CN102161767B - Oxidized-polyethylene-modified organosilicon polymer - Google Patents
Oxidized-polyethylene-modified organosilicon polymer Download PDFInfo
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- CN102161767B CN102161767B CN201110046653.XA CN201110046653A CN102161767B CN 102161767 B CN102161767 B CN 102161767B CN 201110046653 A CN201110046653 A CN 201110046653A CN 102161767 B CN102161767 B CN 102161767B
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- organosilicon polymer
- emulsion
- oxidic polyethylene
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- 229920001558 organosilicon polymer Polymers 0.000 title claims abstract description 70
- -1 polyethylene Polymers 0.000 claims abstract description 73
- 239000004698 Polyethylene Substances 0.000 claims abstract description 66
- 229920000573 polyethylene Polymers 0.000 claims abstract description 66
- 239000000839 emulsion Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims description 51
- 238000012986 modification Methods 0.000 claims description 51
- 239000003995 emulsifying agent Substances 0.000 claims description 20
- 238000004945 emulsification Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 241000282326 Felis catus Species 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 10
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 239000004753 textile Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 239000004568 cement Substances 0.000 abstract description 2
- 238000009941 weaving Methods 0.000 abstract 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 abstract 1
- 239000010440 gypsum Substances 0.000 abstract 1
- 238000004078 waterproofing Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 5
- 238000007789 sealing Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JKHBUPHDVGFRFZ-UHFFFAOYSA-N [Cl-].[NH4+].CCCCCCCCCCCCCCCCCCCCCC Chemical compound [Cl-].[NH4+].CCCCCCCCCCCCCCCCCCCCCC JKHBUPHDVGFRFZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention provides an oxidized-polyethylene-modified organosilicon polymer, an emulsion containing the same and a preparation process thereof. The oxidized-polyethylene-modified organosilicon polymer uses hydrogen-containing silicone oil as the main chain structure, and the side chain structure is formed by esterification of oxidized polyethylene and allyl glycidyl ether. The emulsion containing the oxidized-polyethylene-modified organosilicon polymer is widely used for the demolding processes of lignocellulose, concrete and polyurethane and the waterproofing treatment of cement, gypsum boards and various woods, and can be used as a powerful compensator for textiles and weaving yarns in the weaving field. The invention lowers the cost of the silicon-containing emulsion, widens the application range of the emulsion, is beneficial to the demolding of polyurethane products, effectively improves the strength of textiles, and improves the service efficiency and the like of the oxidized-polyethylene-modified organosilicon polymer.
Description
Technical field
The present invention relates to a kind of organosilicon polymer, particularly relate to a kind of organosilicon polymer of oxidic polyethylene modification, the emulsion containing described organosilicon polymer and preparation method.
Background technology
Organosilicon polymer is the general name of organic polymer containing Siliciumatom in molecule, has the characteristics such as high temperature resistant, low temperature resistant, resistance to chemical attack and hydrophobic and have purposes very widely in industrial production application.Wherein, the linear structure polymkeric substance that molecular weight is lower is called silicone oil, silicone oil has the advantages such as viscosity-temperature coefficient is little, high-low temperature resistant, anti-oxidant, flash-point is high, volatility is little, good insulating, surface tension are little, corrosion-free to metal, steam forces down, and is widely used in each industrial circle as water-resisting agent, antitackiness agent, releasing agent, defoamer, lubricant etc.
The silicone oil emulsification technique that prior art provides has application in a lot of field, as household chemicals field such as makeup, cream frost, washing lotion articles for use; And the hand feeling agent be used as in the lubricant of lamellar material, paper softener, textile softeners, fiber lubricant, the parting agent of paper and coatings industry and polyurethane moulded time releasing agent etc., but simple organosilicon polymer also exists easy breakdown of emulsion, easily the defect such as to come off.
Can the performance of silicon modified organic polymer by physics or chemical modification, at present more report is had to organosilyl method of modifying, the siloxanes of hydrogenated epoxy resin and aminofunctional is adopted to carry out reacting the polysiloxane generated containing multiple functional group in disclosed in patent CN101525519A " polysiloxane coating composition ", and spell and make coating composition into acrylic resin and polyether amine resin, it has good snappiness and excellent interlayer adhesive ability; Patent US3844826 discloses a kind of polycarbonate-polydimethylsiloxanecopolymer copolymer, the frictional force in fabrication processes can be reduced for garment sewing line, patent US4394518 discloses a kind of organosilicon containing aryl, slide or smooth performance to improve organic fibre, patent EP0196698B1 discloses a kind of carboxylic alkyl and replaces silicon composition, to metal substrate, there is good substantivity (substantivity), patent US6147157 discloses a kind of water base silicon polyketone composition, for the surface modification of the substrates such as rubber, to improve wear resistance and oilness.
But organosilicon cost is higher, limit its use; Simultaneously traditional organosilicon polymer or composition function too single, and when the fields such as releasing agent, performance still has some shortcomings part.
Summary of the invention
The invention provides a kind of organosilicon polymer of oxidic polyethylene modification and the emulsion containing described organosilicon polymer, oxidic polyethylene is grafted on organosilicon polymer by the organosilicon polymer of described oxidic polyethylene modification, thus obtained a kind of material with two kinds of effective functional groups, and this material is made corresponding emulsion to meet the application in actual production.
The present invention's first object is to provide a kind of organosilicon polymer of oxidic polyethylene modification, concrete, and the organosilicon polymer of described oxidic polyethylene modification has the structure shown in structural formula (I):
（I）
In structural formula (I), x is the integer of 20 ~ 100, and y is the integer of 1 ~ 10, and n is the integer of 10 ~ 200, and m is the integer of 0 ~ 5.
The present invention's second object is to provide a kind of preparation side of organosilicon polymer of above-mentioned oxidic polyethylene modification, and described preparation method comprises the steps:
Step 1, the compd A (hereinafter referred to as containing hydrogen silicone oil) shown in structural formula (II) reacts the Compound C (hereinafter referred to as epoxy silicon oil) shown in generating structure formula (IV) with compd B (hereinafter referred to as allyl group epoxy compounds) shown in structural formula (III);
Step 2, the Compound D (hereinafter referred to as oxidic polyethylene) shown in the Compound C obtained in step 1 and structure formula V reacts the organosilicon polymer of the oxidic polyethylene modification shown in generating structure formula (I);
Wherein, the structural formula of described compd A is:
（II）；
The structural formula of described compd B is:
（III）；
The structural formula of described Compound C is:
（IV）；
The structural formula of described Compound D is:
（V）。
Wherein, x is the integer of 20 ~ 100, and y is the integer of 1 ~ 10, and m is the integer of 0 ~ 5, and n is the integer of 10 ~ 200.
The preparation method of above-mentioned organosilicon polymer, wherein, in step 1, adds Pt catalyzer in reaction process, insulation reaction 4 ~ 6 hours 60 ~ 80 DEG C time.
The preparation method of above-mentioned organosilicon polymer, wherein, in step 2, adds organic sulfonic acid or organic sulfonate as catalyzer, insulation reaction 2 ~ 4 hours 110 ~ 120 DEG C time.
The preparation method of above-mentioned organosilicon polymer, wherein, described Pt catalyzer is take Pt as the catalyzer of active ingredient or active ingredient is the multicomponent catalyst of Pt and other metals, is preferably Platinic chloride or platinichloride, as sodium platinichloride, potassium platinichloride, ammonium chloroplatinate etc.
The preparation method of above-mentioned organosilicon polymer, wherein, described organic sulfonic acid is p-methyl benzenesulfonic acid.
The preparation method of above-mentioned organosilicon polymer, wherein, epoxy silicon oil described in step 2 is rolled into a ball with the amount of substance of carboxyl in described oxidic polyethylene than carrying out proportioning for 1:1 ~ 1:2 according to described epoxy silicon oil epoxy group with oxidic polyethylene.
3rd object of the present invention is to provide a kind of emulsion of the organosilicon polymer containing oxidic polyethylene modification, concrete, described emulsion includes organosilicon polymer and the emulsifying agent of oxidic polyethylene modification, and described emulsifying agent is preferably the emulsifier system of a kind of or several arbitrarily mixture composition in nonionic surface active agent and cats product.
Above-mentioned emulsion, wherein, described nonionic surface active agent is fatty alcohol-polyoxyethylene ether.
Above-mentioned emulsion, wherein, described cats product is quaternary ammonium salt cationic surfactant, as octadecyl trimethyl ammonium chloride.
Above-mentioned emulsion, wherein, described emulsifier system is 1:5 ~ 1:3 with the amount of substance ratio of organosilicon polymer.
Above-mentioned emulsion, wherein, the mass percentage of described emulsifier system is 10 ~ 50%.
The present invention's the 4th object is to provide a kind of preparation method of above-mentioned emulsion, wherein, the organosilicon polymer of oxidic polyethylene modification shown in structural formula (I) and emulsifying agent circulation homogenizing emulsifying under stress, wherein, emulsifying temperature is 120 ~ 130 DEG C, Emulsification pressure is 20 ~ 30MPa, and emulsification times is 20 ~ 50 minutes.
The organosilicon polymer of a kind of oxidic polyethylene modification of the present invention, advantage is:
1. the organosilicon polymer of the oxidic polyethylene modification of gained of the present invention reduces the cost containing silicon emulsion, increases its range of application.
2. the organosilicon polymer of the oxidic polyethylene modification of gained of the present invention can be conducive to polyurethane product and carries out the demoulding.
3. the organosilicon polymer of the oxidic polyethylene modification of gained of the present invention effectively can improve the brute force of textiles.
4. the organic silican polymer emulsion of the oxidic polyethylene modification of gained of the present invention, effectively can improve the service efficiency of the organosilicon polymer of oxidic polyethylene modification.
figure of description:
Fig. 1 is the reacting flow chart that the present invention prepares the organosilicon polymer of oxidic polyethylene modification, and wherein, x is the integer of 20 ~ 100, and y is the integer of 1 ~ 10, and n is the integer of 10 ~ 200, and m is the integer of 0 ~ 5.
Embodiment
Disclosed in this invention is the organosilicon polymer of the oxidic polyethylene modification shown in a kind of structural formula (I), by the ester of oxidic polyethylene and glycidyl allyl ether esterification being grafted on material containing hydrogen silicone oil made and not only has siliceous composition but also containing oxidic polyethylene.The invention also discloses a kind of by the emulsion of the organosilicon polymer emulsification of described oxidic polyethylene modification.
The organosilicon polymer preparation method of oxidic polyethylene modification provided by the present invention is as follows:
Step 1, first the allyl group epoxy compounds shown in the containing hydrogen silicone oil shown in structural formula (II), structural formula (III) is placed in toluene solvant, put in reactor, after reflection terminates, 60 DEG C time, toluene is removed in vacuum distilling, obtains the intermediate epoxy silicon oil shown in structural formula (IV); Operational condition can with reference to the mensuration of active hydrogen massfraction " in the containing hydrogen silicone oil " (the ten the industrial surface activity agent Technological Economy in the whole nation and application and development proceeding, in August, 2002);
Step 2, drops into described epoxy silicon oil and oxidic polyethylene in reactor subsequently, is obtained by reacting described organosilicon polymer.
Wherein, in step 1, catalysts is preferably Pt catalyzer; Reaction conditions is preferably insulation reaction 4 ~ 6 hours 60 ~ 80 DEG C time; In step 2, catalysts is preferably organic sulfonic acid or organic sulfonate, as p-methyl benzenesulfonic acid; Insulation reaction 2 ~ 4 hours when reaction conditions is preferably 110 ~ 120 DEG C.
The present invention contains the emulsion of the organosilicon polymer of described oxidic polyethylene modification, and emulsifying agent can be the emulsifier system of a kind of or several arbitrarily mixture composition in nonionic surface active agent and cats product.Preferably: the emulsifier system of nonionic surface active agent and quaternary cationics composition is carried out proportioning according to amount of substance than for 1:5 ~ 1:3 with the organosilicon polymer of gained, and the mass percentage concentration of emulsifier system is 10 ~ 50%; The emulsion required for circulation homogenizing emulsifying preparation is carried out subsequently under the condition that emulsifying temperature is 120 ~ 130 DEG C, Emulsification pressure is 20 ~ 30MPa, emulsification times is 20 ~ 50 minutes.
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.
In the organosilicon polymer building-up process of oxidic polyethylene modification, selected oxidic polyethylene is b1:HOOC (CH
2)
50cOOH; Oxidic polyethylene b2:HOOC (CH
2)
100cOOH.
When the emulsification procedure of the organosilicon polymer to oxidic polyethylene modification, circulation homogenizing emulsifying method is adopted to carry out emulsification procedure to the organosilicon polymer of oxidic polyethylene modification.When operating, employing can withstand voltage 5 ~ 8 kilograms of pressure magnetic agitation still, reaction system can be heated to the heating installation of 120 ~ 130 DEG C, reaction system can be cooled in 1 hour the cooling apparatus of room temperature and one external and to circulate with material in reactor and resistance to 150 DEG C of high temperature, circulation connected system can the high-pressure homogeneous mulsers of resistance to 5 ~ 8 kilograms with magnetic force reactor.Emulsifier system of the present invention is the compound system of nonionogenic tenside and cats product, be specially nonionogenic tenside fatty alcohol-polyoxyethylene ether (peregal O-25), cats product octadecyl trimethyl ammonium chloride (1831).
embodiment 1
Get 300 grams of hydrogen contents and be 0.094% and molecular weight is the containing hydrogen silicone oil of 2132,32.1 grams of glycidyl allyl ethers (structural formula be 1 for m in (III)), be used as catalyzer with 80ppm Platinic chloride, toluene 50 grams is as solvent.Said components is put in the four-hole boiling flask being furnished with temperature control device, reflux condensation mode and constant speed whipping device, temperature is controlled between 60 ~ 80 DEG C and operates 5 hours, then 60 DEG C time, toluene is removed in vacuum distilling, obtains the intermediate a1(m=1 containing epoxy-functional of structural formula as (IV)).
Get 300 grams of intermediate a1 containing epoxy-functional, 200 grams of oxidic polyethylene b1 containing carboxyl, 2.5 grams of catalyzer p-methyl benzenesulfonic acids.Said components put in the there-necked flask being furnished with temperature control device and constant speed whipping device, temperature is controlled between 110 ~ 120 DEG C and operates 3 hours, obtains the organosilicon polymer a1b1 of oxidic polyethylene modification.
embodiment 2
Get 300 grams of a1 produced with the same operation step described in embodiment 1,378 grams of oxidic polyethylene b2 containing carboxyl, 3.4 grams of catalyzer p-methyl benzenesulfonic acids.Said components put in the there-necked flask being furnished with temperature control device and constant speed whipping device, temperature is controlled between 110 ~ 120 DEG C and operates 3 hours, obtains the organosilicon polymer a1b2 of oxidic polyethylene modification.
embodiment 3
Get 300 grams of hydrogen contents and be 0.051% and molecular weight is the containing hydrogen silicone oil of 7802,17.44 grams of glycidyl allyl ethers (structural formula be 1 for m in (III)), be used as catalyzer with 80ppm Platinic chloride, toluene 50 grams is as solvent.Said components is put in the four-hole boiling flask being furnished with temperature control device, reflux condensation mode and constant speed whipping device, temperature is controlled between 60 ~ 80 DEG C and operates 5 hours, then 60 DEG C time, toluene is removed in vacuum distilling, obtains the intermediate a2(m=1 containing epoxy-functional of structural formula as (IV)).
Get 300 grams of intermediate a2 containing epoxy-functional, 125 grams of oxidic polyethylene b1 containing carboxyl, 2.1 grams of catalyzer p-methyl benzenesulfonic acids.Said components put in the there-necked flask being furnished with temperature control device and constant speed whipping device, temperature is controlled between 110 ~ 120 DEG C and operates 3 hours, obtains the organosilicon polymer a2b1 of oxidic polyethylene modification.
In above-described embodiment, tosic acid also can replace with other catalyzer, specifically can refer to " new catalyst of carboxylic acid and epoxy compounds addition esterification and application thereof " (catalysis journal, 1982, the 4th phase of year, 303 pages), " research of allyl group silicon (oxygen) alkane platinum complex hydrosilylation catalyst " (fine chemistry industry, 2nd phase in 2000, 82 pages) or " liquid alkali developing solder mask is studied--the reaction of carboxyl and epoxy group(ing) " and (applied chemistry, 1st phase in 2002), also phosphoric acid can be used, boric acid, vitriol, the catalyzer such as beta-diketone metal complex substitute.
embodiment 4
Get 300 grams of a2 produced with the same operation step described in embodiment 1,237 grams of oxidic polyethylene b2 containing carboxyl, 2.7 grams of catalyzer p-methyl benzenesulfonic acids.Said components put in the there-necked flask being furnished with temperature control device and constant speed whipping device, temperature is controlled between 110 ~ 120 DEG C and operates 3 hours, obtains the organosilicon polymer a1b2 of oxidic polyethylene modification.
embodiment 5
Get the organosilicon polymer a1b1 of 120 kg oxidic polyethylene modification, 20 kilograms of peregal O-25s, 10 kilogram 1831,350 kilograms of deionized waters.Said components is put in magnetic force reactor, sealing stirring heating, when system temperature controls between 120 ~ 130 DEG C, start the pump of high-pressure homogeneous mulser, control pressure is between 20 ~ 30MPa, 1.5 hours emulsification procedure time, emulsification procedure terminates the high-pressure homogeneous mulser of rear stopping and emulsifier system is cooled to 30 ~ 40 DEG C, finally obtains the emulsion a1b1-E that concentration is the organosilicon polymer containing oxidic polyethylene modification of 30%.
embodiment 6
Get the organosilicon polymer a1b2 of 120 kg oxidic polyethylene modification, 15 kilograms of peregal O-25s, 15 kilogram 1831,350 kilograms of deionized waters.Said components is put in magnetic force reactor, sealing stirring heating, when system temperature controls between 120 ~ 130 DEG C, start the pump of high-pressure homogeneous mulser, control pressure is between 20 ~ 30MPa, 1.5 hours emulsification procedure time, emulsification procedure terminates the high-pressure homogeneous mulser of rear stopping and emulsifier system is cooled to 30 ~ 40 DEG C, finally obtains the emulsion a1b2-E that concentration is the organosilicon polymer containing oxidic polyethylene modification of 30%.
embodiment 7
Get the organosilicon polymer a2b1 of 120 kg oxidic polyethylene modification, 25 kilograms of peregal O-25s, 5 kilogram 1831,600 kilograms of deionized waters.Said components is put in magnetic force reactor, sealing stirring heating, when system temperature controls between 120 ~ 130 DEG C, start the pump of high-pressure homogeneous mulser, control pressure is between 20 ~ 30MPa, 1.5 hours emulsification procedure time, emulsification procedure terminates the high-pressure homogeneous mulser of rear stopping and emulsifier system is cooled to 30 ~ 40 DEG C, finally obtains the emulsion a2b1-E that concentration is the organosilicon polymer containing oxidic polyethylene modification of 20%.
embodiment 8
Get the organosilicon polymer a2b2 of 120 kg oxidic polyethylene modification, 15 kilograms of peregal O-25s, 15 kilogram 1831,600 kilograms of deionized waters.Said components is put in magnetic force reactor, sealing stirring heating, when system temperature controls between 120 ~ 130 DEG C, start the pump of high-pressure homogeneous mulser, control pressure is between 20 ~ 30MPa, 1.5 hours emulsification procedure time, emulsification procedure terminates the high-pressure homogeneous mulser of rear stopping and emulsifier system is cooled to 30 ~ 40 DEG C, finally obtains the emulsion a2b2-E that concentration is the organosilicon polymer containing oxidic polyethylene modification of 20%.
In above-described embodiment, fatty alcohol-polyoxyethylene ether also can replace with nonionogenic tensides such as the polyvalent alcohol such as glycerin fatty acid ester, polysorbate or long-chain fat alcohol ester such as glyceryl monostearates; Octadecyl trimethyl ammonium chloride also can replace with other quaternary ammonium salt cationic surfactant, as tetradecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, Trimethyllaurylammonium bromide, Cetyltrimethylammonium bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, docosane ammonium chloride, docosyl brometo de amonio etc.
embodiment 9
The releasing process of polyurethane product:
By the a1b1-E emulsion 1 kilogram of above-mentioned preparation, 19 kg of water are evenly in harmonious proportion and are sprayed on different polyurethane product moulds, dry up, filling polyurethane glue, hot briquetting with high-pressure airgun, and goods are taken out in the demoulding.
In releasing process, polyurethane product and mold releasability process smooth, polyurethane product and the situation of die bonds on mould do not occur, and emulsion of the present invention also can be widely used in lignocellulose, concrete releasing process simultaneously, and obtains good technique effect.
embodiment 10
The strength protection technique of textile yarn:
Get a1b1-E emulsion 3.0 kilograms and 3.0 kilograms of softening agents, 1500 kg of water; 100 kilograms, yarn.Finishing technique: by softening agent, emulsion, is poured in the scuffing of cylinder bore finishing rolls with 1500 kg of water and is made into working fluid, be heated to 50 ~ 60 DEG C, yarn is placed on roller, start stirring, yarn circulating rolling in working fluid is infiltrated, and finishing time controls between 20 ~ 30 minutes; Stir after stopping, yarn being transferred in water extracter, centrifuge dehydration; Then yarn is transferred in dryer, dry.
Yarn after process is compared with the strength test result of the yarn arranged without strength protection, and the yarn strength after the strength protection of emulsion arranges improves about 20 ~ 30%, illustrates that emulsion of the present invention can be used as the strong compensation agent of textiles and control yarn.
The emulsion that embodiment 6 ~ 8 obtains, when carrying out the releasing process of polyurethane product, also can obtain the effect identical with embodiment 9; The emulsion that embodiment 6 ~ 8 obtains, when carrying out the strength protection technique of textile yarn, also can obtain the effect identical with embodiment 10.
Above-described embodiment gives the citing of several specific examples of the present invention, prove through overtesting simultaneously, when the integer that the integer that x is integer, the y of 20 ~ 100 is 1 ~ 10 in structural formula (I) ~ (V), m are 0 ~ 5, n are the integer of 10 ~ 200, also can carry out the preparation of the organosilicon polymer of oxidic polyethylene modification and the preparation of described emulsion according to above-described embodiment, and achieve identical technique effect.
Above-mentioned test shows, the emulsion of the organosilicon polymer of oxidic polyethylene modification provided by the present invention and the organosilicon polymer containing oxidic polyethylene modification has good action effect.And the results showed, organosilicon polymer provided by the present invention and the emulsion containing this polymkeric substance can be applied to the WATER REPELLENT field of cement, plasterboard, all kinds of timber, lignocellulose, concrete, urethane releasing process, and the strong compensation agent etc. of textiles and textile yarn.Oxidic polyethylene is directly grafted on organic silicone oil by the present invention, becomes molecular structure complex body, thus better organosilicon and oxidic polyethylene is acted synergistically, and application has more wide prospect.Simultaneous oxidation polyethylene under the prerequisite ensureing organosilicon material fundamental property, significantly can also reduce silicon materials cost.
Preparation process, the method for the emulsion of the organosilicon polymer of oxidic polyethylene modification provided by the present invention and the organosilicon polymer containing oxidic polyethylene modification are simple, are applicable to scale operation.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (14)
1. an organosilicon polymer for oxidic polyethylene modification, is characterized in that, the organosilicon polymer of described oxidic polyethylene modification has the structure shown in structural formula (I):
（I）
Wherein x is the integer of 20 ~ 100, and y is the integer of 1 ~ 10, and n is the integer of 10 ~ 200, and m is the integer of 0 ~ 5.
2. prepare a method for organosilicon polymer as claimed in claim 1, it is characterized in that, comprise the steps;
Step 1, shown in the compd A shown in structural formula (II) and structural formula (III), compd B reacts the Compound C shown in generating structure formula (IV);
Step 2, the Compound D shown in the Compound C obtained in step 1 and structure formula V reacts the organosilicon polymer of the oxidic polyethylene modification shown in generating structure formula (I);
The structural formula of described compd A is:
（II）；
The structural formula of described compd B is:
（III）；
The structural formula of described Compound C is:
（IV）；
The structural formula of described Compound D is:
（V）；
Wherein, x is the integer of 20 ~ 100, and y is the integer of 1 ~ 10, and m is the integer of 0 ~ 5, and n is the integer of 10 ~ 200.
3. preparation method according to claim 2, is characterized in that, in step 1, adds Pt catalyzer and carries out catalysis, insulation reaction 4 ~ 6 hours 60 ~ 80 DEG C time.
4. preparation method according to claim 3, is characterized in that, described Pt catalyzer is Platinic chloride.
5. preparation method according to claim 2, is characterized in that, in step 2, adds organic sulfonic acid or organic sulfonate as catalyzer, 110 ~ 120 DEG C of insulation reaction 2 ~ 4 hours.
6. preparation method according to claim 5, is characterized in that, described organic sulfonic acid is p-methyl benzenesulfonic acid.
7. preparation method according to claim 2, is characterized in that, Compound C described in step 2 is rolled into a ball with the amount of substance of carboxyl in described Compound D than carrying out proportioning for 1:1 ~ 1:2 according to described Compound C epoxy group with Compound D.
8. containing, for example an emulsion for the organosilicon polymer of oxidic polyethylene modification according to claim 1, it is characterized in that, described emulsion comprises organosilicon polymer, the emulsifying agent of the oxidic polyethylene modification shown in structural formula (I).
9. emulsion according to claim 8, is characterized in that, described emulsifying agent is a kind of or several arbitrarily mixture in nonionic surface active agent, cats product.
10. emulsion according to claim 9, is characterized in that, described nonionic surface active agent is fatty alcohol-polyoxyethylene ether.
11. emulsions according to claim 9, is characterized in that, described cats product is quaternary ammonium salt cationic surfactant.
12. emulsions according to claim 8, is characterized in that, described emulsifying agent is 1:5 ~ 1:3 with the amount of substance ratio of the organosilicon polymer of described oxidic polyethylene modification.
13. emulsions according to claim 8, is characterized in that, wherein, the mass percentage of described emulsifying agent is 10 ~ 50%.
14. 1 kinds of methods preparing emulsion as claimed in claim 8, it is characterized in that, the organosilicon polymer of oxidic polyethylene modification shown in structural formula (I) and emulsifying agent under stress circulate homogenizing emulsifying, wherein, emulsifying temperature is 120 ~ 130 DEG C, Emulsification pressure is 20 ~ 30MPa, and emulsification times is 20 ~ 50 minutes.
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| CN106626168B (en) * | 2016-08-23 | 2018-01-23 | 广东工业大学 | A kind of water-based emulsion silicone release and its preparation method and application |
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| CN110357750B (en) * | 2019-07-31 | 2021-02-26 | 北矿亿博(沧州)科技有限责任公司 | Composite oil phase for emulsion explosive, preparation method of composite oil phase, emulsion matrix and emulsion explosive |
| CN110357749B (en) * | 2019-07-31 | 2021-02-26 | 北矿亿博(沧州)科技有限责任公司 | Emulsifier for emulsion explosive, preparation method thereof, emulsion matrix and emulsion explosive |
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