 42 |
| Embodiment 4 | 48 | 8.5 | 58 | 44 |
| Embodiment 5 | 47 | 8.3 | 59 | 43 |
| Embodiment 6 | 29 | 4.8 | 69 | 33 |
| Embodiment 7 | 30 | 5.1 | 67 | 34 |
| Embodiment 8 | 33 | 5.4 | 64 | 38 |
| Embodiment 9 | 32 | 5.3 | 65 | 37 |
| Embodiment 10 | 31 | 5.1 | 66 | 35 |
| Comparative examples 1 | 35 | 5.1 | 95 | 28 |
| Comparative examples 2 | 24 | 3.2 | 100 | 26 |
By data in table one, comparative example 1-5 and comparative examples 1 can be seen that：After melt extrusion processes molded article, its bending strength is 48MPa to the maximum to the composite polyolefine material of present invention preparation, more before modified（Comparative examples 1）Improve 37.1%；Low temperature impact strength is 8.5Kj/m to the maximum2, improve 66.7% more before modified；Minimum 58mg/100 time of Taber Abrasion, reduces by 38.9% more before modified；Shaping speed is 44cm the soonest3/ h, improves 57.1% more before modified.
Comparative example 6-10 and comparative examples 2 can be seen that：After melt extrusion processes molded article, its bending strength is 33MPa to the maximum to the composite polyolefine material of present invention preparation, more before modified（Comparative examples 2）Improve 37.5%；Low temperature impact strength is 5.4Kj/m to the maximum2, improve 68.8% more before modified；Minimum 64mg/100 time of Taber Abrasion, reduces by 36.0% more before modified；Shaping speed is 38cm the soonest3/ h, improves 46.2% more before modified.
In addition, the preparation process is simple of the present invention, the application in rapid shaping field for the polyolefine material can be pushed directly on.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and apply the present invention.Person skilled in the art obviously easily can make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to embodiment here, according to the announcement of the present invention, the improvement made without departing from scope and modification all should be within protection scope of the present invention for those skilled in the art.
Claims (8)
1. a kind of for melting lamination rapid shaping composite polyolefine material it is characterised in that：It is prepared from by weight by following components：
100 parts of resin matrix,
5～45 parts of nitrile rubber of nanometer,
1～5 part of compatilizer,
0.1～0.5 part of antioxidant,
0.1～0.5 part of heat stabilizer,
0.5～5 part of lubricant.
2. composite polyolefine material according to claim 1 it is characterised in that：Described resin matrix is HOPP or polyethylene.
3. composite polyolefine material according to claim 1 it is characterised in that：Described nanometer nitrile rubber is the pale yellow powder shape granule of a diameter of 50～100nm.
4. composite polyolefine material according to claim 1 it is characterised in that：Described compatilizer is maleic anhydride inoculated polypropylene or maleic anhydride grafted polyethylene.
5. composite polyolefine material according to claim 1 it is characterised in that：Described antioxidant be four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propanoic acid] pentaerythritol ester, two kinds in the double octadecyl of three [2.4- di-tert-butyl-phenyl] phosphite esters or thio-2 acid.
6. composite polyolefine material according to claim 1 it is characterised in that：Described heat stabilizer is calcium stearate or barium stearate.
7. composite polyolefine material according to claim 1 it is characterised in that：Described lubricant is ethylidine bis-stearamides or pentaerythritol stearate.
8. a kind of preparation method of composite polyolefine material as claimed in claim 1 it is characterised in that：Comprise the steps of：
（1）By proportioning, by 5～45 parts of resin matrix 100 part, nanometer nitrile rubber, 1～5 part of compatilizer, 0.1～0.5 part of antioxidant, 0.1～0.5 part of heat stabilizer and 0.5～5 part of lubricant, it is placed in high-speed mixer and disperses 10～30 minutes；
（2）Raw material after dispersion is passed through in extruder, after melting, plasticizing, extrusion, traction, composite polyolefine material for melting lamination rapid shaping is obtained.
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| CN107857936A (en) * | 2017-11-19 | 2018-03-30 | 王秋林 | PP, PE, BR tertiary blending formula |
| CN109134993A (en) * | 2017-06-16 | 2019-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of wear-resistant polyolefin composite material and preparation method for rapid shaping |
| CN110066439A (en) * | 2018-01-23 | 2019-07-30 | 合肥杰事杰新材料股份有限公司 | A kind of antiwear heat resisting composite polyolefine material and preparation method thereof |
| CN116041832A (en) * | 2023-02-28 | 2023-05-02 | 江苏惠升管业集团有限公司 | POE grafted GMA and application method thereof in polyethylene gas pipe |
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| CN110066439A (en) * | 2018-01-23 | 2019-07-30 | 合肥杰事杰新材料股份有限公司 | A kind of antiwear heat resisting composite polyolefine material and preparation method thereof |
| CN116041832A (en) * | 2023-02-28 | 2023-05-02 | 江苏惠升管业集团有限公司 | POE grafted GMA and application method thereof in polyethylene gas pipe |
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| CN106479036B (en) | 2020-10-30 |
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