CN107936241A - Polyethers for defoamer and preparation method thereof - Google Patents
Polyethers for defoamer and preparation method thereof Download PDFInfo
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- CN107936241A CN107936241A CN201711204749.8A CN201711204749A CN107936241A CN 107936241 A CN107936241 A CN 107936241A CN 201711204749 A CN201711204749 A CN 201711204749A CN 107936241 A CN107936241 A CN 107936241A
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- polyethers
- defoamer
- preparation
- propylene oxide
- small molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The present invention relates to a kind of polyethers for defoamer and preparation method thereof, belong to polyether polyol technical field.The polyethers is as initiator, as obtained by Catalyzed by Pt/M Bimetallic Nano propylene oxide, propylene oxide/ethane mixtures, epoxy butane carry out polymerisation successively using small molecule glycerin polyether polyalcohol；The preparation process realizes epoxy butane direct polymerization end-blocking, obtains more hydrophobic end group segment, product defoaming effect is more excellent；Invention also provides simple and practicable preparation method, generation of the whole polymerization process without waste water, waste residue and exhaust gas, alkylene oxide monomer conversion ratio can reach more than 99.5%, environment-friendly high-efficiency.
Description
Technical field
The present invention relates to a kind of polyethers for defoamer and preparation method thereof, belongs to polyether polyol synthetic technology neck
Domain.
Background technology
Defoamer is common a kind of chemical raw material in modern industrial production, its main function be eliminate in production process because
Surface reactive material, stirring or foam caused by other factors；In sewage disposal, printing and dyeing, fermentation, papermaking, weaving, doctor
The every field extensive use such as medicine, food processing, oil exploitation and refining, emulsion polymerization.The species of defoamer is various, mainly has
Several major classes such as grease type defoamer, organic silicon defoamer, polyethers defoamer.Wherein grease type defoamer is cheap, but
Antifoam performance is relatively low；Although organic silicon defoamer defoaming effectiveness is high, its suds effect is barely satisfactory；Polyethers
For defoamer after modified, its defoaming capacity and suds ability can reach a preferable balance, therefore in sector application
Quick development is reached.Traditional polyethers is usually used propylene oxide and carries out ring-opening polymerisation and obtain, in defoamer
There is certain application, but since its molecular structure segment is entirely hydrophobic chain, be not easy to disperse in some solution, cause defoaming speed
It is slow to spend, and does not catch up with the lather quickness of solution, have impact on defoaming effect；In order to improve antifoaming speed, in polyethers building-up process
It is modified by introducing ethylene oxide, prepares the polyethers with certain block structure, the defoaming effect of polyethers can be significantly improved
Fruit, but the synthesis of this defoamer polyethers is mostly to be dredged using fatty alcohol as initiator to introduce end group in industrial production at present
Water segment, is catalyzed and synthesized by base metal catalysts such as potassium hydroxide, produce preparation process in can produce substantial amounts of waste water,
The three wastes problem such as waste residue and exhaust gas, for product yield nor especially high, economic and environment-friendly property is not highly desirable.
The content of the invention
The object of the present invention is to provide a kind of polyethers for defoamer, it has more hydrophobic end group segment, defoaming
Effect is more excellent；Invention also provides simple and practicable preparation method, without waste water, waste residue and exhaust gas in whole process
Produce, alkylene oxide monomer conversion ratio can reach more than 99.5%, environment-friendly high-efficiency.
Polyethers of the present invention for defoamer, the structural formula of the polyethers are as follows：
Wherein, m=40~60, n=3~8, x=1~6.
The preparation method of the polyethers for defoamer, be using small molecule glycerin polyether polyalcohol as initiator,
Under bimetallic catalyst effect, ring-opening reaction is carried out with propylene oxide, ethylene oxide and epoxy butane, is carried out using epoxy butane
Dead-end polymerization reacts, and the polyethers for defoamer is made.
Preferably, the molecular weight of small molecule glycerin polyether polyalcohol is 500~1000.
The dosage of the bimetallic catalyst is small molecule glycerin polyether polyalcohol, propylene oxide, ethylene oxide and epoxy
The 0.001%~0.01% of butane gross mass.
The preparation method of the polyethers for defoamer, comprises the following steps：
(1) small molecule glycerin polyether polyalcohol, bimetallic catalyst, acid regulator are added in autoclave,
Nitrogen displacement is warming up to 110 DEG C~130 DEG C to oxygen content≤50ppm, keep vacuum -0.093MPa vacuumize dehydration 0.5~
2h；
(2) first add account for small molecule glycerin polyether polyol quality 5%~15% propylene oxide carry out induced activation it is anti-
Should, inducing temperature is 130 ± 2 DEG C, induced pressure≤0.2MPa；When being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle is anxious
When play rises, show that polymerisation starts, be continuously added to propylene oxide and polymerize, stop adding when reaching propylene oxide design flow
Material, continues 10~20min of aging reaction；
(3) mixed material for continuously adding propylene oxide and ethylene oxide carries out polymerisation, reaches propylene oxide and ring
Stop charging during oxidative ethane design flow, continue 10~20min of aging reaction；
(4) add epoxy butane and carry out polymerisation, continue 0.5~1h of aging reaction after charging, then vacuumize
1~3h of demonomerization, cooling discharge, is made the polyethers for defoamer.
The acid regulator is one or both of for the concentrated sulfuric acid, the phosphoric acid of 85% mass concentration or concentrated hydrochloric acid, dosage
For the 0.001%~0.005% of initiator.
In the step (3), the ratio of polymerization process oxypropylene and ethylene oxide mixture material is 50~90：50~
10。
Compared with prior art, the invention has the advantages that：
(1) polymerization of ethylene oxide and the polymerisation of epoxy butane can be realized using Bimetallic catalyst system, and with ring
Oxygen butane blocks, and the polyethers of preparation has more preferable end group hydrophobic segment, and avoiding alkali metal catalyst system and catalyzing need to be made with fatty alcohol
The technology drawback of end group hydrophobic segment is introduced for initiator, production technology is simpler efficiently；
(2) traditional alkali metal catalyst system and catalyzing is substituted using Bimetallic catalyst system, synthesis has certain block structure
Defoamer polyethers, product yield higher, alkylene oxide monomer conversion ratio can reach more than 99.5%, do not give up in production process
The generation of water, waste residue, exhaust gas, the feature of environmental protection protrude；
(3) the polyethers defoaming effect prepared is more excellent；
(4) preparation method of the defoamer polyethers is simple and practicable, is industrialized beneficial to realizing.
Embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the implementation of the present invention.
Embodiment 1
The concentrated sulfuric acid of the glycerin polyether polyalcohol of 500Kg molecular weight 500, the dmc catalyst of 0.15Kg, 0.015Kg are added
Enter into pressure-resistant reaction kettle, nitrogen displacement to oxygen content 45ppm, be warming up to 110 DEG C, keep vacuum -0.093MPa to vacuumize
It is dehydrated 1h；The PO for adding 50Kg carries out induced activation reaction, when being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle drastically on
When rising, show that polymerisation starts, be continuously added to PO and polymerize, stop charging after PO accumulation chargings 1760Kg, continue aging
React 20min；Then the mixed material for being continuously added to 270Kg PO and 180Kg EO carries out polymerisation, accumulation PO/EO chargings
Stop charging during 450Kg altogether, continue aging reaction 20min；Then the epoxy butane for being continuously added to 290Kg polymerize instead
Should, continue aging reaction 0.5h after charging, pressure tends to balance, and vacuumizes demonomerization 2h, cooling discharge.
Embodiment 2
By the glycerin polyether polyalcohol of 1000Kg molecular weight 1000, the dmc catalyst of 0.1Kg, 0.04Kg 85% phosphoric acid
It is added in pressure-resistant reaction kettle, nitrogen displacement to oxygen content 50ppm, is warming up to 130 DEG C, keeps vacuum -0.093MPa to take out true
Sky dehydration 1h；The PO for adding 60Kg carries out induced activation reaction, when being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle drastically
During rising, show that polymerisation starts, be continuously added to PO and polymerize, stop charging after PO accumulation chargings 895Kg, continue aging
React 15min；Then the mixed material for being continuously added to 820Kg PO and 350Kg EO carries out polymerisation, accumulation PO/EO chargings
Stop charging during 1170Kg altogether, continue aging reaction 10min；Then the epoxy butane for being continuously added to 435Kg polymerize instead
Should, continue aging reaction 1h after charging, pressure tends to balance, and vacuumizes demonomerization 3h, cooling discharge.
Embodiment 3
The glycerin polyether polyalcohol of 500Kg molecular weight 500, the dmc catalyst of 0.105Kg, the 0.01Kg concentrated sulfuric acids are added
Into pressure-resistant reaction kettle, nitrogen displacement to oxygen content 40ppm, is warming up to 120 DEG C, keeps vacuum -0.093MPa to vacuumize de-
Water 2h；The PO for adding 70Kg carries out induced activation reaction, when being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle steeply rises
When, show that polymerisation starts, be continuously added to PO and polymerize, stop charging after PO accumulation chargings 1800Kg, it is anti-to continue aging
Answer 20min；Then the mixed material for being continuously added to 240Kg PO and 240Kg EO carries out polymerisation, and accumulation PO/EO chargings are altogether
Stop charging when counting 480Kg, continue aging reaction 20min；Then the epoxy butane for being continuously added to 220Kg carries out polymerisation,
Continue aging reaction 1h after charging, pressure tends to balance, and vacuumizes demonomerization 3h, cooling discharge.
Index test is carried out to the polyethers for being used for defoamer made from embodiment 1-3 respectively, test index is shown in Table 1.
1 test index of table
Claims (7)
- A kind of 1. polyethers for defoamer, it is characterised in that：The structural formula of the polyethers is as follows：Wherein, m=40~60, n=3~8, x=1~6.
- A kind of 2. preparation method of the polyethers for defoamer described in claim 1, it is characterised in that：Gathered with small molecule glycerine Ethoxylated polyhydric alcohol is initiator, under bimetallic catalyst effect, carries out open loop with propylene oxide, ethylene oxide and epoxy butane and gathers Reaction is closed, the polyethers for defoamer is made.
- 3. the preparation method of the polyethers according to claim 2 for defoamer, it is characterised in that：Small molecule glycerin polyether The molecular weight of polyalcohol is 500~1000.
- 4. the preparation method of the polyethers according to claim 2 for defoamer, it is characterised in that：Bimetallic catalyst Dosage is the 0.001%~0.01% of glycerin polyether polyalcohol, propylene oxide, ethylene oxide and epoxy butane gross mass.
- 5. the preparation method of the polyethers according to claim 2 for defoamer, it is characterised in that comprise the following steps：(1) small molecule glycerin polyether polyalcohol, bimetallic catalyst, acid regulator are added in autoclave, nitrogen Displacement is warming up to 110 DEG C~130 DEG C, vacuumizes 0.5~2h of dehydration to oxygen content≤50ppm；(2) first add and account for the propylene oxide of small molecule glycerin polyether polyol quality 5%~15% and reacted, inducing temperature is 130 ± 2 DEG C, induced pressure≤0.2MPa；When being decreased obviously occurs in reacting kettle inner pressure, temperature in the kettle steeply rises, continuously Add propylene oxide to be polymerize, stop charging when reaching propylene oxide design flow, continue 10~20min of aging reaction；(3) mixed material for continuously adding propylene oxide and ethylene oxide carries out polymerisation, reaches propylene oxide and epoxy second Stop charging during alkane design flow, continue 10~20min of aging reaction；(4) add epoxy butane and carry out polymerisation, continue 0.5~1h of aging reaction after charging, then vacuumize de- single 1~3h of body, cooling discharge, is made the polyethers for defoamer.
- 6. the preparation method of the polyethers according to claim 5 for defoamer, it is characterised in that：Acid regulator is dense One or both of sulfuric acid, the phosphoric acid of 85% mass concentration or concentrated hydrochloric acid, dosage are the 0.001%~0.005% of initiator.
- 7. the preparation method of the polyethers according to claim 5 for defoamer, it is characterised in that：In step (3), polymerization The ratio of process oxypropylene and ethylene oxide mixture material is 50~90：50~10.
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| CN201711204749.8A CN107936241A (en) | 2017-11-27 | 2017-11-27 | Polyethers for defoamer and preparation method thereof |
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| CN201711204749.8A CN107936241A (en) | 2017-11-27 | 2017-11-27 | Polyethers for defoamer and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306053A (en) * | 2018-09-27 | 2019-02-05 | 山东诺威新材料有限公司 | Small molecule polyether polyol efficiently synthesizes new process |
| CN109337062A (en) * | 2018-09-30 | 2019-02-15 | 山东诺威新材料有限公司 | The preparation method of low-density high-mechanic sponge polyether polyol |
| CN111019116A (en) * | 2019-12-23 | 2020-04-17 | 山东益丰生化环保股份有限公司 | Preparation method of high molecular weight block polyether, silicon ether mixed type defoaming agent and preparation method thereof |
| CN111569474A (en) * | 2020-05-28 | 2020-08-25 | 南京澳莉峰环保科技有限公司 | Organic silicon emulsion defoaming agent in textile size and preparation method thereof |
| CN113667529A (en) * | 2021-08-19 | 2021-11-19 | 江苏美科太阳能科技有限公司 | Cooling liquid for large-size solar-grade silicon wafer diamond wire cutting |
| CN113881033A (en) * | 2021-09-30 | 2022-01-04 | 中国石油化工股份有限公司 | Method for preparing high-toughness high-resilience soft foam polyether polyol based on butylene oxide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306053A (en) * | 2018-09-27 | 2019-02-05 | 山东诺威新材料有限公司 | Small molecule polyether polyol efficiently synthesizes new process |
| CN109337062A (en) * | 2018-09-30 | 2019-02-15 | 山东诺威新材料有限公司 | The preparation method of low-density high-mechanic sponge polyether polyol |
| CN109337062B (en) * | 2018-09-30 | 2021-06-18 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol for low-density high-bearing sponge |
| CN111019116A (en) * | 2019-12-23 | 2020-04-17 | 山东益丰生化环保股份有限公司 | Preparation method of high molecular weight block polyether, silicon ether mixed type defoaming agent and preparation method thereof |
| CN111569474A (en) * | 2020-05-28 | 2020-08-25 | 南京澳莉峰环保科技有限公司 | Organic silicon emulsion defoaming agent in textile size and preparation method thereof |
| CN113667529A (en) * | 2021-08-19 | 2021-11-19 | 江苏美科太阳能科技有限公司 | Cooling liquid for large-size solar-grade silicon wafer diamond wire cutting |
| CN113667529B (en) * | 2021-08-19 | 2023-02-24 | 江苏美科太阳能科技股份有限公司 | Cooling liquid for large-size solar-grade silicon wafer diamond wire cutting |
| CN113881033A (en) * | 2021-09-30 | 2022-01-04 | 中国石油化工股份有限公司 | Method for preparing high-toughness high-resilience soft foam polyether polyol based on butylene oxide |
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