CN115400462B - Organic silicon compound with special structure and preparation method thereof - Google Patents
Organic silicon compound with special structure and preparation method thereof Download PDFInfo
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- CN115400462B CN115400462B CN202210943173.1A CN202210943173A CN115400462B CN 115400462 B CN115400462 B CN 115400462B CN 202210943173 A CN202210943173 A CN 202210943173A CN 115400462 B CN115400462 B CN 115400462B
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- polyoxyethylene polyoxypropylene
- organic silicon
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- polyoxypropylene ether
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- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 14
- -1 polysiloxane Polymers 0.000 claims abstract description 142
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000009471 action Effects 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 239000004034 viscosity adjusting agent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 34
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 29
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 25
- 229920002545 silicone oil Polymers 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 150000002009 diols Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 11
- 229920001558 organosilicon polymer Polymers 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 150000001282 organosilanes Chemical class 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 49
- 239000004094 surface-active agent Substances 0.000 abstract description 21
- 230000005764 inhibitory process Effects 0.000 abstract description 14
- 230000008030 elimination Effects 0.000 abstract description 6
- 238000003379 elimination reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000002245 particle Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000004721 Polyphenylene oxide Substances 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 229920000570 polyether Polymers 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 230000002209 hydrophobic effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- SJIDAAGFCNIAJP-UHFFFAOYSA-N 6-methylheptyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCC(C)C SJIDAAGFCNIAJP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 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
- 229950010286 diolamine Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/54—Silicon compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention relates to the field of surfactants, in particular to an organic silicon compound with a special structure and a preparation method thereof. The invention provides an organic silicon compound with a special structure, which comprises the following raw materials: modified hydrogen-containing polysiloxane, alkyne diol polyoxyethylene polyoxypropylene ether, catalyst, viscosity modifier, organic silicon resin and silicon dioxide. Also provided is a preparation method of the organic silicon compound with the special structure, comprising the following steps: the modified hydrogen-containing polysiloxane and the alkyne diol polyoxyethylene polyoxypropylene ether react under the action of a catalyst, then a viscosity regulator is added to improve the performance, and then a premix of the organic silicon resin and the silicon dioxide is added to obtain the organic silicon compound with the special structure. The organic silicon compound with the special structure has the balance of long-acting foam inhibition, instant foam elimination and system compatibility, and can be applied to various systems which need to control the foam and have higher requirements on the compatibility.
Description
Technical Field
The invention relates to the field of surfactants, in particular to an organic silicon compound with a special structure and a preparation method thereof.
Background
The surfactant is a substance capable of significantly reducing the surface tension of the target solution. Has immobilized hydrophilic and lipophilic groups, and can be oriented on the surface of the solution. The molecular structure of the surfactant has amphoteric properties: one end is hydrophilic group, and the other end is hydrophobic group; hydrophilic groups are usually polar groups such as carboxylic acid, sulfonic acid, sulfuric acid, amine groups and salts thereof, hydroxyl groups, amide groups, ether linkages, and the like, and can also be used as polar hydrophilic groups; while hydrophobic groups are often nonpolar hydrocarbon chains, such as hydrocarbon chains of 8 carbon atoms or more. The surfactant is classified into ionic surfactant (including cationic surfactant and anionic surfactant), nonionic surfactant, amphoteric surfactant, etc
Surfactants are an important component of emulsions, and their hydrophilic and lipophilic nature makes them the bridge linking the oil and water phases. In order to keep the system stable over the lifetime, a wide variety of emulsifiers have been developed, either as single components or as a complex, or as universal or as special. Silicone-based surfactants are one of the more representative types.
The organic silicon surfactant mainly refers to a surfactant which is formed by taking polydimethylsiloxane as a hydrophobic main chain and connecting one or more organic polar groups at the middle or terminal positions of the polydimethylsiloxane. It has very high surface activity, can obviously reduce the surface tension of water to about 20N/m, and is a high-efficiency surfactant. Organosilicon surfactants, which are one of the organosilicon compounds, are used in the industrial field since the 60 th century, but rapid and comprehensive development on a large scale starts in the 80 th century. Because of the unique advantages of the surfactant, such as low surface tension, good wetting and spreading performance, large emulsification effect, good compatibility, foaming, foam homogenizing and stabilizing effects, no toxicity and great application to various industries. Currently, they are widely used in textile, cosmetic, plastic, paint, agricultural chemical, pharmaceutical, mechanical processing, and other fields.
In the prior art, in the modification method of hydrogen-containing silicone oil, long-chain alkyl modified hydrogen-containing silicone oil is put into a reaction kettle, the temperature is raised to 60-70 ℃ under stirring, then a mixture of dodecene, a Speier catalyst and amine compounds is dropwise added, the dropwise adding time is controlled to be 15-30 min, and the mixture is reacted for 4-8 h at 90-130 ℃ after the dropwise adding is finished; and (3) carrying out vacuum reduced pressure distillation on the obtained product to obtain the long-chain alkyl modified hydrogen-containing silicone oil lubricating oil. The preparation method of the alkyl phenol acrylate and polyether co-modified phenyl hydrogen silicone oil comprises the steps of adding phenyl hydrogen silicone oil, a polymerization inhibitor and an organic solvent into a container, heating to 70-80 ℃ under stirring, adding an isopropanol solution of a catalyst, then dropwise adding a mixture of the alkyl phenol acrylate and polyether at 90-120 ℃, reacting for 4-7 h after the dripping, and distilling under reduced pressure to obtain the alkyl phenol acrylate and polyether co-modified phenyl hydrogen silicone oil. The problem is that the application range is limited, and the single long-chain alkane modification has a good effect on compatibility; also alkylphenol acrylate modifications have been difficult to achieve with desirable results in terms of performance.
The organic silicon surfactant has the characteristic, and the HLB value of the organic silicon surfactant can be regulated by changing the molecular structure and the proportion of polyoxyethylene and polyoxypropylene, so that the property of the organic silicon surfactant can be changed, and the organic silicon surfactant can be hydrophilic or hydrophobic. Can be used as an emulsifier to stabilize emulsion; can also be used as demulsifier to play a role in breaking the stability of emulsion. In the field of foam control, the structure can be regulated to play a role in stabilizing foam, and the molecules can be regulated to play a role in eliminating foam or removing foam. In the prior art, a method for synthesizing block alkyne diol polyether by reacting alkyne diol serving as a starting material with ethylene oxide and/or propylene oxide under the action of a composite catalyst has been disclosed. However, the application of the alkyne diol polyether is not very wide, and the performance defect exists, mainly when the alkyne diol polyether is used as a defoaming agent or a foam inhibitor, the defoaming or foam inhibition performance can be regulated by regulating the proportion of polyoxyethylene and polyoxypropylene and the molecular weight of polysiloxane, but the defoaming and foam inhibition effect of the polyether modified silicone oil is difficult to be improved essentially, and the application requirements cannot be met in a plurality of fields. Especially in the field of paint and ink, the simple polyether modified silicone oil is difficult to achieve the balance of foam eliminating and inhibiting effects and compatibility.
The organic silicon compound containing the special structure provided by the invention adopts a brand new molecular design, and introduces a new organic group in the synthesis of the organic silicon surfactant, so that the new polymer has the foam inhibition performance on the molecular structure; meanwhile, the foam eliminating and suppressing characteristics and the system compatibility of the final product are regulated by regulating the length of a molecular architecture organosilicon main chain and the ratio of EO (ethylene oxide) to PO (propylene oxide), so that the balance of long-acting foam inhibition, instantaneous foam elimination and system compatibility is achieved, and the foam eliminating agent is applied to various systems which need to control the foam and have higher requirements on the compatibility.
Disclosure of Invention
Aiming at the defects existing in the prior art, one of the purposes of the invention is to provide an organosilicon compound with a special structure, wherein the organosilicon compound adjusts the foam inhibition characteristic and the system compatibility of a final product by adjusting the length of an organosilicon main chain of a molecular framework and the ratio of EO (ethylene oxide) to PO (propylene oxide), so as to achieve the balance of long-acting foam inhibition, instant foam elimination and system compatibility, and is applied to various systems with high requirements on compatibility, wherein the foam needs to be controlled.
The second object of the invention is to provide a preparation method of the organic silicon compound with a special structure, and the organic silicon compound prepared by the preparation method has good foam eliminating and inhibiting characteristics and system compatibility.
In order to achieve one of the above objects, the present invention provides the following technical solutions:
provided is an organosilicon compound with a special structure, which comprises the following raw materials: modified hydrogen-containing polysiloxane, alkyne diol polyoxyethylene polyoxypropylene ether, catalyst, viscosity modifier, organic silicon resin and silicon dioxide.
The modified hydrogen-containing polysiloxane is a composition with one or more than two of structures shown in a formula I.
The alkyne diol polyoxyethylene polyoxypropylene ether is a composition of one or more than two of structures with a molecular structural formula shown as a formula II.
The molecular structural general formula of the modified hydrogen-containing polysiloxane is shown as formula I:
in the formula I, x and y are integers from 1 to 300;
in the formula I, R 1 、R 2 Is H atom or alkyl, and R 1 、R 2 At least one of which is an H atom; r is R 3 Is alkyl;
wherein the molecular structural general formula of the alkyne diol polyoxyethylene polyoxypropylene ether is shown as a formula II:
in the formula II, R 4 、R 5 、R 4 ＇、R 5 ' is alkyl, R 6 、R 6 ' is H or alkyl;
in the formula II, p, q, m, n is an integer of 1 to 300.
Further, the molecular structural formula of the modified hydrogen-containing polysiloxane is shown as formula I:
wherein x and y are the polymerization degree of the corresponding chain units, and x and y are integers of 1-50;
wherein R1 、R 2 Is H atom or alkyl group with 1-20 carbon atoms, and R 1 、R 2 At least one of which is an H atom; r is R 3 Is an alkyl group having 10 to 30 carbon atoms.
The modified hydrogen-containing polysiloxane is one or more than two compositions with a structure shown in a formula I.
Further, R 1 、R 2 When the alkyl group is an alkyl group, the alkyl group may be any one of methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, hexyl, octyl and decyl;
preferably, R 1 、R 2 H atom, methyl and ethyl.
Further, the modified hydrogen-containing polysiloxane comprises the following raw materials: hydrogen-containing silicone oil, long-chain alpha olefin, catalyst, organosilane reducer, strong acid and alkali.
Wherein, the molecular structural general formula of the hydrogen-containing silicone oil is shown as follows:
and x and y are the polymerization degree of the corresponding chain units.
Further, the modified hydrogen-containing polysiloxane is a product obtained by taking hydrogen-containing silicone oil as a raw material, carrying out addition reaction with long-chain alpha olefin under the action of a platinum catalyst, then carrying out reaction with an organosilane reducing agent under the action of strong acid, neutralizing and filtering.
Further, the hydrogen content of the hydrogen-containing silicone oil ranges from 0.01% to 0.5%; the long-chain alpha olefin is mono-olefin with 10-30 carbon atoms and double bonds at the end of a molecular chain; the strong acid is sulfuric acid; the organosilane reducing agent is 1, 3-tetramethyl disiloxane; the alkali is sodium bicarbonate.
Preferably, the preparation method of the modified hydrogen-containing polysiloxane comprises the following reaction steps:
p1, adding hydrogen-containing silicone oil and long-chain alpha olefin in a reactor according to a certain molar ratio, stirring, heating up, adding a catalyst, and carrying out heat preservation reaction to obtain a modified hydrogen-containing polysiloxane intermediate;
p2, reacting the intermediate with an organosilane reducing agent under the action of strong acid, neutralizing with alkali, and filtering to obtain a product, namely the modified hydrogen-containing polysiloxane, wherein the molecular structural formula of the product is shown as formula I:
further, in the step P1, the temperature of the heat preservation reaction is 70-110 ℃, the dosage of the catalyst is 1-10 ppm, and the reaction time is 2-3 hours.
Further, in the step P2, the reaction time is 16 to 24 hours.
Further, the molecular structural general formula of the alkyne diol polyoxyethylene polyoxypropylene ether is shown as a formula II:
wherein ,R4 、R 5 、R 4 ＇、R 5 "is alkyl having 1 to 25 carbon atoms, R 6 、R 6 ' is H atom or alkyl with 1-10 carbon atoms;
wherein p, q, m, n represents the degree of polymerization, and p, q, m, n is an integer in the range of 1 to 50;
the alkyne diol polyoxyethylene polyoxypropylene ether is one or more than two compositions with a molecular structural formula shown as a formula II;
preferably, p, q, m, n is an integer in the range of 1 to 20.
Further, the alkyne diol polyoxyethylene polyoxypropylene ether comprises the following raw materials: acetylenic diol, triethylamine, ethylene oxide, propylene oxide, and acetic acid.
Wherein the alkynediol has a molecular structural general formula shown in a formula III:
further, the alkyne diol polyoxyethylene polyoxypropylene ether is alkyne diol polyoxyethylene polyoxypropylene ether obtained by reacting alkyne diol with ethylene oxide and propylene oxide under certain conditions; the amount of ethylene oxide and propylene oxide is controlled in the reaction process to prepare the alkyne diol polyoxyethylene polyoxypropylene ether with the required polymerization degree. The molar ratio of the ethylene oxide to the alkyne diol is 1:2-100, and the molar ratio of the propylene oxide to the alkyne diol is 1:2-100.
Preferably, the molar ratio of the ethylene oxide to the alkyne diol is 1:2-40, and the molar ratio of the propylene oxide to the alkyne diol is 1:2-40.
Preferably, the preparation method of the alkyne diol polyoxyethylene polyoxypropylene ether comprises the following reaction steps:
q1, sequentially acetylenic diol and triethylamine into a reaction container;
q2, introducing nitrogen into the reaction vessel for one to three times;
q3, stirring, heating to 105-110 ℃ to carry out a water diversion process, and removing water in the system;
q4, controlling the reaction temperature, slowly dripping propylene oxide according to a proportion, and then dripping ethylene oxide to carry out polyether reaction;
q5, removing unreacted propylene oxide/ethylene oxide monomer by controlling the temperature after the reaction is finished;
q6, cooling, adding acetic acid to neutralize and obtain the alkyne diol polyoxyethylene polyoxypropylene ether product.
The molecular structural formula of the obtained target product, namely the alkyne diol polyoxyethylene polyoxypropylene ether disclosed by the invention, is shown as a formula II.
Further, the catalyst is a metal platinum catalyst, and the dosage of the catalyst is 1-10 ppm.
Further, the metal platinum catalyst comprises one or more than two of a complex of platinum divinyl tetramethyl disiloxane, chloroplatinic acid and chloroplatinic acid isopropanol solution.
Further, the viscosity modifier is an alkyl polyoxyethylene polyoxypropylene ether compound. The alkyl polyoxyethylene polyoxypropylene ether compound is a copolymer formed by alkyl alcohol and ethylene oxide/propylene oxide under certain reaction conditions, and the molecular weight of the copolymer is controlled by the use amount of the ethylene oxide and the propylene oxide. Wherein the alkyl is a linear or branched primary or secondary alcohol with 8-20 carbon atoms, the mol ratio of ethylene oxide to propylene oxide is 1:0.5-10, and the ratio of the sum of the mol numbers of ethylene oxide and propylene oxide to the mol number of alkyl alcohol is 1:8-50.
Preferably, the alkyl polyoxyethylene polyoxypropylene ether compound is isomeric trideceth polyoxyethylene (5) polyoxypropylene (5) ether; wherein the polymerization degree of a polyoxyethylene segment represented by polyoxyethylene (5) in the isomeric tridecanol polyoxyethylene (5) polyoxypropylene (5) ether is 5, and the polymerization degree of polyoxypropylene represented by polyoxypropylene (5) is 5.
Further, the viscosity modifier is used in an amount of 20% of the total weight of the modified hydrogen-containing polysiloxane and the acetylenic diol polyoxyethylene polyoxypropylene ether.
Further, the silicone resin is a methyl MQ resin solution.
Further, the methyl MQ resin in the methyl MQ resin solution is formed by hydrolyzing and polymerizing substances of M chain links and Q chain links in a mixture of alcohol, water and acid. The molar ratio of M units to Q units of the resulting polymer MQ resin was 0.6:1 to 2.0:1. in use, the methyl silicone resin may be added to the silicone composition in the form of a solution.
Further, the solvent in the methyl MQ resin solution comprises one or more than two of 2-butyl octanol, toluene or isooctyl stearate. Non-volatile solvents may remain in the silicone composition and volatile solvents may be removed by stripping or other separation means. Methyl MQ resins are viscous liquids or solids with viscosities of greater than 1000 mPa-s at 25 ℃ at standard atmospheric pressure. The weight average molecular weight of the methyl silicone resin is 1000-20000 g/mol by gel permeation chromatography (relative to polystyrene standard).
Further, the silica is one or two of hydrophobic silica by a gas phase method and hydrophobic silica by a precipitation method. The hydrophobic treatment agent of the hydrophobic silicon dioxide comprises one or more than two of polydimethyl siloxane, silane coupling agent, hexamethyldisilazane, hexamethyldisiloxane, fatty acid or fatty alcohol and chlorosilane; the temperature of the hydrophobization process is at least 100 ℃.
In order to achieve the second object, the present invention provides the following technical solutions:
the preparation method of the organic silicon compound with the special structure comprises the following reaction steps:
s1, mixing modified hydrogen-containing polysiloxane and alkyne diol polyoxyethylene polyoxypropylene ether in proportion, reacting under the action of a catalyst to obtain an organosilicon polymer with a molecular structural general formula shown in formula IV, and adding a viscosity regulator to obtain an organosilicon composition;
wherein R7 、R 8 Is R 1 Or R is 2 Or a substituent of the structure shown in formula V or VI, and at least one substituent of the structure shown in formula V or VI:
wherein ,
is the position for connecting the substituent group;
s2, adding an organic silicon resin solvent solution into another reactor, starting stirring, slowly adding silicon dioxide, stirring, mixing, dispersing, and grinding by a grinder to obtain a premix;
and S3, adding the organosilicon composition in the step S1 and the premix in the step S2 together, heating, uniformly stirring, and evaporating the solvent to obtain the organosilicon compound with the special structure.
Further, in the step S2, the stirring speed is 1000-3000 rpm, the dispersing time is 1-5 hours, and the grinding machine grinds the solid particles to the particle size of 2-5 mu m.
Further, in the step S3, the heating temperature is 120-150 ℃, and the heat preservation time is 0.5-2 h.
The invention has the beneficial effects that:
(1) According to the organic silicon compound with the special structure, firstly, the hydrogen-containing silicone oil is subjected to alkylation modification to obtain the alkyl modified hydrogen-containing polysiloxane, the hydrophobicity of the alkyl modified hydrogen-containing polysiloxane is better than that of the hydrogen-containing silicone oil, and meanwhile, the compatibility with an organic system is improved to a certain extent.
(2) The organic silicon compound of the special structure provided by the invention fully utilizes the characteristics of the alkyne diol polyoxyethylene polyoxypropylene ether, and the alkyne diol polyoxyethylene polyoxypropylene ether compound is a novel surfactant, and the polyether has a gemini structure, polyether groups are distributed on two sides of a molecular structure, and has the characteristics of smaller molecular weight, low surface tension, high stability and good foam inhibition. Meanwhile, the detergent has better washing effect, emulsifying effect and dispersing effect. The alkyne diol polyether is easy to prepare, high in reaction yield, low in cost and easy for industrial mass production, and has a wider application prospect in the future.
(3) The organic silicon compound of the special structure provided by the invention is prepared by alkylating and modifying hydrogen-containing silicone oil to obtain modified hydrogen-containing polysiloxane, and then reacting the modified hydrogen-containing polysiloxane with the novel structure of the alkyne diol polyoxyethylene polyoxypropylene ether to obtain the novel special structure organic silicon polymer, and the special structure has the characteristics of hydrophobic property of long-chain alkylated modified polysiloxane and compact gemini structure of the alkyne diol polyoxyethylene polyoxypropylene ether, so that the obtained special structure has more excellent performance, high stability, outstanding defoaming and foam inhibition performance, and the compound with excellent foam inhibition characteristics is obtained, and meanwhile, compatibility is also achieved. Has good universality in the application of paint ink and the like.
(4) The organic silicon compound with the special structure provided by the invention has the advantages that the viscosity regulator is used for reducing the viscosity of a system, improving the operability of a product in a subsequent process and improving the production efficiency.
(5) The organic silicon composite of the special structure provided by the invention has the advantages that the used organic silicon MQ resin has high thermal stability and chemical stability, low surface tension and strong foam breaking capability. The silica particles have an important role in the defoamer, namely adsorption, and because of the small particle size, large specific surface area, high demonstration energy and a three-dimensional network structure, the silica can form a huge acting force for adsorbing bubbles, and the silica can attack the bubbles together with the polysiloxane, namely the silica adsorbs and impacts the weak points of the bubbles, so that the bubbles are broken under the action of low surface tension of the polysiloxane. Therefore, silica corresponds to "needlepoint" in the defoamer, and is used in small amounts but has a great effect. The active component of the efficient defoaming agent is taken together with polysiloxane, and the efficient defoaming agent has a composite efficient and synergistic defoaming effect. Meanwhile, because of the existence of the silicon dioxide particles, the polysiloxane can be rapidly dispersed in the foaming liquid, so that the dispersion efficiency of the polysiloxane is improved, and the defoaming effect is provided. The interaction of the organic MQ resin and the silicon dioxide is more beneficial to the enhancement of the performance, and has important auxiliary effect in the surfactant.
(6) The preparation method of the organic silicon compound with the special structure provided by the invention is used for respectively mixing the prepared organic silicon polymer with the novel special structure with the premix of the organic silicon resin and the silicon dioxide after the viscosity regulator is added, and at the moment, the silicon dioxide particles are fully dissolved or dispersed in the organic silicon resin, so that the production method is more convenient, the production period is shortened, and the productivity is higher. The absence of each formulation of the resulting silicone composite may cause a loss of efficacy and is undesirable as an integral requirement.
In the whole, the novel molecular design is adopted, and a novel organic gemini structural group is introduced in the synthesis of the organic silicon surfactant, so that the three-dimensional property of the whole molecular structure is improved, the incompatibility of the whole molecular structure in a system is improved in application, and the novel polymer has the property of inhibiting foam on the molecular structure; simultaneously, the foam eliminating and inhibiting characteristics and the system compatibility of the final product are regulated by regulating the ratio of EO (ethylene oxide) to PO (propylene oxide) in the molecular architecture; meanwhile, silicone resin and hydrophobic silicon dioxide are added during preparation of the compound, so that the durability of foam elimination and system spreading effect are further improved, the balance of long-acting foam inhibition, instant foam elimination and system compatibility is achieved, and the foam-eliminating agent can be applied to various systems which need to control the foam and have higher requirements on the compatibility.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
P1, adding low-hydrogen silicone oil with hydrogen content of 0.12% and long-chain alpha-dodecene into a reactor, wherein the corresponding molar ratio is 1:10, heating, stirring, adding 5ppm of chloroplatinic acid catalyst at 70 ℃ for reaction for 2 hours, cooling, and filtering to obtain the modified hydrogen-containing polysiloxane intermediate.
P2, mixing the intermediate and 1, 3-tetramethyl disiloxane in a molar ratio of 1:4, and carrying out a reaction for 16 hours under the action of concentrated sulfuric acid with the dosage of 2 percent (based on the weight of hydrogen-containing silicone oil), and neutralizing and filtering by using sodium bicarbonate to obtain the modified hydrogen-containing polysiloxane with the structure shown in the following formula:
wherein R1 、R 2 Is H group or methyl, x=2, y=20, R 3 Is dodecyl.
Example 2
P1, adding low-hydrogen silicone oil with hydrogen content of 0.4% and long-chain alpha-octadecene into a reactor, wherein the corresponding molar ratio is 1: and 20, heating, stirring, adding 3ppm of chloroplatinic acid catalyst at 110 ℃ for reaction for 3 hours, cooling, and filtering to obtain the modified hydrogen-containing polysiloxane intermediate.
P2, mixing the intermediate and 1, 3-tetramethyl disiloxane in a molar ratio of 1:4, and carrying out reaction for 20 hours under the action of concentrated sulfuric acid with the dosage of 2 percent (based on the weight of hydrogen-containing silicone oil), and neutralizing and filtering by using sodium bicarbonate to obtain the modified hydrogen-containing polysiloxane with the structure shown in the following formula:
wherein R1 、R 2 Is H group or methyl, x=4, y=10, R 3 Is octadecyl.
Example 3
P1, adding low-hydrogen silicone oil with hydrogen content of 0.27% and long-chain alpha-docosane into a reactor, wherein the corresponding molar ratio is 1:10, heating, stirring, adding 10ppm of chloroplatinic acid catalyst at 85 ℃ for reaction for 2.5 hours, cooling, and filtering to obtain the modified hydrogen-containing polysiloxane intermediate.
P2, mixing the intermediate and 1, 3-tetramethyl disiloxane in a molar ratio of 1:4, and carrying out reaction for 24 hours under the action of concentrated sulfuric acid with the dosage of 2 percent (based on the weight of hydrogen-containing silicone oil), and neutralizing and filtering by using sodium bicarbonate to obtain modified hydrogen-containing polysiloxane with the structure shown in the formula I:
wherein R1 、R 2 Is H group or methyl group, x=2, y= 8,R 3 Is a behenyl group.
Example 4
Q1, adding acetylenic diol with a molecular structural formula shown in the specification into a reaction container, and adding triethylamine;
wherein R4 、R 4 ＇、R 5 、R 5 ' are both methyl groups;
q2, introducing nitrogen into the reaction vessel for one time for replacement;
q3, stirring, heating to 105-110 ℃ to carry out a water diversion process, and removing water in the system;
q4, controlling the reaction temperature, firstly slowly dropwise adding propylene oxide with the molar quantity being 4 times that of the acetylenic diol according to the proportion, and then dropwise adding ethylene oxide with the molar quantity being 24 times that of the acetylenic diol to carry out polyether reaction;
q5, removing unreacted propylene oxide/ethylene oxide monomer by controlling the temperature after the reaction is finished;
q6, cooling, adding acetic acid to neutralize and obtain the alkyne diol polyoxyethylene polyoxypropylene ether product.
The molecular structural formula of the obtained product, namely the alkyne diol polyoxyethylene polyoxypropylene ether disclosed by the invention is shown as the following formula.
wherein ,R6 、R 6 ' is a hydrogen atom, p=2, q=12, m=2, n=12.
Example 5
Q1, adding acetylenic diol with a molecular structural formula shown in the specification into a reaction container, and adding triethylamine;
wherein R4 、R 4 ' is a methyl group, R 5 、R 5 ' is isobutyl;
q2, introducing nitrogen into the reaction vessel for three times;
q3, stirring, heating to 105-110 ℃ to carry out a water diversion process, and removing water in the system;
q4, controlling the reaction temperature, slowly dripping propylene oxide with the molar quantity 40 times that of the acetylenic diol according to the proportion, and then dripping ethylene oxide with the molar quantity 4 times that of the acetylenic diol for polyether reaction;
q5, removing unreacted propylene oxide/ethylene oxide monomer by controlling the temperature after the reaction is finished;
q6, cooling, adding acetic acid to neutralize and obtain the alkyne diol polyoxyethylene polyoxypropylene ether product.
The molecular structural formula of the obtained product, namely the alkyne diol polyoxyethylene polyoxypropylene ether disclosed by the invention is shown as the following formula:
wherein ,R6 、R 6 ' is a hydrogen atom, p=20, q=2, m=20, n=2.
Example 6
Q1, adding acetylenic diol with a molecular structural formula shown in the specification into a reaction container, and adding triethylamine;
wherein R4 、R 4 ' is a methyl group, R 5 、R 5 ' is octyl;
q2, introducing nitrogen into the reaction vessel for secondary replacement;
q3, stirring, heating to 105-110 ℃ to carry out a water diversion process, and removing water in the system;
q4, controlling the reaction temperature, firstly slowly dropwise adding propylene oxide with the molar quantity being 24 times that of the acetylenic diol according to the proportion, and then dropwise adding ethylene oxide with the molar quantity being 24 times that of the acetylenic diol to carry out polyether reaction;
q5, removing unreacted propylene oxide/ethylene oxide monomer by controlling the temperature after the reaction is finished;
q6, cooling, adding acetic acid to neutralize and obtain the alkyne diol polyoxyethylene polyoxypropylene ether product.
The molecular structural formula of the obtained product, namely the alkyne diol polyoxyethylene polyoxypropylene ether disclosed by the invention is shown as the following formula:
wherein ,R6 、R 6 ' is a hydrogen atom, p=12, q=12, m=12, n=12.
Example 7
S1, mixing the modified hydrogen-containing polysiloxane prepared in the example 1 with the acetylene glycol polyoxyethylene polyoxypropylene ether prepared in the example 4 according to a molar ratio of 1:2, mixing, performing hydrosilylation reaction under the action of 5ppm chloroplatinic acid catalyst to obtain organosilicon polymer with special structure (molecular structural formula is shown as formula IV), and adding the isomeric tridecanol polyoxyethylene (5) polyoxypropylene (5) ether with the total weight of 20% of the total weight of the modified hydrogen-containing polysiloxane and the acetylenic diol polyoxyethylene polyoxypropylene ether as a viscosity regulator to obtain the organosilicon composition with special structure.
wherein R7 、R 8 Is R 1 Or R is 2 Or a substituent of the structure shown in formula V or VI, and at least one substituent of the structure shown in formula V or VI:
wherein ,
for substituent group attachment positions, p=2, q=12, m=2, n=12;
s2, adding 10 parts of methyl MQ resin solution into a reactor, starting stirring, slowly adding 5 parts of hydrophobic silica, stirring and mixing, dispersing at 2000rpm for 3 hours at high speed, and grinding by a grinder until the particle size of solid particles is 3 mu m to obtain a premix;
and S3, adding 100 parts of the organic silicon composition in the step S1 and the premix in the step S2 together, heating to 150 ℃, stirring, preserving heat for 0.5-2 h, and evaporating the solvent to obtain the organic silicon compound with the special structure.
Example 8
S1, mixing the modified hydrogen-containing polysiloxane prepared in the example 2 with the acetylene glycol polyoxyethylene polyoxypropylene ether prepared in the example 5 according to a molar ratio of 1:2, carrying out hydrosilylation reaction under the action of 8ppm chloroplatinic acid catalyst to obtain an organosilicon polymer (molecular structural formula is shown as formula IV) with a special structure, and adding the isomeric tridecanol polyoxyethylene (5) polyoxypropylene (5) ether accounting for 20% of the total weight of the modified hydrogen-containing polysiloxane and the acetylenic diol polyoxyethylene polyoxypropylene ether as a viscosity modifier to obtain the organosilicon composition.
wherein R7 、R 8 Is R 1 Or R is 2 Or a substituent of the structure shown in formula V or VI, and at least one substituent of the structure shown in formula V or VI:
wherein ,
for the substituent group attachment position, p=20, q=2, m=20,n＝2；
s2, adding 10 parts of methyl MQ resin solution into a reactor, starting stirring, slowly adding 5 parts of hydrophobic silica, stirring and mixing, dispersing at 1000rpm for 5 hours at high speed, and grinding by a grinder until the particle size of solid particles is 2 mu m to obtain a premix;
and S3, adding 100 parts of the organic silicon composition in the step S1 and the premix in the step S2 together, heating to 130 ℃, stirring, preserving heat for 0.5-2 h, and evaporating the solvent under reduced pressure to obtain the organic silicon compound with the special structure.
Example 9
S1, mixing the modified hydrogen-containing polysiloxane prepared in the example 3 with the acetylene glycol polyoxyethylene polyoxypropylene ether prepared in the example 6 according to a molar ratio of 1:2, mixing, performing hydrosilylation reaction under the action of 10ppm chloroplatinic acid catalyst to obtain organosilicon polymer with special structure (molecular structural formula is shown as formula IV), and adding the isomeric tridecanol polyoxyethylene (5) polyoxypropylene (5) ether accounting for 20% of the total weight of the modified hydrogen-containing polysiloxane and the acetylenic diol polyoxyethylene polyoxypropylene ether as a viscosity modifier to obtain the organosilicon composition.
wherein R7 、R 8 Is R 1 Or R is 2 Or a substituent of the structure shown in formula V or VI, and at least one substituent of the structure shown in formula V or VI:
wherein ,
is the position of the substituent group connection, p=12，q＝12，m＝12，n＝12；
S2, adding 10 parts of methyl MQ resin solution into a reactor, starting stirring, slowly adding 5 parts of hydrophobic silica, stirring and mixing, dispersing at 3000rpm for 1h at high speed, and grinding by a grinder until the particle size of solid particles is 5 mu m to obtain a premix;
and S3, adding 100 parts of the organic silicon composition in the step S1 and the premix in the step S2 together, heating to 120 ℃, stirring, keeping the temperature for 2 hours, and evaporating the solvent to obtain the organic silicon compound with the special structure.
Example 10
Composition 10A obtained by mixing the modified hydrogen-containing polysiloxane prepared in example 1 and the modified hydrogen-containing polysiloxane prepared in example 2 in an equimolar ratio, and composition 10B obtained by mixing the acetylenic diol polyoxyethylene polyoxypropylene ether prepared in example 4 and the acetylenic diol polyoxyethylene polyoxypropylene ether prepared in example 5 in an equimolar ratio; the organosilicon compound was prepared in the same manner as in example 9, in an amount of 1:2 as a molar ratio of 10A to 10B.
Comparative example 1
S1, mixing the modified hydrogen-containing polysiloxane prepared in the example 3 with allyl polyoxyethylene polyoxypropylene ether (EO and PO polymerization degree are respectively 2 and 12) according to a mole ratio of 1:2, mixing, and carrying out hydrosilylation reaction under the action of 5ppm chloroplatinic acid catalyst, wherein the generated product is an organosilicon polymer shown in a formula VII:
wherein R7 、R 8 A substituent group which is methyl or a structure represented by the following formula:
wherein ,
is a substituent groupGroup attachment position, m=2, n=12;
s2, adding 10 parts of methyl MQ resin solution into a reactor, starting stirring, slowly adding 5 parts of hydrophobic silica, stirring and mixing, dispersing at 2000rpm for 4 hours at high speed, and grinding by a grinder until the particle size of solid particles is 5 mu m to obtain a premix;
and S3, adding 100 parts of the organic silicon composition in the step S1 and the premix in the step S2 together, heating to 130 ℃, stirring and preserving the temperature for 1.5 hours, evaporating the solvent, and cooling to room temperature to obtain the organic silicon compound with the special structure.
Comparative example 2
S1, mixing the modified hydrogen-containing polysiloxane prepared in the example 3 with allyl polyoxyethylene polyoxypropylene ether (EO and PO polymerization degree are respectively 20 and 5) according to a mole ratio of 1:2, carrying out hydrosilylation reaction under the action of 5ppm chloroplatinic acid catalyst, obtaining a product which is an organosilicon polymer shown as a formula VII, and then adding the isomeric tridecanol polyoxyethylene (5) polyoxypropylene (5) ether which is 20 percent of the total weight of the modified hydrogen-containing polysiloxane and the allyl polyoxyethylene polyoxypropylene ether as a viscosity modifier to prepare the organosilicon composition.
wherein R7 、R 8 A substituent group which is methyl or a structure represented by the following formula:
wherein ,
for the substituent group attachment position, m=20, n=5
S2, adding 10 parts of methyl MQ resin solution into a reactor, starting stirring, slowly adding 5 parts of hydrophobic silica, stirring and mixing, dispersing at 2000rpm for 4 hours at high speed, and grinding by a grinder until the particle size of solid particles is 5 mu m to obtain a premix;
and S3, adding 100 parts of the organosilicon composition obtained in the step S1 of the comparative example into the premix obtained in the step S2, stirring, heating and preserving heat for 1.5 hours, distilling under reduced pressure to remove the solvent, and cooling to room temperature to obtain a viscous opaque liquid, namely the organosilicon compound.
Comparative example 3
In accordance with the method steps of example 9, in step S1, a silicone composition was obtained without adding a viscosity modifier. The other steps were the same as in example 9, and the final silicone composite was obtained.
Comparative example 4
In accordance with the method steps of example 9, in step S2, no silicone resin was added to obtain a silicone composition. The other steps were the same as in example 9, and the final silicone composite was obtained.
Comparative example 5:
in accordance with the method step of example 9, in step S2, no silica particles were added to obtain a silicone composition. The other steps were the same as in example 9, and the final silicone composite was obtained.
Comparative example 6:
in accordance with the procedure of example 9, in step S2, the modified hydrogen-containing polysiloxane was changed to a hydrogen-containing silicone oil having a hydrogen content of 0.27% which was not modified by olefin, and the other procedure was the same as that of example 9, to obtain the final silicone compound.
Comparative example 7:
s1, adding a certain amount of isomeric tridecanol polyoxyethylene (5) polyoxypropylene (5) ether into the acetylene glycol polyoxyethylene polyoxypropylene ether prepared in the example 6 as a viscosity modifier to obtain a composition.
S2, adding 10 parts of methyl MQ resin solution into a reactor, starting stirring, slowly adding 5 parts of hydrophobic silica, stirring and mixing, dispersing at 2000rpm for 3 hours at high speed, and grinding by a grinder until the particle size of solid particles is 5 mu m to obtain a premix;
and S3, adding 100 parts of the composition obtained in the step S1 into the premix obtained in the step S2, heating and preserving heat for 2 hours, and distilling under reduced pressure to remove the solvent to obtain the organosilicon compound.
Performance test experiments and results analysis
1. Sample preparation: the silicone composites obtained in the above examples, experimental methods 7 to 10 and comparative examples 1 to 7, were prepared as emulsions and the samples obtained were emulsified as emulsions having an active content of 25% by weight.
2. Selecting commercially available washing powder for eliminating stains, and detecting the foam inhibition performance by using a drum washing machine, wherein the specific detection method is as follows:
1kg of cotton fabric was placed in a drum washing machine, a cotton and hemp program was set, 200 g of washing powder and 1.5 g of the above emulsion were added, and the test temperature was selected to be 50 ℃. The door of the washing machine is provided with graduation marks which are respectively 0%, 25%, 50%, 75% and 100% of the height of the observation hole, and are respectively indicated by letters A, B, C, D, E. "A" indicates no foam, "E" indicates that the drum is full of foam, and "F" indicates that the foam overflows from the top feed inlet of the washing machine. When the drum of the washing machine is stationary, the scale of the foam in the washing cycle is recorded, and the larger the numerical value is, the higher the foam in the washing machine is, so that the foam control performance is poorer, and meanwhile, whether the surface of the washed cotton fabric has stains such as oil spots or not is checked, so that the compatibility of the defoamer is judged. The results of the performance test are shown in table 1:
table 1 results of performance test of organosilicon composite emulsion samples table
As can be seen from the performance test results in the table, the emulsion samples prepared in examples 7 to 10 showed a significantly slower rate of increase in foam than the foam of comparative examples 1 to 7, and in particular, showed a relatively significant defoaming effect within 30 minutes; in comparison, the emulsion samples of comparative examples 1-7 had significantly greater foam amounts.
The result shows that the organic silicon composition provided by the invention adopts a brand new molecular design, and introduces a new organic group in the synthesis of the organic silicon surfactant, so that the new polymer has the foam inhibition performance on the molecular structure; meanwhile, the foam eliminating and suppressing characteristics and the system compatibility of the final product are regulated by regulating the length of a molecular architecture organosilicon main chain and the ratio of EO (ethylene oxide) to PO (propylene oxide), so that the balance of long-acting foam inhibition, instantaneous foam elimination and system compatibility is achieved, and the foam eliminating agent is applied to various systems which need to control the foam and have higher requirements on the compatibility.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (9)
1. A silicone composite of special structure, characterized by comprising the following raw materials: modified hydrogen-containing polysiloxane, alkyne diol polyoxyethylene polyoxypropylene ether, catalyst, viscosity modifier, organic silicon resin and silicon dioxide;
the modified hydrogen-containing polysiloxane is a composition of one or more than two of structures shown in a formula I;
the alkyne diol polyoxyethylene polyoxypropylene ether is a composition of one or more than two of structures with a molecular structural formula shown as a formula II;
the molecular structural general formula of the modified hydrogen-containing polysiloxane is shown as formula I:
In the formula I, x and y are integers from 1 to 300;
in the formula I, R 1 、R 2 Is H atom or alkyl, and R 1 、R 2 At least one of which is an H atom; r is R 3 Is alkyl;
wherein the molecular structural general formula of the alkyne diol polyoxyethylene polyoxypropylene ether is shown as a formula II:
In the formula II, R 4 、R 5 、R 4 ＇、R 5 ' is alkyl, R 6 、R 6 ' is H or alkyl;
in the formula II, p, q, m, n is an integer of 1 to 300;
the modified hydrogen-containing polysiloxane is prepared by taking hydrogen-containing silicone oil as a raw material, reacting with long-chain alpha olefin under the action of a platinum catalyst, and reacting with an organosilane reducing agent under the action of strong acid;
wherein the hydrogen content of the hydrogen-containing silicone oil ranges from 0.01% to 0.5%;
wherein the long-chain alpha olefin is mono-olefin with 10-30 carbon atoms double bond at the end of molecular chain;
mixing modified hydrogen-containing polysiloxane and alkyne diol polyoxyethylene polyoxypropylene ether in proportion, reacting under the action of a catalyst to obtain an organosilicon polymer with a molecular structural general formula shown in formula IV, and adding a viscosity regulator to obtain an organosilicon composition;
wherein ,R7 、R 8 Is R 1 Or R is 2 Or a substituent of the structure shown in formula V or VI, and at least one substituent of the structure shown in formula V or VI:
wherein ,
is the position for connecting the substituent group.
2. The organosilicon compound with a special structure according to claim 1, wherein the molecular structural general formula of the modified hydrogen-containing polysiloxane is shown as formula I:
Wherein x and y are integers of 1 to 50;
wherein ,R1 、R 2 Is H atom or alkyl group with 1-20 carbon atoms, and R 1 、R 2 At least one of which is an H atom; r is R 3 Is an alkyl group having 10 to 30 carbon atoms;
the modified hydrogen-containing polysiloxane is one or more than two compositions with a structure shown in a formula I.
3. A special structure silicone composite according to claim 2, wherein in the modified hydrogen-containing polysiloxane, R 1 、R 2 When the alkyl group is an alkyl group, the alkyl group may be any of methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, hexyl, octyl, and decyl.
4. The organic silicon compound with a special structure according to claim 1, wherein the molecular structural general formula of the alkyne diol polyoxyethylene polyoxypropylene ether is shown as formula II:
wherein , R4 、R 5 、R 4 ＇、R 5 "is an alkyl group having 1 to 25 carbon atoms, R 6 、R 6 ' is H atom or alkyl with 1-10 carbon atoms;
wherein p, q, m, n is an integer of 1 to 50; the alkyne diol polyoxyethylene polyoxypropylene ether is one or more than two compositions with a molecular structural formula shown as a formula II.
5. The organic silicon compound with a special structure according to claim 4, wherein the alkyne diol polyoxyethylene polyoxypropylene ether is alkyne diol polyoxyethylene polyoxypropylene ether obtained by reacting alkyne diol with ethylene oxide and propylene oxide;
wherein the alkynediol has a molecular structural general formula shown in a formula III:
6. A special structure silicone composite according to claim 1, wherein,
the catalyst is a metal platinum catalyst; the dosage of the catalyst is 1-10 ppm;
the viscosity modifier is an alkyl polyoxyethylene polyoxypropylene ether compound;
the organic silicon resin is methyl MQ resin solution.
7. A method for preparing a silicone composite of a specific structure as set forth in any one of claims 1 to 6, comprising the steps of:
s1, mixing modified hydrogen-containing polysiloxane and alkyne diol polyoxyethylene polyoxypropylene ether in proportion, reacting under the action of a catalyst to obtain an organosilicon polymer with a molecular structural general formula shown in formula IV, and adding a viscosity regulator to obtain an organosilicon composition;
wherein ,R7 、R 8 Is R 1 Or R is 2 Or a substituent of the structure shown in formula V or VI and having at least oneA substituent group having a structure represented by formula V or VI:
wherein ,
is the position for connecting the substituent group;
s2, adding organic silicon resin into the reactor, starting stirring, slowly adding silicon dioxide, stirring, mixing, dispersing, and grinding by a grinder to obtain a premix;
and S3, adding the organosilicon composition and the premix in the step S2 together, heating, uniformly stirring, and evaporating the solvent to obtain the organosilicon compound with the special structure.
8. The method for preparing a silicone composite with a special structure according to claim 7, wherein in the step S1, the amount of the viscosity modifier is 20% of the total weight of the modified hydrogen-containing polysiloxane and the acetylenic diol polyoxyethylene polyoxypropylene ether.
9. The method for preparing a special structure organosilicon compound according to claim 7, wherein the heating temperature in the step S3 is 120-150 ℃.
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