CN117777696A - Preparation process of hardened PC panel - Google Patents
Preparation process of hardened PC panel Download PDFInfo
- Publication number
- CN117777696A CN117777696A CN202311602833.0A CN202311602833A CN117777696A CN 117777696 A CN117777696 A CN 117777696A CN 202311602833 A CN202311602833 A CN 202311602833A CN 117777696 A CN117777696 A CN 117777696A
- Authority
- CN
- China
- Prior art keywords
- hardened
- panel
- modified
- preparing
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004417 polycarbonate Substances 0.000 claims abstract description 72
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 20
- 238000001746 injection moulding Methods 0.000 claims abstract description 19
- 239000000805 composite resin Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 14
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims abstract description 5
- 230000002745 absorbent Effects 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- JEUVAEBWTRCMTB-UHFFFAOYSA-N boron;tantalum Chemical compound B#[Ta]#B JEUVAEBWTRCMTB-UHFFFAOYSA-N 0.000 claims description 44
- -1 allyl benzoxazine Chemical compound 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 150000005130 benzoxazines Chemical class 0.000 claims description 26
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 10
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 230000032683 aging Effects 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 3
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to a preparation process of a hardened PC panel, which comprises the following steps: (1) Dissolving polycarbonate resin in an organic solvent, adding modified polybenzoxazine, fully stirring and uniformly mixing, and then removing the organic solvent under reduced pressure to obtain a composite resin; (2) Mixing the composite resin, the antioxidant, the ultraviolet absorbent and the lubricant into a double-screw extruder, and obtaining modified polycarbonate master batch through melting, extrusion and granulation; (3) And (3) placing the modified polycarbonate master batch in an injection molding machine, and performing injection molding to obtain the hardened PC panel. Compared with the PC panel in the prior art, the hardened PC panel prepared by the method does not need to be coated with a coating on the surface, and has the advantages of high strength, high hardness, aging resistance and corrosion resistance.
Description
Technical Field
The invention relates to the field of PC panels, in particular to a preparation process of a hardened PC panel.
Background
With the improvement of living standard, the appearance requirements of household appliances are higher and higher, the highlight panels on various product devices are more and more valued by consumers, and naturally, the development of manufacturers is driven to develop the highlight panels more suitable for the consumption requirements of people so as to facilitate the improvement of the added value of the products, and meanwhile, the highlight panels of the equipment made of PC materials are widely developed and applied with the light advantages. The current global PC board use is developed in the high-utility and specialized directions, in view of the fact that the production capacity and market demand of PC boards in China are rapidly developed, particularly the establishment of a domestic multi-set planning device is combined with the rapid development and pulling of the automobile industry, the PC industry in China enters a new development stage in the coming years, and the PC boards are spread throughout life and production, wherein the most widely applied fields are as follows: building, health care, electronics and electricity, automobiles, and sports equipment.
The PC board is a plastic board made of polycarbonate and has the characteristics of high strength, high transparency, heat resistance, impact resistance, ultraviolet resistance and the like. The PC board has the main component of polycarbonate resin, and the chemical structure of the PC board contains ester groups and benzene rings, so the PC board has higher stability and durability. The most common production process at present of PC boards is an extrusion molding process, and the manufacturing process mainly comprises the steps of raw material proportioning, mixing, extrusion, cooling, cutting and the like. Firstly, mixing polycarbonate resin with other additives according to a certain proportion, extruding the mixture into a plate shape through an extruder, and then processing the plate shape into the required size and shape through processes such as cooling and cutting.
However, the existing polycarbonate resin has low surface hardness and poor impact resistance, and is easy to scratch; and also has the disadvantage of being not corrosion resistant and being prone to ageing, which results in a great limitation in its use as a protective panel material. In order to solve the problems, a high-hardness corrosion-resistant coating is generally required to be coated on the surface of a polycarbonate product to improve the impact resistance and corrosion resistance of the polycarbonate product, however, the method has complex procedures and troublesome operation, and the polycarbonate material is sensitive to chemical solvents, so that the problems of poor processing, cracks and the like easily occur in the post-processing process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation process of a hardened PC panel.
The aim of the invention is realized by adopting the following technical scheme:
a process for preparing a hardened PC panel comprising the steps of:
(1) Dissolving polycarbonate resin in an organic solvent, adding modified polybenzoxazine, fully stirring and uniformly mixing, and then removing the organic solvent under reduced pressure to obtain a composite resin;
(2) Mixing the composite resin, the antioxidant, the ultraviolet absorbent and the lubricant into a double-screw extruder, and obtaining modified polycarbonate master batch through melting, extrusion and granulation;
(3) And (3) placing the modified polycarbonate master batch in an injection molding machine, and performing injection molding to obtain the hardened PC panel.
Preferably, in the step (1), the polycarbonate resin is bisphenol A type polycarbonate, trade name is Mitsubishi PC7025, japan, and Melt Index (MI) is 20g/10min at 300℃under 1.2 kg.
Preferably, in the step (1), the mass-to-volume ratio of the polycarbonate resin, the modified benzoxazine and the organic solvent is 100g: (10-20) g: (100-200) mL.
Preferably, in the step (1), the organic solvent is one of tetrahydrofuran, chloroform and trichloroethane. More preferably tetrahydrofuran.
Preferably, in the step (2), the antioxidant is a hindered phenol antioxidant, including one of an antioxidant-1010, an antioxidant-1076 and an antioxidant-3114.
Preferably, in the step (2), the ultraviolet absorber is a triazine ultraviolet absorber, including one of UV-1577, UV-627 and UV-1164.
Preferably, in step (2), the lubricant is sodium dodecyl sulfate or sodium hexadecyl sulfonate.
Preferably, in the step (2), the mass ratio of the composite resin, the antioxidant, the ultraviolet absorber and the lubricant is 100:0.5-1:0.6-1.2:1-2.
Preferably, in the step (2), the screw speed of the twin-screw extruder is 250-350r/min, the length-diameter ratio of the twin-screw is 35-45:1, and the interval temperature is 260-330 ℃.
Preferably, in the step (3), the temperature of injection molding is 320-350 ℃, the pressure of injection molding is 80-120MPa, and the temperature of demoulding after cooling is 50-60 ℃.
Preferably, the preparation method of the modified polybenzoxazine comprises the following steps:
s1, stirring diallyl bisphenol A, aniline and paraformaldehyde to react under the condition of protective gas, and washing and drying to prepare allyl benzoxazine;
s2, carrying out hydroxylation treatment on the tantalum diboride micropowder by hydrogen peroxide to obtain hydroxylated tantalum diboride; then treating with aqueous solution of silane coupling agent KH-580 to prepare the thiolated tantalum diboride;
s3, dispersing allyl benzoxazine and thiolated tantalum diboride in a solvent, and stirring for reaction under ultraviolet irradiation to obtain modified benzoxazine;
s4, carrying out step-by-step heating treatment on the modified benzoxazine in a vacuum box to obtain the modified benzoxazine.
Preferably, in step S1, the mass ratio of diallyl bisphenol a, aniline and paraformaldehyde is 0.93-1.86:1.54-3.08:0.6-2.
Preferably, in step S1, the reaction conditions are: stirring for 0.4-1h in ice-water bath, heating to 75-80 ℃ for reaction for 1-2h, and heating to 110-130 ℃ for reaction for 2-4h.
Preferably, in the step S1, the liquid after the reaction is poured into ether with the same volume, then 3-5 times of washing is carried out by using 3mol/L sodium hydroxide solution, the addition amount of the sodium hydroxide solution is 2 times of the volume of the reaction liquid each time, and then the washing is carried out to be neutral by using distilled water; drying is performed under vacuum at 80-100deg.C.
Preferably, in the step S2, the granularity of the tantalum diboride micro powder is 10+/-1 mu m, and the purity is higher than 99 percent; the mass concentration of the hydrogen peroxide is 20% -30%.
Preferably, in the step S2, when the hydroxylated tantalum diboride is prepared, the mass volume ratio of the tantalum diboride micro powder to the hydrogen peroxide is 1g (10-20) mL; the reaction temperature is 45-55 ℃ and the reaction time is 4-6h.
Preferably, in the step S2, when preparing the thiolated tantalum diboride, the mass volume ratio of the hydroxylated tantalum diboride, the silane coupling agent KH-580 and the deionized water is 1g (0.1-0.4 g) (10-20) mL; the reaction temperature is 60-80 ℃ and the reaction time is 6-10h.
Preferably, in the step S3, the solvent is acetone, and the mass volume ratio of the tantalum mercapto diboride, the allylbenzoxazine and the acetone is 1g (3.2-6.4 g) (30-50 mL).
Preferably, in the step S3, the reaction temperature is room temperature, the reaction time is 1-2h, and the ultraviolet wavelength is 365nm; the photoinitiator 651 is added in the reaction process, and the addition amount is 1-5% of the mass of the allyl benzoxazine.
Preferably, in step S4, the step-wise temperature increase includes: firstly, heating to 150 ℃ and preserving heat for 1h; then the temperature is raised to 200 ℃, 220 ℃ and 240 ℃ in turn, and heat preservation is needed for 2 hours after each temperature rise.
The beneficial effects of the invention are as follows:
1. the invention prepares a novel PC panel by improving the material of the PC panel in the prior art, and the panel material not only has higher hardness and excellent impact resistance, but also has great improvement on the aspects of strength, aging resistance and corrosion resistance. Compared with the PC panel in the prior art, the hardened PC panel prepared by the method does not need to be coated with a coating on the surface, and has the advantages of high strength, high hardness, aging resistance and corrosion resistance.
2. Compared with the conventional direct melt mixing method, the PC panel material prepared by the invention adopts a mode of dispersing and mixing a solution and then decompressing and removing a solvent, wherein the mode can ensure that the modified polybenzoxazine is dispersed in the polycarbonate resin more uniformly.
3. The modified polybenzoxazine prepared by the method comprises the steps of preparing allyl benzoxazine through bisphenol A containing olefin, then carrying out Click chemistry (Click chemistry) crosslinking reaction on tantalum diboride micropowder containing sulfhydryl groups, so as to prepare modified benzoxazine, and then treating the modified benzoxazine in a stepwise heating mode to prepare the modified polybenzoxazine. Compared with the conventional polybenzoxazine, the modified polybenzoxazine prepared by the invention contains a large amount of tantalum diboride micropowder and thioether bonds in the structure. Tantalum diboride has high hardness and excellent corrosion resistance and oxidation resistance; the thioether bond is obtained by crosslinking sulfhydryl and double bond, and has excellent crosslinking property, so that tantalum diboride and polybenzoxazine have better compatibility, and also have better corrosion resistance and ultraviolet aging resistance. Therefore, when the modified polybenzoxazine is compounded with the polycarbonate, the strength, the hardness, the aging resistance and the corrosion resistance of the polycarbonate are enhanced to a great extent.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the mention of one or more method steps of the present invention does not exclude the presence of other method steps before and after the combination step or that other method steps may be interposed between these explicitly mentioned steps; it should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In order to better understand the above technical solution, exemplary embodiments of the present invention are described in more detail below. While exemplary embodiments of the invention are shown, it should be understood that the invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention is further described with reference to the following examples.
Example 1
A process for preparing a hardened PC panel comprising the steps of:
(1) Dissolving bisphenol A polycarbonate (Mitsubishi PC7025 of Japan) in tetrahydrofuran, adding modified polybenzoxazine, stirring at room temperature until the mixture is uniform, and then heating and decompressing to remove the tetrahydrofuran to obtain composite resin; wherein the mass volume ratio of the polycarbonate resin to the modified benzoxazine to the tetrahydrofuran is 100g:15g:150mL.
(2) Mixing the composite resin, the antioxidant-1010, the UV-1577 and the sodium dodecyl sulfate into a double-screw extruder, wherein the mass ratio of the composite resin to the antioxidant-1010 to the UV-1577 to the sodium dodecyl sulfate is 100:0.75:0.9:1.5; obtaining modified polycarbonate master batch through melting, extruding and granulating; wherein, the screw rotating speed of the double screw extruder is 300r/min, the length-diameter ratio of the double screw is 40:1, and the interval temperature is 260-330 ℃.
(3) Placing the modified polycarbonate master batch into an injection molding machine, wherein the injection molding temperature is 320-350 ℃, the injection molding pressure is 100MPa, cooling and demolding at 55 ℃ to obtain the hardened PC panel.
The preparation method of the modified polybenzoxazine comprises the following steps:
s1, preparing allyl benzoxazine:
weighing 2,2' -diallyl bisphenol A and aniline, mixing in a flask, introducing nitrogen as a shielding gas, fully and uniformly stirring in an ice water bath, and gradually adding paraformaldehyde ((CH) 2 O) n ) Wherein the mass ratio of the 2,2' -diallyl bisphenol A to the aniline to the paraformaldehyde is 1.4:2.31:1.2, after the addition, removing the ice water bath, stirring for 0.6h, heating to 80 ℃, carrying out heat preservation reaction for 1.5h, heating to 120 ℃ again, carrying out heat preservation reaction for 3h, naturally cooling to room temperature after the reaction is finished, pouring the reaction solution into ether with the same volume, washing 5 times by using alkali liquor, wherein the addition amount of the alkali liquor (3 mol/L sodium hydroxide solution) is 2 times of the volume of the reaction solution each time, separating and collecting an organic phase after the washing is finished, washing to be neutral by using distilled water, and then carrying out vacuum drying at 90 ℃ to obtain allyl benzoxazine;
s2, preparing the tantalum mercapto diboride:
weighing tantalum diboride micropowder with the mass-volume ratio of 1g to 15mL in an aqueous solution (mass concentration of 25%) of hydrogen peroxide, stirring for 5 hours at 50 ℃, centrifuging to collect precipitate after stirring, washing with distilled water for three times, and vacuum drying at 90 ℃ to obtain hydroxylated tantalum diboride;
uniformly dispersing hydroxylated tantalum diboride in deionized water by ultrasonic, then adding a silane coupling agent KH-580 (gamma-mercaptopropyl triethoxysilane), wherein the mass volume ratio of the hydroxylated tantalum diboride to the silane coupling agent KH-580 to the deionized water is 1g:0.3g:15mL, stirring for 8 hours at 70 ℃, centrifugally collecting precipitate, washing with distilled water for three times, and vacuum drying at 90 ℃ to obtain the thiolated tantalum diboride;
s3, preparing modified benzoxazine:
dispersing tantalum mercapto diboride in acetone under the protection of nitrogen, adding allyl benzoxazine, wherein the mass volume ratio of the tantalum mercapto diboride to the allyl benzoxazine to the acetone is 1g to 4.8g to 40mL, stirring and dispersing uniformly at room temperature, adding a photoinitiator 651 (DMPA), wherein the addition amount is 3% of the mass of the allyl benzoxazine, stirring the reaction solution under the irradiation of ultraviolet light for 1.5h, and removing the solvent acetone by rotary evaporation after the reaction is finished to obtain modified benzoxazine;
s4, preparing modified polybenzoxazine:
placing the modified benzoxazine in a vacuum box, firstly heating to 150 ℃ and preserving heat for 1h, then heating to 200 ℃, 220 ℃ and 240 ℃ in sequence, preserving heat for 2h after each heating, cooling to room temperature, crushing and screening by a 300-mesh sieve to obtain the modified benzoxazine.
Example 2
A process for preparing a hardened PC panel comprising the steps of:
(1) Bisphenol A polycarbonate (Mitsubishi PC7025, japan) is dissolved in chloroform, modified polybenzoxazine is added (the preparation method is the same as that of example 1), stirred at room temperature until the mixture is uniform, and tetrahydrofuran is removed by heating and decompressing to obtain composite resin; wherein the mass volume ratio of the polycarbonate resin to the modified benzoxazine to the trichloromethane is 100g:10g:100mL.
(2) Mixing the composite resin, an antioxidant-1076, UV-627 and sodium hexadecyl sulfonate into a double-screw extruder, wherein the mass ratio of the composite resin to the antioxidant-1076 to the UV-627 to the sodium hexadecyl sulfonate is 100:0.5:0.6:1; obtaining modified polycarbonate master batch through melting, extruding and granulating; wherein, the screw rotating speed of the double screw extruder is 250r/min, the length-diameter ratio of the double screw is 35:1, and the interval temperature is 260-330 ℃.
(3) Placing the modified polycarbonate master batch into an injection molding machine, wherein the injection molding temperature is 320-350 ℃, the injection molding pressure is 80MPa, cooling and demolding at 50 ℃, and demolding to obtain the hardened PC panel.
Example 3
A process for preparing a hardened PC panel comprising the steps of:
(1) Bisphenol A polycarbonate (Mitsubishi PC7025, japan) is dissolved in trichloroethane, modified polybenzoxazine is added (the preparation method is the same as that of example 1), stirred at room temperature until the mixture is uniform, and tetrahydrofuran is removed by heating and decompressing to obtain composite resin; wherein the mass volume ratio of the polycarbonate resin to the modified benzoxazine to the trichloroethane is 100g:10g:200mL.
(2) Mixing the composite resin, an antioxidant-3114, UV-1164 and sodium dodecyl sulfate into a double-screw extruder, wherein the mass ratio of the composite resin to the antioxidant-3114 to the UV-1164 to the sodium dodecyl sulfate is 100:1:1.2:2; obtaining modified polycarbonate master batch through melting, extruding and granulating; wherein, the screw rotating speed of the double screw extruder is 350r/min, the length-diameter ratio of the double screw is 45:1, and the interval temperature is 260-330 ℃.
(3) Placing the modified polycarbonate master batch into an injection molding machine, wherein the injection molding temperature is 320-350 ℃, the injection molding pressure is 120MPa, cooling and demolding at 60 ℃, and demolding to obtain the hardened PC panel.
Example 4
A process for preparing a hardened PC panel differs from example 1 in that the method for preparing the modified polybenzoxazine is different.
The preparation method of the modified polybenzoxazine comprises the following steps:
s1, preparing allyl benzoxazine:
weighing diallyl bisphenol A and aniline, mixing in a flask, introducing nitrogen as a shielding gas, fully and uniformly stirring in an ice water bath, and gradually adding paraformaldehyde, wherein the mass ratio of the diallyl bisphenol A to the aniline to the paraformaldehyde is 0.93:1.54:0.6, after the addition, removing the ice water bath, stirring for 0.4h, heating to 75 ℃, carrying out heat preservation reaction for 1h, heating to 110 ℃ again, carrying out heat preservation reaction for 2h, naturally cooling to room temperature after the reaction is finished, pouring the reaction solution into ether with the same volume, washing 3-5 times by using alkali liquor, wherein the addition amount of the alkali liquor (3 mol/L sodium hydroxide solution) is 2 times of the volume of the reaction solution each time, separating and collecting an organic phase after the washing is finished, washing to be neutral by using distilled water, and then carrying out vacuum drying at 80 ℃ to obtain allyl benzoxazine;
s2, preparing the tantalum mercapto diboride:
weighing tantalum diboride micropowder with the mass/volume ratio of 1g to 10mL in an aqueous solution (the mass concentration is 20%) of hydrogen peroxide, stirring for 4 hours at 45 ℃, centrifuging to collect precipitate after stirring, washing with distilled water for three times, and vacuum drying at 80 ℃ to obtain hydroxylated tantalum diboride;
uniformly dispersing hydroxylated tantalum diboride in deionized water by ultrasonic, then adding a silane coupling agent KH-580 (gamma-mercaptopropyl triethoxysilane), wherein the mass volume ratio of the hydroxylated tantalum diboride to the silane coupling agent KH-580 to the deionized water is 1g:0.1g:10mL, stirring for 6 hours at 60 ℃, centrifugally collecting precipitate, washing with distilled water for three times, and vacuum drying at 80 ℃ to obtain the thiolated tantalum diboride;
s3, preparing modified benzoxazine:
dispersing tantalum mercapto diboride in acetone under the protection of nitrogen, adding allyl benzoxazine, wherein the mass volume ratio of the tantalum mercapto diboride to the allyl benzoxazine to the acetone is 1g to 3.2g to 30mL, stirring and dispersing uniformly at room temperature, adding a photoinitiator 651 (DMPA) with the addition amount of 1% of the mass of the allyl benzoxazine, stirring the reaction solution under the irradiation of ultraviolet light for 1-2h, and removing the solvent acetone by rotary evaporation after the reaction is finished to obtain modified benzoxazine;
s4, preparing modified polybenzoxazine:
placing the modified benzoxazine in a vacuum box, firstly heating to 150 ℃ and preserving heat for 1h, then heating to 200 ℃, 220 ℃ and 240 ℃ in sequence, preserving heat for 2h after each heating, cooling to room temperature, crushing and screening by a 300-mesh sieve to obtain the modified benzoxazine.
Example 5
A process for preparing a hardened PC panel differs from example 1 in that the method for preparing the modified polybenzoxazine is different.
The preparation method of the modified polybenzoxazine comprises the following steps:
s1, preparing allyl benzoxazine:
weighing diallyl bisphenol A and aniline, mixing in a flask, introducing nitrogen as a shielding gas, fully and uniformly stirring in an ice water bath, and gradually adding paraformaldehyde, wherein the mass ratio of the diallyl bisphenol A to the aniline to the paraformaldehyde is 1.86:3.08:2, removing the ice water bath after the addition is finished, stirring for 1h, heating to 80 ℃, carrying out heat preservation reaction for 2h, heating to 130 ℃ again, carrying out heat preservation reaction for 4h, naturally cooling to room temperature after the reaction is finished, pouring the reaction liquid into ether with equal volume, washing 3-5 times by using alkali liquor, wherein the addition amount of the alkali liquor (3 mol/L sodium hydroxide solution) is 2 times of the volume of the reaction liquid each time, separating and collecting an organic phase after the washing is finished, washing to be neutral by using distilled water, and then carrying out vacuum drying at 100 ℃ to obtain allyl benzoxazine;
s2, preparing the tantalum mercapto diboride:
weighing tantalum diboride micropowder with the mass-volume ratio of 1g to 20mL in aqueous solution (mass concentration of 30%) of hydrogen peroxide, stirring for 6 hours at 55 ℃, centrifuging to collect precipitate after stirring, washing with distilled water for three times, and vacuum drying at 100 ℃ to obtain hydroxylated tantalum diboride;
uniformly dispersing hydroxylated tantalum diboride in deionized water by ultrasonic, then adding a silane coupling agent KH-580 (gamma-mercaptopropyl triethoxysilane), wherein the mass volume ratio of the hydroxylated tantalum diboride to the silane coupling agent KH-580 to the deionized water is 1g to 0.4g to 20mL, stirring for 10 hours at 80 ℃, centrifugally collecting precipitate, washing with distilled water for three times, and vacuum drying at 100 ℃ to obtain the thiolated tantalum diboride;
s3, preparing modified benzoxazine:
dispersing tantalum mercapto diboride in acetone under the protection of nitrogen, adding allyl benzoxazine, wherein the mass volume ratio of the tantalum mercapto diboride to the allyl benzoxazine to the acetone is 1g to 6.4g to 50mL, stirring and dispersing uniformly at room temperature, adding a photoinitiator 651 (DMPA) with the addition amount of 5% of the mass of the allyl benzoxazine, stirring the reaction solution under the irradiation of ultraviolet light for 2 hours, and removing the solvent acetone by rotary evaporation after the reaction is finished to obtain modified benzoxazine;
s4, preparing modified polybenzoxazine:
placing the modified benzoxazine in a vacuum box, firstly heating to 150 ℃ and preserving heat for 1h, then heating to 200 ℃, 220 ℃ and 240 ℃ in sequence, preserving heat for 2h after each heating, cooling to room temperature, crushing and screening by a 300-mesh sieve to obtain the modified benzoxazine.
Comparative example 1
The process for preparing a PC panel differs from example 1 in that the preparation method of the modified polybenzoxazine is different.
In this comparative example, the modified polybenzoxazine was replaced with a conventional polybenzoxazine, and the preparation method includes:
s1, preparing allyl benzoxazine (the preparation mode is the same as that of the example 1);
s2, preparing polybenzoxazine:
and (3) placing the allyl benzoxazine in a vacuum box, heating to 150 ℃ and preserving heat for 1h, then heating to 200 ℃, 220 ℃ and 240 ℃ in sequence, preserving heat for 2h after each heating, cooling to room temperature, crushing and sieving with a 300-mesh sieve to obtain the modified benzoxazine.
Comparative example 2
The process for preparing a PC panel differs from example 1 in that the preparation method of the modified polybenzoxazine is different.
The modified polybenzoxazine was replaced with a conventional blend of polybenzoxazine and tantalum diboride in this comparative example, which was prepared by the following steps:
s1, preparing allyl benzoxazine (the preparation mode is the same as that of the example 1);
s2, preparing hydroxylated tantalum diboride (the preparation mode is the same as that of the example 1);
s3, mixing allyl benzoxazine and hydroxylated tantalum diboride:
weighing 10+/-1 mu m of hydroxylated tantalum diboride to be dispersed in acetone, adding allyl benzoxazine, stirring and dispersing uniformly at room temperature, then removing solvent acetone by rotary evaporation, placing in a vacuum box, firstly heating to 150 ℃ for 1h, then heating to 200 ℃, 220 ℃ and 240 ℃ in sequence, and cooling to obtain a conventional blend of the polybenzoxazine and the tantalum diboride; wherein the mass-volume ratio of the hydroxylated tantalum diboride to the allylbenzoxazine to the acetone is 1g to 3.2g to 30mL.
And (3) result detection:
corresponding performance tests were performed on the performance of the PC panels obtained in example 1 and comparative examples 1 to 2, and included: tensile strength (GB/T1040 2-2006, 23 ℃), flexural strength (GB/T9341-2008), notched impact strength (GB/T1843-2008), heat distortion temperature (GB/T1634.2-2019), surface hardness (GB/T6739-2006). Since the impact strength of the PC material is more obviously affected by the outside, the aging resistance and corrosion resistance are judged by the change maintenance rate of the impact strength, the heat aging (100 ℃,168 hours), pickling (10 wt% sulfuric acid soaking for 6 hours), pickling (10 wt% sodium hydroxide solution soaking for 6 hours) are carried out, and the final detection result is shown in the form of a table, and the following table 1:
TABLE 1 Performance test results for different PC Panel materials
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Tensile Strength (MPa) | 67.8 | 63.4 | 64.2 |
| Flexural Strength (MPa) | 85.3 | 80.7 | 81.9 |
| Notched Izod impact Strength (kJ/m) 2 ) | 43.7 | 39.8 | 40.6 |
| Heat distortion temperature (DEG C) | 135 | 130 | 132 |
| Surface hardness | 3H | 2H | 3H |
| Impact Strength after agingMaintenance rate (%) | 95.7 | 91.0 | 91.3 |
| Impact strength maintenance after pickling (%) | 92.1 | 87.4 | 87.8 |
| Impact strength maintenance after alkali impregnation (%) | 94.3 | 90.5 | 90.4 |
As can be seen from table 1 above, the PC panel material of example 1 exhibits excellent overall properties, not only maintains good hardness and high temperature resistance, but also has very good aging resistance and acid and alkali resistance. Comparative example 1 shows weaker strength and hardness than comparative example 2, indicating that the addition of tantalum diboride hydroxide provides some improvement in strength, but does not provide a significant improvement in aging and corrosion resistance; while comparative example 2 has weaker overall performance surface than example 1, indicating that the modified polybenzoxazine of example 1 performs better in PC materials than the conventional blend of polybenzoxazine and tantalum diboride of comparative example 2. In summary, compared with the prior art, the PC panel prepared in the embodiment 1 of the invention has higher hardness, excellent impact resistance and higher improvement in strength, aging resistance and corrosion resistance.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms should not be understood as necessarily being directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Further, one skilled in the art can engage and combine the different embodiments or examples described in this specification.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A process for preparing a hardened PC panel comprising the steps of:
(1) Dissolving polycarbonate resin in an organic solvent, adding modified polybenzoxazine, fully stirring and uniformly mixing, and then removing the organic solvent under reduced pressure to obtain a composite resin;
(2) Mixing the composite resin, the antioxidant, the ultraviolet absorbent and the lubricant into a double-screw extruder, and obtaining modified polycarbonate master batch through melting, extrusion and granulation;
(3) Placing the modified polycarbonate master batch into an injection molding machine, and performing injection molding to obtain a hardened PC panel;
wherein in the step (1), the mass-volume ratio of the polycarbonate resin, the modified benzoxazine and the organic solvent is 100g: (10-20) g: (100-200) mL;
in the step (2), the mass ratio of the composite resin to the antioxidant to the ultraviolet absorber to the lubricant is 100:0.5-1:0.6-1.2:1-2.
2. The process for producing a hardened PC panel according to claim 1, wherein in step (1), the polycarbonate resin is bisphenol a type polycarbonate, and the Melt Index (MI) is 20g/10min at 300 ℃ and 1.2 kg.
3. The process for preparing a hardened PC panel according to claim 1, wherein in step (2), the antioxidant is a hindered phenol antioxidant, including one of antioxidant-1010, antioxidant-1076, and antioxidant-3114; the ultraviolet absorbent is triazine ultraviolet absorbent, including one of UV-1577, UV-627 and UV-1164; the lubricant is sodium dodecyl sulfate or sodium hexadecyl sulfonate.
4. The process for producing a hardened PC panel as claimed in claim 1, wherein in step (2), the twin screw extruder has a screw speed of 250-350r/min, a twin screw aspect ratio of 35-45:1, and a block temperature of 260-330 ℃.
5. The process for producing a hardened PC panel according to claim 1, wherein in step (3), the injection molding temperature is 320-350 ℃, the injection molding pressure is 80-120MPa, and the temperature for demolding after cooling is 50-60 ℃.
6. The process for preparing a hardened PC panel according to claim 1, wherein the modified polybenzoxazine preparation method comprises:
s1, stirring diallyl bisphenol A, aniline and paraformaldehyde to react under the condition of protective gas, and washing and drying to prepare allyl benzoxazine;
s2, carrying out hydroxylation treatment on the tantalum diboride micropowder by hydrogen peroxide to obtain hydroxylated tantalum diboride; then treating with aqueous solution of silane coupling agent KH-580 to prepare the thiolated tantalum diboride;
s3, dispersing allyl benzoxazine and thiolated tantalum diboride in a solvent, and stirring for reaction under ultraviolet irradiation to obtain modified benzoxazine;
s4, carrying out step-by-step heating treatment on the modified benzoxazine in a vacuum box to obtain the modified benzoxazine.
7. The process for preparing a hardened PC panel as claimed in claim 6, wherein in step S1, the reaction conditions are: stirring for 0.4-1h in an ice-water bath, heating to 75-80 ℃ for reaction for 1-2h, and heating to 110-130 ℃ for reaction for 2-4h; the mass ratio of diallyl bisphenol A to aniline to paraformaldehyde is 0.93-1.86:1.54-3.08:0.6-2.
8. The process for preparing a hardened PC panel according to claim 6, wherein in step S2, the particle size of the tantalum diboride micro powder is 10±1 μm, the purity is higher than 99%; the mass concentration of the hydrogen peroxide is 20% -30%; when the tantalum diboride hydroxylate is prepared, the mass volume ratio of the tantalum diboride micro powder to the hydrogen peroxide is 1g (10-20) mL, the reaction temperature is 45-55 ℃ and the reaction time is 4-6h; when preparing the tantalum mercapto diboride, the mass volume ratio of the tantalum hydroxy diboride, the silane coupling agent KH-580 and the deionized water is 1g (0.1-0.4 g) (10-20) mL; the reaction temperature is 60-80 ℃ and the reaction time is 6-10h.
9. The process for preparing a cured PC panel according to claim 6, wherein in the step S3, the reaction temperature is room temperature, the reaction time is 1-2 hours, and the ultraviolet wavelength is 365nm; the photoinitiator 651 is added in the reaction process, and the addition amount is 1% -5% of the mass of the allyl benzoxazine; the solvent is acetone, and the mass volume ratio of the thiolated tantalum diboride, the allylbenzoxazine and the solvent is 1g (3.2-6.4 g) (30-50) mL.
10. The process for preparing a hardened PC panel as claimed in claim 6, wherein in step S4, the step-wise heating comprises: firstly, heating to 150 ℃ and preserving heat for 1h; then the temperature is raised to 200 ℃, 220 ℃ and 240 ℃ in turn, and heat preservation is needed for 2 hours after each temperature rise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311602833.0A CN117777696A (en) | 2023-11-28 | 2023-11-28 | Preparation process of hardened PC panel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311602833.0A CN117777696A (en) | 2023-11-28 | 2023-11-28 | Preparation process of hardened PC panel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117777696A true CN117777696A (en) | 2024-03-29 |
Family
ID=90388227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311602833.0A Pending CN117777696A (en) | 2023-11-28 | 2023-11-28 | Preparation process of hardened PC panel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777696A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709114A (en) * | 2014-01-13 | 2014-04-09 | 上海交通大学 | Benzoxazine compound containing double bonds as well as preparation method and application thereof |
| CN106995603A (en) * | 2017-05-02 | 2017-08-01 | 湖南峰业光电有限公司 | A kind of transparent flame-retarding glass fiber reinforcement PC materials and preparation method thereof and the application in liquid crystal material preparation |
| JP2020158705A (en) * | 2019-03-27 | 2020-10-01 | 味の素株式会社 | Resin composition, cured product of resin composition, resin sheet, printed wiring board and semiconductor device |
| CN116936174A (en) * | 2023-09-15 | 2023-10-24 | 南方珠江科技有限公司 | Low-voltage cable for smart power grid and preparation method thereof |
-
2023
- 2023-11-28 CN CN202311602833.0A patent/CN117777696A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709114A (en) * | 2014-01-13 | 2014-04-09 | 上海交通大学 | Benzoxazine compound containing double bonds as well as preparation method and application thereof |
| CN106995603A (en) * | 2017-05-02 | 2017-08-01 | 湖南峰业光电有限公司 | A kind of transparent flame-retarding glass fiber reinforcement PC materials and preparation method thereof and the application in liquid crystal material preparation |
| JP2020158705A (en) * | 2019-03-27 | 2020-10-01 | 味の素株式会社 | Resin composition, cured product of resin composition, resin sheet, printed wiring board and semiconductor device |
| CN116936174A (en) * | 2023-09-15 | 2023-10-24 | 南方珠江科技有限公司 | Low-voltage cable for smart power grid and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101418100B (en) | Halogen-free flame retardant long glass fibre reinforcement polypropylene composite material and preparation method thereof | |
| CN103467904B (en) | Toughness reinforcing heat-proof ABS composition and method of making the same | |
| CN106188842A (en) | The preparation method of polypropylene/bamboo granule/ultra micro bamboo charcoal composite material | |
| CN111978641A (en) | High-modulus, high-fluidity and high-impact-resistance glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN109438931A (en) | A kind of method that coir fibre-manioc waste filling prepares biodegradable composite | |
| CN117777696A (en) | Preparation process of hardened PC panel | |
| CN105385031A (en) | High impact resistant high pressure water pump shell material based on long glass fiber modified polypropylene and preparation method thereof | |
| CN105086162A (en) | Fibrilia-reinforced polypropylene engineering composite as well as preparation method and application of fibrilia-reinforced polypropylene engineering composite | |
| CN112552595A (en) | High-strength high-toughness glass fiber reinforced polypropylene material and preparation method thereof | |
| CN111499971A (en) | Preparation method of low-floating-fiber GFRPP composite material | |
| CN116694056A (en) | High heat-resistant mineral reinforced halogen-free flame-retardant PC/ABS alloy and preparation method thereof | |
| CN113429736B (en) | Modified polyformaldehyde engineering plastic and preparation method thereof | |
| CN104974423A (en) | Diatomite/polypropylene composite material and preparation method thereof | |
| CN106700264A (en) | Low-after-contraction polypropylene composite and preparation method thereof | |
| CN106479035B (en) | Flame-retardant impact-resistant polypropylene composite material and preparation method thereof | |
| CN107349918A (en) | A kind of preparation method of diatomite aids,filter | |
| CN114410035A (en) | Anti-aging flame-retardant pipeline material and preparation method thereof | |
| CN114891270B (en) | Modified basalt fiber polysulfone composite material with good weather resistance and preparation method thereof | |
| CN111363304A (en) | Ammonia-free glass fiber composite reinforced material for automobile motor parts and coil framework | |
| CN114854130B (en) | High-impact-resistance halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN116769298B (en) | High-strength modified polyphenyl ether engineering material for vehicles and preparation method thereof | |
| CN115028924B (en) | Modified insulated cable and preparation method thereof | |
| CN115926418B (en) | Chemical-resistant and high-temperature-resistant basalt fiber composite material | |
| CN109836729A (en) | A kind of formula of modified plastics | |
| CN109082065A (en) | A kind of white anti-aging ABS modified material of porcelain and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |