CN103111101B - Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same - Google Patents
Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same Download PDFInfo
- Publication number
- CN103111101B CN103111101B CN201310054599.2A CN201310054599A CN103111101B CN 103111101 B CN103111101 B CN 103111101B CN 201310054599 A CN201310054599 A CN 201310054599A CN 103111101 B CN103111101 B CN 103111101B
- Authority
- CN
- China
- Prior art keywords
- polyether modified
- end capped
- modified silicon
- silicon oil
- double
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 105
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 97
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 17
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 81
- 239000013530 defoamer Substances 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 22
- 230000008676 import Effects 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 10
- -1 polysiloxan Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 7
- 238000007046 ethoxylation reaction Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000006260 foam Substances 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 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
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a double-end-blocked polyether modified silicone-oil defoaming agent and a method for preparing the same. The method comprises the following steps of: stirring and mixing double-end-blocked polyether modified silicone oil, white oil, polyethylene glycol and dodecanol, and heating to obtain a double-end-blocked polyether modified silicone-oil mixture; stirring the double-end-blocked polyether modified silicone-oil mixture and a compound emulsifier, adding a compound stabilizer and hot water gradually, and continuing to stir; cooling to room temperature gradually while stirring, and filtering to obtain the double-end-blocked polyether modified silicone-oil type defoaming agent. The invention also discloses a method for preparing a double-end-blocked polyether modified silicone oil, and the method comprises the following steps of: mixing silicone oil, an initiator and a catalyst, and removing matters with low boiling points and water in vacuum; filling nitrogen to substitute, and introducing an EO/PO (ethylene oxide and propylene oxide) mixture; removing unreacted EO/PO and generated water in the reaction system in vacuum, and filling nitrogen to discharge; and removing the catalyst by filtering to obtain the double-end-blocked polyether modified silicone oil. Compared with the similar defoaming agent, the double-end-blocked polyether modified silicone-oil defoaming agent disclosed by the invention can be adjusted under different conditions to achieve excellent foam removing and inhibiting performances.
Description
Technical field
The present invention relates to field of fine chemical, particularly relate to a kind of two END CAPPED GROUP polyether modified silicon oil type defoamer and preparation method thereof.
Background technology
Polyethers is polyoxyethylene, poiyoxypropylene copolymer.It is a kind of non-ionic surface active agent of function admirable, when contacting with water, in ehter bond, oxygen atom can be combined with faint chemical force by the hydrogen atom in water, forms hydrogen bond, chain element becomes indentation, hydrophobic group is placed in inside molecule, becomes and be easily combined with water around chain, when temperature rising molecular motion is comparatively violent, indentation chain can become zigzag, lose the associativity with water, be warmed up to by dissolution in low temperature state and present muddy temperature, the cloud point of Here it is polyethers; Only have when the temperature of foaming system exceedes cloud point temperature, polyether antifoam agent just plays froth breaking effect.By regulating ratio and the molecular weight of polyoxyethylene, polyoxypropylene in preparation process, just its cloud point can be changed.
Polyether type defoamer is initiator synthesizing polyether or end group Esterification polyether derivative primarily of straight-chain polyether with by alcohol, ammonia.
Reference:
Although Zhao Yantao, Sun Yongqiang, Kangbao County's peace have synthesized polyether ester with fatty acid methyl ester end-blocking, its antifoam performance is studied and has been characterized, also form kinetics equation.
Note: " chemical assistant " 2009(11), 927-930; " textile journal " 2009(9), 59-64; " CDDB " 2009;
Ma Lu, Yu Zhenglang, Guo Rui have studied research and the formula Design of Polyether Modified Polysiloxanes Defoaming Agent.
Note: " printing and dyeing assistant " 2011(12), 29-31; " Hunan papermaking " 2010(1), 24-25 season Yongxin has synthesized rosin ester polyethers and fatty acid polyether, and inquires into each influence factor.
Note: " chemistry of forest product industry " 2005(4), 71-73; " printing during chemical industry " 2004(11), 55-56; The military DMC of Ni Xuemei, Wang Li has catalyzed and synthesized polyethers, the polyether-modified organosilicon of Luo Mengxian, Wu Jirong, Ni Yong.
Note: " modern commerce and trade industry " 2012(19), 194-195; " Hangzhou Normal College " 2003(4), 38-42.
The CN1018110074 patent of Li Li application mainly solves Shrinkage Problem with the defoamer of glycidyl capped polyether.
In sum, above expert research has in various degree been carried out to polyethers, but a main problem is not resolved, the froth breaking of polyethers acts in wider temperature and alkalinity ranges cannot be played with pressing down to steep, and polyethers froth breaking is relevant with the size of pfpe molecule with pressing down bubble effect, good its molecular weight of defoamer monomer should remain on the space of a narrow molecular weight distribution.Therefore, above-mentioned research does not solve the inherent problems of MOLECULE DESIGN.
Summary of the invention
The present invention is in order to solve polyether antifoam agent main monomer molecular weight distribution problem, and two END CAPPED GROUP polyether modified silicon oil type defoamers providing a kind of performance more superior and preparation method thereof, the invention still further relates to the preparation method of two END CAPPED GROUP polyether modified silicon oil.This polyether modified silicon oil type defoamer is that initiator synthesizing polyether or end group Esterification polyether derivative remove modified silicon oil primarily of straight-chain polyether with by alcohol, ammonia, obtain a kind of two END CAPPED GROUP polyether modified silicon oil, and synthesize defoamer by this pair of END CAPPED GROUP polyether modified silicon oil and compound emulsifying agent, compound stabilizer, this pair of END CAPPED GROUP polyether modified polysiloxan defoaming agent thoroughly solves the problem of the defoamer main monomer molecular chain length meeting needs arbitrarily, thus reaches new defoamer and have superior froth breaking and suds suppressing properties.This defoamer and preparation method thereof also can reach different MOLECULE DESIGN requirements according to different fields of employment.
The present invention is realized by following technical proposals.
A kind of two END CAPPED GROUP polyether modified silicon oil type defoamer, comprises the raw material of following mass percent:
Further, described pair of END CAPPED GROUP polyether modified silicon oil mixture mixes according to the raw material of following mass percent:
Further, described compound emulsifying agent is one or more in tween, sapn or stearic acid.
Further, described compound stabilizer be white oil, vinyl bis-stearamides EBS, silica or calcium stearate one or more.
Correspondingly, the present invention gives the preparation method of a kind of pair of END CAPPED GROUP polyether modified silicon oil type defoamer, comprises the steps:
1) according to mass percent be 25 ~ 60% two end capped polyether modified silicon oils, the white oil of 30 ~ 70%, the polyethylene glycol of 10 ~ 45% and 5 ~ 15% lauryl alcohol in container at 40 ~ 60r/min, after under 35 ~ 55r/min mixing speed mix 2 ~ 2.5h, be warmed up to 70 ~ 90 DEG C gradually again, obtain two END CAPPED GROUP polyether modified silicon oil mixture;
2) under 70 ~ 90 DEG C of constant temperature, be that two END CAPPED GROUP polyether modified silicon oil mixture of 12 ~ 47% and the compound emulsifying agent of 2 ~ 8% are placed in container by mass percent, 0.5 ~ 1h is stirred under 30 ~ 50r/min mixing speed, then under 20 ~ 40r/min mixing speed, add the compound stabilizer of 11 ~ 45% and 60 ~ 80 DEG C of hot water of 0 ~ 75% gradually, continue stirring 1 ~ 2h;
3) under 10 ~ 30r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified silicon oil type defoamer.
And then the present invention gives the preparation method of described pair of END CAPPED GROUP polyether modified silicon oil, prepare according to following step:
1) by mass percent be the silicone oil of 60 ~ 75%, the initiator of 3 ~ 10% and 1 ~ 3% catalyst mix after, vacuum sucks magnetic agitation autoclave, is warming up to 80 ~ 100 DEG C, the low-boiling point material in vacuum removal system and water;
2) inflated with nitrogen displacement system 1 ~ 5 time, be filled with the nitrogen that pressure is 0.15 ~ 0.18MPa, be warming up to 180 ~ 210 DEG C, first import 60% in 20 ~ 35%EO/PO amount of the mixture and carry out induced reaction, when pressure drop to 0.10 ~ 0.14MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously;
3) maintain invariablenes pressure of liquid, be cooled to 70 ~ 90 DEG C, the unreacted aqueous vapor of vacuum removal reaction system, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
Further, described catalyst is ester group ethoxylation catalyst (MCT-09).
Further, described initiator is fatty acid methyl ester.
Further, described EO/PO is ethylene oxide/propylene oxide, and ethylene oxide/propylene oxide is EO/PO=1 ~ 3 ratio mixing according to mass ratio.
Compared with prior art, beneficial effect of the present invention is: this defoamer carrys out modified silicon oil using polyethers and derivative thereof as two END CAPPED GROUP, reach the control of defoamer main monomer molecular structure and size to be applicable to different occasion, thus solve the removal of foam and the control problem of high temperature alkali system.The present invention utilizes Long carbon chain fatty acid methyl ester one-step synthesis two END CAPPED GROUP polyester ether modified silicon oil type defoamer main monomer.Constitute defoamer by two end capped polyesters ether modified silicon oil mixture, white oil, EBS, calcium stearate, polyethylene glycol, lauryl alcohol, emulsifying agent etc. newly to fill a prescription, define own preparation technology and technological parameter.Its main monomer molecular weight distribution is controlled, compares, adjust according to different condition with same defoamer.The effective froth breaking of polyether modified silicon oil defoamer, suds suppressing properties can be reached within the scope of high temperature height alkali systems.
Accompanying drawing explanation
Fig. 1 is defoamer process flow diagram of the present invention.
Fig. 2 is two end capped polyether modified silicon oil preparation technology flow charts.
Fig. 3 be different manufacturers defoamer of the same type performance comparison figure.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further details, but is not limited to practical range of the present invention.
The preparation method of the two END CAPPED GROUP polyether modified silicon oil type defoamer of the present invention is according to following step:
First the two end capped polyether modified silicon oil of preparation, its flow process as shown in Figure 2:
1) by mass percent be the silicone oil of 60 ~ 75%, the initiator fatty acid methyl ester of 3 ~ 10% and 1 ~ 3% catalyst ester group ethoxylation catalyst (MCT-09) mixing after, vacuum sucks magnetic agitation autoclave, be warming up to 80 ~ 100 DEG C, the low-boiling point material in vacuum removal system and water;
2) inflated with nitrogen displacement system 1 ~ 5 time, be filled with the nitrogen that pressure is 0.15 ~ 0.18MPa, be warming up to 180 ~ 210 DEG C, first import 60% in 20 ~ 35%EO/PO mixture (oxirane and expoxy propane are EO/PO=1 ~ 3 ratio mixing according to mass ratio) total amount and carry out induced reaction, when pressure drop to 0.10 ~ 0.14MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously;
3) maintain invariablenes pressure of liquid, be cooled to 70 ~ 90 DEG C, the unreacted aqueous vapor of vacuum removal reaction system, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
Prepare pair END CAPPED GROUP polyether modified silicon oil type defoamer after mixing with compound emulsifying agent, compound stabilizer and water after more two END CAPPED GROUP polyether modified silicon oil being prepared into mixture, its flow process as shown in Figure 1:
1) according to mass percent be 15 ~ 60% two end capped polyether modified silicon oils, the white oil of 20 ~ 70%, the polyethylene glycol of 10 ~ 45% and 5 ~ 15% lauryl alcohol in container at 40 ~ 60r/min, after under 35 ~ 55r/min mixing speed mix 2 ~ 2.5h, be warmed up to 70 ~ 90 DEG C gradually again, obtain two END CAPPED GROUP polyether mixture;
2) under 70 ~ 90 DEG C of constant temperature, be that two END CAPPED GROUP polyether modified silicon oil mixture of 12 ~ 47% and the compound emulsifying agent (in tween, sapn or stearic acid one or more) of 2 ~ 8% are placed in container by mass percent, 0.5 ~ 1h is stirred under 30 ~ 50r/min mixing speed, then under 20 ~ 40r/min mixing speed, add the compound stabilizer (white oil, vinyl bis-stearamides EBS, silica or calcium stearate one or more) of 11 ~ 45% and 60 ~ 80 DEG C of hot water of 0 ~ 75% gradually, continue stirring 1 ~ 2h;
3) under 10 ~ 30r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified polysiloxan defoaming agent.
Further illustrate embodiment of the present invention below by specific embodiment.
Embodiment 1
First the two end capped polyether modified silicon oil of preparation:
After the silicone oil of 60%, the initiator fatty acid methyl ester of 10% and the catalyst ester group ethoxylation catalyst (MCT-09) of 3% being mixed, vacuum sucks magnetic agitation autoclave, is warming up to 80 DEG C, the low-boiling point material in vacuum removal system and water; Inflated with nitrogen displacement system 1 time, be filled with the nitrogen that pressure is 0.15MPa, be warming up to 180 DEG C, first import 60% in 27%EO/PO mixture (oxirane and expoxy propane are the mixing of EO/PO=1 ratio according to mass ratio) total amount and carry out induced reaction, when pressure drop is to 0.10MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously; Maintain invariablenes pressure of liquid, be cooled to 70 DEG C, the unreacted aqueous vapor of vacuum removal reaction system, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
After more two END CAPPED GROUP polyether modified silicon oil being prepared into mixture with compound emulsifying agent, compound stabilizer and who mix after prepare pair END CAPPED GROUP polyether modified silicon oil type defoamer:
By two for the end of 25% envelope polyether modified silicon oil, the white oil of 35%, the polyethylene glycol of 25% and 15% lauryl alcohol in container at 40r/min, after under 35r/min mixing speed, mix 2h, then be warmed up to 70 DEG C gradually, obtain two END CAPPED GROUP polyether modified silicon oil mixture; Under 70 DEG C of constant temperature, be that two END CAPPED GROUP polyether mixture of 12% and the compound emulsifying agent of 8% are placed in container by mass percent, under 30r/min mixing speed, stir 1h, then under 20r/min mixing speed, add the compound stabilizer of 45% and 60 DEG C of hot water of 35% gradually, continue to stir 1h; Under 10r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified silicon oil type defoamer.
Embodiment 2
First the two end capped polyether modified silicon oil of preparation:
After the silicone oil of 75%, the initiator fatty acid methyl ester of 3% and the catalyst ester group ethoxylation catalyst (MCT-09) of 1% being mixed, vacuum sucks magnetic agitation autoclave, is warming up to 100 DEG C, the low-boiling point material in vacuum removal system and water; Inflated with nitrogen displacement system 5 times, be filled with the nitrogen that pressure is 0.18MPa, be warming up to 210 DEG C, first import 60% in 21%EO/PO mixture (oxirane and expoxy propane are the mixing of EO/PO=3 ratio according to mass ratio) total amount and carry out induced reaction, when pressure drop is to 0.14MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously; Maintain invariablenes pressure of liquid, be cooled to 90 DEG C, the unreacted aqueous vapor of vacuum removal reaction system, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
After more two END CAPPED GROUP polyether modified silicon oil being prepared into mixture with compound emulsifying agent, compound stabilizer and who mix after prepare pair END CAPPED GROUP polyether modified silicon oil type defoamer:
By two end capped polyether modified silicon oils of 15%, the white oil of 70%, the polyethylene glycol of 10% and 5% lauryl alcohol in container at 60r/min, after under 40r/min mixing speed, mix 2.5h, then be warmed up to 80 DEG C gradually, obtain two END CAPPED GROUP polyether mixture; Under 80 DEG C of constant temperature, be that two END CAPPED GROUP polyether modified silicon oil mixture of 47% and the compound emulsifying agent sapn of 3% are placed in container by mass percent, 0.5h is stirred under 50r/min mixing speed, then under 40r/min mixing speed, add 80 DEG C of hot water of the compound stabilizer vinyl bis-stearamides EBS and 39% of 11% gradually, continue to stir 2h; Under 30r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified silicon oil type defoamer.
Embodiment 3
First the two end capped polyether modified silicon oil of preparation:
After the silicone oil of 60%, the initiator fatty acid methyl ester of 3% and the catalyst ester group ethoxylation catalyst (MCT-09) of 2% being mixed, vacuum sucks magnetic agitation autoclave, is warming up to 90 DEG C, the low-boiling point material in vacuum removal system and water; Inflated with nitrogen displacement system 3 times, be filled with the nitrogen that pressure is 0.16MPa, be warming up to 200 DEG C, first import 60% in 35%EO/PO mixture (oxirane and expoxy propane are the mixing of EO/PO=2 ratio according to mass ratio) total amount and carry out induced reaction, when pressure drop to 0.10 ~ 0.14MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously; Maintain invariablenes pressure of liquid, be cooled to 80 DEG C, the unreacted aqueous vapor of vacuum removal reaction system, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
Two END CAPPED GROUP polyether modified silicon oil type defoamer is prepared after mixing with compound emulsifying agent, compound stabilizer and water after more two END CAPPED GROUP polyether modified silicon oil being prepared into mixture:
By two end capped polyether modified silicon oils of 60%, the white oil of 20%, the polyethylene glycol of 10% and 10% lauryl alcohol in container at 50r/min, after under 45r/min mixing speed, mix 2h, be warmed up to 850 DEG C gradually again, obtain two END CAPPED GROUP polyether modified silicon oil mixture; Under 85 DEG C of constant temperature, be that two END CAPPED GROUP polyether modified silicon oil mixture of 12% and the compound emulsifying agent of 2% are placed in container by mass percent, 0.5h is stirred under 40r/min mixing speed, then under 30r/min mixing speed, add the compound stabilizer silica of 11% and 60 DEG C of hot water of 75% gradually, continue to stir 1h; Under 20r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified silicon oil type defoamer.
Embodiment 4
First the two end capped polyether modified silicon oil of preparation:
After the silicone oil of 65%, the initiator fatty acid methyl ester of 4% and the catalyst ester group ethoxylation catalyst (MCT-09) of 1% being mixed, vacuum sucks magnetic agitation autoclave, is warming up to 100 DEG C, the low-boiling point material in vacuum removal system and water; Inflated with nitrogen displacement system 4 times, be filled with the nitrogen that pressure is 0.16MPa, be warming up to 190 DEG C, first import 60% in 30%EO/PO mixture (oxirane and expoxy propane are the mixing of EO/PO=3 ratio according to mass ratio) total amount and carry out induced reaction, when pressure drop is to 0.14MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously; Maintain invariablenes pressure of liquid, be cooled to 70 DEG C, the unreacted low-boiling-point substance of vacuum removal reaction system and water, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
Two END CAPPED GROUP polyether type defoamer is prepared after mixing with compound emulsifying agent, compound stabilizer and water after more two END CAPPED GROUP polyether modified silicon oil being prepared into mixture:
By two end capped polyether modified silicon oils of 20%, the white oil of 25%, the polyethylene glycol of 45% and 10% lauryl alcohol in container at 50r/min, after under 40r/min mixing speed, mix 2h, then be warmed up to 80 DEG C gradually, obtain two END CAPPED GROUP polyether modified silicon oil mixture; Under 80 DEG C of constant temperature, two END CAPPED GROUP polyether modified silicon oil mixture of 47% and the compound emulsifying agent constant temperature of 8% and stearic acid are placed in container according to the mixture of arbitrary proportion, 1h is stirred under 50r/min mixing speed, then under 40r/min mixing speed, add the compound stabilizer white oil of 45%, vinyl bis-stearamides EBS and the calcium stearate mixture according to arbitrary proportion gradually, continue stirring 1 ~ 2h; Under 20r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified silicon oil type defoamer.
The invention solves polyether modified polysiloxan defoaming agent main monomer molecular weight distribution problem, the imagination that have employed the two end-blocking of Long carbon chain fatty acid methyl ester makes polyether modified polysiloxan defoaming agent main monomer molecular weight can obtain controlled.Through repeatedly repeatedly research and design go out two END CAPPED GROUP polyether modified silicon oil type defoamer formulations, and define exclusive preparation technology.
Fig. 3 is the present invention and existing defoamer at 80 ~ 150 DEG C, antifoam performance, suds suppressing properties Contrast on effect under basicity >7mg/L.
Visible in figure, the antifoam performance of defoamer of the present invention is when evaluating by Bubbling method, and antifoam performance is lower than 110mm foam height, and suds suppressing properties, lower than 220mm foam height, is starkly lower than other dissimilar defoamers foam height under the same conditions.Show that this defoamer has superior froth breaking, suds suppressing properties.Prove through a large amount of experiments, two end capped polyether modified silicon oil type defoamer has wider temperature and basicity accommodation, is adapted to the removal of foam and the control of high temperature height alkali systems especially.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (5)
1. a preparation method for two END CAPPED GROUP polyether modified silicon oil type defoamer, is characterized in that, comprise the steps:
1) according to mass percent be 15 ~ 60% two end capped polyether modified silicon oils, the white oil of 20 ~ 70%, the polyethylene glycol of 10 ~ 45% and 5 ~ 15% lauryl alcohol low whipping speed in container be mix under 40 ~ 60r/min, after under 35 ~ 55r/min mixing speed mix 2 ~ 2.5h, be warmed up to 70 ~ 90 DEG C gradually again, obtain two END CAPPED GROUP polyether modified silicon oil mixture;
2) under 70 ~ 90 DEG C of constant temperature, be that two END CAPPED GROUP polyether modified silicon oil mixture of 12 ~ 47% and the compound emulsifying agent of 2 ~ 8% are placed in container by mass percent, 0.5 ~ 1h is stirred under 30 ~ 50r/min mixing speed, then under 20 ~ 40r/min mixing speed, add the compound stabilizer of 11 ~ 45% and 60 ~ 80 DEG C of hot water of 0 ~ 75% gradually, continue stirring 1 ~ 2h;
3) under 10 ~ 30r/min mixing speed, be cooled to room temperature gradually, filter, obtain two END CAPPED GROUP polyether modified polysiloxan defoaming agent.
2. the preparation method of according to claim 1 pair of END CAPPED GROUP polyether modified silicon oil type defoamer, is characterized in that, described pair of END CAPPED GROUP polyether modified silicon oil is prepared according to following step:
1) by mass percent be the silicone oil of 60 ~ 75%, the initiator of 3 ~ 10% and 1 ~ 3% catalyst mix after, vacuum sucks magnetic agitation autoclave, is warming up to 80 ~ 100 DEG C, the low-boiling point material in vacuum removal system and water;
2) inflated with nitrogen displacement system 1 ~ 5 time, be filled with the nitrogen that pressure is 0.15 ~ 0.18MPa, be warming up to 180 ~ 210 DEG C, first import 60% in 20 ~ 35%EO/PO amount of the mixture and carry out induced reaction, when pressure drop to 0.10 ~ 0.14MPa, import remaining 40%EO/PO mixture in EO/PO amount of the mixture continuously;
3) maintain invariablenes pressure of liquid, be cooled to 70 ~ 90 DEG C, the unreacted low-boiling point material of vacuum removal reaction system and water, inflated with nitrogen discharging; Vacuum filtration falls catalyst, obtains two END CAPPED GROUP polyether modified silicon oil.
3. the preparation method of according to claim 2 pair of END CAPPED GROUP polyether modified silicon oil type defoamer, is characterized in that, described catalyst is ester group ethoxylation catalyst MCT-09.
4. the preparation method of according to claim 2 pair of END CAPPED GROUP polyether modified silicon oil type defoamer, is characterized in that, described initiator is fatty acid methyl ester.
5. the preparation method of according to claim 2 pair of END CAPPED GROUP polyether modified silicon oil type defoamer, is characterized in that, described EO/PO is ethylene oxide/propylene oxide, and ethylene oxide/propylene oxide is EO/PO=1 ~ 3 ratio mixing according to mass ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310054599.2A CN103111101B (en) | 2013-02-20 | 2013-02-20 | Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310054599.2A CN103111101B (en) | 2013-02-20 | 2013-02-20 | Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103111101A CN103111101A (en) | 2013-05-22 |
| CN103111101B true CN103111101B (en) | 2015-01-07 |
Family
ID=48409509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310054599.2A Active CN103111101B (en) | 2013-02-20 | 2013-02-20 | Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103111101B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104906832B (en) * | 2015-05-22 | 2016-08-31 | 陕西省石油化工研究设计院 | A kind of compound defoamer of polyether ester/mineral oil and preparation method thereof |
| CN106943773A (en) * | 2017-04-20 | 2017-07-14 | 天津亿利科能源科技发展股份有限公司 | A kind of preparation method of offshore platform middle matter crude oil defoamer |
| US11957126B2 (en) | 2018-08-08 | 2024-04-16 | Kop-Coat, Inc. | Granulated agricultural adjuvant and method of making and using same |
| CN110465119A (en) * | 2019-08-28 | 2019-11-19 | 启东曦瑞新材料科技有限公司 | A kind of preparation method of mineral oil antifoam agent |
| CN113069796B (en) * | 2020-01-03 | 2022-11-08 | 万华化学集团股份有限公司 | Organic silicon defoaming agent for water-based paint and preparation method thereof |
| CN115400464A (en) * | 2022-09-29 | 2022-11-29 | 深哲新材料（广州）有限公司 | Defoaming auxiliary agent for water-based paint and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9301347A0 (en) * | 1992-04-27 | 1993-10-28 | Nikko Chemical Inst Inc | Anti-foaming composition of emulsion type and anti-foaming method using the same |
| JP3676042B2 (en) * | 1997-06-27 | 2005-07-27 | 信越化学工業株式会社 | Foam suppressant composition |
| CN1250313C (en) * | 2004-09-22 | 2006-04-12 | 曹治平 | High-temperature defoamer and its preparation |
| CN1919936A (en) * | 2006-08-31 | 2007-02-28 | 南京四新科技应用研究所有限公司 | Organosilicon defoaming agent for water-based system and preparation method thereof |
| CN100531850C (en) * | 2007-04-30 | 2009-08-26 | 南京四新科技应用研究所有限公司 | Preparation for general defoaming agent and its application |
| CN102527096B (en) * | 2011-05-12 | 2015-02-18 | 湖北新四海化工股份有限公司 | Organic silicon defoaming agent and preparation method thereof |
-
2013
- 2013-02-20 CN CN201310054599.2A patent/CN103111101B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103111101A (en) | 2013-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103111101B (en) | Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same | |
| CN104130879B (en) | Defoaming agent for liquid detergent | |
| CN104436766B (en) | A kind of silicon composition | |
| CN103923323B (en) | Preparation method of terpolymer defoamer | |
| US7776929B2 (en) | Method for the production of defoamer formulations | |
| CN105498305B (en) | A kind of organosilicon defoaming composition | |
| CN103641195A (en) | Organic silicon defoamer and preparation method thereof | |
| CN107469411B (en) | A kind of preparation method of organic silicon defoamer | |
| CN102961897B (en) | Electrostatic flocking adhesive defoamer and application thereof | |
| CN101298027A (en) | Method for dispersing highly viscous organosilicon mixture | |
| CN106492707A (en) | Surface activator composition | |
| CN109173351A (en) | A kind of organic-silicon-modified castor oil polyether antifoam agent of emulsion-type and preparation method | |
| CN103669108A (en) | Organic silicon defoamer for paper making industry and preparation method thereof | |
| CN107469414B (en) | One kind defoaming agent containing poly-organosilicon and preparation method thereof | |
| CN102781534B (en) | Method for deaerating liquids | |
| CN105152255A (en) | Preparation method of defoaming agent for wastewater treatment | |
| CN111760333A (en) | Defoaming agent composition and preparation method and application thereof | |
| CN106362441A (en) | Organic silicon defoamer containing hydroxyl polyether modified epoxidized soybean oil and preparation method thereof | |
| CN106474775A (en) | A kind of hyperbranched polyether modified organic silicon defoamer of nano-silica-containing and preparation method thereof | |
| CN107537185A (en) | A kind of self-emulsifying type defoamer and preparation method thereof | |
| CN113069796B (en) | Organic silicon defoaming agent for water-based paint and preparation method thereof | |
| CN103275493A (en) | Organosilicon composition | |
| CN104606926A (en) | Silicone-modified vegetable oil polymer polyether defoamer and preparation method thereof | |
| CN100396353C (en) | Process for suppressing the foaming of an aqueous system | |
| CN109289255A (en) | A kind of Sudo controlling compositions and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same Effective date of registration: 20150410 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2015990000279 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20160121 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2015990000279 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same Effective date of registration: 20160121 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2016990000064 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20161222 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2016990000064 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same Effective date of registration: 20161222 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2016990001158 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180122 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2016990001158 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Double-end-blocked polyether modified silicone-oil defoaming agent and method for preparing same Effective date of registration: 20180122 Granted publication date: 20150107 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Suny Fine Chemicals Co., Ltd. Registration number: 2018990000070 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 710075 SoHO Alliance A Block 1804-1805, Zhangbayi Green Space, Xi'an High-tech Zone, Shaanxi Province Patentee after: Xi'an Sanye New Materials Co., Ltd. Address before: 710075 SoHO Alliance A Block 1801-1807, Zhangbayi Green Space, Xi'an High-tech Zone, Shaanxi Province Patentee before: Xi'an Suny Fine Chemicals Co., Ltd. |