CN115197411B - Long fatty chain modified polyether and polyether defoamer composition and preparation method thereof - Google Patents
Long fatty chain modified polyether and polyether defoamer composition and preparation method thereof Download PDFInfo
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- CN115197411B CN115197411B CN202210706311.4A CN202210706311A CN115197411B CN 115197411 B CN115197411 B CN 115197411B CN 202210706311 A CN202210706311 A CN 202210706311A CN 115197411 B CN115197411 B CN 115197411B
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- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/53—Polyethers; Polyesters
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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Abstract
The invention discloses a long fatty chain modified polyether, polyether defoamer composition and a preparation method thereof, wherein the long fatty chain modified polyether consists of 10-47% of long-chain fatty alcohol, 5-10% of ethylene oxide, 30-60% of propylene oxide, 10-30% of butylene oxide and 50-200ppm of bimetallic catalyst, has better spreadability and permeability to foam on the surface of the foam, and can better inhibit the foam. The long fatty chain modified polyether is prepared by mixing fatty alcohols with twelve, sixteen, twenty and twenty-eight carbon atoms according to a proportion, taking the fatty alcohols as an initiator, and accessing ethylene oxide, propylene oxide and butylene oxide, and controlling the pressure, temperature and time of the reaction without harsh reaction conditions. The polyether defoamer composition prepared from the long fatty chain modified polyether, the white carbon black and the alkali catalyst has the advantages of simple preparation method, simple composition, and product performance meeting the industrial production requirement, and can be applied to white water, adhesives, printing ink and the like in the wet end of papermaking.
Description
Technical Field
The invention belongs to the field of fine chemical defoamers, and particularly relates to a long fatty chain modified polyether and polyether defoamer composition and a preparation method thereof.
Background
Defoamers have evolved over decades to become an essential fine chemical aid in industrial production. The defoamer mainly comprises a (modified) organosilicon defoamer, a polyether (ester) defoamer, a fatty alcohol defoamer, a mineral oil defoamer and the like according to the difference of defoaming substances, and also comprises a small amount of alkynols and tributyl phosphate.
Because of the different defoaming environments and defoaming requirements, different classes of defoaming agents are used in different industries, such as organic silicon defoaming agents, which have lower surface tension, so that defoaming in an alcohol surfactant system has certain advantages and is commonly used in the industries of textile printing and dyeing, sewage treatment, petroleum exploitation, metal cleaning and the like, but organic silicon defoaming agents are easy to generate 'silicon spots', and the application of the organic silicon defoaming agents is limited; the fatty alcohol defoamer is mainly used for deaeration of the wet end of papermaking; mineral oil defoamers are relatively more used in latex systems and are popular in exterior wall architectural coatings; the polyether defoamer is used in the fields of papermaking wet end defoaming, industrial fermentation and industrial coating.
In view of various problems with defoamers, attempts have been made to improve their defoaming function by various methods to meet the needs of industrial production. Patent CN201410532431.2 discloses polyether with glycerin and dipropylene glycol as initiator, and then esterifying with stearic acid to obtain a defoamer with good hydrophilicity and wide application range as polyether defoamer; patent CN201710715946.X discloses a branched structure polyether defoamer, which uses trimethylolpropane, pentaerythritol or polyethylene polyamine as an initiator, connects ethylene oxide, propylene oxide and epoxy to finish under the action of a base catalyst, and the final product is compounded with octanoic acid, so that the obtained defoamer has excellent defoaming and foam inhibition effects when being used for metal spray cleaning. Patent CN200910213190.4 discloses a defoamer consisting of polyether, distearylethylenediamine, phosphate, peregal O-20, oleic acid diethanolamide and co-emulsifier for use in coating production. U.S. patent No. 5994415a discloses the use of oxyalkylated products of oligomeric glycerol fatty acids, products of propylene oxide and butylene oxide/styrene oxide reactions, as defoamers in coatings, wherein phenyl groups impart hydrophobicity to polyethers, improving defoamer performance. US6001887a discloses the use of silicone polyethers with white carbon black as defoamers in coatings. Patent CN201410634621.5 discloses a high-carbon fatty acid-terminated polyether ester defoamer for papermaking, which consists of high-carbon fatty acid-terminated polyether ester, high-carbon alcohol, high-carbon fatty acid ester, surfactant and dispersant, and has the characteristics of excellent defoaming and foam inhibiting performance under high-temperature strong alkali environment and low cost, does not form spots, and can improve the quality of paper. Therefore, attempts have been made to improve the defoaming function thereof by various methods to satisfy the needs of industrial production.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide the long fatty chain modified polyether, which is prepared by mixing fatty alcohol with specific carbon atoms in proportion as an initiator and then inoculating a plurality of alkylene oxides, can be used as an effective defoaming component, and has a good foam control effect.
The second object of the present invention is to provide a process for producing the above-mentioned long fatty chain-modified polyether.
It is a third object of the present invention to provide a polyether defoamer composition.
The fourth object of the present invention is to provide a method for preparing the polyether defoamer composition.
One of the purposes of the invention can be achieved by adopting the following technical scheme:
the long fatty chain modified polyether consists of the following components in percentage by mass:
further, the long-chain fatty alcohol is a composition of dodecanol, hexadecanol, eicosyl alcohol and octacosyl alcohol; wherein, the weight portions are 2-12 portions of dodecanol, 4-15 portions of hexadecanol, 2-12 portions of eicosanol and 2-8 portions of octacosanol.
Further, the mass of octacosanol is 1 of the total mass of dodecanol, hexadecanol and eicosanol: 12-1:2.5.
Further, the bimetallic catalyst is a double metal cyanide complex catalyst.
The second aim of the invention can be achieved by adopting the following technical scheme:
the preparation method of any one of the long fatty chain modified polyethers comprises the following steps:
adding long-chain fatty alcohol and a bimetallic catalyst into a reaction kettle, heating to 40-80 ℃ in vacuum, and adding mixed alkylene oxide for reaction, wherein the method comprises the following steps: continuously adding propylene oxide to react, and continuously introducing butylene oxide into the reaction kettle to react after the induction pressure is reached; wherein, in any process of adding propylene oxide and butylene oxide, ethylene oxide is added simultaneously for reaction; and (3) continuously maintaining the mixed alkylene oxide for 20-60min after the mixed alkylene oxide is completely filled, continuously filling propylene oxide into the reaction kettle, maintaining the temperature and aging for 30-80min after the reaction is completed, and cooling to obtain the polyether.
Further, the addition of mixed alkylene oxide reactions, including: continuously adding a mixture of ethylene oxide and propylene oxide for reaction, and continuously introducing the mixture of ethylene oxide and butylene oxide into the reaction kettle for reaction after the induction pressure is reached. Further, when mixed alkylene oxide is added, the temperature in the reaction kettle is 90-200 ℃ and the pressure is 0.01-1.0 MPa; and continuously introducing propylene oxide into the reaction kettle, wherein the temperature in the reaction kettle is 80-130 ℃ and the pressure is 0.01-0.8 MPa.
Further, before the temperature is raised in vacuum, nitrogen is used for sweeping air, and the materials are vacuumized and stirred.
The third object of the invention can be achieved by adopting the following technical scheme:
the polyether defoamer composition comprises any one of the long fatty chain modified polyether, and consists of the following components in percentage by mass:
90-97% of long fatty chain modified polyether
White carbon black 1-9%
1-5% of alkaline catalyst.
Further, the white carbon black is fumed silica and/or precipitated silica, the surface of the white carbon black is hydrophilic or hydrophobic, and the specific surface area of the white carbon black is 60-500m 2 /g。
Further, the alkaline catalyst is one or a combination of more than two of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, monoethanolamine, triethanolamine and ammonium bicarbonate.
The fourth object of the invention can be achieved by adopting the following technical scheme:
the preparation method of the polyether defoamer composition comprises the following steps:
adding long fatty chain modified polyether and an alkaline catalyst into a reaction container, adding white carbon black at a rotating speed of 500-3000rpm for 10-30min, then heating to react, and cooling after the reaction is finished to obtain the polyether defoamer composition.
Further, the conditions of the temperature rising reaction are as follows: vacuum-pumping and dewatering at 40-90deg.C and vacuum degree of-0.01-0.09 MPa for 0.5-2 hr, and then continuously raising temperature to 90-150deg.C for 0.5-4 hr.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the long fatty chain modified polyether, fatty alcohols with twelve, sixteen, twenty and twenty-eight carbon atoms are mixed according to a certain proportion to serve as an initiator, and ethylene oxide, propylene oxide and butylene oxide are added to obtain the long fatty chain modified polyether; the carbon atoms in the twelve-carbon, sixteen-carbon and twenty-carbon fatty alcohols differ by four, wherein the polyether with low carbon number has both an emulsifying function and a defoaming function, the polyether formed by the high-carbon twenty-eight fatty alcohol mainly has the defoaming function, and the emulsifying function of the polyether with low carbon number can disperse the polyether formed by the high-carbon twenty-eight fatty alcohol into fine particles. The polyether is beneficial to spreading on the surface of the foam, and the foam is better inhibited from forming or crushing; meanwhile, the ordered arrangement of the ethylene oxide and the propylene oxide, the ordered arrangement of the ethylene oxide and the butylene oxide and the arrangement of the terminal propylene oxide form a block structure, so that the permeability of the long-fatty-chain modified polyether is improved, and the long-fatty-chain modified polyether has a good foam control effect.
2. According to the preparation method of the long-fatty-chain modified polyether, the alkylene oxide is added into three parts of ethylene oxide and propylene oxide, and ethylene oxide and butylene oxide and propylene oxide, so that the formed long-fatty-chain modified polyether can form a certain block structure, and the permeability of the long-fatty-chain modified polyether is improved; the method is characterized in that the pressure, temperature and time of the reaction are controlled, and the harsh reaction conditions are not needed.
3. The polyether defoamer composition provided by the invention only comprises long fatty chain modified polyether, white carbon black and an alkali catalyst, has a good foam control effect, and can be applied to white water, adhesives, printing ink and the like in a papermaking wet end; the composition is simple, and the product performance meets the requirements of industrial production.
4. According to the preparation method of the polyether defoamer composition, the polyether defoamer composition with a good foam control effect is obtained by uniformly stirring the long fatty chain modified polyether and the white carbon black under the condition of the alkali catalyst, the reaction condition is mild, the preparation method is simple, and the preparation method is suitable for industrial production.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention, the following embodiments are used to clearly and completely describe the technical solution of the present invention:
along with the subdivision of industry, the content of the defoamer is more and more abundant, and the defoamer is changed into a current multifunctional and customized product with high compatibility requirement from the original simple defoaming. The same industry or the same process, the requirements of the anti-foaming agent can be quite different due to the fact that the technological parameters, raw material manufacturers and charging sequence are changed. Meanwhile, due to the differences of various application systems, the defoamers have different requirements.
Polyether defoamer is an important defoamer, has good hydrophile-lipophile adjustability, generally changes the proportion of ethylene oxide to propylene oxide, can obtain innumerable different hydrophile-lipophile polyethers, and selects the structure of the polyethers according to different use temperatures, but the defoaming function is difficult to meet the requirements of industrial production.
The inventor finds out through a large number of experiments that after mixing fatty alcohols with twelve, sixteen, twenty and twenty-eight carbon atoms according to a certain proportion and taking the fatty alcohols as an initiator to access ethylene oxide, propylene oxide and butylene oxide in a certain mode, a long fatty chain modified polyether product is obtained; among the aliphatic alcohol polyethers of different chain lengths, if the same amount of ethylene oxide, propylene oxide or butylene oxide is added, the hydrophobicity of the long-chain polyether is stronger due to the chain length of the initiator, and the defoaming and foam suppressing functions are also stronger. The long fatty chain modified polyether product thus obtained is somewhat less hydrophobic than twenty carbon; if the polyether of carbon twenty is not self-emulsifying, the polyether of carbon twelve can be self-emulsifying, so that other extra emulsifying agents are not needed to be added, the polyether of carbon twenty can be emulsified and dispersed, the polyether can be spread on the surface of the foam, and foam formation or foam breaking can be better inhibited.
Therefore, the long fatty chain modified polyether product is fully stirred and dispersed with the white carbon black to obtain the polyether defoamer composition, and the composition has a good foam control effect and can be applied to white water, adhesives, printing ink and the like in a papermaking wet end. The technical scheme of the invention is clearly and completely described by combining with the embodiment.
Example 1
A long fatty chain modified polyether and preparation thereof:
adding 26% of long-chain fatty alcohol and 65ppm of a bimetallic catalyst into a reaction kettle, wherein the long-chain fatty alcohol comprises 2 parts of dodecanol, 10 parts of cetyl alcohol, 12 parts of eicosanol and 2 parts of octacosanol; sweeping air by using nitrogen, vacuumizing, stirring, heating to 40 ℃, continuously adding a mixture of 2% of ethylene oxide and 30% of propylene oxide by mass fraction to enable the reaction kettle to reach induction pressure, continuously introducing a mixture of 3% of ethylene oxide and 30% of butylene oxide by mass fraction into the reaction kettle, and keeping the temperature in the reaction kettle at 130 ℃ and the pressure at 0.02MPa in the reaction process; and after the mixed alkyl is completely introduced, the mixed alkyl is continuously maintained for 40 minutes, and then the residual mass fraction of propylene oxide is continuously introduced into the mixed alkyl, wherein the content of materials in the reaction kettle reaches 100 percent. Keeping the temperature in the reaction kettle at 100 ℃ and the pressure at 0.8MPa, preserving heat and aging for 30min after the reaction is finished, and cooling and discharging to obtain the long-fatty-chain modified polyether.
Example 2
A long fatty chain modified polyether and preparation thereof:
adding 22% of long-chain fatty alcohol and 120ppm of a bimetallic catalyst into a reaction kettle, wherein the long-chain fatty alcohol comprises 12 parts of dodecanol, 4 parts of hexadecanol, 2 parts of icosanol and 4 parts of octacosanol, sweeping air by using nitrogen, vacuumizing, stirring, heating to 65 ℃, continuously adding a mixture of 4% of ethylene oxide and 40% of propylene oxide in mass fraction to enable the reaction kettle to reach induction pressure, and continuously introducing a mixture of 4% of ethylene oxide and 10% of butylene oxide into the reaction kettle, wherein the temperature in the reaction kettle is kept at 90 ℃ and the pressure is kept at 0.5MPa in the reaction process; and (3) continuously maintaining for 20min after the completion of the mixing, continuously introducing the residual mass fraction of propylene oxide into the mixture, maintaining the temperature in the reaction kettle at 85 ℃ and the pressure at 0.5MPa, maintaining the temperature and aging for 75min after the reaction is completed, and cooling and discharging to obtain the long-fatty-chain modified polyether.
Example 3
A long fatty chain modified polyether and preparation thereof:
adding 35% of long-chain fatty alcohol and 200ppm of a bimetallic catalyst into a reaction kettle, wherein the long-chain fatty alcohol comprises 2 parts of dodecanol, 15 parts of hexadecanol, 10 parts of icosanol and 8 parts of octacosanol, sweeping air by using nitrogen, vacuumizing, stirring, heating to 78 ℃, continuously adding a mixture of 4% of ethylene oxide and 20% of propylene oxide in mass fraction to enable the reaction kettle to reach induction pressure, and continuously introducing a mixture of 6% of ethylene oxide and 20% of butylene oxide into the reaction kettle, wherein the temperature in the reaction kettle is kept at 190 ℃ and the pressure is kept at 0.95MPa in the reaction process; continuously maintaining for 60min after the completion of the mixing of the alkylene oxide, continuously introducing the residual mass fraction of propylene oxide into the mixture, maintaining the temperature in the reaction kettle at 125 ℃ and the pressure at 0.02MPa, maintaining the temperature and aging for 45min after the reaction is completed, and cooling and discharging to obtain the long-fatty-chain modified polyether.
Example 4
A long fatty chain modified polyether and preparation thereof:
adding long-chain fatty alcohol with the mass fraction of 25% and 130ppm of a bimetallic catalyst into a reaction kettle, wherein the long-chain fatty alcohol comprises 6 parts of dodecanol, 8 parts of hexadecanol, 4 parts of icosanol and 7 parts of octacosanol, sweeping air by using nitrogen, vacuumizing, stirring, heating to 60 ℃, continuously adding a mixture with the mass fraction of 8% of ethylene oxide and 25% of propylene oxide to enable the reaction kettle to reach induction pressure, and continuously introducing a mixture with the mass fraction of 2% of ethylene oxide and 20% of butylene oxide into the reaction kettle, wherein the temperature in the reaction kettle is kept at 120 ℃ and the pressure is kept at 0.5MPa in the reaction process; and (3) continuously maintaining for 45min after the completion of the mixing, continuously introducing the residual mass fraction of propylene oxide into the mixture, maintaining the temperature in the reaction kettle at 125 ℃ and the pressure at 0.1MPa, maintaining the temperature after the reaction is completed, aging for 40min, and cooling and discharging to obtain the long-fatty-chain modified polyether.
Comparative example 1
Adding 25 parts of hexadecanol and 130ppm of a bimetallic catalyst into a reaction kettle, sweeping air with nitrogen, vacuumizing, stirring, heating to 60 ℃, continuously adding a mixture of 8 parts of ethylene oxide and 25 parts of propylene oxide to enable the reaction kettle to reach induction pressure, and continuously introducing a mixture of 2 parts of ethylene oxide and 20 parts of butylene oxide into the reaction kettle, wherein the temperature in the reaction kettle is kept at 120 ℃ and the pressure is kept at 0.5MPa in the reaction process; continuously maintaining for 45min after the completion of the mixing, continuously introducing 20 parts of propylene oxide into the mixture, maintaining the temperature in the reaction kettle at 125 ℃ and the pressure at 0.1MPa, maintaining the temperature and aging for 40min after the reaction is finished, and cooling and discharging to obtain the polyether.
Comparative example 2
Adding 6 parts of dodecanol, 8 parts of hexadecanol, 4 parts of eicosanol, 7 parts of octacosanol and 130ppm of a bimetallic catalyst into a reaction kettle, sweeping air by using nitrogen, vacuumizing, stirring, heating to 60 ℃, and then continuously adding a mixture of 10 parts of ethylene oxide, 45 parts of propylene oxide and 20 parts of butylene oxide to ensure that the reaction kettle reaches the induction pressure, wherein the temperature in the reaction kettle is kept at 120 ℃ and the pressure is kept at 0.5MPa in the reaction process; and (5) continuously maintaining for 45min after the completion of the mixing, and cooling and discharging to obtain the polyether.
Comparative example 3
The difference from example 4 is that 12 parts of dodecanol, 8 parts of cetyl alcohol, 4 parts of arachidyl alcohol and 1 part of octacosanol are included in the long-chain fatty alcohol.
Comparative example 4
The difference from example 4 is that 11 parts of dodecanol, 2 parts of hexadecanol, 4 parts of eicosyl alcohol and 8 parts of octacosyl alcohol are included in the long-chain fatty alcohol.
Comparative example 5
The difference from example 4 is that 3 parts of dodecanol, 5 parts of cetyl alcohol, 15 parts of arachidyl alcohol and 2 parts of octacosanol are included therein.
Comparative example 6
The difference from example 4 is that 16 parts of dodecanol, 4 parts of cetyl alcohol, 2 parts of arachidyl alcohol and 3 parts of octacosanol are included therein.
Example 5
Polyether defoamer composition and preparation thereof:
90 parts of the long fatty chain modified polyether of the embodiment 1 and 1 part of potassium hydroxide are added into a container in parts by weight, 9 parts of precipitated hydrophobic white carbon black is added within 30 minutes at the rotation speed of 550rpm, then the temperature is raised, the vacuum dehydration is carried out for 1 hour under the condition that the temperature is 45 ℃ and the vacuum degree is minus 0.05MPa, then the temperature is continuously raised to 140 ℃, the reaction is carried out for 2 hours, and the polyether defoamer composition is obtained after the reaction is completed and the cooling is carried out.
Example 6
Polyether defoamer composition and preparation thereof:
92 parts of the long fatty chain modified polyether of the example 2 and 5 parts of ammonium bicarbonate are added into a container in parts by weight, 3 parts of gas phase hydrophobic white carbon black is added in 12min at the rotating speed of 3000rpm, then the temperature is raised, the vacuum dehydration is carried out for 2h under the condition that the temperature is 70 ℃ and the vacuum degree is minus 0.09MPa, then the temperature is continuously raised to 120 ℃, the reaction is carried out for 0.5h, and the polyether defoamer composition is obtained after the reaction is cooled down.
Example 7
Polyether defoamer composition and preparation thereof:
94 parts of the long fatty chain modified polyether of the example 3 and 3 parts of sodium methoxide are added into a container in parts by weight, 3 parts of precipitated hydrophobic white carbon black is added in 18min at the rotation speed of 2200rpm, then the temperature is raised, the vacuum dehydration is carried out for 0.5h under the condition that the temperature is 90 ℃ and the vacuum degree is minus 0.02MPa, then the temperature is continuously raised to 95 ℃, the reaction is carried out for 4h, and the polyether defoamer composition is obtained after the reaction is cooled down.
Example 8
Polyether defoamer composition and preparation thereof:
97 parts of the long fatty chain modified polyether of the example 4 and 1 part of monoethanolamine are added into a container in parts by weight, 2 parts of gas-phase hydrophobic white carbon black is added in 25min at the rotation speed of 1200rpm, then the temperature is raised, the vacuum dehydration is carried out for 0.5h under the condition that the temperature is 80 ℃ and the vacuum degree is minus 0.06MPa, then the temperature is continuously raised to 95 ℃, the reaction is carried out for 4h, and the polyether defoamer composition is obtained after the reaction is completed and the cooling is carried out.
Comparative example 7
Preparation of polyether compositions
According to parts by weight, 97 parts of polyether of comparative example 1 and 1 part of monoethanolamine are added into a container, 2 parts of gas phase hydrophobic white carbon black is added within 25 minutes at the rotation speed of 1200rpm, then the temperature is raised, vacuum dehydration is carried out for 0.5 hour under the condition that the temperature is 80 ℃ and the vacuum degree is minus 0.06MPa, then the temperature is continuously raised to 95 ℃, the reaction is carried out for 4 hours, and the polyether composition is obtained after the reaction is completed, the cooling is carried out.
Comparative example 8
Preparation of polyether compositions
According to parts by weight, 97 parts of polyether of comparative example 2 and 1 part of monoethanolamine are added into a container, 2 parts of gas phase hydrophobic white carbon black is added within 25 minutes at the rotation speed of 1200rpm, then the temperature is raised, vacuum dehydration is carried out for 0.5h under the condition that the temperature is 80 ℃ and the vacuum degree is minus 0.06MPa, then the temperature is continuously raised to 95 ℃, the reaction is carried out for 4h, and the polyether composition is obtained after the reaction is completed, the cooling is carried out.
Comparative example 9
The polyether of comparative example 3 was used as the polyether, except that the other composition and the preparation method were the same, except that example 8 was used.
Comparative example 10
The polyether of comparative example 4 was used as the polyether, except that the other composition and the preparation method were the same, except that example 8 was used.
Comparative example 11
The polyether of comparative example 5 was used as the polyether, and the other composition and preparation method were the same, except for example 8.
Comparative example 12
The polyether of comparative example 6 was used as the polyether, except that the other composition and the preparation method were the same, except that example 8 was used.
Test examples
The foam inhibition performance of the sample is tested by using on-site newsprint papermaking white water as a test medium and a circulating bubbling instrument. The longer the foam takes to reach the same height, the better the foam suppression performance of the sample.
Test conditions: (1) temperature: 50 ℃; (2) white water usage: 300ml; (3) sample addition amount: 10. Mu.L; (4) test flow rate: 5L/min.
The test results are shown in table 1:
table 1 results of inhibition test of foam by the compositions of examples 5-8 and comparative examples 7-12
Note that: the volume is the total volume of foam and liquid.
As can be seen from Table 1, examples 5 to 8 use fatty alcohols having twelve, sixteen, twenty and twenty-eight carbon atoms mixed in a certain ratio as an initiator and were introduced with ethylene oxide, propylene oxide and butylene oxide to obtain long fatty chain modified polyethers; when the polyether defoamer composition is prepared by the white carbon black and alkali, the time required for the foam and the liquid of the sample to reach 1100ml is more than 10min in the test, and the time of comparative example 8 is greatly shortened, which shows that the addition sequence and the addition mode of the alkylene oxide have great influence on the foam inhibition effect of the formed polyether.
While comparative example 7 and comparative examples 9-10, varying the amounts of dodecanol, hexadecanol, eicosyl alcohol, and octacosanol resulted in different combinations; only hexadecanol was added as in comparative example 7, with only half of the foam suppressing effect of example 8; the ratio of alcohols was varied so that the ratio of the amounts of octacosanol used to the amounts of the other alcohols exceeded the limit value, as in comparative examples 9 and 10, and the foam suppressing effect was far less than that achieved by the ratios of the alcohol compositions of examples 5 to 8; while comparative examples 11 and 12 show that even though the ratio between the amount of octacosanol and the amount of other alcohols is within the limited range, the foam suppressing effect is significantly inferior to that of examples 5 to 8 because the amount of icosanol or dodecanol is not within the limited range. It also shows that the long fatty chain modified polyether obtained by mixing the fatty alcohols with twelve, sixteen, twenty and twenty-eight carbon atoms according to the proportion of the invention and adding ethylene oxide, propylene oxide and butylene oxide according to the preparation method of the invention as the initiator has better foam control effect after fully stirring and dispersing the obtained long fatty chain modified polyether and white carbon black.
In summary, according to the long-fatty-chain modified polyether disclosed by the invention, fatty alcohols with twelve, sixteen, twenty and twenty-eight carbon atoms are mixed according to a certain proportion to be used as an initiator, and ethylene oxide, propylene oxide and butylene oxide are added to obtain the long-fatty-chain modified polyether; has better spreadability and permeability to foam on the surface of the foam, and has better foam inhibition effect. The polyether defoamer composition prepared by the white carbon black and the alkali catalyst can be applied to white water, adhesives, printing ink and the like in a papermaking wet end; the composition is simple, and the product performance meets the requirements of industrial production; and the reaction condition is mild, the preparation method is simple, and the method is suitable for industrial production.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (7)
1. The long fatty chain modified polyether is characterized by comprising the following components in percentage by mass:
the long-chain fatty alcohol is a composition of dodecanol, hexadecanol, eicosyl alcohol and octacosyl alcohol; wherein, the weight portions are 2 to 12 portions of dodecanol, 4 to 15 portions of hexadecanol, 2 to 12 portions of eicosanol and 2 to 8 portions of octacosanol; the mass of the octacosanol is 1 of the total mass of the dodecanol, the hexadecanol and the eicosanol: 12-1:2.5;
the long fatty chain modified polyether is prepared by the following preparation method:
adding long-chain fatty alcohol and a bimetallic catalyst into a reaction kettle, heating to 40-80 ℃ in vacuum, and adding mixed alkylene oxide for reaction, wherein the method comprises the following steps: continuously adding propylene oxide to react, and continuously introducing butylene oxide into the reaction kettle to react after the induction pressure is reached; wherein, in any process of adding propylene oxide and butylene oxide, ethylene oxide is added simultaneously for reaction; and (3) continuously maintaining the mixed alkylene oxide for 20-60min after the mixed alkylene oxide is completely filled, continuously filling propylene oxide into the reaction kettle, maintaining the temperature and aging for 30-80min after the reaction is completed, and cooling and discharging to obtain the polyether.
2. A long fatty chain modified polyether according to claim 1, characterized in that,
when mixed alkylene oxide is added, the temperature in the reaction kettle is 90-200 ℃ and the pressure is 0.01-1.0 MPa; and continuously introducing propylene oxide into the reaction kettle, wherein the temperature in the reaction kettle is 80-130 ℃ and the pressure is 0.01-0.8 MPa.
3. A polyether defoamer composition, characterized by comprising the long fatty chain modified polyether of claim 1 or 2, and consisting of the following components in percentage by mass:
90-97% of long fatty chain modified polyether
White carbon black 1-9%
1-5% of alkaline catalyst.
4. A polyether defoamer composition according to claim 3, wherein,
the white carbon black is fumed silica and/or precipitated silica, the surface of the white carbon black is hydrophilic or hydrophobic, and the specific surface area of the white carbon black is 60-500m 2 /g。
5. A polyether defoamer composition according to claim 3, wherein,
the alkaline catalyst is one or a combination of more than two of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, monoethanolamine, triethanolamine and ammonium bicarbonate.
6. A process for preparing a polyether defoamer composition as claimed in any of claims 3 to 5, characterized in that it is prepared by the following preparation method:
adding long fatty chain modified polyether and an alkaline catalyst into a reaction container, adding white carbon black at a rotating speed of 500-3000rpm for 10-30min, then heating to react, and cooling after the reaction is finished to obtain the polyether defoamer composition.
7. The method for preparing a polyether defoamer composition according to claim 6, wherein:
the conditions of the temperature rising reaction are as follows: vacuum-pumping and dewatering at 40-90deg.C and vacuum degree of-0.01-0.09 MPa for 0.5-2 hr, and then continuously raising temperature to 90-150deg.C for 0.5-4 hr.
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