CN117402429A - Processing method of high-toughness MPP power tube - Google Patents
Processing method of high-toughness MPP power tube Download PDFInfo
- Publication number
- CN117402429A CN117402429A CN202311535509.1A CN202311535509A CN117402429A CN 117402429 A CN117402429 A CN 117402429A CN 202311535509 A CN202311535509 A CN 202311535509A CN 117402429 A CN117402429 A CN 117402429A
- Authority
- CN
- China
- Prior art keywords
- temperature
- neck flask
- glass fiber
- fiber powder
- power tube
- 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.)
- Granted
Links
- 238000003672 processing method Methods 0.000 title claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 87
- 239000002131 composite material Substances 0.000 claims abstract description 51
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 polypropylene Polymers 0.000 claims abstract description 34
- 239000004743 Polypropylene Substances 0.000 claims abstract description 27
- 229920001155 polypropylene Polymers 0.000 claims abstract description 27
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 17
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 14
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000012065 filter cake Substances 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000967 suction filtration Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229920002873 Polyethylenimine Polymers 0.000 claims description 20
- 239000008213 purified water Substances 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 15
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- MUUOUUYKIVSIAR-UHFFFAOYSA-N 2-but-3-enyloxirane Chemical compound C=CCCC1CO1 MUUOUUYKIVSIAR-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- JRLLJITWABKEKE-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-4-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=C(C(C)(C)N=C=O)C=C1 JRLLJITWABKEKE-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 239000012968 metallocene catalyst Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- RSJWKIDVVZWYTD-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C(C)(C)N=C=O RSJWKIDVVZWYTD-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims 5
- 239000003795 chemical substances by application Substances 0.000 claims 5
- 239000003063 flame retardant Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000009044 synergistic interaction Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000004355 nitrogen functional group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004073 vulcanization 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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 discloses a processing method of a high-toughness MPP power tube, which belongs to the technical field of power tube processing and is used for solving the technical problems that in the prior art, the toughness of the MPP power tube is low, the composition components of the MPP are lack of cooperative coordination, and the flame retardant property of the MPP power tube needs to be further improved, and the processing method of the high-toughness MPP power tube comprises the following steps: adding the glass fiber powder and the activating solution into a three-neck flask, performing ultrasonic dispersion for 30-50min, and performing post-treatment to obtain the pretreated glass fiber powder. According to the invention, polypropylene and high-density polyethylene are mixed to be used as the base material of the power tube, and the prepared composite glass fiber powder and the active compatilizer are used for improving the base material, so that the crosslinking and synergistic interaction exists among all components of the composite MPP power tube, and the mechanical property, the wear resistance and the flame retardance of the composite MPP power tube are improved.
Description
Technical Field
The invention relates to the technical field of power tube processing, in particular to a processing method of a high-toughness MPP power tube.
Background
The MPP pipe is also called MPP power cable protection pipe, and adopts modified polypropylene as main raw material. The high-temperature-resistant and external-pressure-resistant composite material has the characteristics of high temperature resistance, external pressure resistance, portability, good insulating property and corrosion resistance, and is widely applied to engineering industries such as electric power, communication and the like. Traditional pipes such as polyvinyl chloride (PVC) and Polyethylene (PE) have certain insulating properties, but the wear resistance and the environmental protection are difficult to meet the requirements of modern engineering. To meet market demands, MPP power pipes are beginning to be widely focused and applied as a new type of power pipe.
However, conventional MPP power pipes may face challenges in certain applications, one of which is their relatively low toughness, poor flame retardant properties. In some special cases, such as when the power line needs to be bent or subjected to external impact, the conventional MPP power line may be easily broken, thereby affecting the safety and reliability of the cable. In the prior art, in order to improve the toughness and flame retardant performance of the MPP power tube, additives such as fiber, a toughening agent, a flame retardant and the like are generally added into the MPP power tube, however, due to structural differences between the additives and the constituent components of the MPP power tube, the dispersibility of the additives in the MPP power tube and the poor compatibility with the constituent components of the MPP power tube are caused, a weak interface layer is formed in the MPP power tube due to the large use of the additives, the mechanical performance of the MPP power tube is reduced, the flame retardant performance of the MPP power tube is generally improved by the flame retardant per se, and the flame retardant performance of the MPP power tube needs to be further improved due to the lack of cooperative coordination between the flame retardant and the constituent components of the MPP power tube.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a processing method of a high-toughness MPP power tube, which is used for solving the technical problems that in the prior art, the toughness of the MPP power tube is low, due to structural differences of additives and MPP power tube components, the dispersibility and compatibility of the additives such as fibers, a toughening agent, a flame retardant and the like in the MPP power tube are poor, the components of the flame retardant and the MPP are lack of cooperative coordination, and the flame retardant performance of the MPP power tube needs to be further improved.
The aim of the invention can be achieved by the following technical scheme:
a processing method of a high-toughness MPP power tube comprises the following steps:
s1, adding glass fiber powder and an activating solution into a three-neck flask, performing ultrasonic dispersion for 30-50min, and performing post-treatment to obtain pretreated glass fiber powder;
s2, adding the pretreated glass fiber powder and N, N-dimethylformamide into a three-neck flask protected by nitrogen, performing ultrasonic dispersion for 30-50min, fixing the three-neck flask on an iron stand with mechanical stirring, dripping a polyethyleneimine solution into the three-neck flask, raising the temperature of the three-neck flask to 60-70 ℃, performing heat preservation reaction for 3-5h, and performing post treatment to obtain modified glass fiber powder;
the synthetic reaction principle of the modified glass fiber powder is as follows:
wherein:to pretreat glass fiber powder
S3, adding the modified glass fiber powder, the modified flame retardant and tetrahydrofuran into a three-neck flask, stirring, increasing the temperature of the three-neck flask until the system flows back, carrying out heat preservation reaction for 20-24 hours, and carrying out post treatment to obtain composite glass fiber powder;
the synthetic reaction principle of the composite glass fiber powder is as follows:
s4, adding polypropylene, high-density polyethylene, composite glass fiber powder, an active compatilizer and an auxiliary additive into a double-screw extruder, and cooling and forming after melt extrusion to prepare the composite MPP power tube.
Further, the activating solution in the step S1 consists of 1mol/L hydrochloric acid, sodium fluoride, sodium nitrate, 15vt% hydrogen peroxide, sodium dodecyl sulfate and purified water according to the dosage ratio of 10mL:1g:1g:4mL:0.5g:60g, the dosage ratio of the glass fiber powder to the activating solution is 1g:5mL, the particle size of the glass fiber powder is 150-200 mu m, and the post-treatment operation comprises: after the reaction is finished, carrying out suction filtration, respectively washing a filter cake with purified water and absolute ethyl alcohol for three times, then carrying out suction drying, transferring the filter cake into a drying oven with the temperature of 60-70 ℃, and drying to constant weight to obtain the pretreated glass fiber powder.
Further, in the step S2, the use amount ratio of the pretreated glass fiber powder, the N, N-dimethylformamide to the polyethyleneimine solution is 1g:6mL:3g, and the polyethyleneimine solution is prepared from polyethyleneimine and N, N-dimethylformamide according to the use amount ratio of 1g:1g of a composition, said polyethyleneimine having a molecular weight of about 600, obtained from Shanghai Katsumadai chemical Co., ltd, said post-treatment operation comprising: after the reaction is finished, the temperature of the three-mouth flask is reduced to room temperature, purified water is added into the three-mouth flask, stirring is carried out for 20-30min, suction filtration is carried out, a filter cake is respectively washed for three times by the purified water and absolute ethyl alcohol and then is dried, the filter cake is transferred into a drying oven with the temperature of 70-80 ℃ and is dried to constant weight, and the modified glass fiber powder is obtained.
Further, the modified flame retardant is processed by the following steps:
a1, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a three-neck flask, stirring, heating the three-neck flask to 45-50 ℃, adding phosphorus pentasulfide into the three-neck flask in three batches, carrying out heat preservation reaction for 8-10h, and carrying out aftertreatment to obtain modified DOPO;
the synthesis reaction principle of the modified DOPO is as follows:
and A2, adding the modified DOPO, tetrahydrofuran and 1, 2-epoxy-5-hexene into a three-neck flask protected by nitrogen, stirring, increasing the temperature of the three-neck flask to the reflux of the system, carrying out heat preservation reaction for 6-8h, and carrying out aftertreatment to obtain the modified flame retardant.
The synthetic reaction principle of the modified flame retardant is as follows:
further, in the step A1, the dosage ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene and phosphorus pentasulfide is 2g:6mL:1g, the phosphorus pentasulfide is added into a three-neck flask in three batches, the time interval between two adjacent phosphorus pentasulfide additions is 90min, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-mouth flask is increased to 70-80 ℃, toluene is distilled off under reduced pressure, the temperature of the three-mouth flask is reduced to room temperature, chloroform is added into the three-mouth flask for ultrasonic treatment for 15min, suction filtration is carried out, saturated sodium carbonate solution is added into filtrate, stirring is carried out for 15min, standing and liquid separation are carried out, an organic phase is dried by using anhydrous magnesium sulfate, a rotary evaporator is used, the water bath temperature is set to 50 ℃, and chloroform is distilled off, so that modified DOPO is obtained.
Further, in the step A2, the dosage ratio of the modified DOPO to the 1, 2-epoxy-5-hexene is 1mol to 1mol, the tetrahydrofuran is 10 times of the weight of the modified DOPO, and the post-treatment operation comprises: after the reaction is finished, the temperature of the three-neck flask is reduced to room temperature, suction filtration is carried out, a filter cake and acetone are added into the flask according to the dosage ratio of 1g to 3mL, the temperature is raised to a system solution, the temperature is naturally reduced to room temperature, suction filtration is carried out, the filter cake is transferred into a drying oven with the temperature of 50-55 ℃, and vacuum drying is carried out to constant weight, thus obtaining the modified flame retardant.
Further, the active compatilizer is prepared by the following steps:
b1, adding 1, 6-hexamethylene diisocyanate and acetone into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to 45-50 ℃, dropwise adding 2-methacrylic acid into the three-neck flask, carrying out heat preservation reaction for 30-50min after the dropwise adding is finished, and carrying out aftertreatment to obtain an intermediate I;
the synthesis reaction principle of the intermediate I is as follows:
and B2, adding the intermediate I, styrene, low-density polypropylene, p-isopropenyl dimethylbenzyl isocyanate, toluene and a catalyst into a three-neck flask, stirring, heating the three-neck flask until the system flows back, carrying out heat preservation reaction for 8-10h, and carrying out aftertreatment to obtain the active compatilizer.
The synthesis reaction principle of the active compatilizer is as follows:
further, the ratio of 1mol to 1mol of 1, 6-hexamethylene diisocyanate to 2-methacrylic acid in the step B1, the amount of acetone being 4 times the weight of 1, 6-hexamethylene diisocyanate, the post-treatment operation comprising: after the reaction is completed, acetone is distilled off under reduced pressure to obtain an intermediate I; the dosage ratio of the intermediate I, styrene, low-density polypropylene, p-isopropenyl dimethylbenzyl isocyanate, toluene and catalyst in the step B2 is 2g:3g:15g:3g:70g:0.05g, wherein the catalyst is a Ziegler-Natta catalyst or a metallocene catalyst, the low-density polypropylene is selected from Shanghai creek's trade company, model number TKC2007NG82765, and the post-treatment operation comprises: after the reaction was completed, toluene was distilled off under reduced pressure to obtain an active compatibilizer.
Further, in the step S3, the dosage ratio of the modified glass fiber powder, the modified flame retardant and the tetrahydrofuran is 5g to 2g to 50g, and the post-treatment operation comprises: after the reaction is finished, steaming tetrahydrofuran under reduced pressure, reducing the temperature of a three-neck flask to room temperature, adding absolute ethyl alcohol into the three-neck flask, performing ultrasonic dispersion for 50-60min, performing suction filtration, washing a filter cake with the absolute ethyl alcohol for three times, performing suction drying, transferring the filter cake into a drying oven with the temperature of 65-75 ℃, and performing vacuum drying to constant weight to obtain the composite glass fiber powder.
Further, in the step S4, the dosage ratio of polypropylene to high-density polyethylene to composite glass fiber powder to active compatilizer to auxiliary additive is 20g to 15g to 7g to 5g to 1g, the molecular weight of polypropylene is 600-700, the high-density polyethylene is selected from Shanghai Haohou trade company, model number is 540-NA60, the auxiliary additive is composed of plasticizer, dispersing agent, lubricant, antioxidant and antistatic agent according to the dosage ratio of 1g to 1g, wherein the plasticizer is one or more of dioctyl phthalate, di-isodecyl phthalate and tricresyl phosphate, the dispersing agent is one or more of calcium stearate, zinc stearate, magnesium stearate and cadmium stearate, the lubricant is one or more of oleamide and microcrystalline paraffin, the antioxidant is one or two of antioxidant DPPD, antioxidant PPD and antioxidant H, the antistatic agent is octadecyl dimethyl hydroxyethyl nitrate, sodium sulfanyl sulfonate or sodium sulfonate, the two extrusion temperatures are sequentially set at 275 ℃ from one end to two ends of a twin screw extruder at 275 ℃ and a twin screw speed of 270 min/275 ℃, and the two screw extruder at a discharge temperature of two ends at a temperature of 275 r/6 min.
The invention has the following beneficial effects:
1. the composite MPP power tube is prepared by melt extrusion of polypropylene, high-density polyethylene, composite glass fiber powder, an active compatilizer and auxiliary additives through a double-screw extruder, and when the composite MPP power tube is prepared, the polypropylene has higher toughness and can absorb energy, the high-density polyethylene has higher rigidity, the impact force can be dispersed, the polypropylene and the high-density polyethylene are mixed for use, the composition ratio is controlled, and the balance of the materials is realized, so that the materials have enough strength to bear load and enough rigidity to prevent deformation or bending, and the influence of the impact on the materials is reduced; in the processing process, the glass fiber powder is pretreated and modified, so that the composite glass fiber powder can be uniformly dispersed in the composite MPP power tube, the wear resistance of the composite MPP power tube is improved, and meanwhile, the composite MPP power tube is endowed with good flame retardant property; the prepared active compatilizer has good compatibility with polypropylene and high-density polyethylene, can be crosslinked with active functional groups on the surface of the composite glass fiber powder, promotes the crosslinking between the composite glass fiber powder and the polypropylene and the high-density polyethylene, enhances the adhesive force between different components, reduces the interfacial tension in the material, and further improves the toughness of the composite MPP power tube.
2. In the preparation process of the composite MPP power tube, glass fiber powder is pretreated through an activating solution, the activating solution contains sodium dodecyl sulfate, which is a surfactant, so that the liquid can wet the surface of the glass fiber more easily, hydrochloric acid can neutralize alkaline dirt, sodium fluoride can be used for removing some pollutants which are difficult to dissolve, sodium fluoride, sodium nitrate and hydrogen peroxide are all strong oxidants, surface oxidation reaction of the glass fiber powder is initiated under an acidic condition, and active oxygen-containing functional groups such as hydroxyl, carboxyl and the like are introduced to the surface of the glass fiber powder; after the pretreated glass fiber powder is subjected to ultrasonic dispersion in N, N-dimethylformamide, self-assembly is carried out on polyethylene imine on the pretreated glass fiber powder, a coating layer of the polyethylene imine is formed on the pretreated glass fiber powder, and modified glass fiber powder with a large amount of amino groups on the surface is prepared; DOPO and phosphorus pentasulfide are subjected to oxygen deoxidation and vulcanization reaction in a toluene system, oxygen atoms are replaced by sulfur atoms from DOPO molecules to generate corresponding thio compounds to generate modified DOPO with sulfur functional groups, then the modified DOPO and 1, 2-epoxy-5-hexene are subjected to substitution addition reaction to prepare a modified flame retardant containing epoxy groups, the epoxy groups on the modified flame retardant react with amino groups on the surface of modified glass fiber powder, and the modified flame retardant is grafted to the surface of the modified glass fiber powder to prepare the composite glass fiber powder; the modified flame retardant contains sulfur element, and is matched with glass fiber powder, so that the thermal stability of the material can be improved, the burning or decomposition rate of the material is reduced, the glass fiber powder can avoid the candle wick effect of glass fiber on the material during burning, the pretreated glass fiber has higher surface activity, a compact protective layer is formed on the surface of the composite MPP material during burning, the release of smoke and flame is reduced, the glass fiber powder has larger specific surface area, plays the role of a catalyst during burning, accelerates the thermal decomposition of the modified flame retardant, generates sulfur compounds such as phosphate and high temperature resistance, inhibits the formation of burning flame, plays the role of preventing the spread of fire, and further improves the flame retardant property of the material; the modified glass fiber powder contains a large amount of nitrogen functional groups, the modified flame retardant contains sulfur and phosphorus functional groups, a nitrogen-phosphorus-sulfur synergistic effect is formed in flame retardance, the flame retardance is further improved, the flame propagation speed is slowed down, and the flame retardance is enhanced.
3. In the preparation process, 1, 6-hexamethylene diisocyanate and 2-methacrylic acid react according to the dosage ratio to prepare an intermediate I of an isocyanate-terminated olefin polymer, and the intermediate I is subjected to free radical polymerization reaction with styrene, low-density polypropylene and p-isopropenyl dimethylbenzyl isocyanate under the conditions of toluene and a catalyst to prepare an active compatilizer with an isocyanate-modified long straight-chain structure; the long straight chain polypropylene is introduced into the active compatilizer, so that the crystal structure of the active compatilizer is closer to that of polypropylene and polyethylene, the long straight chain structure can increase the cross effect and attractive force between molecules, reduce the repulsive force between molecular chains, reduce the chain motion degree of high molecules, enable the long straight chain to be more difficult to generate phase separation or phase layering, further improve the compatibility between the active compatilizer and polypropylene and polyethylene, and during preparation, isocyanate groups on the active compatilizer can also form chemical crosslinking with active functional groups on composite glass fiber powder, and a space net-shaped supporting structure taking the glass fiber powder as an anchor point is formed in a composite MPP power tube, so that the mechanical property of the composite MPP power tube is improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The processing method of the high-toughness MPP power tube comprises the following steps:
s1, preparing modified glass fiber powder
Adding 1mol/L hydrochloric acid, sodium fluoride, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water into a beaker according to the dosage ratio of 10mL:1 g:4mL:0.5g:60g, and uniformly mixing to obtain an activation liquid;
adding glass fiber powder with the particle size of 150-200 mu m and an activating solution into a three-neck flask according to the dosage ratio of 1g to 5mL, performing ultrasonic dispersion for 30min, performing suction filtration, respectively washing a filter cake with purified water and absolute ethyl alcohol for three times, performing suction drying, transferring the filter cake into a drying oven with the temperature of 60 ℃, and drying to constant weight to obtain pretreated glass fiber powder;
adding polyethylenimine with molecular weight of about 600 and N, N-dimethylformamide into a beaker according to the dosage ratio of 1g to 1g, and stirring until the system is dissolved to obtain polyethylenimine solution;
weighing the following components in parts by weight: 10g of pretreated glass fiber powder and 60mL of N, N-dimethylformamide are added into a three-neck flask protected by nitrogen, ultrasonic dispersion is carried out for 30min, the three-neck flask is fixed on an iron stand with mechanical stirring, 30g of polyethyleneimine solution is dripped into the three-neck flask, the temperature of the three-neck flask is increased to 60 ℃, the temperature of the three-neck flask is kept for 3h, the temperature of the three-neck flask is reduced to room temperature, 80mL of purified water is added into the three-neck flask, stirring is carried out for 20min, suction filtration is carried out, filter cakes are respectively washed three times by the purified water and absolute ethyl alcohol and then are pumped out, the filter cakes are transferred into a drying box with the temperature of 70 ℃ and are dried to constant weight, and the modified glass fiber powder is obtained.
S2, preparing modified flame retardant
Weighing: adding 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 60mL of toluene into a three-neck flask, stirring, heating the three-neck flask to 45 ℃, adding 10g of phosphorus pentasulfide into the three-neck flask in three batches, wherein the time interval between two adjacent phosphorus pentasulfide additions is 90min, carrying out heat preservation reaction for 8h, heating the three-neck flask to 70 ℃, carrying out reduced pressure distillation to remove toluene, reducing the temperature of the three-neck flask to room temperature, adding chloroform into the three-neck flask for ultrasonic treatment for 15min, carrying out suction filtration, adding saturated sodium carbonate solution into filtrate, stirring for 15min, standing for liquid separation, drying an organic phase by using anhydrous magnesium sulfate, and then using a rotary evaporator to set the water bath temperature to 50 ℃, and evaporating to remove the chloroform to obtain modified DOPO;
weighing: adding 25g of modified DOPO, 250g of tetrahydrofuran and 10.6g of 1, 2-epoxy-5-hexene into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to reflux the system, carrying out heat preservation reaction for 6 hours, lowering the temperature of the three-neck flask to room temperature, carrying out suction filtration, adding a filter cake and acetone into the flask according to the dosage ratio of 1g to 3mL, raising the temperature to dissolve the system, naturally cooling to room temperature, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 50 ℃, and carrying out vacuum drying to constant weight to obtain the modified flame retardant.
S3, preparing composite glass fiber powder
Weighing: 50g of modified glass fiber powder, 20g of modified flame retardant and 500g of tetrahydrofuran are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to the reflux of the system, the heat preservation reaction is carried out for 20h, the tetrahydrofuran is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to the room temperature, 500g of absolute ethyl alcohol is added into the three-neck flask, the three-neck flask is subjected to ultrasonic dispersion for 50min, suction filtration is carried out, a filter cake is washed three times by the absolute ethyl alcohol and then is dried by suction, the filter cake is transferred into a drying box with the temperature of 65 ℃, and the filter cake is dried to constant weight in vacuum, thus obtaining the composite glass fiber powder.
S4, preparing an active compatilizer
Weighing: 30.0g of 1, 6-hexamethylene diisocyanate and 120g of acetone are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 45 ℃, 15.4g of 2-methacrylic acid is dropwise added into the three-neck flask, the reaction is carried out for 30min after the dropwise addition, and the acetone is distilled off under reduced pressure to obtain an intermediate I;
weighing: 20g of intermediate I, 30g of styrene, 150g of low-density polypropylene, 30g of isopropenyl dimethylbenzyl isocyanate, 700g of toluene and 0.5g of Ziegler-Natta catalyst are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to the reflux of the system, the temperature is kept for reaction for 8 hours, and the toluene is distilled off under reduced pressure to obtain the active compatilizer.
S5, preparing composite MPP power tube
Weighing: 2000g of polypropylene with molecular weight of 600-700, 1500g of high-density polyethylene, 700g of composite glass fiber powder, 500g of active compatilizer, 20g of dioctylphthalate, 20g of calcium stearate, 20g of oleamide, 20g of antioxidant DPPD and 20g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are added into a double-screw extruder, the temperature of the double-screw extruder from a feeding end to a discharging end in 6 temperature intervals is sequentially set to 270 ℃, 275 ℃, 280 ℃ and 18r/min of main shaft rotation speed of the double-screw extruder, and after melt extrusion, cooling molding is carried out, so that the composite MPP power tube is prepared.
Example 2
The processing method of the high-toughness MPP power tube comprises the following steps:
s1, preparing modified glass fiber powder
Adding 1mol/L hydrochloric acid, sodium fluoride, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water into a beaker according to the dosage ratio of 10mL:1 g:4mL:0.5g:60g, and uniformly mixing to obtain an activation liquid;
adding glass fiber powder with the particle size of 150-200 mu m and an activating solution into a three-neck flask according to the dosage ratio of 1g to 5mL, performing ultrasonic dispersion for 40min, performing suction filtration, respectively washing a filter cake with purified water and absolute ethyl alcohol for three times, performing suction drying, transferring the filter cake into a drying oven with the temperature of 65 ℃, and drying to constant weight to obtain pretreated glass fiber powder;
adding polyethylenimine with molecular weight of about 600 and N, N-dimethylformamide into a beaker according to the dosage ratio of 1g to 1g, and stirring until the system is dissolved to obtain polyethylenimine solution;
weighing the following components in parts by weight: 10g of pretreated glass fiber powder and 60mL of N, N-dimethylformamide are added into a three-neck flask protected by nitrogen, ultrasonic dispersion is carried out for 40min, the three-neck flask is fixed on an iron stand with mechanical stirring, 30g of polyethyleneimine solution is dripped into the three-neck flask, the temperature of the three-neck flask is increased to 65 ℃, the temperature of the three-neck flask is kept for 4h, the temperature of the three-neck flask is reduced to room temperature, 80mL of purified water is added into the three-neck flask, stirring is carried out for 25min, suction filtration is carried out, filter cakes are respectively washed three times by the purified water and absolute ethyl alcohol and then are pumped out, the filter cakes are transferred into a drying box with the temperature of 75 ℃ and are dried to constant weight, and the modified glass fiber powder is obtained.
S2, preparing modified flame retardant
Weighing: adding 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 60mL of toluene into a three-neck flask, stirring, heating the three-neck flask to 47 ℃, adding 10g of phosphorus pentasulfide into the three-neck flask in three batches, wherein the time interval between two adjacent phosphorus pentasulfide additions is 90min, carrying out heat preservation reaction for 9h, heating the three-neck flask to 75 ℃, carrying out reduced pressure distillation to remove toluene, reducing the temperature of the three-neck flask to room temperature, adding chloroform into the three-neck flask for ultrasonic treatment for 15min, carrying out suction filtration, adding saturated sodium carbonate solution into filtrate, stirring for 15min, standing for liquid separation, drying an organic phase by using anhydrous magnesium sulfate, and then using a rotary evaporator to set the water bath temperature to 50 ℃, and evaporating to remove the chloroform to obtain modified DOPO;
weighing: adding 25g of modified DOPO, 250g of tetrahydrofuran and 10.6g of 1, 2-epoxy-5-hexene into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to reflux the system, carrying out heat preservation reaction for 7h, lowering the temperature of the three-neck flask to room temperature, carrying out suction filtration, adding a filter cake and acetone into the flask according to the dosage ratio of 1g to 3mL, raising the temperature to dissolve the system, naturally cooling to room temperature, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 53 ℃, and carrying out vacuum drying to constant weight to obtain the modified flame retardant.
S3, preparing composite glass fiber powder
Weighing: 50g of modified glass fiber powder, 20g of modified flame retardant and 500g of tetrahydrofuran are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to the reflux of the system, the heat preservation reaction is carried out for 22 hours, the tetrahydrofuran is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to the room temperature, 500g of absolute ethyl alcohol is added into the three-neck flask, the ultrasonic dispersion is carried out for 55min, the suction filtration is carried out, the filter cake is washed three times by the absolute ethyl alcohol and then is dried by suction, the filter cake is transferred into a drying box with the temperature of 70 ℃, and the filter cake is dried to constant weight in vacuum, thus obtaining the composite glass fiber powder.
S4, preparing an active compatilizer
Weighing: 30.0g of 1, 6-hexamethylene diisocyanate and 120g of acetone are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 47 ℃, 15.4g of 2-methacrylic acid is dropwise added into the three-neck flask, the reaction is carried out for 40min after the dropwise addition, and the acetone is distilled off under reduced pressure to obtain an intermediate I;
weighing: 20g of intermediate I, 30g of styrene, 150g of low-density polypropylene, 30g of p-isopropenyl dimethylbenzyl isocyanate, 700g of toluene and 0.5g of metallocene catalyst are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to the reflux of the system, the temperature is kept for 9h, and the toluene is distilled off under reduced pressure to obtain the active compatilizer.
S5, preparing composite MPP power tube
Weighing: 2000g of polypropylene with molecular weight of 600-700, 1500g of high-density polyethylene, 700g of composite glass fiber powder, 500g of active compatilizer, 20g of phthalic diester, 20g of zinc stearate, 20g of microcrystalline paraffin, 20g of antioxidant PPD and 20g of sodium p-nonylphenoxy propyl sulfonate are added into a double-screw extruder, the temperature of the double-screw extruder from a feeding end to a discharging end in 6 temperature intervals is sequentially set to 270 ℃, 275 ℃, 280 ℃, the main shaft rotation speed of the double-screw extruder is 18r/min, and after melt extrusion, cooling molding is carried out, so that the composite MPP power tube is prepared.
Example 3
The processing method of the high-toughness MPP power tube comprises the following steps:
s1, preparing modified glass fiber powder
Adding 1mol/L hydrochloric acid, sodium fluoride, sodium nitrate, 15vt percent hydrogen peroxide, sodium dodecyl sulfate and purified water into a beaker according to the dosage ratio of 10mL:1 g:4mL:0.5g:60g, and uniformly mixing to obtain an activation liquid;
adding glass fiber powder with the particle size of 150-200 mu m and an activating solution into a three-neck flask according to the dosage ratio of 1g to 5mL, performing ultrasonic dispersion for 50min, performing suction filtration, respectively washing a filter cake with purified water and absolute ethyl alcohol for three times, performing suction drying, transferring the filter cake into a drying oven with the temperature of 70 ℃, and drying to constant weight to obtain pretreated glass fiber powder;
adding polyethylenimine with molecular weight of about 600 and N, N-dimethylformamide into a beaker according to the dosage ratio of 1g to 1g, and stirring until the system is dissolved to obtain polyethylenimine solution;
weighing the following components in parts by weight: 10g of pretreated glass fiber powder and 60mL of N, N-dimethylformamide are added into a three-neck flask protected by nitrogen, ultrasonic dispersion is carried out for 50min, the three-neck flask is fixed on an iron stand with mechanical stirring, 30g of polyethyleneimine solution is dripped into the three-neck flask, the temperature of the three-neck flask is increased to 70 ℃, the temperature of the three-neck flask is kept for 5h, the temperature of the three-neck flask is reduced to room temperature, 80mL of purified water is added into the three-neck flask, stirring is carried out for 30min, suction filtration is carried out, filter cakes are respectively washed three times by the purified water and absolute ethyl alcohol and then are pumped out, the filter cakes are transferred into a drying box with the temperature of 70-80 ℃ and are dried to constant weight, and the modified glass fiber powder is obtained.
S2, preparing modified flame retardant
Weighing: adding 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 60mL of toluene into a three-neck flask, stirring, heating the three-neck flask to 50 ℃, adding 10g of phosphorus pentasulfide into the three-neck flask in three batches, wherein the time interval between two adjacent phosphorus pentasulfide additions is 90min, carrying out heat preservation reaction for 10h, heating the three-neck flask to 80 ℃, carrying out reduced pressure distillation to remove toluene, reducing the temperature of the three-neck flask to room temperature, adding chloroform into the three-neck flask for ultrasonic treatment for 15min, carrying out suction filtration, adding saturated sodium carbonate solution into filtrate, stirring for 15min, standing for liquid separation, drying an organic phase by using anhydrous magnesium sulfate, and then using a rotary evaporator to set the water bath temperature to 50 ℃, and evaporating to remove the chloroform to obtain modified DOPO;
weighing: adding 25g of modified DOPO, 250g of tetrahydrofuran and 10.6g of 1, 2-epoxy-5-hexene into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask until the system flows back, carrying out heat preservation reaction for 6-8h, lowering the temperature of the three-neck flask to room temperature, carrying out suction filtration, adding a filter cake and acetone into the flask according to the dosage ratio of 1g to 3mL, raising the temperature until the system is dissolved, naturally cooling to room temperature, carrying out suction filtration, transferring the filter cake into a drying box with the temperature of 55 ℃, and carrying out vacuum drying until the weight is constant, thus obtaining the modified flame retardant.
S3, preparing composite glass fiber powder
Weighing: 50g of modified glass fiber powder, 20g of modified flame retardant and 500g of tetrahydrofuran are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to the reflux of the system, the heat preservation reaction is carried out for 24 hours, the tetrahydrofuran is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to the room temperature, 500g of absolute ethyl alcohol is added into the three-neck flask, the ultrasonic dispersion is carried out for 60 minutes, the suction filtration is carried out, the filter cake is washed three times by the absolute ethyl alcohol and then is dried by suction, the filter cake is transferred into a drying box with the temperature of 75 ℃, and the filter cake is dried to constant weight in vacuum, thus obtaining the composite glass fiber powder.
S4, preparing an active compatilizer
Weighing: 30.0g of 1, 6-hexamethylene diisocyanate and 120g of acetone are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 50 ℃, 15.4g of 2-methacrylic acid is dropwise added into the three-neck flask, the reaction is carried out for 50min after the dropwise addition, and the acetone is distilled off under reduced pressure to obtain an intermediate I;
weighing: 20g of intermediate I, 30g of styrene, 150g of low-density polypropylene, 30g of p-isopropenyl dimethylbenzyl isocyanate, 700g of toluene and 0.5g of Ziegler-Natta catalyst are added into a three-neck flask to be stirred, the temperature of the three-neck flask is increased to the reflux of the system, the temperature is kept for 10h, and the toluene is distilled off under reduced pressure to obtain the active compatilizer.
S5, preparing composite MPP power tube
Weighing: 2000g of polypropylene with molecular weight of 600-700, 1500g of high-density polyethylene, 700g of composite glass fiber powder, 500g of active compatilizer, 20g of diisodecyl phthalate, 20g of magnesium stearate, 20g of oleamide, 20g of age inhibitor H and 20g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate are added into a double-screw extruder, the temperature of the double-screw extruder from a feeding end to a discharging end in 6 temperature intervals is sequentially set to 270 ℃, 275 ℃, 280 ℃, the main shaft rotation speed of the double-screw extruder is 18r/min, and after melt extrusion, cooling molding is carried out, so that the composite MPP power tube is prepared.
Comparative example 1
This comparative example differs from example 3 in that steps S2 and S3 were omitted, and the composite glass fiber powder in step S5 was replaced with a mixture of modified glass fiber powder and DOPO at 5g:2g in equal amounts.
Comparative example 2
This comparative example differs from example 3 in that steps S1 and S3 were omitted and the composite glass fiber powder in step S5 was replaced by an equal amount of a mixture of glass fiber powder and modified flame retardant in a ratio of 5g to 2 g.
Comparative example 3
The difference between this comparative example and example 3 is that step S4 is eliminated and no active compatibilizer is added in step S5.
Performance test:
the composite MPP power pipes prepared in examples 1-3 and comparative examples 1-3 were tested for tensile properties, impact toughness, abrasion resistance, and flammability, with tensile properties in reference to standard GB/T8804.1-2003 thermoplastic pipe tensile properties determination part 1: test method general rule "test sample tensile yield stress and elongation at break", impact toughness reference standard GB/T1451-2005 "fiber reinforced plastics simply supported beam impact toughness test method" test sample impact toughness, abrasion resistance reference standard QB/T5101-2017 "Plastic pipe abrasion resistance test method" test sample mass abrasion loss, combustion performance reference UL-94 vertical combustion test standard, test sample flame retardant rating, specific test results are shown in the following table:
data analysis:
as shown by comparing and analyzing the data in the table, the tensile yield stress of the composite MPP power tube prepared by the invention reaches 47.56MPa, the elongation at break reaches 253.7%, and the impact toughness reaches 16.6kJ/m 2 The mass abrasion loss is reduced to 2.1g, the flame retardant property reaches V-0 level, and all detection data are superior to those of comparative examples, which shows that the composite MPP power tube prepared by the invention has the mechanical property, the wear resistance and the flame retardant property.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean 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 do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The processing method of the high-toughness MPP power tube is characterized by comprising the following steps of:
s1, adding glass fiber powder and an activating solution into a three-neck flask, performing ultrasonic dispersion for 30-50min, and performing post-treatment to obtain pretreated glass fiber powder;
s2, adding the pretreated glass fiber powder and N, N-dimethylformamide into a three-neck flask protected by nitrogen, performing ultrasonic dispersion for 30-50min, fixing the three-neck flask on an iron stand with mechanical stirring, dripping a polyethyleneimine solution into the three-neck flask, raising the temperature of the three-neck flask to 60-70 ℃, performing heat preservation reaction for 3-5h, and performing post treatment to obtain modified glass fiber powder;
s3, adding the modified glass fiber powder, the modified flame retardant and tetrahydrofuran into a three-neck flask, stirring, increasing the temperature of the three-neck flask until the system flows back, carrying out heat preservation reaction for 20-24 hours, and carrying out post treatment to obtain composite glass fiber powder;
s4, adding polypropylene, high-density polyethylene, composite glass fiber powder, an active compatilizer and an auxiliary additive into a double-screw extruder, and cooling and forming after melt extrusion to prepare the composite MPP power tube.
2. The method for processing the high-toughness MPP power pipe according to claim 1, wherein the activating solution in the step S1 is composed of 1mol/L hydrochloric acid, sodium fluoride, sodium nitrate, 15vt% hydrogen peroxide, sodium dodecyl sulfate and purified water in a dosage ratio of 10ml:1g:1g:4ml:0.5g:60g, the dosage ratio of the glass fiber powder to the activating solution is 1g:5ml, and the post-treatment operation comprises: after the reaction is finished, carrying out suction filtration, respectively washing a filter cake with purified water and absolute ethyl alcohol for three times, then carrying out suction drying, transferring the filter cake into a drying oven with the temperature of 60-70 ℃, and drying to constant weight to obtain the pretreated glass fiber powder.
3. The method for processing the high-toughness MPP power tube according to claim 1, wherein the amount ratio of the pretreated glass fiber powder, the N, N-dimethylformamide and the polyethyleneimine solution in the step S2 is 1g:6mL:3g, and the polyethyleneimine solution is prepared from polyethyleneimine and N, N-dimethylformamide according to the amount ratio of 1g:1g, the post-treatment operation comprising: after the reaction is finished, the temperature of the three-mouth flask is reduced to room temperature, purified water is added into the three-mouth flask, stirring is carried out for 20-30min, suction filtration is carried out, a filter cake is respectively washed for three times by the purified water and absolute ethyl alcohol and then is dried, the filter cake is transferred into a drying oven with the temperature of 70-80 ℃ and is dried to constant weight, and the modified glass fiber powder is obtained.
4. The method for processing the high-toughness MPP power pipe according to claim 1, wherein the modified flame retardant is processed by the following steps:
a1, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a three-neck flask, stirring, heating the three-neck flask to 45-50 ℃, adding phosphorus pentasulfide into the three-neck flask in three batches, carrying out heat preservation reaction for 8-10h, and carrying out aftertreatment to obtain modified DOPO;
and A2, adding the modified DOPO, tetrahydrofuran and 1, 2-epoxy-5-hexene into a three-neck flask protected by nitrogen, stirring, increasing the temperature of the three-neck flask to the reflux of the system, carrying out heat preservation reaction for 6-8h, and carrying out aftertreatment to obtain the modified flame retardant.
5. The method of claim 4, wherein in step A1, the ratio of the amount of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene, and phosphorus pentasulfide is 2g:6ml:1g, the phosphorus pentasulfide is added into a three-necked flask in three batches, and the time interval between two adjacent phosphorus pentasulfide additions is 90min, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-mouth flask is increased to 70-80 ℃, toluene is distilled off under reduced pressure, the temperature of the three-mouth flask is reduced to room temperature, chloroform is added into the three-mouth flask for ultrasonic treatment for 15min, suction filtration is carried out, saturated sodium carbonate solution is added into filtrate, stirring is carried out for 15min, standing and liquid separation are carried out, an organic phase is dried by using anhydrous magnesium sulfate, a rotary evaporator is used, the water bath temperature is set to 50 ℃, and chloroform is distilled off, so that modified DOPO is obtained.
6. The method for processing a high-toughness MPP power tube according to claim 4, wherein the modified DOPO, 1, 2-epoxy-5-hexene is used in the ratio of 1mol to 1mol in the step A2, the tetrahydrofuran is used in an amount 10 times the weight of the modified DOPO, and the post-treatment operation comprises: after the reaction is finished, the temperature of the three-neck flask is reduced to room temperature, suction filtration is carried out, a filter cake and acetone are added into the flask according to the dosage ratio of 1g to 3mL, the temperature is raised to a system solution, the temperature is naturally reduced to room temperature, suction filtration is carried out, the filter cake is transferred into a drying oven with the temperature of 50-55 ℃, and vacuum drying is carried out to constant weight, thus obtaining the modified flame retardant.
7. The method of claim 1, wherein the reactive compatibilizer is prepared by the steps of:
b1, adding 1, 6-hexamethylene diisocyanate and acetone into a three-neck flask protected by nitrogen, stirring, raising the temperature of the three-neck flask to 45-50 ℃, dropwise adding 2-methacrylic acid into the three-neck flask, carrying out heat preservation reaction for 30-50min after the dropwise adding is finished, and carrying out aftertreatment to obtain an intermediate I;
and B2, adding the intermediate I, styrene, low-density polypropylene, p-isopropenyl dimethylbenzyl isocyanate, toluene and a catalyst into a three-neck flask, stirring, heating the three-neck flask until the system flows back, carrying out heat preservation reaction for 8-10h, and carrying out aftertreatment to obtain the active compatilizer.
8. The method of claim 7, wherein the 1, 6-hexamethylene diisocyanate and 2-methacrylic acid are used in the ratio of 1mol to 1mol in the step B1, the acetone is used in an amount of 4 times the weight of the 1, 6-hexamethylene diisocyanate, and the post-treatment comprises: after the reaction is completed, acetone is distilled off under reduced pressure to obtain an intermediate I; the dosage ratio of the intermediate I, the styrene, the low-density polypropylene, the isopropenyl dimethylbenzyl isocyanate, the toluene and the catalyst in the step B2 is 2g to 3g to 15g to 3g to 70g to 0.05g, wherein the catalyst is a Ziegler-Natta catalyst or a metallocene catalyst, and the post-treatment operation comprises: after the reaction was completed, toluene was distilled off under reduced pressure to obtain an active compatibilizer.
9. The method for processing a high-toughness MPP power pipe according to claim 1, wherein the usage amount ratio of the modified glass fiber powder, the modified flame retardant and the tetrahydrofuran in step S3 is 5g:2g:50g, and the post-treatment operation comprises: after the reaction is finished, steaming tetrahydrofuran under reduced pressure, reducing the temperature of a three-neck flask to room temperature, adding absolute ethyl alcohol into the three-neck flask, performing ultrasonic dispersion for 50-60min, performing suction filtration, washing a filter cake with the absolute ethyl alcohol for three times, performing suction drying, transferring the filter cake into a drying oven with the temperature of 65-75 ℃, and performing vacuum drying to constant weight to obtain the composite glass fiber powder.
10. The method for processing the high-toughness MPP power tube according to claim 1, wherein in the step S4, the dosage ratio of polypropylene, high-density polyethylene, composite glass fiber powder, active compatilizer and auxiliary additive is 20g:15 g:5g:1g, the auxiliary additive is composed of one or two of plasticizer, dispersant, lubricant, anti-aging agent and antistatic agent according to the dosage ratio of 1g:1g, wherein the plasticizer is one or more of dioctyl phthalate, di-phthalate, diisodecyl phthalate and tricresyl phosphate, the dispersant is one or more of calcium stearate, zinc stearate, magnesium stearate and cadmium stearate, the lubricant is one of oleamide and microcrystalline paraffin, the anti-aging agent is one or two of anti-aging agent DPPD, anti-aging agent PPD and anti-aging agent H, the antistatic agent is one or two of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and sodium p-nonylphenoxy propyl sulfonate, the temperature of the twin-screw extruder is set to be at a temperature of 275 ℃ from a discharge end to a main shaft of 270 ℃ and a temperature of 275 ℃ from a discharge end of a twin-screw extruder of a temperature of 6 min to a main shaft of a temperature of 275 ℃ and a temperature of 18 r/a main shaft of 270.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311535509.1A CN117402429B (en) | 2023-11-17 | 2023-11-17 | Processing method of high-toughness MPP power tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311535509.1A CN117402429B (en) | 2023-11-17 | 2023-11-17 | Processing method of high-toughness MPP power tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117402429A true CN117402429A (en) | 2024-01-16 |
| CN117402429B CN117402429B (en) | 2024-07-19 |
Family
ID=89499874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311535509.1A Active CN117402429B (en) | 2023-11-17 | 2023-11-17 | Processing method of high-toughness MPP power tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117402429B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117601456A (en) * | 2024-01-22 | 2024-02-27 | 四川省宜宾普什建材有限责任公司 | Processing technology of large-caliber electric melting type plastic pipe fitting |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641158A (en) * | 2018-05-07 | 2018-10-12 | 合肥浦尔菲电线科技有限公司 | A kind of High-temperature-rescablet cablet material of high tenacity |
| CN109651800A (en) * | 2019-01-11 | 2019-04-19 | 四川大学 | A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of shape memory polyurethane flame retardant composite material |
| CN116515244A (en) * | 2023-05-10 | 2023-08-01 | 江苏耀鸿电子有限公司 | Phosphorus-nitrogen composite modified epoxy resin and copper-clad plate prepared from same |
| CN116789997A (en) * | 2023-07-17 | 2023-09-22 | 安徽中纤新材料有限公司 | Preparation process of glass fiber reinforced flame-retardant PA single 6 composite material |
-
2023
- 2023-11-17 CN CN202311535509.1A patent/CN117402429B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641158A (en) * | 2018-05-07 | 2018-10-12 | 合肥浦尔菲电线科技有限公司 | A kind of High-temperature-rescablet cablet material of high tenacity |
| CN109651800A (en) * | 2019-01-11 | 2019-04-19 | 四川大学 | A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of shape memory polyurethane flame retardant composite material |
| CN116515244A (en) * | 2023-05-10 | 2023-08-01 | 江苏耀鸿电子有限公司 | Phosphorus-nitrogen composite modified epoxy resin and copper-clad plate prepared from same |
| CN116789997A (en) * | 2023-07-17 | 2023-09-22 | 安徽中纤新材料有限公司 | Preparation process of glass fiber reinforced flame-retardant PA single 6 composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117601456A (en) * | 2024-01-22 | 2024-02-27 | 四川省宜宾普什建材有限责任公司 | Processing technology of large-caliber electric melting type plastic pipe fitting |
| CN117601456B (en) * | 2024-01-22 | 2024-03-26 | 四川省宜宾普什建材有限责任公司 | Processing technology of large-caliber electric melting type plastic pipe fitting |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117402429B (en) | 2024-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117402429B (en) | Processing method of high-toughness MPP power tube | |
| CN116731453B (en) | Anti-cracking low-smoke flame-retardant polyolefin cable material and preparation method thereof | |
| CN114605746B (en) | Masterbatch for flame retardant material and preparation method thereof | |
| CN110157133B (en) | Phosphorus-containing acrylate elastomer flame retardant and preparation method thereof | |
| CN118027379B (en) | Preparation process and application of organic silicon halogen-free flame retardant | |
| CN118290863B (en) | Flame-retardant anti-radiation photovoltaic cable sheath material and preparation method thereof | |
| CN118165316B (en) | Preparation process of glass fiber composite reinforced modified PET material | |
| CN110845779B (en) | Modified composite flame-retardant TPO resin and preparation method thereof | |
| CN117050438A (en) | Flame-retardant PVC composite material and preparation method thereof | |
| CN114907634A (en) | Flame-retardant reinforced modified plastic particle and preparation method thereof | |
| CN110156840B (en) | Phosphorus-nitrogen flame retardant containing DOPO and preparation method thereof | |
| CN118325228A (en) | High-strength flame-retardant composite current collector base film and preparation method thereof | |
| CN117327388B (en) | Starch modified degradable plastic and preparation method thereof | |
| CN117024921A (en) | High-temperature-resistant network crosslinking epoxy resin and preparation method thereof | |
| CN112724627B (en) | PC/ABS alloy material and application thereof | |
| CN116874944B (en) | Preparation process of hyperbranched polymer modified polyvinyl chloride cable material | |
| CN114854187B (en) | Flame-retardant polycarbonate composition and preparation method thereof | |
| CN113429736B (en) | Modified polyformaldehyde engineering plastic and preparation method thereof | |
| CN1257935C (en) | Toughened flame-retarded poly propylene composition and its preparing method | |
| CN112143138A (en) | Recycled plastic particles and preparation method thereof | |
| CN113744923A (en) | MPP cable sheath pipe with high heat resistance and production process thereof | |
| CN118222149B (en) | Insulating fireproof water-based paint for new energy automobile battery and preparation method | |
| CN118185180B (en) | Weather-resistant polypropylene composite material for new energy battery shell and preparation method thereof | |
| CN117186393B (en) | Sulfonate flame retardant applied to polycarbonate and synthesis method | |
| CN117363031B (en) | Phosphorus-containing flame-retardant master batch 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |