CN110746607B - Auxiliary product applied to spandex spinning oil agent and having effects of isolating and adjusting friction - Google Patents
Auxiliary product applied to spandex spinning oil agent and having effects of isolating and adjusting friction Download PDFInfo
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- CN110746607B CN110746607B CN201911171414.XA CN201911171414A CN110746607B CN 110746607 B CN110746607 B CN 110746607B CN 201911171414 A CN201911171414 A CN 201911171414A CN 110746607 B CN110746607 B CN 110746607B
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 40
- 239000004759 spandex Substances 0.000 title claims abstract description 40
- 238000009987 spinning Methods 0.000 title claims abstract description 15
- 230000000694 effects Effects 0.000 title claims description 24
- 239000003795 chemical substances by application Substances 0.000 title claims description 15
- 239000003921 oil Substances 0.000 claims abstract description 31
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 229920001296 polysiloxane Polymers 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- -1 silicate ester Chemical class 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000008096 xylene Substances 0.000 claims description 24
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 16
- 239000012043 crude product Substances 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 229920002050 silicone resin Polymers 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 238000000935 solvent evaporation Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 9
- 229910004674 SiO0.5 Inorganic materials 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000011343 solid material Substances 0.000 description 6
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 3
- 239000008041 oiling agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses an auxiliary product with the functions of isolating and regulating friction, which is applied to spandex spinning oil, and relates to the technical field of functional organic silicon materials3SiO0.5)a(BMe2SiO0.5)b(CMe2SiO0.5)c(DMe2SiO0.5)d(Me2SiO)e(SiO2) f, wherein A is a mixed structure of methyl and hydroxyl, B is long-chain alkyl, C is glycidyl ether group, D is polyether group, and Me is methyl. The auxiliary agent provided by the invention is characterized in that dimethyl siloxane chain links, long-chain alkyl chain links, epoxy alkyl chain links and polyether chain links are introduced on the basis of the traditional MQ silicon resin structure, and part of active hydroxyl groups are reserved, so that the auxiliary agent and spandex fibers generate chemical bonding force, and the auxiliary agent not only provides durable intermiscibility and storage stability, but also provides antistatic property and proper strand untying tension.
Description
Technical Field
The invention relates to the technical field of functional organic silicon materials, in particular to an auxiliary agent product which is applied to spandex spinning oil and plays a role in isolating and regulating friction.
Background
The spandex spinning industry in China has been a world-wide filament-producing nation with the rapid development tendency in recent years. The matched high-end spandex spinning oil is mainly prepared by Japanese ' Songben ' (China) "bamboo ' (China), ' Golston ' oil in America. The reason is that day and beauty oil agents are unique in product quality, yield and performance.
After the domestic oil agent is applied to spandex fibers, on one hand, the isolation between the fibers is poor, and as time goes on, chemical reaction type adhesion occurs between the fibers, so that the fibers cannot be used in bundle splitting, and a large amount of spandex filaments are wasted. On the other hand, the friction between the fibers is too small, so that the spinning is loose and difficult to form. The invention provides an auxiliary product for compounding and producing a spandex spinning oil agent, aiming at the problems of oiling agents in the market, wherein the auxiliary product is 'rail yarns' and 'convex fibers' which are slightly generated, and the auxiliary product is non-spinnable due to disordered yarns.
Disclosure of Invention
The invention aims to provide an auxiliary product which is applied to a spandex spinning oil agent and has the effects of isolating and adjusting friction, so as to solve the technical problem.
An assistant product applied to spandex spinning oil agent and having the effects of isolating and adjusting friction, wherein the structure of the assistant product is (A)3SiO0.5)a(BMe2SiO0.5)b(CMe2SiO0.5)c(DMe2SiO0.5)d(Me2SiO)e(SiO2) f, wherein A is a mixed structure of methyl and hydroxyl, B is long-chain alkyl, C is glycidyl ether group, D is polyether group, and Me is methyl; wherein a, b, c, d, e and f represent the number of chain links or the degree of polymerization, a is 3-10, b is 2-5, c is 2-5, d is 2-5, e is 1-5, and f is 5-8.
The preparation process of the auxiliary agent product comprises the following steps:
firstly, dissolving silicate ester, dimethyl siloxane tetramer and hydrogen-containing double seal heads in a mixed solvent, and then dropwise adding hydrochloric acid as a catalyst to carry out hydrolytic condensation at 70-80 ℃ for 30-90min to synthesize a silicon resin base material;
step two, separating an oil phase in the mixed liquid containing the silicone base material obtained in the step one to obtain a silicone crude product, and sequentially neutralizing, filtering, washing and drying the crude product to obtain the silicone base material;
and step three, carrying out hydrosilylation reaction on the silicone resin base material, the unsaturated olefin, the allyl glycidyl ether and the unsaturated polyether according to a certain proportion and sequence, and finally separating the solvent and the low-boiling-point substance.
Preferably, the mixed solvent in the first step is prepared by mixing water, an alcohol and a benzene substance, wherein the alcohol is ethanol or propanol, and the benzene substance is one of toluene, ethylbenzene or p-xylene.
Preferably, the mass ratio of the active ingredients in the silicate ester, the water, the alcohols, the benzenes, the dimethyl siloxane tetramer, the hydrogen-containing double seal heads and the hydrochloric acid in the step one is 35-42:10-13:9-11:8-10:8.5-9.2:4-7: 2.2-2.8.
Preferably, in the first step, the hydrogen-containing double end enclosure is tetramethyldihydrodisiloxane.
Preferably, the silicate in the first step is methyl orthosilicate.
Preferably, in the second step, the filtered substance is neutralized to neutrality by using sodium hydroxide, and is washed by using distilled water, and in the second step, the solvent is distilled off under reduced pressure at 150 ℃ until no liquid is distilled off.
Preferably, the solvent is distilled off under reduced pressure in the second step at 150 ℃, until no liquid is distilled off.
As a preferable scheme, the concrete operation in the third step is that xylene is used as a solvent, the silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether are sequentially dissolved in the xylene, and a high-activity platinum catalyst is adopted to perform catalytic reaction for 6-18h at normal temperature to prepare a crude spandex oil agent intermediate
Preferably, the mass ratio of the xylene to the silicone resin base material to the unsaturated olefin to the allyl glycidyl ether to the unsaturated polyether to the platinum catalyst is 9-11:18-22:1-3:1-3:1-3:1, wherein the mass ratio of the unsaturated olefin to the allyl glycidyl ether to the unsaturated polyether is 1:1: 1. .
Preferably, the solvent and low boiling point substance are separated in the third step by distilling the solvent and the small molecular alcohol at 80-90 deg.C and 0.10-0.15MPa after the hydrosilylation reaction.
The invention has the beneficial effects that:
1. dimethyl siloxane chain links, long-chain alkyl chain links, epoxy alkyl chain links and polyether chain links are introduced on the basis of the traditional MQ silicon resin structure, and part of active hydroxyl groups are reserved, so that the dimethyl siloxane chain links, the long-chain alkyl chain links, the epoxy alkyl chain links and the polyether chain links generate chemical bonding force with spandex fibers, and the permanent intermiscibility, the storage stability and the antistatic property and the proper bundle untying tension are provided.
2. On the basis of the traditional MQ silicon resin structure, dimethyl siloxane chain links, long-chain alkyl chain links, epoxy alkyl chain links and polyether chain links are introduced, active hydroxyl groups are reserved, products with different molar masses, densities, viscosities, softening points, toughness and tackifying performances are obtained by adjusting the proportion of M, D, Q, and the toughness adjustment of the silicon resin becomes possible.
3. The long-chain alkyl structure is introduced on the basis of the traditional MQ silicon resin structure, so that the intermediate auxiliary agent has better intermiscibility with mineral oil and other auxiliary agents, the phenomenon that surface oiling agents cannot be dissociated and migrated in the long-time storage process of fiber oiling is reflected, and the condition that spandex filaments are either deformed or adhered due to the precipitation of the surface oiling agents is prevented.
4. The introduction of the epoxy alkyl on the basis of the traditional MQ silicon resin structure is beneficial to increasing the cohesive force between the filaments, so that the filament cake is not deformed and yellowed due to long-time storage.
Drawings
FIG. 1 is a schematic view of the structure of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Weighing 35mg of methyl orthosilicate, 10mg of water, 9mg of ethanol, 8mg of toluene, 8.5mg of dimethyl siloxane tetramer, 4mg of tetramethyl dihydrodisiloxane and 220mg of hydrochloric acid with the mass fraction of 1% for later use;
mixing and dissolving water, ethanol and toluene to prepare a mixed solvent, dissolving silicate ester, dimethyl siloxane tetramer and a hydrogen-containing double end enclosure in the mixed solvent, dropwise adding hydrochloric acid serving as a catalyst, and performing hydrolytic condensation at 70 ℃ for 50min to synthesize a silicon resin base material;
and (2) filtering the oil phase in the mixed liquid containing the silicone base material obtained in the first step to obtain a silicone crude product, sequentially dropwise adding a sodium hydroxide solution with the mass fraction of 1% to neutralize the crude product to be neutral, then filtering again, washing the obtained solid with distilled water for three times, 5ml each time, then putting the solid in an oven, adjusting the pressure to be 1.5Mpa and the temperature to be 150 ℃ to perform pressure distillation, and evaporating until no liquid is evaporated to obtain the silicone base material.
9mg of xylene, 18mg of silicone base, 1mg of unsaturated olefin, 1mg of allyl glycidyl ether, 1mg of unsaturated polyether and 1mg of platinum catalyst were weighed out for use.
Dissolving a silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene in sequence, carrying out catalytic reaction for 6-18h at normal temperature by adopting a high-activity platinum catalyst to prepare a rough spandex oil agent intermediate, and distilling the xylene and micromolecular alcohol at 80 ℃ and under the pressure of 0.10Mpa after the reaction is finished to obtain the silicone resin solid material.
Example two
42mg of methyl orthosilicate, 13mg of water, 11mg of propanol, 10mg of ethylbenzene, 9.2mg of dimethyl siloxane tetramer, 7mg of tetramethyl dihydrodisiloxane and 280mg of hydrochloric acid with the mass fraction of 1% are weighed for later use;
mixing and dissolving water, propanol and ethylbenzene to prepare a mixed solvent, dissolving silicate ester, dimethyl siloxane tetramer and hydrogen-containing double end enclosure in the mixed solvent, dropwise adding hydrochloric acid serving as a catalyst, and performing hydrolytic condensation at 80 ℃ for 90min to synthesize a silicon resin base material;
and (2) filtering the oil phase in the mixed liquid containing the silicone base material obtained in the first step to obtain a silicone crude product, neutralizing the crude product to be neutral by sequentially passing through a sodium hydroxide solution with the mass fraction of 1%, then filtering again, washing the obtained solid by using distilled water for three times, wherein 5ml of the distilled water is used for each time, then putting the solid in an oven, adjusting the pressure to be 1.5Mpa and the temperature to be 150 ℃ for pressure distillation, and evaporating until no liquid is evaporated out to obtain the silicone base material.
11mg of xylene, 22mg of silicone base, 3mg of unsaturated olefin, 3mg of allyl glycidyl ether, 3mg of unsaturated polyether and 1mg of platinum catalyst were weighed out for use.
Dissolving a silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene in sequence, carrying out catalytic reaction for 8 hours at normal temperature by adopting a high-activity platinum catalyst to prepare a rough spandex oil agent intermediate, and distilling the xylene and micromolecular alcohol at 85 ℃ and under the pressure of 0.15Mpa after the reaction is finished to obtain the silicone resin solid material.
EXAMPLE III
Weighing 37mg of methyl orthosilicate, 11mg of water, 10mg of ethanol, 9mg of p-xylene, 8.6mg of dimethyl siloxane tetramer, 4.5mg of tetramethyl dihydrodisiloxane and 230mg of hydrochloric acid with the mass fraction of 1% for later use;
mixing and dissolving water, ethanol and p-xylene to prepare a mixed solvent, dissolving silicate ester, dimethyl siloxane tetramer and a hydrogen-containing double end enclosure in the mixed solvent, dropwise adding hydrochloric acid serving as a catalyst, and performing hydrolytic condensation at 72 ℃ for 45min to synthesize a silicon resin base material;
and (2) filtering the oil phase in the mixed liquid containing the silicone base material obtained in the first step to obtain a silicone crude product, neutralizing the crude product to be neutral by sequentially passing through a sodium hydroxide solution with the mass fraction of 1%, then filtering again, washing the obtained solid by using distilled water for three times, wherein 5ml of the distilled water is used for each time, then putting the solid in an oven, adjusting the pressure to be 1.5Mpa and the temperature to be 150 ℃ for pressure distillation, and evaporating until no liquid is evaporated out to obtain the silicone base material.
10mg of xylene, 20mg of silicone base, 2mg of unsaturated olefin, 2mg of allyl glycidyl ether, 2mg of unsaturated polyether and 1mg of platinum catalyst were weighed out for use.
Dissolving a silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene in sequence, carrying out catalytic reaction for 6-18h at normal temperature by adopting a high-activity platinum catalyst to prepare a rough spandex oil agent intermediate, and distilling the xylene and micromolecular alcohol at 85 ℃ and under the pressure of 0.13Mpa after the reaction is finished to obtain the silicone resin solid material.
Example four
Weighing 38mg of methyl orthosilicate, 12mg of water, 10mg of propanol, 9mg of p-xylene, 8.7mg of dimethyl siloxane tetramer, 5.6mg of tetramethyl dihydrodisiloxane and 260mg of hydrochloric acid with the mass fraction of 1% for later use;
mixing and dissolving water, propanol and p-xylene to prepare a mixed solvent, dissolving silicate ester, dimethyl siloxane tetramer and a hydrogen-containing double end enclosure in the mixed solvent, dropwise adding hydrochloric acid serving as a catalyst, and performing hydrolytic condensation at 75 ℃ for 40min to synthesize a silicon resin base material;
and (2) filtering the oil phase in the mixed liquid containing the silicone base material obtained in the first step to obtain a silicone crude product, neutralizing the crude product to be neutral by sequentially passing through a sodium hydroxide solution with the mass fraction of 1%, then filtering again, washing the obtained solid by using distilled water for three times, wherein 5ml of the distilled water is used for each time, then putting the solid in an oven, adjusting the pressure to be 1.5Mpa and the temperature to be 150 ℃ for pressure distillation, and evaporating until no liquid is evaporated out to obtain the silicone base material.
10mg of xylene, 20mg of silicone base, 2mg of unsaturated olefin, 2mg of allyl glycidyl ether, 2mg of unsaturated polyether and 1mg of platinum catalyst were weighed out for use.
Dissolving a silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene in sequence, carrying out catalytic reaction for 16 hours at normal temperature by adopting a high-activity platinum catalyst to prepare a rough spandex oil agent intermediate, and distilling the xylene and micromolecular alcohol at 88 ℃ and under the pressure of 0.14Mpa after the reaction is finished to obtain the silicone resin solid material.
EXAMPLE five
Weighing 40mg of methyl orthosilicate, 12mg of water, 10mg of propanol, 9mg of ethylbenzene, 9.1mg of dimethyl siloxane tetramer, 6mg of tetramethyl dihydrodisiloxane and 270mg of hydrochloric acid with the mass fraction of 1% for later use;
mixing and dissolving water, propanol and ethylbenzene to prepare a mixed solvent, dissolving silicate ester, dimethyl siloxane tetramer and hydrogen-containing double end enclosure in the mixed solvent, dropwise adding hydrochloric acid serving as a catalyst, and performing hydrolytic condensation at 78 ℃ for 88min to synthesize a silicon resin base material;
and (2) filtering the oil phase in the mixed liquid containing the silicone base material obtained in the first step to obtain a silicone crude product, neutralizing the crude product to be neutral by sequentially passing through a sodium hydroxide solution with the mass fraction of 1%, then filtering again, washing the obtained solid by using distilled water for three times, wherein 5ml of the distilled water is used for each time, then putting the solid in an oven, adjusting the pressure to be 1.5Mpa and the temperature to be 150 ℃ for pressure distillation, and evaporating until no liquid is evaporated out to obtain the silicone base material.
10mg of xylene, 20mg of silicone base, 2mg of unsaturated olefin, 2mg of allyl glycidyl ether, 2mg of unsaturated polyether and 1mg of platinum catalyst were weighed out for use.
Dissolving a silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene in sequence, carrying out catalytic reaction for 16 hours at normal temperature by adopting a high-activity platinum catalyst to prepare a rough spandex oil agent intermediate, and distilling the xylene and micromolecular alcohol at 87 ℃ and under the pressure of 0.14Mpa after the reaction is finished to obtain the silicone resin solid material.
EXAMPLE six
Weighing 41mg of methyl orthosilicate, 12mg of water, 10mg of ethanol, 8mg of p-xylene, 8.6mg of dimethyl siloxane tetramer, 4.5mg of tetramethyl dihydrodisiloxane and 275mg of hydrochloric acid with the mass fraction of 1% for later use;
mixing and dissolving water, ethanol and p-xylene to prepare a mixed solvent, dissolving silicate ester, dimethyl siloxane tetramer and a hydrogen-containing double end enclosure in the mixed solvent, dropwise adding hydrochloric acid serving as a catalyst, and performing hydrolytic condensation at 78 ℃ for 85min to synthesize a silicon resin base material;
and (2) filtering the oil phase in the mixed liquid containing the silicone base material obtained in the first step to obtain a silicone crude product, neutralizing the crude product to be neutral by sequentially passing through a sodium hydroxide solution with the mass fraction of 1%, then filtering again, washing the obtained solid by using distilled water for three times, wherein 5ml of the distilled water is used for each time, then putting the solid in an oven, adjusting the pressure to be 1.5Mpa and the temperature to be 150 ℃ for pressure distillation, and evaporating until no liquid is evaporated out to obtain the silicone base material.
10mg of xylene, 21mg of silicone base, 2mg of unsaturated olefin, 2mg of allyl glycidyl ether, 2mg of unsaturated polyether and 1mg of platinum catalyst were weighed out for use.
Dissolving a silicone resin base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene in sequence, carrying out catalytic reaction for 17 hours at normal temperature by adopting a high-activity platinum catalyst to prepare a rough spandex oil agent intermediate, and distilling the xylene and micromolecular alcohol at 88 ℃ and under the pressure of 0.14Mpa after the reaction is finished to obtain the silicone resin solid material.
The auxiliary agent products prepared in the first embodiment, the second embodiment, the third embodiment, the fourth embodiment, the fifth embodiment and the sixth embodiment are added into spandex products to be used as a first experimental group, a second experimental group, a third experimental group, a fourth experimental group, a fifth experimental group and a sixth experimental group respectively, and a group of spandex without addition of auxiliary agent is used as a first comparative example to measure unwinding tension, resistivity and unwinding tension after high-temperature deterioration at normal temperature of the first experimental group, the second experimental group, the third experimental group, the fourth experimental group, the fifth experimental group, the sixth experimental group and the first comparative example respectively, and the results are shown in tables 1, 2 and 3, and it can be known from tables 1, 2 and 3 that the addition of the auxiliary agent provided by the invention can effectively reduce the unwinding tension of spandex, reduce the specific resistance of the spandex and reduce the unwinding tension of the spandex after high-temperature deterioration.
TABLE 1 Effect of auxiliaries on Spandex unwinding tension
| Surface unwinding tension (N) | Intermediate unwinding tension (N) | Inner layer unwinding tension (N) | |
| Example one | 1.87 | 2.07 | 2.55 |
| Example two | 1.88 | 2.09 | 2.56 |
| EXAMPLE III | 1.84 | 2.03 | 2.52 |
| Example four | 1.86 | 2.06 | 2.54 |
| EXAMPLE five | 1.83 | 2.02 | 2.51 |
| EXAMPLE six | 1.89 | 2.11 | 2.57 |
| Comparative example 1 | 2.01 | 2.26 | 2.97 |
TABLE 2 Effect of auxiliaries on Spandex resistivity
| Specific resistance (ohm) | |
| Example 1 | 1.09*1011 |
| Example 2 | 1.11*1011 |
| Example 3 | 1.10*1011 |
| Example 4 | 1.08*1011 |
| Example 5 | 1.06*1011 |
| Example 6 | 1.07*1011 |
| Comparative example 1 | 1.8*1011 |
TABLE 3 Effect of auxiliary on the yield tension of spandex after high temperature deterioration
| High temperature deterioration of surface layer and rewinding tension (N) | Middle layer high temperature deterioration back winding tension (N) | Inner layer high temperature deterioration back winding tension (N) | |
| Example one | 2.37 | 3.21 | 3.97 |
| Example two | 2.38 | 3.22 | 3.96 |
| EXAMPLE III | 2.35 | 3.23 | 3.93 |
| Example four | 2.33 | 3.2 | 3.94 |
| EXAMPLE five | 2.39 | 3.22 | 3.99 |
| EXAMPLE six | 2.40 | 3.24 | 3.91 |
| Comparative example 1 | 3.01 | 4.11 | 4.79 |
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. An auxiliary product which is applied to a spandex spinning oil agent and has the effects of isolating and regulating friction is characterized in that the structure of the auxiliary product is (A3SiO0.5) a (BMe2SiO0.5) B (CMe2SiO0.5) C (DMe2SiO0.5) D (Me2SiO) e (SiO2) f, wherein A refers to a mixed structure of methyl and hydroxyl, B refers to long-chain alkyl, C refers to glycidyl ether group, D refers to polyether group, and Me refers to methyl; wherein a, b, c, d, e and f represent the number of chain links or the degree of polymerization, a is 3-10, b is 2-5, c is 2-5, d is 2-5, e is 1-5, and f is 5-8.
2. The auxiliary product with effects of isolating and regulating friction applied in spandex spinning oil according to claim 1, characterized in that the preparation process of the auxiliary product is as follows:
firstly, dissolving silicate ester, dimethyl siloxane tetramer and hydrogen-containing double seal heads in a mixed solvent, and then dropwise adding hydrochloric acid as a catalyst to carry out hydrolytic condensation at 70-80 ℃ for 30-90min to synthesize a silicon resin base material;
step two, separating an oil phase in the mixed liquid containing the silicone base material obtained in the step one to obtain a silicone crude product, and sequentially neutralizing, filtering, washing and drying the crude product to obtain the silicone base material;
and step three, carrying out hydrosilylation reaction on the silicone resin base material, the unsaturated olefin, the allyl glycidyl ether and the unsaturated polyether according to a certain proportion and sequence, and finally separating the solvent and the low-boiling-point substance.
3. The auxiliary agent product with effects of isolating and adjusting friction applied to spandex spin finish according to claim 2, characterized in that the mixed solvent in the first step is prepared by mixing water, alcohol and benzene, wherein the alcohol is ethanol or propanol, and the benzene is one of toluene, ethylbenzene or p-xylene.
4. The auxiliary agent product with the effects of isolating and regulating friction applied to spandex spinning oil according to claim 2, characterized in that the mass ratio of active ingredients in silicate ester, water, alcohols, benzenes, dimethyl siloxane tetramers, hydrogen-containing double heads and hydrochloric acid in the first step is 35-42:10-13:9-11:8-10:8.5-9.2:4-7: 2.2-2.8.
5. The auxiliary product with effects of isolating and regulating friction for spandex spin finish according to claim 2, wherein the hydrogen-containing double end cap in step one is tetramethyldihydrodisiloxane.
6. The adjuvant product for spandex spin finish application to provide traction control and friction control as claimed in claim 2 wherein the silicate used in step one is methyl orthosilicate.
7. The auxiliary agent product with effects of isolating and regulating friction applied to spandex spin finish according to claim 2, characterized in that in step two, sodium hydroxide is used to neutralize the filtered substance to neutrality, and distilled water is used to wash the filtered substance, and in step two, the reduced pressure solvent evaporation is performed at 150 ℃ until no liquid is evaporated.
8. The auxiliary agent product with the effects of isolating and regulating friction applied to spandex spinning oil according to claim 2, characterized in that the specific operation in step three is to use xylene as a solvent, sequentially dissolve the silicone base material, unsaturated olefin, allyl glycidyl ether and unsaturated polyether in xylene, and perform catalytic reaction for 6-18h at normal temperature by using a high-activity platinum catalyst to prepare a crude spandex oil intermediate.
9. The auxiliary product with effects of isolating and regulating friction applied to spandex spinning oil according to claim 8, wherein the mass ratio of xylene to silicone base material to unsaturated olefin to allyl glycidyl ether to unsaturated polyether to platinum catalyst is 9-11:18-22:1-3:1-3:1-3:1, wherein the mass ratio of unsaturated olefin to allyl glycidyl ether to unsaturated polyether is 1:1: 1.
10. The auxiliary agent product with effects of isolating and adjusting friction applied in spandex spin finish according to claim 2, characterized in that the specific operation of separating solvent and low-boiling-point substance in step three is distillation of solvent and small-molecule alcohol at 80-90 ℃ and 0.10-0.15Mpa after hydrosilylation reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101440574A (en) * | 2008-12-18 | 2009-05-27 | 宁波经济技术开发区希科新材料有限公司 | Oil solution for spandex spinning by dry method, and preparation and use thereof |
| CN101597377A (en) * | 2009-06-29 | 2009-12-09 | 山东大易化工有限公司 | Compound of a kind of methyl blocking co-modified with alkyl, polyether, epoxy and phenyl polysiloxane and its production and application |
| KR20110079299A (en) * | 2009-12-31 | 2011-07-07 | 주식회사 효성 | Spin finishing oil for spandex including non-ion surfactant, manufactured method thereof and spandex thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101440574A (en) * | 2008-12-18 | 2009-05-27 | 宁波经济技术开发区希科新材料有限公司 | Oil solution for spandex spinning by dry method, and preparation and use thereof |
| CN101597377A (en) * | 2009-06-29 | 2009-12-09 | 山东大易化工有限公司 | Compound of a kind of methyl blocking co-modified with alkyl, polyether, epoxy and phenyl polysiloxane and its production and application |
| KR20110079299A (en) * | 2009-12-31 | 2011-07-07 | 주식회사 효성 | Spin finishing oil for spandex including non-ion surfactant, manufactured method thereof and spandex thereof |
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