CN114316146A - Organosilicon modified polypropylene compound, preparation method and application in melt-blown material - Google Patents
Organosilicon modified polypropylene compound, preparation method and application in melt-blown material Download PDFInfo
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- CN114316146A CN114316146A CN202011084661.9A CN202011084661A CN114316146A CN 114316146 A CN114316146 A CN 114316146A CN 202011084661 A CN202011084661 A CN 202011084661A CN 114316146 A CN114316146 A CN 114316146A
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- -1 polypropylene Polymers 0.000 title claims abstract description 154
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 138
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 131
- 150000001875 compounds Chemical class 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 16
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 15
- CHEFFAKKAFRMHG-UHFFFAOYSA-N ethenyl-tris(trimethylsilyloxy)silane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C=C CHEFFAKKAFRMHG-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 abstract description 22
- 238000001914 filtration Methods 0.000 abstract description 9
- 230000035699 permeability Effects 0.000 abstract description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 2
- 229910000077 silane Inorganic materials 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 29
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 12
- MEJKOGNPFBXLMR-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-ethenyl-dimethylsilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C=C MEJKOGNPFBXLMR-UHFFFAOYSA-N 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 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 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 239000004750 melt-blown nonwoven Substances 0.000 description 6
- 239000005051 trimethylchlorosilane Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229960003750 ethyl chloride Drugs 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920001410 Microfiber Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000012754 barrier agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NELRINSZCVVEAD-UHFFFAOYSA-N chloro-ethenyl-methylsilane Chemical compound C[SiH](Cl)C=C NELRINSZCVVEAD-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- ROPULXQBMNVQNU-UHFFFAOYSA-N ethoxy(2-methylprop-1-enyl)silane Chemical compound CCO[SiH2]C=C(C)C ROPULXQBMNVQNU-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000289 melt material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
The invention relates to an organic silicon modified polypropylene compound, a preparation method and application thereof in melt-blown materials. In the invention, a proper amount of silane or siloxane containing vinyl is added in the degradation process of polypropylene, and the silane or siloxane can react with a free substrate segment generated in the degradation process, or a vinyl organic silicon compound generates free radicals under the action of an initiator and reacts with polypropylene molecules or a free substrate segment with small molecular weight, so that the vinyl silane or siloxane is grafted to a polypropylene molecular chain, and the process and the degradation of the polypropylene occur simultaneously. The melt-blown cloth and the filter material are made of polypropylene melt-blown material grafted with organic silicon monomer. The composite material has excellent flexibility and silky hand feeling, and the filtering material has excellent air permeability, greatly reduced air permeability resistance and excellent hydrophobicity.
Description
Technical Field
The invention belongs to the field of organosilicon modified polymers, and particularly relates to an organosilicon compound grafted polypropylene compound using a vinyl end capping, a preparation method and application in melt spraying.
Background
Polypropylene is an important high molecular compound. The polypropylene with high melt index is often used as a spray melt material for preparing melt-blown non-woven fabrics, and because the polypropylene melt is subjected to high-speed airflow spray drafting in the melt-blown fiber forming process to form superfine fibers with the diameter of several microns, the polypropylene melt has good barrier filtering property, air permeability and oil absorption property, and is widely applied to the fields of medical protection, sanitary materials, oil absorption materials, heat insulation and sound absorption materials, battery separators and the like.
In the prior art, polypropylene is required to have a very high melt index (more than or equal to 500g/10min) when polypropylene melt-blown non-woven fabrics are prepared, and a reaction extrusion degradation control method is usually adopted in a common polypropylene melt-blown material preparation process to obtain polypropylene with a high melt index. The reactive extrusion method has low production cost and accurate and adjustable melt finger, and is more applied to the production of the existing melt-blown non-woven fabric.
The polypropylene melt-blown material has too large resistance in the melt-blown process, which causes uneven spinning, hole blockage and the like. Meanwhile, the melt-blown cloth made of polypropylene melt-blown materials has larger air permeability resistance, and particularly when the middle layer is added to improve the filtering effect, the air resistance is too large, so that the breathing of a wearer is difficult.
Polypropylene meltblown materials are reported in numerous patent documents, for example: chinese patent document CN 111410913A reports a melt-blown polypropylene composition, a preparation method and application thereof. The melt-blown polypropylene composition comprises 90-99 parts of polypropylene resin, 0.5-10 parts of fiber-forming adjusting master batch and 0.1-1 part of free radical initiator, wherein the fiber-forming adjusting master batch comprises 30-90 parts of polypropylene resin, 5-35 parts of hyperbranched associated polymer and 5-35 parts of interfacial barrier agent in parts by weight. The melt-blown nonwoven fabric fibers prepared from the composition have uniform diameter, good hand feeling and bulkiness. Chinese patent document No. 103747951A, filed by 3M innovative limited, usa, reports a process for the preparation of filter materials comprising melt-spinnable microfibers of polydiorganosiloxane polyimide copolymer, together with other melt-fabricable microfibers.
It has also been reported that silicone oil is added as a lubricant or a release agent in the processing of polymer materials such as polyethylene, polyvinyl chloride, polypropylene, etc., but the silicone oil is easily precipitated on the surface of the product due to incompatibility between the silicone oil and the polymer materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an organic silicon modified polypropylene compound, a preparation method and application in melt-blown materials. The research of the invention discovers that in the process of degrading polypropylene, certain organic silicon monomers or low molecular weight polysiloxane are grafted, so that the gas resistance of the filter material prepared by the method can be greatly reduced. Moreover, the melt-blowing process is smooth, the filamentation is uniform, and the surface of the material feels silky.
Several vinyl silicone containing monomers and low molecular weight vinyl mono-terminated polysiloxanes are prepared and preferred in the present invention. And simultaneously, the operating conditions of the free radical initiated extrusion degradation of the polypropylene are adjusted, and the grafting reaction of the polypropylene is completed under the condition of obtaining the degraded polypropylene with qualified melt index. The polypropylene melt-blown material with excellent performance is obtained. The melt-blown non-woven fabric prepared by the method shows excellent air permeability, good hand feeling and slightly improved filtering effect through tests.
The technical scheme of the invention is as follows:
an organic silicon modified polypropylene compound is obtained by grafting modified polypropylene through chemical reaction of an organic silicon compound; the organic silicon compound has a structure shown in a formula (I) or a formula (II);
a compound of the formula (I),
formula (II);
in formula (I): r is H or C1-C7 alkyl; r1、R2、R3Is H or C1-C5 alkyl, or phenyl or substituted phenyl or trimethylsiloxyalkyl;
in the formula (II): r is H or C1-C7 alkyl; r1、R2、R3、R4、R5Is C1-C5 alkyl or phenyl or substituted phenyl, or R1、R2、R3One of them is hydroxyl, m is less than or equal to 10.
According to the invention, it is preferred that in formula (I): r is C1-C3 alkyl; r1、R2、R3Is C1-C2 alkyl, or phenyl or substituted phenyl or trimethylsiloxyalkyl;
in the formula (II): preferably, R is H or methyl; r1、R2、R3、R4、R5Is C1-C2 alkyl or phenyl or substituted phenyl, or R1、R2、R3One of them is hydroxyl, m is less than or equal to 10.
According to the invention, the compounds of the formula (I) are preferably 1, 1, 1, 2, 3, 3, 3-heptamethyl-2-vinyltrisiloxane (abbreviated to vinylheptamethyltrisiloxane), vinyltris (trimethylsiloxy) silane.
According to the invention, the compound of formula (II) is preferably a trimethylsilyl-and vinyl-terminated polydimethylsiloxane or a hydroxy-and vinyl-terminated polydimethylsiloxane.
According to the invention, the organosilicon compounds can be prepared by the prior art.
According to the invention, the grafted organosilicon compound monomer preferably accounts for 1-6% of the polypropylene by mass.
According to the present invention, the preparation method of the above silicone-modified polypropylene compound comprises the steps of:
mixing the organic silicon compound and the polypropylene uniformly, adding the initiator and the antioxidant, and performing degradation and grafting reaction in an extruder at the temperature of 160-180 ℃ simultaneously to obtain the polypropylene modified polypropylene.
According to the invention, the mass ratio of the polypropylene, the organic silicon compound, the initiator and the antioxidant is preferably 100: (0.5-15): (0.1-0.5): (0.05-0.3);
further preferably, the mass ratio of the polypropylene to the organic silicon compound to the initiator to the antioxidant is 100: (1-6): (0.2-0.4): (0.1-0.2).
According to the invention, the temperature of the grafting reaction is preferably 160-180 ℃.
According to the invention, the application of the organic silicon modified polypropylene compound is used as a melt-blown material for producing melt-blown cloth and non-woven fabrics.
According to the invention, the master batch obtained from the organic silicon modified polypropylene compound is also provided.
According to the present invention, there is also provided a mask comprising a meltblown prepared from the above silicone-modified polypropylene compound.
The principle of the invention is as follows:
the usual polypropylene meltblown preparation is usually carried out in reactive extrusion equipment such as twin-screw extruders. The high molecular weight polypropylene is subjected to chain scission degradation under the action of an initiator at a high temperature of an extruder to obtain the high melt index polypropylene. The reaction system of this process has a large number of polypropylene fragments with free radicals. The invention pre-mixes organosilicon compound containing vinyl functional group in polypropylene raw material, the vinyl organosilicon compound reacts with a large amount of polypropylene free substrate segments under the action of initiator, and realizes the grafting reaction of polypropylene while degrading the polypropylene.
The invention has not been described in detail, but is in accordance with the state of the art.
The invention has the beneficial effects that:
1. the polypropylene melt-blown material grafted with the organic silicon compound shows excellent lubricating performance in the spray-melt process of producing melt-blown cloth, so that the spray-melt process is smooth, and the spinning is uniform.
2. The spray-fused fabric made of the polypropylene melt-spray material grafted with the organic silicon compound shows flexibility and silkiness. Compared with the melt-blown cloth made of ungrafted degraded polypropylene, the air permeability resistance is greatly reduced and can be reduced by 29-32%, and meanwhile, the filtration efficiency is improved compared with that of the ungrafted polypropylene melt-blown cloth.
3. The spray-melt cloth made of the polypropylene melt-spray material grafted with the organic silicon compound has good hydrophobicity.
Drawings
FIG. 1 is an infrared spectrum of a polypropylene melt spray grafted vinyltris (trimethylsiloxy) silane of example 1.
FIG. 2 is an IR spectrum of a melt-blown vinyl heptamethyltrisiloxane polypropylene graft in example 2.
FIG. 3 shows the IR spectra of the vinyl and trimethylsilyl terminated polydimethylsiloxane polypropylenes grafted, respectively, in example 3.
FIG. 4 is an IR spectrum of vinyl heptamethyl disiloxane monomer.
FIG. 5 is an infrared spectrum of trimethylsilyl and vinyl terminated polydimethylsiloxane monomers.
FIG. 6 shows the IR spectrum of ungrafted polypropylene.
FIG. 7 is a graph showing the hydrophobic contact angle test of silicone grafted polypropylene prepared in example 1 of the present invention.
FIG. 8 is a graph showing a hydrophobic contact angle test of a product obtained without adding vinyltris (trimethylsiloxy) silane in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The starting materials mentioned in the examples are all conventional commercial products or are prepared according to the prior art. Wherein:
polypropylene PP: homo-polypropylene, PP 320 powder, melt flow rate 30g/10min (230 ℃/2.16 kg);
vinyl heptamethyl trisiloxane), molecular weight 248.46, boiling point, 210-;
vinyltris (trimethylsiloxy) silane, boiling point 248-;
trimethylsilyl and vinyl terminated polydimethylsiloxane, molecular weight 550-650, colorless transparent liquid.
Hydroxyl and vinyl mono-terminated polydimethylsiloxane, molecular weight 500-.
Free radical initiator: 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, commercially available;
antioxidant: 1010: y-001; 168: y-002; is commercially available.
In the examples, the preparation of meltblown fabrics can be carried out according to the prior art.
1. Vinyl tris (trimethylsiloxy) silane, prepared as follows:
the instrument comprises the following steps: a1000 ml four-necked flask was equipped with mechanical stirring, thermometer, reflux condenser, condenser connected to a condenser and collection flask for introduction of chilled saline.
190.5g (1mol) of vinyltriethoxysilane and 6g of anhydrous ferric trichloride are added into a bottle, the bottle is heated to 60 ℃, 435g (4mol) of trimethylchlorosilane is dropwise added, the solution is dropwise added for 2 hours, and the reaction is continued for 12 hours at the same temperature. A20-ml round-bottomed flask was sampled by 5g, low-boiling substances were evacuated under negative pressure, the vinyl content was measured, and when the vinyl content was reduced to 3.20mmol/g in mmol/g (iodine bromide/sodium thiosulfate method), the reaction was terminated, and the collected ethyl chloride was appropriately charged in a pressure vessel. Then, the excessive trimethylchlorosilane is recovered by negative pressure distillation. The yield was 325g, brownish. The content of vinyl is 3.15-3.20mmol/g, 5% active carbon is added for decolorization, and colorless transparent liquid is obtained.
2. Vinyl heptamethyl trisiloxane prepared as follows:
the instrument comprises the following steps: a1000 ml four-necked flask was equipped with mechanical stirring, thermometer, reflux condenser, condenser connected to a condenser and collection flask for introduction of chilled saline.
141.5g (1mol) of vinylmethyldichlorosilane and 5g of anhydrous ferric trichloride are put into a bottle, heated to 60 ℃, and 326g (3mol) of trimethylchlorosilane is added dropwise and added dropwise for 2 hours. Then the reaction is carried out for 8 hours at the same temperature. A20-mL round-bottom flask was used to take a sample of 5g, the low-boiling components were removed under reduced pressure, the vinyl content (mmol/g, iodine bromide/sodium thiosulfate method) was determined, and when the vinyl content was reduced to 4.01mmol, g, the reaction was complete and the collected ethyl chloride was properly placed in a pressure vessel. Then, the excessive trimethylchlorosilane is recovered by negative pressure distillation. The yield was 250 g. Slightly brownish. The vinyl content is 4.01-4.02 mmol. Adding 5% active carbon for decolorization to obtain colorless transparent liquid.
3. Hydroxyl-and vinyl-terminated polydimethylsiloxane, prepared as follows:
the instrument comprises the following steps: a1000 ml four-necked flask was equipped with mechanical stirring, thermometer, reflux condenser, condenser connected to a condenser and collection flask for introduction of chilled saline.
500g (1mol, hydroxyl content 4.6mmol/g) of hydroxyl silicone oil, 156g (1.2mol) of dimethylvinyl ethoxy silane and 8g of tin laurate are put into a bottle and subjected to reflux reaction for 16-18 h. Sampling 5g with a 20ml round bottom flask, extracting low-boiling-point substances under negative pressure, determining that the vinyl content (mmol/g, iodine bromide/sodium thiosulfate method) is more than 2.3mmol/g, finishing the reaction, collecting chloroethane, and properly filling a pressure container. Then, the excessive vinyl methyl chlorosilane is recovered by negative pressure distillation. The bottle had a product yield of 550 g. The vinyl content was 2.28mmol/g and the hydroxyl content was 2.32 mmol/g. Slightly light yellow, adding a small amount of active carbon for decolorization to obtain colorless transparent liquid.
4. Trimethylsilyl and vinyl-terminated polydimethylsiloxane, prepared as follows:
the instrument comprises the following steps: a1000 ml four-necked flask was equipped with mechanical stirring, thermometer, reflux condenser, and the condenser was connected to an HCl absorption unit.
550g (1mol, prepared in example 3) of hydroxy-and vinyl-terminated polydimethylsiloxane were charged into a flask, 114g (1.01mol) of trimethylchlorosilane were added dropwise over 2 hours with stirring at 30 to 40 ℃ and reacted for 2 hours. A20-ml round-bottom flask was used to take 5g of the product, and the low-boiling substance was removed under negative pressure to determine that the hydroxyl group content was less than 0.001mmol/g (phthalic anhydride esterification method). After the reaction is finished, the excessive trimethylchlorosilane is recovered by negative pressure distillation. The bottle had a product yield of 620 g. Slightly light yellow, adding a small amount of active carbon for decolorization to obtain colorless transparent liquid.
5. In order to verify that the organic silicon monomer is grafted to the polypropylene molecular chain, infrared spectrum detection is carried out on the purified grafted melt-blown material.
The purification method comprises the steps of taking 5-6g of grafted polypropylene melt-spray material, adding 100mL of dimethylbenzene, heating to dissolve the grafted polypropylene melt-spray material, then cooling to about 50 ℃, adding 100mL of acetone to separate out a precipitate, filtering, repeating purification once on a filter cake, dissolving an ungrafted organosilicon monomer in a solvent to be completely removed, and drying the filter cake to constant weight. Samples for infrared detection were taken.
The solubility of the grafting monomer in a mixed solvent of xylene and acetone (1: 1) at room temperature was tested beforehand and was greater than 10%. Twice purification, the non-grafted silicone monomer will dissolve into the solvent and be completely removed.
Except that the purified polypropylene grafted with the organic silicon monomer is used as an infrared spectrum, the polypropylene not grafted with the organic silicon monomer is also used as an infrared spectrum for comparison analysis.
The analysis basis is as follows:
silicon-containing organic compounds, having their own characteristic infrared absorption, see fig. 6, 7, and in particular the characteristic peaks that occur at this point in the polypropylene with little or no absorption, are most interesting for determining whether silicone monomers are grafted onto the polypropylene chain, such as: Si-CH3 at 1261cm-1A strong absorption peak is nearby; (Polypropylene here has no water absorption peak); Si-O-Si has a strong stretching peak near 1077 (polypropylene has no water absorption peak here); a strong and wide absorption peak exists at 1100-1000; (Polypropylene here has no water absorption peak).
Example 1
The weight ratio is as follows:
100 portions of polypropylene
Vinyltris (trimethylsiloxy) silane, 3 parts
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.3 part
Antioxidant: 10100.05 parts
Antioxidant: 1680.05 parts of a binder;
all the materials are mixed evenly, and are extruded, pulled into strips and cut into granules by a double-screw extruder to obtain the organic silicon grafted polypropylene, and the reaction extrusion temperature is 160-180 ℃.
The infrared spectrum of the silicone-grafted polypropylene obtained in this example was measured, as shown in fig. 1. FIG. 4 is an IR spectrum of vinyl heptamethyl disiloxane monomer. FIG. 5 shows the IR spectra of trimethyl and vinyl terminated polydimethylsiloxane monomers. FIG. 6 shows the IR spectrum of ungrafted polypropylene.
As is clear from comparative analysis of FIGS. 1, 4 and 6, the distance was 1053.87cm-1The polypropylene has a strong absorption broad peak, which is an Si-O stretching vibration absorption peak, and the polypropylene has no absorption peak; 841.78cm-1There is a sharp strong absorption peak, which should be Si- (CH)3)2The methyl plane of the polypropylene has a swinging absorption peak, and the polypropylene has only a small absorption peak. Successful grafting of vinyltris (trimethylsiloxy) silane into polypropylene was demonstrated.
The test data for the meltblown nonwoven prepared from the meltblown material obtained are given in table 1.
TABLE 1 Polypropylene meltblown Fabric air resistance test results grafted with vinyltris (trimethylsiloxy) silane
As can be seen from Table 1, the air resistance of the polypropylene melt-blown fabric grafted with vinyltris (trimethylsiloxy) silane is obviously reduced, and the filtration efficiency is slightly improved.
Example 2
The weight ratio is as follows:
100 portions of polypropylene PP
3 parts of vinyl heptamethyl trisiloxane
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.3 part
Antioxidant: 10100.05 parts
Antioxidant: 1680.05 parts.
All the materials are mixed evenly, and the mixture is extruded by a double-screw extruder to be pulled into strips and cut into granules, so that the organic silicon grafted polypropylene is obtained. The reaction extrusion temperature is 160 ℃ and 180 ℃.
The infrared spectrum of the silicone-modified polypropylene compound obtained in this example was measured, as shown in FIG. 2. As is clear from comparative analyses of FIGS. 2, 4 and 6, the thickness of the film was 1000.10cm-1There is a strong absorption broad peak, which should be Si-O stretching vibration absorption peak, where polypropylene has no absorption peak, 808.19cm-1There is a sharp and strong absorption peak, which should be Si- (CH)3)2The methyl plane of the polypropylene has a swinging absorption peak, and the polypropylene has only a small absorption peak. Successful grafting of vinyl heptamethyltrisiloxane into polypropylene was demonstrated.
The test results of the meltblown prepared with the silicone-modified polypropylene compound are shown in table 2.
TABLE 2 air resistance test results for polypropylene melt-blown fabric grafted with vinyl heptamethyltrisiloxane
As can be seen from Table 2, the polypropylene melt-blown fabric grafted with vinyl heptamethyltrisiloxane has obvious air resistance reduction effect and slightly improved filtration efficiency.
Example 3
The weight ratio is as follows:
1100 parts of polypropylene PP
3 parts of trimethyl silicon and vinyl-terminated polydimethylsiloxane
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.3 part
Antioxidant: 10100.05 parts
Antioxidant: 1680.05 parts.
And (3) uniformly mixing all the materials, extruding, bracing and cutting into granules by using a double-screw extruder to obtain the organic silicon grafted polypropylene compound. The reaction extrusion temperature is 160 ℃ and 180 ℃.
The silicone-grafted polypropylene compound obtained in this example was tested for infrared lightSpectrum, as shown in fig. 3. As is clear from comparative analyses of FIGS. 3, 5 and 6, the thickness was 1005.16cm-1There is a strong absorption broad peak, which should be Si-O stretching vibration absorption peak, where polypropylene has no absorption peak, 804.26cm-1There is a sharp strong absorption peak, which should be Si- (CH)3)2The methyl plane of the polypropylene has a swinging absorption peak, and the polypropylene has only a small absorption peak. Successful grafting of trimethyl and vinyl terminated polydimethylsiloxanes into polypropylene was demonstrated.
The test results of the meltblown prepared with the silicone-modified polypropylene compound are shown in Table 3
TABLE 3 air resistance test results for polypropylene melt-blown fabric grafted with vinyl heptamethyltrisiloxane
As can be seen from Table 3, similar to the data in tables 1 and 2, the polypropylene meltblown fabric grafted with trimethylsilyl and vinyl-terminated polydimethylsiloxane has a significant air resistance reduction effect and a slightly improved filtration efficiency.
Example 4
As described in example 1, except that the following components are mixed by mass:
100 portions of polypropylene PP
Vinyl tri (trimethylsiloxy) silane (abbreviated as nonamethylsilane) 5 parts
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.4 part
Antioxidant: 10100.1 parts
Antioxidant: 1680.1 parts of a binder;
all the materials are mixed evenly, and are extruded, pulled into strips and cut into granules by a double-screw extruder to obtain the organic silicon grafted polypropylene compound, and the reaction extrusion temperature is 160-180 ℃.
The test results of the meltblown prepared with this silicone-modified polypropylene compound are similar to those in table 1.
Example 5
As described in example 2, except that the following components are mixed by mass:
100 portions of polypropylene PP
Vinyl heptamethyl trisiloxane 5 parts
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.5 part
Antioxidant: 10100.1 parts
Antioxidant: 1680.05 parts.
And (3) uniformly mixing all the materials, extruding, bracing and cutting into granules by using a double-screw extruder to obtain the organic silicon grafted polypropylene compound. The reaction extrusion temperature is 160 ℃ and 180 ℃.
The test results of the meltblown prepared with this silicone-modified polypropylene compound are similar to those listed in table 2.
Example 6
As described in example 3, except that the following components are mixed by mass:
100 portions of polypropylene PP
Trimethylsilyl and vinyldimethylsilyl end-capped polydimethylsiloxane 5 parts
2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane 0.4 part
Antioxidant: 10100.05 parts
Antioxidant: 1680.2 parts.
And (3) uniformly mixing all the materials, extruding, bracing and cutting into granules by using a double-screw extruder to obtain the organic silicon grafted polypropylene compound. The reaction extrusion temperature is 160 ℃ and 180 ℃.
The test results of the meltblown prepared with this silicone-modified polypropylene compound are similar to those in table 3.
Test example 1
The silicone-grafted polypropylene obtained in example 1 was tested for its hydrophobic contact angle and the polypropylene for its hydrophobic contact angle, as shown in fig. 7, 8. Wherein, fig. 7 is a test chart of a hydrophobic contact angle of the silicone-grafted polypropylene obtained in example 1, and fig. 8 is a test chart of a hydrophobic contact angle of the product obtained in example 1 without adding vinyltris (trimethylsiloxy) silane.
As can be seen from fig. 7 and 8, the product obtained without addition of vinyltris (trimethylsiloxy) silane exhibited some hydrophobicity, but the hydrophobicity was not so strong. The hydrophobic contact angle of the organosilicon grafted polypropylene is obviously increased, and the hydrophobic property is greatly improved.
Claims (10)
1. An organic silicon modified polypropylene compound is characterized in that the organic silicon modified polypropylene compound is obtained by grafting modified polypropylene through chemical reaction of an organic silicon compound; the organic silicon compound has a structure shown in a formula (I) or a formula (II);
in formula (I): r is H or C1-C7 alkyl; r1、R2、R3Is H or C1-C5 alkyl, or phenyl or substituted phenyl or trimethylsiloxyalkyl;
in the formula (II): r is H or C1-C7 alkyl; r1、R2、R3、R4、R5Is C1-C5 alkyl or phenyl or substituted phenyl, or R1、R2、R3One of them is hydroxyl, m is less than or equal to 10.
2. The silicone-modified polypropylene compound according to claim 1, wherein in formula (I): r is C1-C3 alkyl; r1、R2、R3Is C1-C2 alkyl, or phenyl or substituted phenyl or trimethylsiloxyalkyl;
in the formula (II): preferably, R is H or methyl; r1、R2、R3、R4、R5Is C1-C2 alkyl or phenyl or substituted phenyl, or R1、R2、R3One of them is hydroxyM is less than or equal to 10.
3. The silicone-modified polypropylene compound of claim 1, wherein the compound of formula (I) is 1, 1, 1, 2, 3, 3, 3 heptamethyl-2-vinyltrisiloxane, vinyltris (trimethylsiloxy) silane.
4. The silicone-modified polypropylene compound of claim 1, wherein the compound of formula (II) is a trimethylsilyl and vinyl-terminated polydimethylsiloxane or a hydroxy and vinyl-terminated polydimethylsiloxane.
5. The silicone-modified polypropylene compound according to claim 1, wherein the grafted silicone compound monomer is 1 to 6% by mass of the polypropylene.
6. The process for producing the silicone-modified polypropylene compound according to claim 1, comprising the steps of:
mixing the organic silicon compound and the polypropylene uniformly, adding the initiator and the antioxidant, and performing degradation and grafting reaction in an extruder at the temperature of 160-180 ℃ simultaneously to obtain the polypropylene modified polypropylene.
7. The method for preparing the organosilicon modified polypropylene compound according to claim 6, wherein the mass ratio of the polypropylene, the organosilicon compound, the initiator and the antioxidant is 100: (0.5-15): (0.1-0.5): (0.05-0.3).
8. Use of the silicone-modified polypropylene compound of claim 1 as a meltblown for the production of meltblown and non-woven fabrics.
9. A master batch obtained from the silicone-modified polypropylene compound according to claim 1.
10. A mask comprising a meltblown fabric made from the silicone-modified polypropylene compound of claim 1.
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| JP2000290390A (en) * | 1999-04-02 | 2000-10-17 | Hitachi Cable Ltd | Production of waterproof sheet |
| CN102329405A (en) * | 2011-06-22 | 2012-01-25 | 华东理工大学 | Preparation method of continuous high-melt-strength polypropylene based on grafting reaction |
| CN107286473A (en) * | 2017-08-01 | 2017-10-24 | 山东圣泉新材料股份有限公司 | A kind of modified polypropylene agglomerate, fusion spray cloth and its preparation method and application |
| CN109593163A (en) * | 2018-12-05 | 2019-04-09 | 佳易容相容剂江苏有限公司 | A kind of Polypropylene-based graft object and preparation method thereof |
| CN110066463A (en) * | 2019-05-22 | 2019-07-30 | 青岛海尔新材料研发有限公司 | A kind of PP composite material of autoreaction toughening |
| CN111685415A (en) * | 2020-05-26 | 2020-09-22 | 界首市圣通无纺布有限公司 | High-efficiency antiviral protective mask produced by using modified PP (polypropylene) non-woven fabric |
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2020
- 2020-10-12 CN CN202011084661.9A patent/CN114316146A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000290390A (en) * | 1999-04-02 | 2000-10-17 | Hitachi Cable Ltd | Production of waterproof sheet |
| CN102329405A (en) * | 2011-06-22 | 2012-01-25 | 华东理工大学 | Preparation method of continuous high-melt-strength polypropylene based on grafting reaction |
| CN107286473A (en) * | 2017-08-01 | 2017-10-24 | 山东圣泉新材料股份有限公司 | A kind of modified polypropylene agglomerate, fusion spray cloth and its preparation method and application |
| CN109593163A (en) * | 2018-12-05 | 2019-04-09 | 佳易容相容剂江苏有限公司 | A kind of Polypropylene-based graft object and preparation method thereof |
| CN110066463A (en) * | 2019-05-22 | 2019-07-30 | 青岛海尔新材料研发有限公司 | A kind of PP composite material of autoreaction toughening |
| CN111685415A (en) * | 2020-05-26 | 2020-09-22 | 界首市圣通无纺布有限公司 | High-efficiency antiviral protective mask produced by using modified PP (polypropylene) non-woven fabric |
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