CN111073244B - Polycarbonate composition and preparation method thereof - Google Patents
Polycarbonate composition and preparation method thereof Download PDFInfo
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- CN111073244B CN111073244B CN201911222647.8A CN201911222647A CN111073244B CN 111073244 B CN111073244 B CN 111073244B CN 201911222647 A CN201911222647 A CN 201911222647A CN 111073244 B CN111073244 B CN 111073244B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 60
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000314 lubricant Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012765 fibrous filler Substances 0.000 claims abstract description 5
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 3
- 239000003365 glass fiber Substances 0.000 claims description 50
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- -1 glycidyl ester Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- ZRGWIXMPMASFPS-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[NH+]1CN(C)C=C1 ZRGWIXMPMASFPS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002614 Polyether block amide Polymers 0.000 claims description 2
- GQLRFPJNVQIFPK-UHFFFAOYSA-N dihydrogen phosphate;3-methyl-1h-imidazol-3-ium Chemical compound OP(O)(O)=O.CN1C=CN=C1 GQLRFPJNVQIFPK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 2
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- TVEOIQKGZSIMNG-UHFFFAOYSA-N hydron;1-methyl-1h-imidazol-1-ium;sulfate Chemical compound OS([O-])(=O)=O.C[NH+]1C=CN=C1 TVEOIQKGZSIMNG-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polycarbonate composition, which comprises the following raw material formula in percentage by mass: 75-95% of polycarbonate, 5-20% of fibrous filler, 1-3% of macromolecular graft, 0.1-0.5% of acidic ionic liquid and 0.1-0.4% of lubricant. The polycarbonate composition effectively improves the strength, toughness and surface energy of materials by adding the ionic liquid, the polymer graft and the polymer lubricant, and the preparation method is simple and easy to obtain and is easy to realize industrialization.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.
Background
Polycarbonate PC is one of five engineering plastics, has the characteristics of high impact resistance, heat resistance and the like, is widely applied to various aspects of production and life of people, but has some defects, such as low strength, sharp reduction of toughness after glass fiber is added, low surface energy, low bonding strength and the like, so that the application of the polycarbonate in some fields is limited.
The glass reinforced PC material is widely applied to the fields of automobiles, electronic appliances, household appliance materials and the like due to good strength, toughness and thermal performance, however, in the conventional glass fiber reinforced PC material, glass fibers can endow the material with stronger rigidity, but the toughness of the material is greatly damaged; the surface energy of the glass fiber reinforced PC is generally low, and the glass fiber reinforced PC is limited in some application fields needing high bonding strength, and meanwhile, the strength of the obtained material is greatly different from that of a nylon reinforced material and a polyester reinforced material in strength by the currently reported glass fiber reinforcing means.
Disclosure of Invention
In view of the above, the present invention is directed to a polycarbonate composition with high toughness and low surface tension and a method for preparing the same.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a polycarbonate composition comprises the following raw material formula in percentage by mass: 75-95% of polycarbonate, 5-20% of fibrous filler, 1-3% of macromolecular graft, 0.1-0.5% of acidic ionic liquid and 0.1-0.4% of lubricant.
Further, the viscosity average molecular weight of the polycarbonate is 13000-40000.
Preferably, the viscosity average molecular weight of the polycarbonate is 16000-.
Further, the fibrous filler is glass fiber, the glass fiber is one or more of roving fiber, long glass fiber and short glass fiber, and the diameter of the glass fiber is 1um-25 um.
Preferably, the glass fibers have a diameter of 2um to 20um, most preferably 4um to 15 um.
Further, the ionic liquid is one or more of 1-butyl-3-methylimidazole hydrogen sulfate, 1-butyl-3-methylimidazole dihydrogen phosphate, 1-methylimidazole hydrogen sulfate and 1-methylimidazole dihydrogen phosphate.
Further, the polymer graft is one or more of styrene (S) -Maleic Anhydride (MA) or grafted glycidyl ester, ABS grafted maleic anhydride or glycidyl ester, acrylate grafted maleic anhydride or glycidyl ester, and acrylate-methacrylate grafted maleic anhydride or glycidyl ester.
Further, the lubricant is one or more of polyethylene oxide, polyether ester amide, polyether amide imine and sodium polystyrene sulfonate.
A method for preparing the polycarbonate composition of any one of claims 1 to 9, comprising the steps of:
1) adding a certain proportion of ionic liquid into glass fiber, and stirring for 10 minutes in a preheated high-speed mixer at 40-80 ℃;
2) uniformly mixing the pre-dried polycarbonate, the polymer graft and the lubricant at the temperature of 20-50 ℃ for 5-15 min to obtain a uniformly mixed mixture A of the three;
3) feeding the mixture A obtained in the step 2) at a first section of a screw cylinder, feeding the glass fiber pretreated in the step 1) at the 4 th-6 th section of the screw cylinder, and adding the glass fiber into a double-screw vacuum extruder, wherein the vacuum extruder is provided with at least 1 vacuumizing device which can be positioned at the tail end of a material conveying section, the front end of a melting section or a metering section part, and the temperature of the double-screw extruder is set to be 200-300 ℃ to obtain an extrudate B;
4) cooling the extrudate B obtained in the step 3) through a water tank, and then cutting the extrudate B into particles by a granulator to obtain the final polycarbonate composition.
Compared with the prior art, the polycarbonate composition and the preparation method thereof have the following advantages:
(1) according to the polycarbonate composition, the surface of the glass fiber is effectively treated by the ionic liquid, so that the polarity of the surface of the glass fiber is effectively improved, and the surface energy is greatly increased.
(2) According to the polycarbonate composition, due to the increase of the polarity of the surface of the glass fiber, the interaction between the glass fiber and a polycarbonate chain is improved, the glass fiber is more effectively dispersed in a resin matrix, and the retention length and the dispersion degree of the glass fiber are effectively improved.
(3) According to the polycarbonate composition, the high-molecular graft can effectively improve the interfacial force between the glass fiber and the resin, and the dispersion uniformity and the interfacial strength of the glass fiber are further improved.
(4) According to the polycarbonate composition, the addition of the macromolecular lubricant improves the processing performance of the material, and simultaneously avoids the risk of reduction of the surface energy of the material caused by the precipitation of the micromolecular lubricant.
(5) The polycarbonate composition has the advantages of simple and easily obtained preparation method and easy realization of industrialization.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Examples 1 to 6
A polycarbonate composition is shown in a raw material formula in a table 1, and the preparation method comprises the following steps:
1) adding a certain proportion of ionic liquid into glass fiber, and stirring for 10 minutes in a preheated 60 ℃ high-speed mixer;
2) uniformly mixing the pre-dried polycarbonate, the polymer graft and the lubricant at 35 ℃ for 10min to obtain a uniformly mixed mixture A of the three;
3) feeding the mixture A obtained in the step 2) at the first section of the screw cylinder, feeding the glass fiber pretreated in the step 1) at the 4 th-6 th section of the screw cylinder, and adding the glass fiber into a double-screw vacuum extruder, wherein the temperature of the double-screw extruder is controlled to be 250 ℃, so as to obtain an extrudate B;
4) cooling the extrudate B obtained in the step 3) through a water tank, and then cutting the extrudate B into particles by a granulator to obtain the final polycarbonate composition.
Comparative example 1
Weighing the components according to the mass percent, wherein the polycarbonate is 94.8 percent, the glass fiber is 5 percent, and the lubricant A is 0.2 percent.
The preparation method comprises the following steps: 1) stirring the glass fibers in a preheated 60 ℃ high-speed mixer for 10 minutes;
2) uniformly mixing the pre-dried polycarbonate and the lubricant A at the mixing temperature of 35 ℃ for 10min to obtain a uniformly mixed mixture A of the polycarbonate and the lubricant A;
3) same as step 3) in examples 1-6;
4) same as in step 4) in examples 1-6.
Comparative example 2
Weighing the components according to the mass percent, wherein the polycarbonate is 93.3 percent, the glass fiber is 5 percent, the ionic liquid is 0.5 percent, the polymer graft is 1 percent, and the lubricant A is 0.2 percent.
The preparation method comprises the following steps: the same procedure was followed as in examples 1 to 6.
Comparative example 3
Weighing the components according to the mass percent, wherein the polycarbonate is 93.65 percent, the glass fiber is 5 percent, the ionic liquid is 0.15 percent, the polymer graft is 1 percent, and the micromolecular lubricant B is 0.2 percent.
The preparation method comprises the following steps: the same procedure was followed as in examples 1 to 6.
Comparative example 4
Weighing the components according to the mass percent, wherein the mass percent of the components is 87.7 percent of polycarbonate, 10 percent of glass fiber, 2 percent of polymer graft and 0.3 percent of lubricant A.
The preparation method comprises the following steps: 1) stirring the glass fibers in a preheated 60 ℃ high-speed mixer for 10 minutes;
2) uniformly mixing the pre-dried polycarbonate, the polymer graft and the lubricant A at the temperature of 35 ℃ for 10min to obtain a uniformly mixed mixture A of the three;
3) same as step 3) in examples 1-6;
4) same as in step 4) in examples 1-6.
Comparative example 5
Weighing the components according to the mass percent, wherein the mass percent of the components is 87.1 percent of polycarbonate, 10 percent of glass fiber, 0.6 percent of ionic liquid, 2 percent of polymer graft and 0.3 percent of lubricant A.
The preparation method comprises the following steps: the same procedure was followed as in examples 1 to 6.
Comparative example 6
Weighing the components according to the mass percent, wherein the mass percent of the components is 87.5 percent of polycarbonate, 10 percent of glass fiber, 0.5 percent of ionic liquid and 2 percent of polymer graft.
The preparation method comprises the following steps: 1) adding a certain proportion of ionic liquid into glass fiber, and stirring for 10 minutes in a preheated 60 ℃ high-speed mixer;
2) uniformly mixing the pre-dried polycarbonate and the polymer graft, wherein the mixing temperature is 35 ℃, and the mixing time is set to 10min, so as to obtain a uniformly mixed mixture A of the three;
3) same as step 3) in examples 1-6;
4) same as in step 4) in examples 1-6.
Comparative example 7
Weighing the components according to mass percent, wherein the polycarbonate is 79.6 percent, the glass fiber is 20 percent, and the lubricant A is 0.4 percent.
The preparation method comprises the following steps: 1) stirring the glass fibers in a preheated 60 ℃ high-speed mixer for 10 minutes;
2) uniformly mixing the pre-dried polycarbonate and the lubricant A at the mixing temperature of 35 ℃ for 10min to obtain a uniformly mixed mixture A of the polycarbonate and the lubricant A;
3) same as step 3) in examples 1-6;
4) same as in step 4) in examples 1-6.
Comparative example 8
Weighing the components according to the mass percent, wherein the polycarbonate accounts for 75.9 percent, the glass fiber accounts for 20 percent, the ionic liquid accounts for 0.7 percent, the polymer graft accounts for 3 percent, and the lubricant A accounts for 0.4 percent.
The preparation method comprises the following steps: the same procedure was followed as in examples 1 to 6.
Comparative example 9
Weighing the components according to the mass percent, wherein 76.1 percent of polycarbonate, 20 percent of glass fiber, 0.5 percent of ionic liquid, 3 percent of polymer graft and 0.4 percent of micromolecular lubricant B.
The preparation method comprises the following steps: the same procedure was followed as in examples 1 to 6.
Type and manufacturer of raw materials
| Raw materials | Model number | Manufacturer of the product |
| Polycarbonate resin | 1300-22NP | Korean LG |
| Glass fiber | Diameter of 13um | Mountain Taishan mountain |
| Lubricant A | PELESTAT-6500 | Formation of ocean |
| Lubricant B | Gly-plube | Dragon sand |
| Ionic liquids | 1-butyl-3-methylimidazole dihydrogen phosphate | Beijing Hanlong |
| Polymer graft | SZ 23110 | POLYSCOPE IN the Netherlands |
Test example
The pellets obtained in the examples and comparative examples were injection molded into corresponding test specimens and tested, and the test standards or methods for each property were as follows:
method for testing surface tension of polycarbonate composition: the modified material is injected into a square plate with the thickness of 100mm x 2mm, and then the surface tension of the material is tested in a surface contact angle mode, wherein the specific formula is gammasv＝γsl+γlv×cosθe；
Tensile strength test method: ISO 527;
test method of impact strength: ISO180, test conditions 23 ℃.
The test results are shown in tables 1 and 2.
TABLE 1 concrete compounding ratios (in parts by weight) of examples 1 to 6 and test performance results thereof
TABLE 2 concrete compounding ratio (parts by weight) of comparative examples 1 to 9 and test performance results thereof
From a comparison of the examples and comparative examples of table 1, it can be seen that: the invention is selected in the formula of the polycarbonate composition, the glass fiber is treated by the ionic liquid, the rigidity and the toughness of the material and the surface energy of the material are obviously improved, and meanwhile, the addition of the polymer lubricant further improves the surface energy of the material and the stability of the surface energy of the material after high-temperature baking; the addition of small molecule lubricants is a negative effect on the surface energy at high temperatures. At the same time, the addition of the ionic liquid is within a reasonable range, otherwise the performance of the composition is deteriorated and the performance of the composition cannot be maintained within an optimal range (such as example 5 and comparative example 8). In some special application occasions (such as a sound bracket needing curtain cloth bonding, a workpiece needing paint spraying and the like), the surface energy of the applied material can be greatly improved, the adhesive force and the bonding effect of the material are improved, and the applicability and the practicability of the material are improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A polycarbonate composition characterized by: the formula comprises the following raw materials in percentage by mass: 75 to 95 percent of polycarbonate, 5 to 20 percent of fibrous filler, 1 to 3 percent of macromolecular graft, 0.1 to 0.5 percent of acidic ionic liquid, 0.1 to 0.4 percent of lubricant,
the ionic liquid is one or two of 1-butyl-3 methylimidazole dihydrogen phosphate and 1-methylimidazole dihydrogen phosphate,
the polymer graft is one or more of styrene (S) -Maleic Anhydride (MA) or grafted glycidyl ester, ABS grafted maleic anhydride or glycidyl ester, acrylate grafted maleic anhydride or glycidyl ester, and acrylate-methacrylate grafted maleic anhydride or glycidyl ester,
the lubricant is one or more of polyethylene oxide, polyether ester amide, polyether amide imine and sodium polystyrene sulfonate.
2. The polycarbonate composition of claim 1, wherein: the viscosity average molecular weight of the polycarbonate is 13000-40000.
3. The polycarbonate composition of claim 2, wherein: the viscosity average molecular weight of the polycarbonate is 16000-.
4. The polycarbonate composition of claim 1, wherein: the fibrous filler is glass fiber, the glass fiber is one or more of roving fiber, long glass fiber and short glass fiber, and the diameter of the glass fiber is 1-25 um.
5. The polycarbonate composition of claim 4, wherein: the diameter of the glass fiber is 2um-20 um.
6. The polycarbonate composition of claim 5, wherein: the diameter of the glass fiber is 4um-15 um.
7. A method for preparing the polycarbonate composition of any one of claims 1 to 6, comprising the steps of:
1) adding a certain proportion of ionic liquid into glass fiber, and stirring for 10 minutes in a preheated high-speed mixer at 40-80 ℃;
2) uniformly mixing the pre-dried polycarbonate, the polymer graft and the lubricant at the temperature of 20-50 ℃ for 5-15 min to obtain a uniformly mixed mixture A of the three;
3) feeding the mixture A obtained in the step 2) at the first section of the screw cylinder, feeding the glass fiber pretreated in the step 1) at the 4 th to 6 th sections of the screw cylinder, and adding the mixture into a double-screw vacuum extruder, wherein the temperature of the double-screw vacuum extruder is set to be 200-300 ℃, so as to obtain an extrudate B;
4) cooling the extrudate B obtained in the step 3) through a water tank, and then cutting the extrudate B into particles by a granulator to obtain the final polycarbonate composition.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911222647.8A CN111073244B (en) | 2019-12-03 | 2019-12-03 | Polycarbonate composition and preparation method thereof |
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| CN201911222647.8A CN111073244B (en) | 2019-12-03 | 2019-12-03 | Polycarbonate composition and preparation method thereof |
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| CN111073244B true CN111073244B (en) | 2022-04-08 |
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| CN112143198A (en) * | 2020-09-18 | 2020-12-29 | 金发科技股份有限公司 | Polycarbonate alloy composition and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503184A (en) * | 2011-11-10 | 2012-06-20 | 山东建筑大学 | High-stability temperature-resistant glass fiber impregnating agent |
| CN104629288A (en) * | 2013-11-06 | 2015-05-20 | 殷培花 | Glass fiber reinforced anti-ageing polycarbonate (PC) and preparation method thereof |
| CN106164153A (en) * | 2014-04-09 | 2016-11-23 | 提克纳有限责任公司 | Antistatic polymer composite |
| CN108050183A (en) * | 2017-12-12 | 2018-05-18 | 北京启顺京腾科技有限责任公司 | A kind of friction material and its locomotive brake shoe of preparation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503184A (en) * | 2011-11-10 | 2012-06-20 | 山东建筑大学 | High-stability temperature-resistant glass fiber impregnating agent |
| CN104629288A (en) * | 2013-11-06 | 2015-05-20 | 殷培花 | Glass fiber reinforced anti-ageing polycarbonate (PC) and preparation method thereof |
| CN106164153A (en) * | 2014-04-09 | 2016-11-23 | 提克纳有限责任公司 | Antistatic polymer composite |
| CN108050183A (en) * | 2017-12-12 | 2018-05-18 | 北京启顺京腾科技有限责任公司 | A kind of friction material and its locomotive brake shoe of preparation |
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