CN109629237B - Hydrophilic cool silicone oil and preparation method thereof - Google Patents
Hydrophilic cool silicone oil and preparation method thereof Download PDFInfo
- Publication number
- CN109629237B CN109629237B CN201811576313.6A CN201811576313A CN109629237B CN 109629237 B CN109629237 B CN 109629237B CN 201811576313 A CN201811576313 A CN 201811576313A CN 109629237 B CN109629237 B CN 109629237B
- Authority
- CN
- China
- Prior art keywords
- parts
- emulsifier
- silicone oil
- crude oil
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000010779 crude oil Substances 0.000 claims abstract description 45
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910001868 water Inorganic materials 0.000 claims abstract description 43
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZGFLMSYIISDCLO-UHFFFAOYSA-N 2-chloro-1h-quinolin-4-one Chemical compound C1=CC=C2NC(Cl)=CC(=O)C2=C1 ZGFLMSYIISDCLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- -1 β -aminoethyl Chemical group 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 238000004945 emulsification Methods 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 claims description 7
- 239000004359 castor oil Substances 0.000 claims description 7
- 235000019438 castor oil Nutrition 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- DTIFFOYIBPJUET-UHFFFAOYSA-N n'-(3-trimethylsilylpropyl)ethane-1,2-diamine Chemical compound C[Si](C)(C)CCCNCCN DTIFFOYIBPJUET-UHFFFAOYSA-N 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 52
- 230000035699 permeability Effects 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000004043 dyeing Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 33
- 235000019198 oils Nutrition 0.000 description 33
- 229920013822 aminosilicone Polymers 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 11
- 238000004383 yellowing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/313—Unsaturated compounds containing phosphorus atoms, e.g. vinylphosphonium compounds
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- 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
- D06M15/53—Polyethers
-
- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2101/34—Polyamides
-
- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses hydrophilic cool silicone oil, and relates to the field of textile dyeing and finishing auxiliaries, wherein the product comprises the following raw materials in parts by weight: crude oil: 30-50 parts of an emulsifier A: 10-20 parts of an emulsifier B: 10-20 parts of glycerol: 5-10 parts of water: 25-40 parts of glacial acetic acid: 5-10 parts of triethylamine: 1-5 parts; the crude oil comprises the following raw materials in percentage by mass: octamethylcyclotetrasiloxane: 65-85%, amino silane coupling agent: 1-20%, basic catalyst: 1-5%, trifluoromethyl maleic anhydride: 1 to 10 percent. The preparation method comprises the following steps: s1: preparing each reagent; s2: synthesizing crude oil; s3: and (4) emulsifying the crude oil. The composition has good permeability, alkali resistance, high temperature resistance and good hygroscopicity by reasonably compounding the raw materials, and can endow the fabric with smooth and cool hand feeling.
Description
Technical Field
The invention relates to the technical field of fabric dyeing and finishing auxiliaries, in particular to hydrophilic cool silicone oil and a preparation method thereof.
Background
With the development of society and the improvement of living standard of people, people have higher and higher requirements on the hand feeling of textiles, particularly knitted fabrics. At present, people also need to have excellent rebound resilience and drapability, fine and smooth touch feeling, cool feeling, good air permeability, moisture absorption and sweat releasing performance besides the requirements on softness and smoothness of knitted fabrics. Therefore, a higher demand has been placed on the finishing agent for knitted fabrics to achieve the above effects.
The amino modified silicone oil has good chemical reactivity, strong two-phase lubricity and compatibility, so that the amino modified silicone oil is widely applied to the fields of textile after-finishing, textile dyeing and finishing and the like. The amino modified silicone oil mainly comprises two types of side chain amino modified silicone oil and straight chain block amino modified silicone oil, wherein the side chain amino modified silicone oil has stronger molecular chain flexibility and most of the side chain amino modified silicone oil belongs to hydrophobic additives, so the silicone oil stays on the surface of the fabric after the fabric is finished, and the fabric can be endowed with soft, smooth and other handfeel; the straight-chain block amino modified silicone oil has strong group linking capacity, and most of the straight-chain block amino modified silicone oil belongs to hydrophilic or semi-hydrophilic auxiliaries, so that the silicone oil can permeate into the interior of the fabric during dyeing and finishing, and the fabric can be endowed with soft, fluffy and fine handfeel. However, under the influence of different processing means and reaction mechanisms of the side chain amino-modified silicone oil and the straight chain block amino-modified silicone oil, the side chain amino-modified silicone oil and the straight chain block amino-modified silicone oil can only be used alternatively in the post-finishing or dyeing and finishing process, and the silicone oil cannot have good permeability and can also impart smooth hand feeling to the fabric.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the hydrophilic cool silicone oil and the preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the hydrophilic cool silicone oil comprises the following raw materials in parts by weight: crude oil: 30-50 parts of an emulsifier A: 10-20 parts of an emulsifier B: 10-20 parts of glycerol: 5-10 parts of water: 25-40 parts of glacial acetic acid: 5-10 parts of triethylamine: 1-5 parts;
the crude oil comprises the following raw materials in percentage by mass: octamethylcyclotetrasiloxane: 65-85%, amino silane coupling agent: 1-20%, basic catalyst: 1-5%, trifluoromethyl maleic anhydride: 1 to 10 percent.
By adopting the technical scheme, the octamethylcyclotetrasiloxane and the aminosilane coupling agent can form the polyamino siloxane after ring-opening polymerization under the action of the alkaline catalyst. The primary amino group or/and the secondary amino group is introduced into a silicone oil molecular chain, so that the hydrophilicity of the whole silicone oil molecular structure is improved, the fabric finished by the finishing agent has the functions of ventilation, moisture permeability, moisture absorption and perspiration, and meanwhile, a certain humidity can be kept, and the fabric gives people a comfortable and cool feeling after being worn.
Emulsifiers improve the surface tension between the various constituent phases of an emulsion to form a uniform and stable dispersion or emulsion of material. The product has excellent stability, and the defects that the traditional amino silicone oil is easy to demulsify, float and generate oil stains and the like are overcome.
Triethylamine can react with amino silicone oil to increase the hydrophilic group-COO in emulsion-The content of (3) improves the hydrophilicity of the amino silicone oil, so that the intersolubility of the amino silicone oil and water is enhanced. Meanwhile, after the prepolymer in the amino silicone oil is dispersed, hydrophobic molecular chains are curled to be nucleated, and hydrophilic ion groups are positioned on the surfaces of the particles and face to water when a large amount of-COO-The negative ions gather on the particle surface and attract corresponding positive ions, and after stabilization, an electric double layer can be formed on the particle surface to generate electromotive force. The electromotive force can prevent the particles from approaching each other and condensing, plays a role similar to an emulsifier, improves the emulsification effect of the amino silicone oil, ensures that the obtained emulsion has small and stable particle size, and does not have the phenomenon of oil floating.
The trifluoromethyl maleic anhydride can be amidated with amino silicone oil, so that amino active hydrogen in the amino silicone oil structure is reduced, carboxyl is increased, the yellowing effect is reduced, and the alkali resistance, high temperature resistance and washability of ice silicone oil are improved.
Further, the crude oil comprises the following raw materials in percentage by mass: octamethylcyclotetrasiloxane: 65-85%, amino silane coupling agent: 8-15%, basic catalyst: 1-5%, trifluoromethyl maleic anhydride: 1-10%, ethyl acrylate: 1-10%, end-capping agent: 0.5 to 1 percent.
By adopting the technical scheme, the ethyl acrylate can acylate 30-70% of amino groups in the amino silicone oil by mole fraction, and then the rest amino groups react with the epoxy compound, so that the hydrophilicity of the fabric can be improved, and the yellowing of the fabric can be effectively inhibited.
Further, the end-capping reagent comprises the following raw materials in percentage by mass: hexamethyldisiloxane: 30-50%, benzyltrimethylammonium bromide: 20-40%, isopropanol: 20 to 40 percent.
By adopting the technical scheme, the siloxane group in the hexamethyldisiloxane reacts with the active group at the end part in the amino silicone oil, so that the molecular weight of the product is controlled within a certain range, the generation of a product with high molecular weight is prevented, the effective component in the amino silicone oil is reduced, and the finishing effect of the amino silicone oil on cloth is reduced.
Further, the amino silane coupling agent comprises the following raw materials in percentage by mass: n- (β -aminoethyl) - γ -aminopropylmethyldimethylsilane: 30-50%, polyether amine: 10-20%, phosphate starch: 10-20%, water: 20 to 40 percent.
By adopting the technical scheme, the N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethylsilane and the octamethylcyclotetrasiloxane can form the amino silicone oil after ring-opening polymerization under the action of the catalyst. The polyether amine can improve the wear resistance of the cloth, and the segmented copolymer of the amino silicone oil and the polyether amine can improve the hydrophilicity of the amino silicone oil and improve the antistatic property, and an emulsifier can be reduced or not used. Meanwhile, N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethylsilane can form-OH with high activity after being hydrolyzed, and can form hydrogen bond connection with-OH existing on the cloth, so that the adhesion degree of amino silicone oil and the cloth is improved.
The paste of the phosphate starch has high transparency, high viscosity and strong tackiness, has high stability and weak retrogradation, and can improve the flexibility of a film formed on a fabric by a product and improve the hand feeling of a fabric. Meanwhile, the phosphate ester has excellent emulsifying capacity on animal and vegetable oil, fatty acid ester, silicone oil and mineral oil, and can initially emulsify amino silicone oil and improve the emulsifying degree of the silicone oil; and the antistatic and skin-friendly detergent has antistatic property, good skin affinity, good surface activity at low concentration, excellent wetting and washing performance and synergistic effect.
Further, the emulsifier A comprises the following raw materials in percentage by mass: isotridecanol polyoxyethylene ether: 20-45%, castor oil phosphate salt: 20-40%, polyoxyethylene glyceryl ether: 20-30%, isopropanol: 10 to 20 percent.
By adopting the technical scheme, the isotridecanol polyoxyethylene ether, the castor oil phosphate and the polyoxyethylene glyceryl ether can emulsify the amino silicone oil, improve the surface tension among various phases in the emulsion and form a uniform and stable dispersion system or an emulsion material.
The softening agent prepared from the segmented copolymer of the amino silicone oil and the polyether can improve the hydrophilicity of the amino silicone oil softening agent and improve the antistatic property.
The castor oil phosphate salt has negative charge in water, can form a stable charge layer around dispersed particles in the amino silicone oil, keeps the dispersed particles of the amino silicone oil in a dispersed suspension state through electrostatic repulsion, and improves the emulsification effect of the amino silicone oil.
Further, the emulsifier B comprises the following raw materials in percentage by mass: ethylene vinyl acetate copolymer: 10-40%, glycol ether: 10-40%, sodium dicetyldiphenyloxide disulfonate: 10-15%, calcium carbonate: 1-5%, carbon nanotubes: 0.1-0.5%, water: 10 to 65 percent.
By adopting the technical scheme, the synergistic effect among the ethylene-vinyl acetate copolymer, the glycol ether and the carbon nano tube ensures that the emulsified silicone oil has strong interface stability, enhances the emulsion stability, is not easy to be layered or demulsified due to the influence of factors such as pH value, salt concentration, temperature, oil phase composition and the like of a receptor system, and has long stabilization time. Meanwhile, the amino silicone oil is matched with the ethylene-vinyl acetate copolymer, so that the color depth effect can be improved.
Benzyl trimethyl ammonium bromide can modify the produced amino silicone to produce quaternized amino silicone oil, so that the produced amino silicone oil has antibacterial and bactericidal effects. Meanwhile, organic bromide is introduced into the amino silicone oil to be compounded with the phosphate in the phosphate starch, so that the flame retardance of the fabric can be improved.
The isopropanol is used for dissolving hexamethyldisiloxane and benzyl trimethyl ammonium bromide, can improve the emulsification of amino silicone oil and can be used as an auxiliary emulsifier.
Further, the alkaline catalyst is one or more of potassium hydroxide, sodium hydroxide and tetramethyl ammonium hydroxide.
A preparation method of an organic silicon darkening finishing agent comprises the following steps:
s1: preparing an aminosilane coupling agent: mixing N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethylsilane, polyether amine, phosphate ester starch and water in a container, heating, and stirring for 0.5-1h to obtain an aminosilane coupling agent;
preparing an emulsifier A: mixing isotridecanol polyoxyethylene ether, castor oil phosphate ester salt, polyoxyethylene glyceryl ether and isopropanol in a container, heating, and stirring for 0.5-1h to obtain an emulsifier A;
preparing an emulsifier B: mixing ethylene-vinyl acetate copolymer, glycol ether, sodium dicetyl diphenyl ether disulfonate, calcium carbonate, carbon nano tubes and water in a container, heating, and stirring for 0.5-1h to obtain an emulsifier B;
preparing a blocking agent: mixing hexamethyldisiloxane, benzyl trimethyl ammonium bromide and isopropanol in a container, and stirring for 0.5-1h to obtain an end-capping agent;
s2: synthesizing crude oil, namely adding octamethylcyclotetrasiloxane and aminosilane coupling agent into a three-neck flask provided with a stirrer and a thermometer, stirring and heating to 70-90 ℃, adding an alkaline catalyst, stirring for 20-30min, heating to 120-14000 mpa, carrying out heat preservation reaction for 4-6h, adding trifluoromethyl maleic anhydride and the alkaline catalyst, stirring for 20-30min, heating to 130-150 ℃, carrying out heat preservation reaction for 2-3h, cooling to 80-100 ℃ after the reaction viscosity reaches 12000-14000mpa.s, adding ethyl acrylate and an end-capping reagent, continuing the reaction for 1-3h, vacuumizing for 1-2h after the heat preservation is finished, cooling to 50-70 ℃, and discharging to obtain the crude oil;
s3: emulsifying crude oil, adding an emulsifier A, performing high-speed shearing emulsification on an emulsifier B and the crude oil according to a certain mass ratio, adding a glycerol additive, adding water while stirring, adding 10-20% of the total water amount, adding triethylamine, stirring, performing system phase inversion, slowly adding the residual water amount while stirring, adding glacial acetic acid to adjust the pH value of the system to 6.5-6.9, and obtaining milky white hydrophilic cool silicone oil with blue light.
Further, the alkaline catalyst added in S2 for the first time comprises potassium hydroxide, the alkaline catalyst added for the second time comprises tetramethylammonium hydroxide, the potassium hydroxide accounts for 50-80% of the total weight of the alkaline catalyst, and the tetramethylammonium hydroxide accounts for 20-50% of the total weight of the alkaline catalyst.
By adopting the technical scheme, the catalytic activity of the tetramethylammonium hydroxide is stronger than that of potassium hydroxide, but the temperature needs to be raised to 135-140 ℃ for cracking for 1 h. In general, tetramethylammonium hydroxide is not completely decomposed and remains in a small amount in the system, resulting in residual ammonia odor, yellowing and poor stability of the crude oil. Therefore, the potassium hydroxide is selected as the catalyst when the catalyst is added for the first time, and the quality of the product is improved.
In conclusion, the invention has the following beneficial effects:
1. according to the invention, the raw materials are reasonably compounded to obtain the ice silicone oil, which has good permeability, alkali resistance, high temperature resistance and good hygroscopicity, and can endow the fabric with smooth and cool hand feeling;
2. the polyether modified polysiloxane used in the invention has excellent emulsifying property and good hygroscopicity, and can greatly reduce surface tension and improve permeability.
Detailed Description
Example (b):
example 1:
a preparation method of an organic silicon darkening finishing agent comprises the following steps:
s1: preparing an amino silane coupling agent, wherein the amino silane coupling agent comprises the following raw materials in percentage by mass: n- (β -aminoethyl) - γ -aminopropylmethyldimethylsilane: 40%, polyether amine: 15%, phosphate starch: 15% and water: 30 percent of amino silane coupling agent is mixed in a container, heated and stirred for 0.7 hour under a magnetic stirrer to obtain the amino silane coupling agent;
preparing an emulsifier A: the emulsifier A comprises the following raw materials in percentage by mass: isotridecanol polyoxyethylene ether: 30%, castor oil phosphate salt: 30%, polyoxyethylene glyceryl ether: 25%, isopropyl alcohol: 15 percent of the raw materials are mixed in a container, heated and stirred for 0.7 hour under a magnetic stirrer to obtain an emulsifier;
preparing an emulsifier B: the emulsifier B comprises the following raw materials in percentage by mass: the emulsifier B comprises the following components in parts by weight: ethylene vinyl acetate copolymer: 25% of glycol ether: 25%, sodium dicetyldiphenyloxide disulfonate: 12%, calcium carbonate: 3%, carbon nanotube: 0.3%, water: 34.7 percent.
Preparing a blocking agent: the end-capping agent comprises the following raw materials in percentage by mass: hexamethyldisiloxane: 40%, benzyltrimethylammonium bromide 30%, isopropanol: 30 percent of the mixture is mixed in a container and stirred for 0.7 hour under a magnetic stirrer to obtain a blocking agent;
s2: synthesizing crude oil, wherein the crude oil comprises the following components in parts by weight: adding octamethylcyclotetrasiloxane and aminosilane coupling agent into a three-neck flask provided with a stirrer and a thermometer, stirring, heating to 80 ℃, adding an alkaline catalyst, stirring for 25min, heating to 125 ℃, carrying out heat preservation reaction for 5h, adding trifluoromethyl maleic anhydride and the alkaline catalyst, stirring for 25min, heating to 140 ℃, carrying out heat preservation reaction for 2.5h, cooling to 90 ℃ after the reaction viscosity reaches 140000mpa.s, adding ethyl acrylate and an end-capping agent, continuing the reaction for 2h, vacuumizing for 1.5h after the heat preservation is finished, cooling to 60 ℃, and discharging to obtain crude oil;
the crude oil comprises the following components in percentage by mass: octamethylcyclotetrasiloxane: 75%, aminosilane coupling agent: 11%, basic catalyst: 3%, ethyl acrylate: 5.3%, trifluoromethyl maleic anhydride: 5%, end-capping agent: 0.7 percent.
The alkaline catalyst added for the first time comprises potassium hydroxide, the alkaline catalyst added for the second time comprises tetramethylammonium hydroxide, the potassium hydroxide accounts for 65% of the total weight of the alkaline catalyst, and the tetramethylammonium hydroxide accounts for 35% of the total weight of the alkaline catalyst.
S3: emulsifying crude oil, adding an emulsifier A, carrying out high-speed shearing emulsification on an emulsifier B and the crude oil according to a certain mass ratio, adding a glycerol additive, adding 15% of the total water, adding triethylamine, stirring, carrying out system phase inversion, slowly adding the residual water, stirring while adding, adding glacial acetic acid to adjust the pH value of the system to 6.7, and obtaining the milky blue organosilicon darkening finishing agent.
The product comprises the following components in parts by weight: crude oil: 40 parts, emulsifier A: 15 parts, emulsifier B: 15 parts, water: 33 parts, glacial acetic acid: 8 parts, triethylamine: and 3 parts.
Examples 2-5 differ from example 1 in that the amino silane coupling agent of step 1 is as follows, in mass percent:
example 6-example 9 differ from example 1 in that the substances in emulsifier a of step 1 are, in mass percent, as follows:
example 10-example 13 differs from example 1 in that the substances in emulsifier B of step 1 are, in mass percent, as follows:
example 14-example 17 differs from example 1 in that the end-capping agents of step 1 are listed in the following table in mass percent:
example 18-example 21 differs from example 1 in that the crude oil of step 2 has the following components in mass percent:
example 22-example 25 differs from example 1 in that the weight ratio of the components in the basic catalyst of step 2 is as follows:
example 26-example 29 differs from example 1 in that the product of step 3 has the following composition in parts by weight:
example 30-example 33 differs from example 1 in that the preliminary temperature rise in step 2 crude oil synthesis is as follows:
| examples | Example 30 | Example 31 | Example 32 | Example 33 |
| Temperature/. degree.C | 70 | 75 | 85 | 90 |
Example 34-example 37 differs from example 1 in that the temperature rise after addition of trifluoromethyl maleic anhydride in the crude oil synthesis in step 2 is as follows:
| examples | Example 34 | Example 35 | Example 36 | Example 37 |
| Temperature/. degree.C | 130 | 135 | 145 | 150 |
Example 38-example 41 differs from example 1 in that the preliminary lowering temperature in the crude oil synthesis in step 2 is as follows:
| examples | Example 38 | Example 39 | Example 40 | EXAMPLE 41 |
| Temperature/. degree.C | 80 | 85 | 95 | 100 |
Example 42-example 45 differs from example 1 in that the temperature drop after addition of the capping agent in the crude oil synthesis of step 2 is as follows:
| examples | Example 42 | Example 43 | Example 44 | Example 45 |
| Temperature/. degree.C | 50 | 55 | 65 | 70 |
Example 46-example 49 differs from example 1 in the following percentage of first water addition to total water in the crude oil emulsification of step 3:
| examples | Example 46 | Example 47 | Example 48 | Example 49 |
| Amount of added water | 10 | 13 | 17 | 20 |
Example 50-example 53 differs from example 1 in that the pH values in the emulsification of the crude oil in step 3 are as follows:
| examples | Example 50 | Example 51 | Example 52 | Example 53 |
| pH value | 6.5 | 6.6 | 6.8 | 6.9 |
Comparative example 1:
compared with the example 1, in the crude oil synthesis in the step 2, the components are as follows by weight percent: octamethylcyclotetrasiloxane: 75%, aminosilane coupling agent: 11%, basic catalyst: 3%, trifluoromethyl maleic anhydride: 5.3%, end-capping agent: 0.7%, water: 5 percent.
Comparative example 2:
compared with the example 1, in the crude oil synthesis in the step 2, the components are as follows by weight percent: octamethylcyclotetrasiloxane: 75%, aminosilane coupling agent: 11%, basic catalyst: 3%, ethyl acrylate: 5%, end-capping agent: 0.7%, water: 5.3 percent.
Comparative example 3:
compared with the example 1, in the crude oil synthesis in the step 2, the components are as follows by weight percent: octamethylcyclotetrasiloxane: 75%, aminosilane coupling agent: 11%, basic catalyst: 3%, end-capping agent: 0.7%, water: 10.3 percent.
Comparison of hand feeling: the effect of the finishing agent on the treated fabric is evaluated by feeling comprehensive factors such as bulkiness, softness, rebound resilience, smoothness, cool feeling and the like of the treated fabric in a hand touch mode, the hand feeling is divided into 5 grades, the higher the grade is, the better the grade is, the best grade is 5 grade, the lowest grade is 1 grade, and hand feeling grade data in the table are obtained through the evaluation of five experienced technicians in a hand touch mode.
Comparison of hydrophilicity: the time taken for the 1 drop of water to completely wet, diffuse and penetrate the fabric surface was measured from a static state by dropping 1 drop of water with a standard dropper from a height of 10cm from the fabric to the horizontally spread fabric surface, the shorter the time taken, the better the hydrophilic effect was.
Determination of yellowing: the whiteness of the surface of the bleached fabric is measured by a whiteness meter before the bleached fabric is treated by the finishing agent (original fabric), the whiteness of the surface of the fabric is measured by the whiteness meter after the fabric is treated and shaped by the finishing agent, the yellowing performance of the finishing agent is evaluated by comparing two whiteness values, and the smaller the value difference is, the better the yellowing resistance performance of the finishing agent is.
The products of example 1, and of comparative examples 1 to 3, were subjected to the following operations:
fabric: nylon cotton Roman fabric;
the product dosage is as follows: 20g/L (30% emulsion, Roman fabric);
the process comprises the following steps: padding (two times of padding and two times of padding, and the rolling allowance is 75%) → sizing (Roman fabric 180 ℃, 90s) → moisture regain, color measurement and hand feeling evaluation.
The instrument comprises the following steps: WSD-3C full-automatic whiteness meter (northern light century), M-6 type setting machine (Shaoxing Seiko mechanical Co., Ltd.), RJ-350 type III padder (Shanghai Shuangye Industrial Co., Ltd.).
| Sample number | Hand feeling | Hydrophilicity | Whiteness degree |
| Example 1 | 4.6 stage | 22s | 89.4 |
| Comparative example 1 | 4.1 level | 27s | 88.9 |
| Comparative example 2 | 4.0 stage | 25s | 89.1 |
| Comparative example 3 | Grade 3.5 | 35s | 88.7 |
| Original cloth | Level 1 | 40s | 89.5 |
As can be seen from the above table: the ice-feeling silicone oil has the advantages of shorter penetration time, best hand feeling and minimum difference with the whiteness of the original cloth under the same condition, and the product of the invention has excellent performances in the aspects of penetration, hand feeling and yellowing reduction. Shows that the trifluoromethyl maleic anhydride and the ethyl acrylate can reduce the yellowing effect of the produced hydrophilic cool silicone oil on the fabric and can improve the hand feeling and the hydrophilicity of the fabric.
Comparative example 4:
compared with the example 1, in the amino silane coupling agent prepared in the step 1, the components are as follows by weight percent: n- (β -aminoethyl) - γ -aminopropylmethyldimethylsilane: 40%, phosphate starch: 15% and water: 45 percent.
Comparative example 5:
compared with the example 1, in the amino silane coupling agent prepared in the step 1, the components are as follows by weight percent: n- (β -aminoethyl) - γ -aminopropylmethyldimethylsilane: 40%, polyether amine: 15% and water: 45 percent.
Comparative example 6:
compared with the example 1, in the amino silane coupling agent prepared in the step 1, the components are as follows by weight percent: n- (β -aminoethyl) - γ -aminopropylmethyldimethylsilane: 40% and water: 60 percent.
Comparative example 7:
compared with the example 1, in the crude oil emulsification in the step 3, the components in parts by weight are as follows: crude oil: 40 parts, emulsifier A: 15 parts, emulsifier B: 15 parts, water: 36 parts, glacial acetic acid: 8 parts.
Comparative example 8:
compared with the example 1, in the crude oil emulsification in the step 3, the components in parts by weight are as follows: crude oil: 40 parts, emulsifier A: 15 parts, water: 48, glacial acetic acid: 8 parts, triethylamine: and 3 parts.
Comparative example 9:
compared with the example 1, in the crude oil emulsification in the step 3, the components in parts by weight are as follows: crude oil: 40 parts, emulsifier B: 15 parts, 48 parts of water, glacial acetic acid: 8 parts, triethylamine: and 3 parts.
Comparative example 10:
compared with example 1: in the step 3, in the crude oil emulsification, the components in parts by weight are as follows: crude oil: 40 parts of water: 63 parts, glacial acetic acid: 8 parts, triethylamine: and 3 parts.
Comparative example 11:
compared with the example 1, in the crude oil emulsification in the step 3, the components in parts by weight are as follows: crude oil: 40 parts of water: 66 parts, glacial acetic acid: 8 parts.
And (3) testing high-temperature stability: in 50g/L silicone oil emulsion, the stability is observed at 90 ℃ within a certain time, and no floc and floating oil are observed to be stable within 4 hours.
Alkali resistance stability test: the stability of 5g/L silicone oil emulsion was observed with NaOH solution at pH 12 over a period of time, and the emulsion was stable without flocs and floating oil over 24 hours.
Comparison of hand feeling: the effect of the finishing agent on the treated fabric is evaluated by feeling comprehensive factors such as bulkiness, softness, rebound resilience, smoothness, cool feeling and the like of the treated fabric in a hand touch mode, the hand feeling is divided into 5 grades, the higher the grade is, the better the grade is, the best grade is 5 grade, the lowest grade is 1 grade, and hand feeling grade data in the table are obtained through the evaluation of five experienced technicians in a hand touch mode.
Comparison of hydrophilicity: dropping 1 drop of water from a height of 10cm from the fabric to the surface of the horizontally spread fabric by using a standard dropper, and measuring the time for the 1 drop of water to completely wet, diffuse and permeate on the surface of the fabric under a static condition, wherein the shorter the time, the better the hydrophilic effect is
The following operations were carried out on the products of example 1, and comparative examples 4 to 12:
fabric: nylon cotton Roman fabric;
the product dosage is as follows: 20g/L (30% emulsion, Roman fabric);
the process comprises the following steps: padding (two times of padding and 75% of padding is remained), shaping (Roman fabric 180 ℃, 90s), dampening, color measurement and hand feeling evaluation.
The instrument comprises the following steps: m-6 type forming machine (Shaoxing precision machines, Inc.), RJ-350 type III padder (Shanghai double leaf industries, Inc.).
As can be seen from the above table: the ice-feeling silicone oil has the advantages of shorter penetration time, best hand feeling and best stability to alkali and high temperature under the same condition, and the product of the invention has excellent performances in the aspects of permeability, hand feeling and emulsification stability. Example 1 compares with comparative examples 4 to 6: the polyether amine and the phosphate starch are added, so that the hand feeling and the hydrophilicity of the cloth can be improved, and the stability of the product can be improved. Example 1 compares with comparative examples 7 to 11: the triethylamine, the emulsifier A and the emulsifier B are added, so that the hand feeling and the hydrophilicity of the cloth can be improved, and the stability of the product can be improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (7)
1. The hydrophilic cool silicone oil is characterized by comprising the following raw materials in parts by weight: crude oil: 30-50 parts of an emulsifier A: 10-20 parts of an emulsifier B: 10-20 parts of glycerol: 5-10 parts of water: 25-40 parts of glacial acetic acid: 5-10 parts of triethylamine: 1-5 parts;
the crude oil comprises the following raw materials in percentage by mass: octamethylcyclotetrasiloxane: 65-85%, amino silane coupling agent: 8-15%, basic catalyst: 1-5%, trifluoromethyl maleic anhydride: 1-10%, ethyl acrylate: 1-10%, end-capping agent: 0.5-1%;
the end-capping reagent comprises the following raw materials in percentage by mass: hexamethyldisiloxane: 30-50%, benzyltrimethylammonium bromide: 20-40%, isopropanol: 20 to 40 percent.
2. The hydrophilic cool silicone oil according to claim 1, wherein the aminosilane coupling agent comprises the following raw materials and mass percentages thereof: n- (β -aminoethyl) - γ -aminopropylmethyldimethylsilane: 30-50%, polyether amine: 10-20%, phosphate starch: 10-20%, water: 20 to 40 percent.
3. The hydrophilic cool silicone oil according to claim 2, wherein the emulsifier A comprises the following raw materials by mass percent: isotridecanol polyoxyethylene ether: 20-45%, castor oil phosphate salt: 20-40%, polyoxyethylene glyceryl ether: 20-30%, isopropanol: 10 to 20 percent.
4. The hydrophilic cool silicone oil according to claim 1, wherein the emulsifier B comprises the following raw materials by mass percent: ethylene vinyl acetate copolymer: 10-40%, glycol ether: 10-40%, sodium dicetyldiphenyloxide disulfonate: 10-15%, calcium carbonate: 1-5%, carbon nanotubes: 0.1-0.5%, water: 10 to 65 percent.
5. The hydrophilic cool silicone oil according to claim 1, wherein the basic catalyst is one or more of potassium hydroxide, sodium hydroxide, and tetramethylammonium hydroxide.
6. The preparation method of the hydrophilic cool silicone oil is characterized by comprising the following steps:
s1: preparing an aminosilane coupling agent: mixing N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethylsilane, polyether amine, phosphate ester starch and water in a container, heating, and stirring for 0.5-1h to obtain an aminosilane coupling agent;
preparing an emulsifier A: mixing isotridecanol polyoxyethylene ether, castor oil phosphate ester salt, polyoxyethylene glyceryl ether and isopropanol in a container, heating, and stirring for 0.5-1h to obtain an emulsifier A;
preparing an emulsifier B: mixing ethylene-vinyl acetate copolymer, glycol ether, sodium dicetyl diphenyl ether disulfonate, calcium carbonate, carbon nano tubes and water in a container, heating, and stirring for 0.5-1h to obtain an emulsifier B;
preparing a blocking agent: mixing hexamethyldisiloxane, benzyl trimethyl ammonium bromide and isopropanol in a container, and stirring for 0.5-1h to obtain an end-capping agent;
s2: synthesizing crude oil, namely adding octamethylcyclotetrasiloxane and aminosilane coupling agent into a three-neck flask provided with a stirrer and a thermometer, stirring and heating to 70-90 ℃, adding an alkaline catalyst, stirring for 20-30min, heating to 120-plus-130 ℃, carrying out heat preservation reaction for 4-6h, adding trifluoromethyl maleic anhydride and the alkaline catalyst, stirring for 20-30min, heating to 130-plus-150 ℃, carrying out heat preservation reaction for 2-3h, cooling to 80-100 ℃ after the reaction viscosity reaches 12000-plus-15000 mpa.s, adding ethyl acrylate and an end-capping reagent, continuing the reaction for 1-3h, vacuumizing for 1-2h after the heat preservation is finished, cooling to 50-70 ℃, and discharging to obtain the crude oil;
s3: emulsifying crude oil, adding an emulsifier A, performing high-speed shearing emulsification on an emulsifier B and the crude oil according to a certain mass ratio, adding a glycerol additive, adding water while stirring, adding 10-20% of the total water amount, adding triethylamine, stirring, performing system phase inversion, slowly adding the residual water amount while stirring, adding glacial acetic acid to adjust the pH value of the system to 6.5-6.9, and obtaining milky white hydrophilic cool silicone oil with blue light.
7. The method of claim 6, wherein the first basic catalyst added in S2 comprises potassium hydroxide, the second basic catalyst added comprises tetramethylammonium hydroxide, the potassium hydroxide is 50-80% of the total weight of the basic catalysts, and the tetramethylammonium hydroxide is 20-50% of the total weight of the basic catalysts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811576313.6A CN109629237B (en) | 2018-12-22 | 2018-12-22 | Hydrophilic cool silicone oil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811576313.6A CN109629237B (en) | 2018-12-22 | 2018-12-22 | Hydrophilic cool silicone oil and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109629237A CN109629237A (en) | 2019-04-16 |
| CN109629237B true CN109629237B (en) | 2021-06-25 |
Family
ID=66076597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811576313.6A Active CN109629237B (en) | 2018-12-22 | 2018-12-22 | Hydrophilic cool silicone oil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109629237B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110184822A (en) * | 2019-05-06 | 2019-08-30 | 绍兴柯桥欧利助剂有限公司 | A kind of fabric fluffy softening agent and preparation method thereof |
| CN110698691A (en) * | 2019-11-06 | 2020-01-17 | 常州市宁河新材料科技有限公司 | Preparation method of hydrophobic amino silicone oil emulsion |
| CN110615898A (en) * | 2019-11-07 | 2019-12-27 | 常州市宁河新材料科技有限公司 | Preparation method of high-temperature-resistant alkali-type amino silicone oil emulsion |
| CN110756732B (en) * | 2019-12-03 | 2020-12-04 | 安徽省含山县皖中减速机械有限公司 | Casting process for improving casting defects of speed reducer pin gear shell |
| CN112321834A (en) * | 2020-11-21 | 2021-02-05 | 英德市东鸿化工科技有限公司 | Preparation method of hydrophilic silicone oil |
| CN113957720B (en) * | 2021-09-27 | 2024-01-05 | 广东仙图科技研究有限公司 | Hydrophilic deepened dust-free silicone oil and preparation method and use method thereof |
| CN114032030A (en) * | 2021-12-16 | 2022-02-11 | 杭州崇耀科技发展有限公司 | Noise-reducing hand feeling agent |
| CN117700757B (en) * | 2023-12-18 | 2024-08-16 | 宁波润禾高新材料科技股份有限公司 | Cool sense polysiloxane material, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418518A (en) * | 2008-12-11 | 2009-04-29 | 绍兴文理学院 | Method for preparing durable hydrophilic polyether modified amino polysiloxane soft agent |
| CN104862967A (en) * | 2014-02-24 | 2015-08-26 | 香港纺织及成衣研发中心有限公司 | Fabric with surface cooling function and preparation method thereof |
| CN105155280A (en) * | 2015-10-10 | 2015-12-16 | 珠海华大浩宏化工有限公司 | Ice feeling finishing agent and preparation method thereof |
| CN106319975A (en) * | 2016-09-22 | 2017-01-11 | 清远市宏图助剂有限公司 | Hydrophilic ice-cold skin touch finishing agent for cotton fabric and preparation method of hydrophilic ice-cold skin touch finishing agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02221462A (en) * | 1989-02-22 | 1990-09-04 | Toray Ind Inc | Cloth having cold feeling |
-
2018
- 2018-12-22 CN CN201811576313.6A patent/CN109629237B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418518A (en) * | 2008-12-11 | 2009-04-29 | 绍兴文理学院 | Method for preparing durable hydrophilic polyether modified amino polysiloxane soft agent |
| CN104862967A (en) * | 2014-02-24 | 2015-08-26 | 香港纺织及成衣研发中心有限公司 | Fabric with surface cooling function and preparation method thereof |
| CN105155280A (en) * | 2015-10-10 | 2015-12-16 | 珠海华大浩宏化工有限公司 | Ice feeling finishing agent and preparation method thereof |
| CN106319975A (en) * | 2016-09-22 | 2017-01-11 | 清远市宏图助剂有限公司 | Hydrophilic ice-cold skin touch finishing agent for cotton fabric and preparation method of hydrophilic ice-cold skin touch finishing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109629237A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109629237B (en) | Hydrophilic cool silicone oil and preparation method thereof | |
| CN107129578B (en) | Preparation method of amino modified silicone oil finishing agent with net structure | |
| EP0342834B1 (en) | Treatment of fibrous materials | |
| CN104086779B (en) | Sliding block silicone oil of a kind of ultra-soft and preparation method thereof | |
| CN101809069B (en) | Organo-functional silicone in emulsion systems and process for preparing same | |
| US5593611A (en) | Method for imparting softness with reduced yellowing to a textile using a low amine content, high molecular weight aminopolysiloxane | |
| CN101418518A (en) | Method for preparing durable hydrophilic polyether modified amino polysiloxane soft agent | |
| CN110184822A (en) | A kind of fabric fluffy softening agent and preparation method thereof | |
| CN113914104B (en) | Antibacterial crease-resistant cotton-flax fabric and preparation method thereof | |
| CN109667154A (en) | A kind of organic silicon rigidity-increasing depth finishing agent and its preparation process | |
| CN115198520A (en) | Bio-based softening agent and preparation method and application thereof | |
| CN106758249A (en) | Fabric softener and preparation method thereof | |
| CN102644200B (en) | Super-soft finishing agent of silicone oil | |
| CN110627828B (en) | Organosilicon quaternary ammonium salt for improving antibacterial performance and preparation method and application thereof | |
| CN110656500B (en) | Non-silicon type hydrophilic softening agent and preparation method and application thereof | |
| CN106750324A (en) | A kind of poly- quaternary ammonium polyethers dimethyl silicone polymer and preparation method thereof and hand feel finishing agent | |
| CN113461969B (en) | Organic functional group modified polysiloxane polymerization emulsion and preparation method thereof | |
| CN112661966A (en) | Quaternary ammonium salt modified organic silicon and preparation method and application thereof | |
| CN102660029B (en) | Cation modified supersoft hydrophilic block silicone oil compound and preparation method and application | |
| CN116043538A (en) | Softening agent in biological base bath and preparation method and application thereof | |
| CN113308765B (en) | Spinning oil for polyester staple fibers and preparation method thereof | |
| CN113930973A (en) | Fabric and preparation method thereof | |
| CN108221390B (en) | Hydrophilic softening agent for silk fabrics and preparation method thereof | |
| CN114481611A (en) | Soft antistatic finishing agent and preparation method and application thereof | |
| CN117306263B (en) | Far infrared anion antibacterial multifunctional health quilt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200117 Address after: 312030 intersection of Qiyuan road and Shuangzha Road, Binhai Industrial Zone, Keqiao District, Shaoxing City, Zhejiang Province Applicant after: Zhejiang Zhendong New Material Co.,Ltd. Address before: Binhai Industrial Zone, Zhejiang road 312073, Shaoxing District of Keqiao City Applicant before: SHAOXING ZHENDONG TECHNOLOGY CO.,LTD. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: Buildings 1-6, 7A-7B, and 8-11 of Zhejiang Zhendong New Materials Co., Ltd. in the Jiuyiqiu area of Binhai Industrial Zone, Ma'an Street, Keqiao District, Shaoxing City, Zhejiang Province, 312030 Patentee after: Zhejiang Yayun Zhendong New Materials Co.,Ltd. Country or region after: China Address before: 312030 intersection of Qiyuan road and Shuangzha Road, Binhai Industrial Zone, Keqiao District, Shaoxing City, Zhejiang Province Patentee before: Zhejiang Zhendong New Material Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |