CN116516508B - Special material for high melt index random copolymer polypropylene fiber and preparation method thereof - Google Patents
Special material for high melt index random copolymer polypropylene fiber and preparation method thereof Download PDFInfo
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- CN116516508B CN116516508B CN202310221049.9A CN202310221049A CN116516508B CN 116516508 B CN116516508 B CN 116516508B CN 202310221049 A CN202310221049 A CN 202310221049A CN 116516508 B CN116516508 B CN 116516508B
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- -1 polypropylene Polymers 0.000 title claims abstract description 161
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 160
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 160
- 229920005604 random copolymer Polymers 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000000835 fiber Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000006254 rheological additive Substances 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005977 Ethylene Substances 0.000 claims abstract description 33
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000000155 melt Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000004611 light stabiliser Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 230000003078 antioxidant effect Effects 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 150000002978 peroxides Chemical class 0.000 claims description 9
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002530 phenolic antioxidant Substances 0.000 claims description 8
- 239000002516 radical scavenger Substances 0.000 claims description 8
- ITUZAAYHAPMLCR-UHFFFAOYSA-N 2,6-diethyl-2,6-dimethylpiperidine Chemical compound CCC1(C)CCCC(C)(CC)N1 ITUZAAYHAPMLCR-UHFFFAOYSA-N 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 238000007580 dry-mixing Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 4
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- PPRWPCMILDCTGF-UHFFFAOYSA-N 2,6-diethylpiperidine Chemical compound CCC1CCCC(CC)N1 PPRWPCMILDCTGF-UHFFFAOYSA-N 0.000 claims description 3
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003386 piperidinyl group Chemical group 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 description 16
- 239000004745 nonwoven fabric Substances 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 12
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000002657 fibrous material Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The application provides a special material for high melt index random copolymer polypropylene fiber and a preparation method thereof, wherein the mass ratio of raw materials of the special material, namely low melt index random copolymer polypropylene powder, a polypropylene controllable rheology modifier and an ethylene polymerization inhibitor is 1 (3.5 to 8 per mill) (0.3 to 0.5 per mill), the melt index of the special material for high melt index random copolymer polypropylene fiber is 25g/10min to 120g/10min, and the melt index of the low melt index random copolymer polypropylene powder is 2g/10min to 15g/10min. The special material for the high melt index random copolymer polypropylene fiber prepared by the application has the advantages of high melt index, narrow molecular weight distribution, low hardness, low flexural modulus, low number of broken filaments, higher fluidity, better softness and better spinnability.
Description
Technical Field
The application relates to the technical field of chemical materials, in particular to a special material for high melt index random copolymer polypropylene fibers and a preparation method thereof.
Background
In recent years, the demand for polypropylene fiber-dedicated materials in China continues to increase. The special high-end polypropylene fiber materials such as 3155E series of Exxon and 562S of Basel are homo-polypropylene with good mechanical properties, but the materials are hard, so that the requirement of customers on the softness of polypropylene non-woven fabrics is not met; for soft polypropylene non-woven fabrics, it is generally used in China to produce the polypropylene with 10 to 40 percent of propylene-based elastomer, but the cost is too high; the copolymerization polypropylene with the melt index of 25g/10min to 120g/10min is directly polymerized by copolymerization, and the production stability and the product performance of the copolymerization polypropylene non-woven fabric cannot be ensured due to the fact that the molecular weight distribution is wider, the processing spinning performance is unstable and the filaments are easy to break; the ethylene chain segment in the low melt index random copolymer polypropylene is easily crosslinked into netlike macromolecules through common peroxide degradation, the spinning performance is poor, the filaments are extremely easy to break, and the product cannot be used for producing non-woven fabrics. Therefore, developing a special material for polypropylene copolymer fiber with high fluidity and good spinnability in the technical field of chemical materials becomes a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The application provides a special material for high melt index random copolymer polypropylene fiber and a preparation method thereof, so as to obtain the special material for copolymer polypropylene fiber with high fluidity and good spinnability. The specific technical scheme is as follows:
the first aspect of the application provides a special material for high-melt-index random copolymer polypropylene fibers, which comprises raw materials of low-melt-index random copolymer polypropylene powder, a polypropylene controllable rheology modifier and an ethylene polymerization inhibitor in a mass ratio of 1 (3.5-8 mill) (0.3-0.5 mill), wherein the melt index of the special material for high-melt-index random copolymer polypropylene fibers is 25g/10 min-120 g/10min, and the melt index of the low-melt-index random copolymer polypropylene powder is 2g/10 min-15 g/10min.
In some embodiments of the application, the polypropylene controlled rheology modifier comprises, based on the total mass of the polypropylene controlled rheology modifier: 50 to 74 percent of polypropylene, 10 to 30 percent of peroxide, 5 to 10 percent of non-phenolic antioxidant, 2 to 7 percent of non-phenolic light stabilizer, 5 to 10 percent of auxiliary antioxidant, 2 to 5 percent of antistatic agent and 2 to 5 percent of acid scavenger.
In some embodiments of the application, the polypropylene has a melt index of 2.8g/10min to 30g/10min; the peroxide is at least one selected from di-tert-butyl peroxide and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; the non-phenolic antioxidant is at least one selected from antioxidant s-9228 and antioxidant FS-042; the non-phenolic light stabilizer is at least one selected from the group consisting of light stabilizer 944, light stabilizer 770, light stabilizer 622, light stabilizer 2020, light stabilizer 3050, light stabilizer 5050; the auxiliary antioxidant is at least one selected from an antioxidant 168 and an antioxidant 626; the antistatic agent is at least one of glyceryl monostearate and ethoxylated octadecyl amine; the acid scavenger is at least one selected from calcium stearate, zinc oxide and hydrotalcite.
In some embodiments of the present application, the ethylene polymerization inhibitor is a piperidine derivative, at least one selected from the group consisting of 2, 6-dimethylpiperidine, 2, 6-diethylpiperidine, 2, 6-tetramethylpiperidine and 2, 6-dimethyl-2, 6-diethylpiperidine, preferably 2, 6-dimethyl-2, 6-diethylpiperidine.
In some embodiments of the present application, the low melt index random copolymer polypropylene powder is obtained by copolymerizing under the influence of a catalyst a mixed olefin comprising a first monomer propylene and a second monomer; the second monomer is selected from at least one of ethylene, 1-butene, 1-hexene and 1-octane, preferably ethylene or 1-butene.
In some embodiments of the present application, the first monomer is contained in an amount of 95% to 99.9% and the second monomer is contained in an amount of 0.1% to 5% based on the mass of the mixed olefin.
The second aspect of the application provides a preparation method of the special material for high melt index random copolymer polypropylene fiber, which comprises the following steps:
(1) Uniformly mixing the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor according to the mass ratio of 1 (3.5-8 mill): (0.3-0.5 mill), and then placing the mixture into a high-speed mixer with the rotating speed of 60-300 r/min for dry mixing at the temperature of 0-80 ℃ for 1-15 min to obtain a high melt index random copolymer polypropylene fiber premix;
(2) Adding the high melt index random copolymer polypropylene fiber premix in the step (1) into a double-screw granulator with the screw speed of 360r/min to 600r/min for melt extrusion and granulation to obtain the special material for the high melt index random copolymer polypropylene fiber, wherein the specific process parameters of the melt extrusion comprise: the first stage to second stage temperatures are 225 ℃ to 235 ℃, the third stage to fifth stage temperatures are 235 ℃ to 255 ℃, the sixth stage temperatures are 215 ℃ to 225 ℃, the seventh stage temperatures are 205 ℃ to 215 ℃, the eighth stage temperatures are 195 ℃ to 205 ℃, the ninth stage temperatures are 185 ℃ to 195 ℃, the die stage temperatures are 175 ℃ to 185 ℃, the residence time is 0.2min to 1min, and the pressure is 10MPa to 15MPa.
The application has the beneficial effects that:
the application provides a special material for high melt index random copolymer polypropylene fiber and a preparation method thereof, wherein the mass ratio of low melt index random copolymer polypropylene powder to polypropylene controllable rheology modifier to ethylene polymerization inhibitor is controlled within the scope of the application, and the polypropylene controllable rheology modifier can be effectively dispersed and ensure the controllable degradation of the low melt index random copolymer polypropylene powder; the ethylene polymerization inhibitor can effectively avoid the generation of netlike macromolecules caused by ethylene crosslinking in low melt index random copolymer polypropylene powder in the degradation process, so that the spinnability is poor, the consumption of a polypropylene controllable rheology modifier can be reduced, and the degradation efficiency is improved, so that the special material for the high melt index random copolymer polypropylene fiber with high fluidity, low hardness and flexural modulus and good spinnability is obtained.
Of course, it is not necessary for any one product or method of practicing the application to achieve all of the advantages set forth above at the same time.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. Based on the embodiments of the present application, all other embodiments obtained by the person skilled in the art based on the present application are included in the scope of protection of the present application.
The first aspect of the application provides a special material for high-melt-index random copolymer polypropylene fibers, which comprises the raw materials of low-melt-index random copolymer polypropylene powder, a polypropylene controllable rheology modifier and an ethylene polymerization inhibitor in a mass ratio of 1 (3.5-8 mill) (0.3-0.5 mill), wherein the melt index of the special material for high-melt-index random copolymer polypropylene fibers is 25g/10 min-120 g/10min, and the melt index of the low-melt-index random copolymer polypropylene powder is 2g/10 min-15 g/10min.
Through intensive research, the inventor discovers that the polypropylene controllable rheology modifier can effectively disperse and ensure the controllable degradation of the low melt index random copolymerization polypropylene powder by controlling the mass ratio of the low melt index random copolymerization polypropylene powder to the polypropylene controllable rheology modifier to the ethylene polymerization inhibitor within the range; the ethylene polymerization inhibitor can effectively avoid the generation of netlike macromolecules caused by ethylene crosslinking in the low melt index random copolymer polypropylene powder in the degradation process, so that the spinnability is poor, the consumption of a polypropylene controllable rheology modifier can be reduced, and the degradation efficiency is improved, so that the special material for the high melt index random copolymer polypropylene fiber with high fluidity and good spinnability is obtained.
In some embodiments of the application, the polypropylene controlled rheology modifier comprises, based on the total mass of the polypropylene controlled rheology modifier: 50 to 74 percent of polypropylene, 10 to 30 percent of peroxide, 5 to 10 percent of non-phenolic antioxidant, 2 to 7 percent of non-phenolic light stabilizer, 5 to 10 percent of auxiliary antioxidant, 2 to 5 percent of antistatic agent and 2 to 5 percent of acid scavenger. The mass percentage of each component in the polypropylene controllable rheology modifier is controlled within the above range, so that the obtained polypropylene controllable rheology modifier can be effectively dispersed and ensure the controllable degradation of low melt index random copolymer polypropylene powder, thereby being beneficial to obtaining the special material for the high melt index random copolymer polypropylene fiber with high fluidity and good spinnability.
In some embodiments of the application, the polypropylene has a melt index of 2.8g/10min to 30g/10min; the peroxide is selected from at least one of di-tert-butyl peroxide and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; the non-phenolic antioxidant is at least one selected from antioxidant s-9228 and antioxidant FS-042; the non-phenolic light stabilizer is at least one selected from the group consisting of light stabilizer 944, light stabilizer 770, light stabilizer 622, light stabilizer 2020, light stabilizer 3050, light stabilizer 5050; the auxiliary antioxidant is at least one selected from an antioxidant 168 and an antioxidant 626; the antistatic agent is at least one of glyceryl monostearate and ethoxylated octadecyl amine; the acid scavenger is at least one selected from calcium stearate, zinc oxide and hydrotalcite. The polypropylene controllable rheology modifier can be effectively dispersed and ensure the controllable degradation of low melt index random copolymer polypropylene powder by selecting the polypropylene, the peroxide, the non-phenolic antioxidant, the non-phenolic light stabilizer, the auxiliary antioxidant, the antistatic agent and the acid scavenger, thereby being beneficial to obtaining the special material for the high melt index random copolymer polypropylene fiber with high fluidity and good spinnability.
In some embodiments of the present application, the ethylene polymerization inhibitor is a piperidine derivative selected from at least one of 2, 6-dimethylpiperidine, 2, 6-diethylpiperidine, 2, 6-tetramethylpiperidine and 2, 6-dimethyl-2, 6-diethylpiperidine, preferably 2, 6-dimethyl-2, 6-diethylpiperidine. By selecting the ethylene polymerization inhibitor, the problem that the spinnability is poor due to the fact that ethylene in low-melt-index random copolymer polypropylene powder is crosslinked to produce net macromolecules in the degradation process can be effectively avoided, the consumption of a polypropylene controllable rheology modifier can be reduced, the degradation efficiency is improved, and therefore the special material for the high-melt-index random copolymer polypropylene fiber with high fluidity and good spinnability is obtained.
In some embodiments of the present application, the low melt index random copolymer polypropylene powder is obtained by copolymerizing a mixed olefin comprising a first monomer propylene and a second monomer under the action of a catalyst; the second monomer is selected from at least one of ethylene, 1-butene, 1-hexene and 1-octane, preferably ethylene or 1-butene; the catalyst is at least one of spherical, gas phase and small bulk in the Z-N catalyst.
In some embodiments of the application, the first monomer is present in an amount of 95% to 99.9% and the second monomer is present in an amount of 0.1% to 5% based on the mass of the mixed olefins.
In some embodiments of the application, the low melt index random copolymer polypropylene powder may have a molecular weight distribution of 4 to 6, a hardness of 38 to 50, and a flexural modulus of 1100 to 1300MPa. In some embodiments of the application, the polypropylene controlled rheology modifier is prepared as follows: uniformly mixing polypropylene, peroxide, a non-phenolic antioxidant, a non-phenolic light stabilizer, an auxiliary antioxidant, an antistatic agent and an acid scavenger according to the mass ratio of (50 to 74): 10 to 30): (5 to 10): (2 to 7): (5 to 10): (2 to 5): 2 to 5), putting the mixture into a high-speed mixer with the rotation speed of 400r/min to 800r/min for dry mixing at the temperature of 0 ℃ to 60 ℃ for 15min to 30min to obtain a polypropylene controllable rheology modifier premix, adding the polypropylene controllable rheology modifier premix into a twin-screw granulator with the screw rotation speed of 360r/min to 600r/min for melt extrusion and granulation to obtain the polypropylene controllable rheology modifier, wherein the specific process parameters of the melt extrusion comprise: the first stage to second stage temperatures are 225 ℃ to 235 ℃, the third stage to fifth stage temperatures are 235 ℃ to 255 ℃, the sixth stage temperatures are 215 ℃ to 225 ℃, the seventh stage temperatures are 205 ℃ to 215 ℃, the eighth stage temperatures are 195 ℃ to 205 ℃, the ninth stage temperatures are 185 ℃ to 195 ℃, the die stage temperatures are 175 ℃ to 185 ℃, the residence time is 0.2min to 1min, and the pressure is 10MPa to 15MPa. The mass ratio of each component of the polypropylene controllable rheology modifier and the specific process parameters of melt extrusion of the polypropylene controllable rheology modifier are controlled within the above range, so that the obtained polypropylene controllable rheology modifier can be effectively dispersed and ensure the controllable degradation of low melt index random copolymer polypropylene powder, thereby being beneficial to obtaining the special material for the high melt index random copolymer polypropylene fiber with high fluidity, low hardness and flexural modulus and good spinnability.
The length-diameter ratio of the screws in the double-screw granulator in the preparation process of the polypropylene controllable rheology modifier is not particularly limited, and can be the length-diameter ratio parameter known by a person skilled in the art.
The second aspect of the application provides a preparation method of the special material for high melt index random copolymer polypropylene fiber, which comprises the following steps:
(1) Uniformly mixing low melt index random copolymer polypropylene powder, a polypropylene controllable rheology modifier and an ethylene polymerization inhibitor according to the mass ratio of 1 (3.5 to 8 mill): (0.3 to 0.5 mill), and then placing the mixture into a high-speed mixer with the rotating speed of 60 to 300r/min for dry mixing for 1 to 15 minutes at the temperature of 0 to 80 ℃ to obtain a high melt index random copolymer polypropylene fiber premix;
(2) Adding the high melt index random copolymer polypropylene fiber premix in the step (1) into a double-screw granulator with the screw speed of 360r/min to 600r/min for melt extrusion and granulation to obtain the special material for the high melt index random copolymer polypropylene fiber, wherein the specific process parameters of melt extrusion comprise: the first stage to second stage temperatures are 225 ℃ to 235 ℃, the third stage to fifth stage temperatures are 235 ℃ to 255 ℃, the sixth stage temperatures are 215 ℃ to 225 ℃, the seventh stage temperatures are 205 ℃ to 215 ℃, the eighth stage temperatures are 195 ℃ to 205 ℃, the ninth stage temperatures are 185 ℃ to 195 ℃, the die stage temperatures are 175 ℃ to 185 ℃, the residence time is 0.2min to 1min, and the pressure is 10MPa to 15MPa.
Through intensive researches, the inventor discovers that the mass ratio of the raw materials of the special high-melt-index random copolymer polypropylene fiber material and the specific process parameters of the special high-melt-index random copolymer polypropylene fiber material are controlled within the range, so that the special high-melt-index random copolymer polypropylene fiber material is beneficial to effectively dispersing and ensuring the controllable degradation of low-melt-index random copolymer polypropylene powder, and is also beneficial to avoiding the generation of netlike macromolecules by ethylene crosslinking in the low-melt-index random copolymer polypropylene powder in the degradation process, so that the spinnability is poor, meanwhile, the consumption of a polypropylene controllable rheological modifier can be reduced, the degradation efficiency is improved, and the special high-melt-index random copolymer polypropylene fiber material obtained by the method has high melt index, narrow molecular weight distribution, low hardness, low flexural modulus, low filament breakage times, higher flowability, better softness and better spinnability.
The length-diameter ratio of the screw in the double screw granulator in the preparation process of the special material for the high melt index random copolymer polypropylene fiber is not particularly limited, and can be the length-diameter ratio parameter known by a person skilled in the art.
Test method and apparatus：
Melt index test method:
determination of melt Mass Flow Rate (MFR) and melt volume flow Rate (MVR) of Plastic thermoplastics according to the national standards section 1: standard method (GB/T3682.1-2018) test: 5g of a sample to be measured (the sample to be measured is a process sample collected at the outlet of a vibrating screen of a granulator every 15min after the production of the extrusion granulator is stable, 6 times of process samples and homogenized samples after the homogenization is finished after the production are collected) are put into a charging barrel of an LSD-450C melt flow rate measuring instrument (manufactured by Xiamen group-long instruments Co., ltd.) at a set temperature of 230 ℃, weight of 2.16kg, set cutting time of 2.5s and melt density of 0.730g/cm 3 After preheating the melt flow rate instrument for 4min, starting the test, opening the outlet valve below the charging barrel, and recording when the marking line on the piston moves to the top surface of the charging barrel, ending the testThe melt index (MFR) of the sample to be measured is recorded, and the average value is taken as the melt index of the special material of the high melt index random copolymer polypropylene, wherein the unit is: g/10min.
Hardness testing method:
indentation hardness (Shore hardness) was measured using a durometer according to national Standard "Plastic and hard rubber (GB/T2411-2008).
Flexural modulus test method
According to the national standard "determination of Plastic flexural Property" (GB/T9341-2008).
The method for testing the number of broken wires comprises the following steps:
in the process of producing the SS polypropylene non-woven fabric by using the special high melt index random copolymer polypropylene fiber material, according to the 72h monitoring result of a Smart Vision on-line non-woven fabric surface defect detection system (manufactured by the technology Co., ltd. In the tin-free east city), counting the number of broken filaments per hour, counting the number of broken filaments obtained per hour, taking the average number of broken filaments as the special high melt index random copolymer polypropylene material, wherein the unit is: times/hour.
Molecular weight distribution test method:
the average molecular weight and molecular weight distribution of the polymers were determined according to the national standard "Plastic volume exclusion chromatography", part 4: high temperature method (GB/T36214.4-2018).
Example 1
< preparation of Polypropylene controlled rheology modifier >
Uniformly mixing polypropylene, di-tert-butyl peroxide, an antioxidant s-9228, an antioxidant FS-042, a light stabilizer 944, a light stabilizer 622, an auxiliary antioxidant 168, glyceryl monostearate and calcium stearate according to the mass ratio of 60:15:6:1.5:1:1.5:8:3:4, putting the mixture into a high-speed mixer with the rotating speed of 500r/min, dry-mixing the mixture for 20min at 25 ℃ to obtain a polypropylene controllable rheological modifier premix, adding the polypropylene controllable rheological modifier premix into a double-screw granulator with the length-diameter ratio of 42 and the rotating speed of 580r/min, and carrying out melt extrusion and granulation to obtain the polypropylene controllable rheological modifier, wherein the specific process parameters of the melt extrusion comprise: the temperature of the first section to the second section is 230 ℃, the temperature of the third section to the fifth section is 240 ℃, the temperature of the sixth section is 220 ℃, the temperature of the seventh section is 210 ℃, the temperature of the eighth section is 200 ℃, the temperature of the ninth section is 190 ℃, the temperature of the die head section is 180 ℃, the residence time is 1min, and the pressure is 12MPa.
The polypropylene used in this example had a melt index of 2.8g/10min.
< preparation of high melt index random copolymer Polypropylene Material >
Uniformly mixing low melt index random copolymer polypropylene powder, a polypropylene controllable rheology modifier and an ethylene polymerization inhibitor 2, 6-dimethyl-2, 6-diethyl piperidine according to the mass ratio of 1:3.5%o to 0.3%o, putting the mixture into a high-speed mixer with the rotating speed of 120r/min, dry-mixing the mixture at 55 ℃ for 3min to obtain high melt index random copolymer polypropylene fiber premix, putting the high melt index random copolymer polypropylene fiber premix into a double-screw granulator with the length-diameter ratio of 48 and the rotating speed of 450r/min, and carrying out melt extrusion and granulation to obtain the special material for the high melt index random copolymer polypropylene, wherein the specific process parameters of the melt extrusion comprise: the temperature of the first section to the second section is 230 ℃, the temperature of the third section to the fifth section is 245 ℃, the temperature of the sixth section is 220 ℃, the temperature of the seventh section is 210 ℃, the temperature of the eighth section is 200 ℃, the temperature of the ninth section is 190 ℃, the temperature of the die head section is 180 ℃, the residence time is 0.5min, and the pressure is 12MPa.
The low-melt-index random copolymer polypropylene powder used in the embodiment is obtained by copolymerizing a first monomer propylene and a second monomer ethylene in mixed olefins under the action of a catalyst, wherein the content of the first monomer is 97%, the content of the second monomer is 3%, the adding amount of the catalyst is 0.0025%, and the catalyst is a Z-N gas phase catalyst based on the mass of the mixed olefins.
<17g/m 2 Production of SS polypropylene nonwoven fabrics>
Putting the special material for high melt index random copolymer polypropylene into special production equipment for SS polypropylene non-woven fabric, setting the temperature of a melt-blowing die head to be 235 ℃, the wiring speed of production to be 350m/min, and processing to obtain 17g/m 2 SS polypropylene nonwoven fabric.
Examples 2 to 4
The procedure of example 1 was repeated except that the relevant preparation parameters were adjusted in accordance with tables 1 and 2.
Comparative examples 1 to 2
The procedure of example 1 was repeated except that the relevant preparation parameters were adjusted in accordance with tables 1 and 2.
The relevant preparation parameters and performance parameters for each example and comparative example are shown in tables 1 and 2.
From the embodiment 1 to the embodiment 4, the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor within the scope of the application are selected to degrade the low melt index random copolymer polypropylene powder, and the obtained high melt index random copolymer polypropylene fiber special material has high melt index, narrow molecular weight distribution, low hardness and low flexural modulus, and the hardness of the material can reach the hardness of homo-polypropylene with the same melt index; the special material for the high melt index random copolymer polypropylene fiber prepared by the application is applied to the production of non-woven fabrics, and the non-woven fabrics have low yarn breakage times, so that the special material for the high melt index random copolymer polypropylene fiber has high fluidity and good softness and spinnability.
As can be seen from examples 1 to 4 and comparative example 1, the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor within the scope of the application are selected, and compared with the method for degrading the low melt index random copolymer polypropylene powder by using only the polypropylene controllable rheology modifier, the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor are granulated, so that the consumption of the polypropylene controllable rheology modifier can be reduced; meanwhile, the obtained special material for the high melt index random copolymer polypropylene fiber has high melt index, narrow molecular weight distribution, low hardness and low flexural modulus; the special material for the random copolymer polypropylene fiber prepared by the embodiment of the application is applied to the production of non-woven fabrics, and the non-woven fabrics have low yarn breakage times, so that the special material for the high-melt-index random copolymer polypropylene fiber has high fluidity and good softness and spinnability.
As can be seen from examples 1 to 4 and comparative example 2, the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor within the scope of the application are selected, and compared with the degradation of the low melt index random copolymer polypropylene powder by using only di-tert-butyl peroxide, the special material for the high melt index random copolymer polypropylene fiber, which is obtained by granulating the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor, has high melt index, narrow molecular weight distribution, low hardness and low flexural modulus; the special material for the random copolymer polypropylene fiber prepared by the embodiment of the application is applied to the production of non-woven fabrics, and the non-woven fabrics have low yarn breakage times, so that the special material for the high-melt-index random copolymer polypropylene fiber has high fluidity and good softness and spinnability.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (7)
1. The mass ratio of the raw materials of the high melt index random copolymer polypropylene fiber special material is 1 (3.5 to 8 mill): (0.3 to 0.5 mill), wherein the melt index of the high melt index random copolymer polypropylene fiber special material is 25 to 120g/10min, and the melt index of the low melt index random copolymer polypropylene powder is 2 to 15g/10min;
the polypropylene controlled rheology modifier comprises, based on the total mass of the polypropylene controlled rheology modifier: 50 to 74 percent of polypropylene, 10 to 30 percent of peroxide, 5 to 10 percent of non-phenolic antioxidant, 2 to 7 percent of non-phenolic light stabilizer, 5 to 10 percent of auxiliary antioxidant, 2 to 5 percent of antistatic agent and 2 to 5 percent of acid scavenger; the peroxide is at least one selected from di-tert-butyl peroxide and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; the non-phenolic antioxidant is at least one selected from antioxidant s-9228 and antioxidant FS-042; the non-phenolic light stabilizer is at least one selected from the group consisting of light stabilizer 944, light stabilizer 770, light stabilizer 622, light stabilizer 2020, light stabilizer 3050, light stabilizer 5050; the auxiliary antioxidant is at least one selected from an antioxidant 168 and an antioxidant 626; the antistatic agent is at least one of glyceryl monostearate and ethoxylated octadecyl amine; the acid scavenger is at least one selected from calcium stearate, zinc oxide and hydrotalcite;
the ethylene polymerization inhibitor is piperidine derivative and is at least one selected from 2, 6-dimethylpiperidine, 2, 6-diethylpiperidine, 2, 6-tetramethylpiperidine and 2, 6-dimethyl-2, 6-diethylpiperidine.
2. The high melt index random copolymer polypropylene fiber dedicated material according to claim 1, wherein the polypropylene has a melt index of 2.8g/10min to 30g/10min.
3. The high melt index random copolymer polypropylene fiber dedicated material according to claim 1, wherein said ethylene polymerization inhibitor is selected from the group consisting of 2, 6-dimethyl-2, 6-diethylpiperidine.
4. The high melt index random copolymer polypropylene fiber dedicated material according to claim 1, wherein the low melt index random copolymer polypropylene powder is obtained by copolymerizing a mixed olefin comprising a first monomer propylene and a second monomer under the action of a catalyst; the second monomer is selected from at least one of ethylene, 1-butene, 1-hexene and 1-octane.
5. The high melt index random copolymer polypropylene fiber dedicated material according to claim 4, wherein said second monomer is selected from the group consisting of ethylene and 1-butene.
6. The high melt index random copolymer polypropylene fiber dedicated material according to claim 4, wherein the content of the first monomer is 95 to 99.9% and the content of the second monomer is 0.1 to 5% based on the mass of the mixed olefin.
7. A method for producing the high melt index random copolymer polypropylene fiber special material according to any one of claims 1 to 6, comprising the steps of:
(1) Uniformly mixing the low melt index random copolymer polypropylene powder, the polypropylene controllable rheology modifier and the ethylene polymerization inhibitor according to the mass ratio of 1 (3.5-8 mill): (0.3-0.5 mill), and then placing the mixture into a high-speed mixer with the rotating speed of 60-300 r/min for dry mixing at the temperature of 0-80 ℃ for 1-15 min to obtain a high melt index random copolymer polypropylene fiber premix;
(2) Adding the high melt index random copolymer polypropylene fiber premix in the step (1) into a double-screw granulator with the screw speed of 360r/min to 600r/min for melt extrusion and granulation to obtain the special material for the high melt index random copolymer polypropylene fiber, wherein the specific process parameters of the melt extrusion comprise: the first stage to second stage temperatures are 225 ℃ to 235 ℃, the third stage to fifth stage temperatures are 235 ℃ to 255 ℃, the sixth stage temperatures are 215 ℃ to 225 ℃, the seventh stage temperatures are 205 ℃ to 215 ℃, the eighth stage temperatures are 195 ℃ to 205 ℃, the ninth stage temperatures are 185 ℃ to 195 ℃, the die stage temperatures are 175 ℃ to 185 ℃, the residence time is 0.2min to 1min, and the pressure is 10MPa to 15MPa.
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