CN100358607C - Preparation of highly efficient water phase system non-organic silicon defoaming agent - Google Patents
Preparation of highly efficient water phase system non-organic silicon defoaming agent Download PDFInfo
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- CN100358607C CN100358607C CNB2005100947178A CN200510094717A CN100358607C CN 100358607 C CN100358607 C CN 100358607C CN B2005100947178 A CNB2005100947178 A CN B2005100947178A CN 200510094717 A CN200510094717 A CN 200510094717A CN 100358607 C CN100358607 C CN 100358607C
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- defoaming agent
- higher aliphatic
- phase system
- organic silicon
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 8
- 229910052710 silicon Inorganic materials 0.000 title claims description 8
- 239000010703 silicon Substances 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- -1 fatty acid ester Chemical class 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 239000002480 mineral oil Substances 0.000 claims abstract description 14
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 32
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000001294 propane Substances 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 3
- 229940063655 aluminum stearate Drugs 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 235000021357 Behenic acid Nutrition 0.000 claims description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000002199 base oil Substances 0.000 claims description 2
- 229940116226 behenic acid Drugs 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002885 octadecanoids Chemical class 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 239000000123 paper Substances 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000004945 emulsification Methods 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 230000009897 systematic effect Effects 0.000 abstract 1
- 239000013530 defoamer Substances 0.000 description 37
- 239000006260 foam Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- SRKUMCYSWLWLLS-UHFFFAOYSA-N docosyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC SRKUMCYSWLWLLS-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N 2-stearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229940075507 glyceryl monostearate Drugs 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 2
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229960002666 1-octacosanol Drugs 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000008931 Tadenan Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229960001777 castor oil Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003866 digestant Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014903 tadenan Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Paper (AREA)
- Degasification And Air Bubble Elimination (AREA)
Abstract
The present invention relates to a defoaming agent which mainly comprises the following components: high-grade fatty alcohol, high-grade fatty alcohol polyether, polyether containing nitrogen, fatty acid ester, a mixture of hydrophobic particles and mineral oil, an emulsifying agent and water. In the process of preparation: premixing defoaming active substances and the emulsifying agent; raising systematic temperature to a certain DEG C, and then adding water slowly into the mixture; after adding water, determining whether to pass a colloid mill according to the size of the particle diameter of emulsion, and generally, making the particle diameter of the emulsion smaller than 15 um. The preparation of the defoaming agent mainly solves the problems of high temperature emulsification, defoaming agent property attenuation with the elevation of temperature, etc. The present invention has the characteristics of safety, high efficiency, economy, etc., and is suitable for paper making coating and papermaking white water defoaming.
Description
Technical field
The present invention relates to a kind of preparation of antifoaming agent of non-silicone of aqueous phase system use, defoamer is a kind of fine chemicals additive.Therefore, belong to technical field of fine chemical preparations.
Background technology
In national economy is produced, as in the processes such as textile printing and dyeing, coating, papermaking, cleaning, metal processing owing to used a large amount of chemical assistants, in the hope of having reached different purposes, but because employed auxiliary agent is based on surfactant, their drawback is exactly to produce a large amount of foams, and is especially serious with anion and non-ionic surface active agent.The untimely elimination of these harm foams meeting produces serious influence to subsequent handling, is easy to cause the instability of product.At this problem, relatively high-efficiency method is to add defoamer in the foaming system at present, defoamer at first must possess lower surface tension as a kind of auxiliary agent, be easy to sprawl on the surface of vacuolar membrane, thereby cause the uneven collapse of bubbles that causes of vacuolar membrane intensity.General defoamer must possess antifoam performance and suds suppressing properties, antifoam performance is meant that mainly defoamer can be very fast with the foam elimination that produces, and suds suppressing properties refers to mainly how long the froth breaking activity of defoamer in the foaming medium can be kept, if activity descends significantly, then the effect of defoamer also just loses.
China is paper industry big country, and papermaking output occupied the third place in the world in 2004, is in second in 2005.Paper industry is generally passed through slurrying (certainly, domestic a lot of enterprises are that raw material is produced with American waste paper, Japanese waste paper all), is copied master operations such as paper and coating.In pulping process, adopt sulfate process to carry out boiling, remove materials such as lignin in timber or straw, the wheat straw etc. and resin.In digestion process, use a lot of auxiliary agents, as digestant etc.; Paper-making process mainly is the process that paper pulp is formed cardboard, to add retention agent, filter aid, wet strength agent, sizing agent etc. in online as last, these materials all are based on macromolecular compound, the foam that they form in water has strengthened the intensity of vacuolar membrane because of high molecular absorption, make froth breaking become difficult, be exactly that micro-bubble all may be adsorbed in fiber fines surface, inside on the other hand, these bubbles are difficult to eliminate with common defoamer, therefore, these operations more lay particular emphasis on the degassing, remove the micro-bubble of liquid internal; Painting process is with to be coated with material process similar, mainly be that pigment, filler, film forming matter and some auxiliary agents are fully mixed through particular device, but because film forming matter is a macromolecule, and the particle of pigment and filler is generally all very little, be very easy to be adsorbed on the gas-liquid interface of foam, make the easier foaming of coating, the bubble that has adsorbed solia particle simultaneously is difficult to remove from liquid phase.
The O/W type defoamer of EP-A-0149812 invention is with acrylic acid, methacrylic acid, acrylamide or the Methacrylamide used as stabilizers of 0.05～0.5% high molecular weight water-soluble.Oil phase component mainly comprises: C
12～26(the expression carbon number is 12～26, down together) alcohol, C
12～22Carboxylic acid and C
1～18The ester or the boiling point of the single, double or pure generation of trihydroxy surpass 200 ℃ hydrocarbons or C
12～22Aliphatic acid, the emulsion particle diameter that obtains is 0.5～15um.It is liquid hydrocarbons that the water-based emulsion of EP-A-3001387 invention comprises under dystectic pure and mild room temperature, and oil phase substance can also comprise dystectic non-aryl hydrocarbon, aliphatic acid and derivative thereof further.The oil phase of the water-based emulsion of EP-A-0531713 invention comprises C at least
12Alcohol, C at least
22Alcohol and C
1～36The carboxylic acid ester or the C that generate
12～22Carboxylic acid and C
1～18Single, double or triatomic ester, or boiling point surpasses 200 ℃ hydrocarbons, perhaps uses polyglycereol and C
12～22Carboxylic acid reaction generate the ester of esterification yield at least 20%.The emulsion type defoaming agent oil phase of EP-A-0662172 invention mainly comprises: (a) C
12～22Carboxylic acid and C
1～18Single, double or triatomic ester; (b) with containing the polyglycereol of 2 glycerine chain links and C at least at least
12～36Carboxylic acid the ester that 20% esterification generates takes place; (c) C
12～22Carboxylic acid and the ester that generates of polyoxy alkane alkene (molecular weight is 5000g/mol) reaction, oil phase can also comprise C at least if desired further
12Alcohol, boiling point surpass 200 ℃ hydrocarbons.Above component forms the emulsion of O/W by means of the emulsification of emulsifying agent.The water-based system defoamer of EP-A-0696224 invention comprises that mainly fusing point surpasses 40 ℃ alcohol, fusing point surpasses 45 ℃ ketone, can also comprise that fusing point surpasses 50 ℃ synthetic paraffin.The oil phase of the water-based emulsion of EP-A-0732134 invention comprises C at least
12The esterification products of alcohol, at least a glucide and carboxylic acid.It is the defoamer of froth breaking main body that CA02493055 has introduced with components such as the two stearic amides of higher alcohols, polyglycereol stearate, mineral oil, ethylenediamine, fatty acid esters, and with the degassing situation of the above-mentioned defoamer of ultrasonic measuring.USP6649721 has introduced with C
12～24Fatty alcohol mixture, polyglycerol ester (polyglycereol is made up of diglycerol, triglycerin, triglycerin and polyglycereol), C
16～18The glyceryl ester of carboxylic acid is the defoamer of main body, and average particle size is 1～10um.
Sum up above-mentioned patent, the froth breaking active matter mainly comprises as can be known: (1) higher aliphatic; (2) monobasic is to ternary higher aliphatic and C
16～22The ester that aliphatic acid generates; (3) polyglycerol ester, the degree of polymerization are 2～5 polyglycereol and C
12～36The ester that carboxylic acid generates, the degree of polymerization is preferably 2～3, and degree of esterification is preferably 60～80%; (4) fusing point preferably surpasses 45 ℃ ketone compounds, and it often mixes application with higher aliphatic; (5) molecular weight surpasses the natural paraffin wax of 2000g/mol; (6) hydrocarbon compound, general boiling point will surpass 200 ℃, be preferably liquid wax or white oil, and fusing point surpasses 50 ℃ the most suitable.But, be rising with the shortcoming of the defoamer of these active matters preparation along with temperature, downward trend can appear in antifoaming performance.And because the application of part high melting compound needs high temperature emulsification, general emulsifying temperature is 90～100 ℃, and this brings certain difficulty to production.Higher aliphatic, higher aliphatic polyethers, nitrogen-containing polyether, fatty acid ester, hydrophobic particles and mineral wet goods component are mainly used in this patent invention, and they are formed O/W type emulsion by specific emulsifying process.Mainly solved a high temperature emulsification difficult problem, Zhi Bei defoamer performance is not subjected to Temperature Influence simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of efficient antifoaming agent of non-silicone of aqueous phase system that is used for.In coating, starch processing, copying in the operations such as paper, coating, pulp washing, sewage disposal of paper industry can both be eliminated harmful foam efficiently, is not subjected to Temperature Influence.Because this defoamer does not contain organosilicon, therefore have advantages such as safe, stable.
Defoamer of the present invention mainly comprises following active component:
(1) higher aliphatic.The higher aliphatic that is suitable for this defoamer can comprise C
12～28Monobasic to trihydroxylic alcohol, these alcohol can be saturated, also can be undersaturated; Can be straight chain, also can be side chain, if side chain, hydroxy position is unrestricted; If undersaturated fatty alcohol, position of functional group is unrestricted.Higher aliphatic generally can be dodecanol, tetradecanol, hexadecanol, octadecanol, icosane alcohol, tadenan, the pure and mild n-octacosanol of lignocerane.These alcohol can be natural, also can be synthetic by the Ziegler method.Can adopt a kind of alcohol in the actual use, also can be that multiple alcohol mixes composite.If the active matter component is 100 parts, then the consumption of higher aliphatic can be 5～80 parts.
(2) higher aliphatic polyethers.The higher aliphatic polyethers mainly by the addition and getting under the effect of base catalyst of higher aliphatic and oxirane (EO) and expoxy propane (PO), generally can represent with following structural formula,
RO(EO)
m(PO)
nH
Wherein R is C
12～28Chain alkyl, m and n represent to contain in the molecule number of EO and PO, m is 0～50, n is 1～80, the molecular weight of this polyethers is generally 1000～4000, cloud point is 10～20 ℃.The higher aliphatic polyethers can be that random block forms, and also can be block polyether.If the active matter component is 100 parts, then the consumption of higher aliphatic polyethers can be 5～70 parts.
(3) nitrogen-containing polyether.Nitrogen-containing polyether mainly is to utilize the hydrogen-oxygen key (H-O) in hydrogen bound to nitrogen (N-H) and the hydrone that stronger interaction force is arranged, and nitrogen-containing polyether has special contribution to froth breaking.The structural formula of this nitrogen-containing polyether can be expressed as:
Wherein subscript a, b, c are integers, and a is 0～50, and b is 1～60, and c is 1～10.Molecular weight is 1000～5000 to be advisable.If the active matter component is 100 parts, then the consumption of higher aliphatic polyethers can be 10～30 parts.
(4) fatty acid ester.Fatty acid ester mainly is to serve as the froth breaking synergist in the present invention, generally the monobasic by chain alkyl aliphatic carboxylic acid and C1～18 gets to the trihydroxylic alcohol reaction, and chain alkyl aliphatic acid can be dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoid acid, arachic acid, behenic acid; Alcohol generally can be monobasic, also can be binary and ternary, can be side chain, also can be straight chain.The chain alkyl fatty acid ester can be glyceryl monostearate, octanol stearate, 18 pure stearates, docosanol stearate, docosanol behenic acid ester, preferably glycerine monostearate or docosanol stearate, if the active matter component is 100 parts, then the consumption of chain alkyl fatty acid ester can be 1～20 part.
(5) hydrophobic particles and mineral oil body.Hydrophobic particles mainly comprises materials such as hydrophobic silicic aerogels, titanium dioxide, magnesia, aluminium oxide, the two stearic amides (EBS) of ethylenediamine, aluminum stearate, if white carbon, titanium dioxide, magnesia, aluminium oxide, the specific area that then requires hydrophobic particles is greater than 50m
2/ g is preferably greater than 200m
2/ g; If materials such as EBS and aluminum stearate then need they at high temperature are dispersed in the mineral oil, and through special process, with their grains in mineral oil through being controlled at less than 5um.The mineral oil that adopts in the patent can be thick liquid wax, base oil, alkylbenzene, machinery oil.The mixture of hydrophobic particles and mineral oil is one of main froth breaking material of this defoamer, and hydrophobic particles accounts for 5～15% in the general this mixture, and mineral oil accounts for 95～85%.If the active matter component is 100 parts, then the mixture of hydrophobic particles and mineral oil accounts for 5～20 parts.
More than the total amount of (1)～(5) count 100 parts, the listed froth breaking active material of this defoamer is (1)～(5), can be a kind of component wherein, also can be the mixture of several components.Except this, the emulsifying agent that also is necessary is dispersed in active component in the water by them, forms O/W type emulsion.Emulsifying agent can be anionic, nonionic, cationic surfactant, for example can be NPE, OPEO, S-60, T-60, S-80, T-80, stearic acid polyoxyethylene ether, glyceryl monostearate, castor oil polyoxyethylene ether, lauryl sodium sulfate, neopelex, octanol polyoxyethylene ether phosphate etc.The preparation method of emulsion mainly adopts " agent in oil method ".The consumption of emulsifying agent generally accounts for 10～40% of froth breaking active component, and is preferred 25～20%, and emulsifying temperature can be 50～80 ℃, generally is preferably 60～70 ℃.The grain of emulsion is through being controlled at 2～15um.
Defoamer of the present invention can be in coating, starch processing, and paper industry is copied in the operations such as paper, coating, pulp washing, sewage disposal can both eliminate harmful foam efficiently, is not subjected to Temperature Influence.If with the emulsion of content 30%, add 0.02～0.5 part of defoamer in general 100 parts of foaming media, preferably at 0.05～0.3 part.
The specific embodiment
Embodiment 1
10 parts of higher aliphatics, 2 parts of glyceryl monostearates, (structural formula is i-C to 5 parts of higher aliphatic polyethers
13H
27O (EO)
5(PO)
7H), 10 parts of white oils, 2 parts of S-60 and 1 part of T-60 be added in the reaction bulb, system is warming up to 80 ℃, stirs a moment, makes component mix; Slowly to wherein adding 70 parts of water, water adds the back and grinds dispersion by colloid mill, through less than 15um, obtains defoamer A up to the emulsion grain then.
Embodiment 2
The thick liquid wax and the white carbon of equivalent are mixed dispersed with stirring evenly as active component (1).
Add 5 parts of higher aliphatics in reaction bulb, (structural formula is C to 5 parts of higher aliphatic polyethers
18H
37O (PO)
10H), 4 parts of nitrogen-containing polyether (a=10 in the structural formula, b=15, c=1), 6 parts of active components (1), 6 parts of docosanol stearates, 2 parts of TX-10,2 parts of TX-3, system heats up then, temperature rises to 70 ℃ of insulation 10min, begins to add 70 parts of water, after water adds, grind dispersion by colloid mill and make the emulsion grain, obtain defoamer B through less than 15min.
Comparative examples
5 parts of higher aliphatics, 2 parts of glyceryl monostearates, (structural formula is i-C to 10 parts of higher aliphatic polyethers
13H
27O (EO)
5(PO)
7H), 10 parts of white oils, 2 parts of S-60 and 1 part of T-60 be added in the reaction bulb, system is warming up to 80 ℃, stirs a moment, makes component mix; Slowly to wherein adding 70 parts of water, water adds the back to be disperseed by colloid mill emulsification, through less than 15um, obtains defoamer C up to the emulsion grain then.
The performance test of defoamer:
1. measure the performance of defoamer at laboratory simulation papermaking painting process
Under the room temperature, the styrene-butadiene latex foam liquid 200ml that packs in the 500ml graduated cylinder that has air bubbling gas head to wherein adding the 0.005g defoamer, opens air pump then, allow air be injected in the foam liquid with the flow of 100ml/min, the record foam reaches the corresponding time of certain volume.
Test result:
| Foam volume/ml | Defoamer A | Defoamer B | Defoamer C | External sample |
| 250 | 1′30″ | 15″ | 13″ | 35″ |
| 300 | 2′55″ | 45″ | 45″ | 1′45″ |
| 350 | 3′50″ | 1′20″ | 1′25″ | 2′30″ |
| 400 | 4′30″ | 2′40” | 2′05″ | 3′05″ |
| 450 | 5′ | 4′40″ | 2′55″ | 3′25″ |
| 500 | 6′10″ | 6′30″ | 3′55″ | 4′05″ |
2. copy the performance that paper plain boiled water environment is measured defoamer in laboratory simulation
Testing equipment: 250ml container, thermostat, air pump, flowmeter, stopwatch
Probe temperature: 40 ℃
Test airflow: 80l/h
Test defoamer consumption: 0.010g
Method of testing: add the mthod of white water from paper making of about 200ml in the 500ml container, and add defoamer, be warming up to probe temperature, open air pump and stopwatch, the record foam rises to the time of certain altitude.
Test result:
| Foam height/ml | Defoamer A | Defoamer B | Defoamer C | External sample |
| 215 | 1’55” | 1’ | 45” | 40” |
| 250 | 3’05” | 1’55” | 2’ | 2’35” |
| 300 | 5’40” | 2’35” | 2’50” | 3’10” |
| 350 | 7’20” | 5’45” | 4’05” | 4’55” |
| 400 | 9’05” | 6’25” | 5’55” | 6’15” |
| 450 | 13’35” | 11’35” | 7’05” | 8’05” |
Claims (6)
1, a kind of water phase system non-organic silicon defoaming agent, form by following component:
(1) froth breaking active material: be made up of higher aliphatic, higher aliphatic polyethers, nitrogen-containing polyether, fatty acid ester, hydrophobic particles and mineral oil body, described higher aliphatic polyether structure formula is: RO (EO)
m(PO)
nH, wherein R is C
12～28Chain alkyl, m and n represent to contain in the molecule number of EO and PO, 0＜m≤50, n is 1～80, molecular weight is 1000～4000, described higher aliphatic polyethers cloud point is 10～20 ℃; Wherein said nitrogen-containing polyether structural formula is expressed as:
Wherein subscript a, b, c are integers, and 0＜a≤50, b are 1～60, c is 1～10, and molecular weight is 1000～5000; Hydrophobic particles in wherein said hydrophobic particles and the mineral oil body is selected from hydrophobic silicic aerogels, titanium dioxide, magnesia, aluminium oxide, the two stearic amides of ethylenediamine or aluminum stearate, and the mineral oil in described hydrophobic particles and the mineral oil body is selected from waxy stone, base oil, alkylbenzene or machinery oil;
(2) emulsifying agent is selected from anionic, nonionic or cationic surfactant;
(3) decentralized medium water.
2, water phase system non-organic silicon defoaming agent according to claim 1, wherein said higher aliphatic are C
12～28Monobasic to trihydroxylic alcohol, be 5～80 parts at the consumption of the higher aliphatic described in 100 parts of froth breaking active materials.
3, water phase system non-organic silicon defoaming agent according to claim 1, wherein said higher aliphatic polyethers is mainly by the addition and getting under the effect of base catalyst of higher aliphatic and oxirane and expoxy propane, is 5～70 parts at the consumption of the higher aliphatic polyethers described in 100 parts of froth breaking active materials.
4, water phase system non-organic silicon defoaming agent according to claim 1 is 10～30 parts at the consumption of the nitrogen-containing polyether described in 100 parts of froth breaking active materials.
5, water phase system non-organic silicon defoaming agent according to claim 1, wherein said fatty acid ester is by chain alkyl aliphatic carboxylic acid and C
1～18Monobasic to trihydroxylic alcohol reaction and get, described chain alkyl aliphatic carboxylic acid is selected from dodecylic acid, tetradecanoic acid, hexadecanoic acid, octadecanoid acid, arachic acid or behenic acid, is 1～20 part at the consumption of the fatty acid ester described in 100 parts of froth breaking active materials.
6, water phase system non-organic silicon defoaming agent according to claim 1 is 5～20 parts at the consumption of the mixture of hydrophobic particles described in 100 parts of froth breaking active materials and mineral oil.
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