CN113026415A - Organic silicon modified oil, emulsion type drying cylinder stripping agent for papermaking and preparation method thereof - Google Patents
Organic silicon modified oil, emulsion type drying cylinder stripping agent for papermaking and preparation method thereof Download PDFInfo
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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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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
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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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
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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
- D21H21/22—Agents rendering paper porous, absorbent or bulky
- D21H21/24—Surfactants
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Abstract
The invention belongs to the field of papermaking materials, and particularly relates to organic silicon modified oil, which has the following structure as shown in formula 1:
wherein m, n and l are positive integers; m is more than or equal to 50, n is more than or equal to 10, and l is more than or equal to 7; alkane- (CH)2)l‑CH3The molar mass of the organic silicon modified oil is 10 to 35 percent of the molar mass of the organic silicon modified oil. After the organic silicon modified oil is applied to the emulsion type drying cylinder stripping agent for papermaking, the compatibility of organic silicon, a cylinder sticking agent and other auxiliaries is improved by compounding an emulsifier, a super wetting agent and a solubilizer, the produced paper has good bulk and softness, and the organic silicon modified oil is uniformly spread on the surface of the paper, is well wetted and cannot be gathered to generate oil spots.
Description
Technical Field
The invention relates to the field of papermaking materials, in particular to organic silicon modified oil, an emulsion type drying cylinder stripping agent for papermaking and a preparation method thereof.
Background
The tissue drying process is carried out in a young's dryer where the paper sheet is subjected to a doctor blade creping process to impart the appropriate softness, bulk and elongation to the paper. In the process, the wrinkling process can be guaranteed to be stably carried out at a high speed by the synergistic effect of multiple auxiliaries, so that a drying cylinder is protected, the paper drying efficiency is improved, the production efficiency is improved, the replacement speed of the wrinkling scraper is reduced, the service life of the scraper is prolonged, and the paper quality is improved. The auxiliary agents include a cylinder sticking agent, a stripping agent, a softening agent, a coating modifying agent and the like.
Among them, the release agent and the softening agent have a great influence on the sheet quality of the household paper. Firstly, the modern paper making industry mostly uses regenerated paper pulp which contains impurities and colloidal substances and generates larger adhesion force to a drying cylinder, in addition, the production efficiency is seriously influenced by the occurrence of cylinder sticking, paper dusting, napping, paper breaking and other phenomena due to the large use of non-wood fibers, particularly the continuous increase of the proportion of secondary fibers for making paper, and in the process, the stripping agent plays a good lubricating role and ensures that a paper machine stably runs at a high speed. The creping process transfers the paper sheet to the surface of a drying cylinder, and then the adhered paper sheet is creped and peeled off by a scraper, in the process, the drying cylinder peeling agent not only reduces the cylinder sticking phenomenon of the paper sheet, but also ensures the cleanness of a dry net, has a lubricating effect on the scraper and prolongs the service life of the scraper.
Conventional strippers are generally non-aqueous and are typically oily compositions of mineral oil, a combination emulsifier, solubilizer, and activator. Firstly, the dosage of the compound emulsifier is large, the emulsifier is remained on the household paper and is easy to generate yellowing and odor problems, and secondly, if the diffusion speed of the oily substance in water is not fast enough, the oily substance has poor compatibility with the water-soluble cylinder sticking agent, so that the spray head is easy to block, and the production efficiency is influenced. For example, Chinese patent CN110484138A discloses a paper-making dryer peeling agent and a preparation method thereof, which comprises 15-80 parts of alkane oil, 20-60 parts of oiliness agent, 5-50 parts of emulsifier and 2-15 parts of activator by weight; the oiliness agent is one or more of tall oil fatty acid, tall oil, erucic acid and oleic acid hydroxyethyl imidazoline, and the emulsifier is one or more of oleic acid triethanolamine soap, tween 80, span 80, polyethylene glycol dioleate, polyethylene glycol monooleate and alkylphenol ethoxylates.
The organic siloxane has better lubricating effect and soft hand feeling than mineral oil, and stable emulsion can be prepared by using the organic siloxane as base oil and matching with a small amount of emulsifier. For example, Chinese patent CN110964436A discloses an organic silicon emulsion type paper machine dry net stripping agent, which comprises dimethyl silicone oil, double-end amino modified silicone oil, a compound emulsifier and glacial acetic acid; the stripping agent is prepared by emulsifying dimethyl silicone oil serving as a main component and a small amount of amino-terminated silicone oil serving as an auxiliary component, so that the product is stable in structure, the quality of finished paper is not influenced by yellowing, and the problem of dry net adhesion is solved.
Chinese patent CN109267422A discloses another water-based silicone drying cylinder stripping agent and a preparation method thereof, wherein the water-based silicone drying cylinder stripping agent comprises the following raw materials in parts by weight: 30-40 parts of polydimethylsiloxane emulsion, 10-20 parts of hydroxyl modified polydimethylsiloxane, 10-20 parts of polymethylhydrosiloxane, 5-10 parts of polymethylvinylsiloxane, 5-10 parts of emulsifier, 50-70 parts of deionized water, 1-5 parts of acid, 10-20 parts of solubilizer and 0.01-0.001 part of preservative. Compared with the traditional mineral oil products, the water-based organic silicon drying cylinder stripping agent is a water-based product, is mainly applied to toilet paper, and has the advantages of no peculiar smell, environmental protection, no pollution and excellent effect.
Because the surface properties of the organic silicon oil and other additives are greatly different, some organic silicon emulsions are easy to gather into oil spots on the surface of paper.
Disclosure of Invention
The invention aims to provide organic silicon modified oil, an emulsion type drying cylinder stripping agent for papermaking and a preparation method thereof.
Unless otherwise specified, the percentages and parts in the present invention are in weight percent.
In order to achieve the purpose, the invention provides the following technical scheme:
an organosilicon modified oil, the structure of which is described in formula 1 below:
wherein m, n and l are positive integers;
m is more than or equal to 50, n is more than or equal to 10, and l is more than or equal to 7; alkane- (CH)2)l-CH3The molar mass of the organic silicon modified oil is 10 to 35 percent of the molar mass of the organic silicon modified oil.
In the above silicone-modified oil, l is 11, alkane- (CH)2)11-CH3The molar mass of (b) is 13.9-23.23% of the molar mass of the organosilicon modified oil.
In the organic silicon modified oil, the viscosity is 5-2000 mPa.
In the organic silicon modified oil, the viscosity is 100-1000 mPa.s.
Meanwhile, the invention also discloses a preparation method of the organic silicon modified oil, which is prepared by the one-step reaction of hydrogen-containing polysiloxane and vinyl-containing alkane in the presence of a catalyst;
the structural formula of the hydrogenpolysiloxane is shown as formula 2:
the vinyl-containing alkane has a carbon number greater than 8.
In the above-described method for producing an organosilicon-modified oil; the mass ratio of the hydrogen-containing polysiloxane to the vinyl-containing alkane is 65-90: 10-35; the catalyst is one of chloroplatinic acid, Speier catalyst and Karstedt catalyst.
The catalyst has the dosage of 5-25ppm converted into Pt content, the reaction temperature is 50-100 ℃, and the reaction time is 2-4 hours.
Meanwhile, the invention also discloses an emulsion type dryer stripping agent for papermaking, which comprises the following materials:
20-50 parts of any one of the above organosilicon modified oils;
2-10 parts of surfactant
2-5 parts of solubilizer
40-70 parts of deionized water.
In the emulsion type drying cylinder stripping agent for papermaking, the surfactant comprises one or a mixture of more of linear chain or branched chain fatty alcohol-polyoxyethylene ether and super wetting agent
The oil-soluble emulsifier and the water-soluble emulsifier are matched with each other, which is beneficial to reducing the dosage of the emulsifier.
The water-soluble emulsifier has a longer EO chain segment, so that the emulsion prepared by compounding the emulsifier has better stability at high temperature, and the emulsion breaking phenomenon is not easy to occur due to high temperature when the stripping agent is sprayed on the surface of paper.
The compound surfactant contains super wetting agent, the super wetting agent comprises but is not limited to super wetting agent of organic silicon, or dioctyl sulfosuccinate and super wetting agent with similar structure, the super wetting agent can rapidly reduce surface tension, so that the surface tension of the emulsion is reduced to be less than 27 dynes, and the organic silicon emulsion type stripping agent has good wetting capability.
The dosage of the compounded surfactant is 2-10 parts, preferably 3-6 parts, wherein the dosage of the oil-soluble emulsifier (super wetting agent) is preferably 1.5-2 parts, the dosage of the water-soluble emulsifier (fatty alcohol-polyoxyethylene ether) is preferably 2-2.5 parts, and the dosage of the super wetting agent is preferably 0.5-1 part.
In the emulsion type dryer peeling agent for papermaking, the solubilizer is one or a combination of more of propylene glycol, glycerol, polyethylene glycol, polyglycerol and polypropylene glycol monomethyl ether.
The function of the solubilizer is to enhance the diffusion speed of the emulsion in water, so that the organic silicon emulsion type stripping agent can be quickly diluted and is mutually soluble with other additives, and the difference of surface properties is not generated. The solubilizer is a polyalcohol chemical capable of mutually dissolving water and organic matters, the solubilizer is suitable for proper amount, cannot play a role if the solubilizer is too small, and can cause emulsion instability if the solubilizer is too high, wherein the solubilizer is 2-5 parts, and the preferable amount is 2.5-4 parts.
Finally, the invention also discloses a preparation method of the emulsion type drying cylinder stripping agent for papermaking, which comprises the following steps:
step 1: mixing oil-soluble surfactant and organic silicon modified oil uniformly to obtain an oil phase;
step 2: dissolving fatty alcohol-polyoxyethylene ether and a solubilizer in a water-soluble surfactant in water to prepare an emulsifier aqueous solution with certain solubility;
and (3) slowly adding the emulsifier aqueous solution in the step (2) into the oil phase in the step (1), stirring the emulsifier aqueous solution into a water-in-oil paste while adding the emulsifier aqueous solution, and finally adding deionized water to ensure that the paste is converted into a stable emulsion of the water-in-oil.
Fatty alcohol polyoxyethylene ethers are oily and aqueous, being oily if the EO chain is short and aqueous if the EO chain is long. For example, in the examples AEO-3 is oil soluble and suitable for blending with the silicone modified oil of the oil phase, while L-23 is aqueous and must be blended with water to disperse well. In addition, super wetting agents are generally aqueous and must be mixed with water to disperse well.
The D50 particle size range of the emulsion type drying cylinder stripping agent is between 0.26nm and 0.87nm through the detection of a laser particle size analyzer. The preparation method comprises but is not limited to homogenizing the emulsion prepared in the step above for 2-3 times under 40-100 MPa by a high-pressure homogenizer. After passing through the high pressure homogenizer, the particle size of the emulsion is further reduced.
Compared with the prior art, the invention has the beneficial effects that:
the emulsion type drying cylinder stripping agent for papermaking improves the compatibility of organic silicon, a cylinder sticking agent and other auxiliaries by compounding an emulsifier, a super wetting agent and a solubilizer, and produced paper has good bulk and softness, and organic silicon modified oil is uniformly spread on the surface of the paper, is well wetted and cannot be gathered to generate oil spots.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Synthesizing organic silicon modified oil:
the organosilicon modified oil synthesized by hydrosilylation has a general structural formula
Wherein m, n and l are natural numbers more than 1, preferably m is more than 50, n is more than 10, the ratio of m/n is more than 5, preferably l is more than or equal to 7, and the molar mass of the alkane accounts for 10-35% of the molecular molar mass.
TMS stands for tetramethylsilane.
The organosilicon modified oil is prepared by the one-step reaction of hydrosiloxane and alkane containing vinyl in the presence of catalyst, and the alkane containing vinyl is known to be a thin gas at carbon atoms of 2 and 3, and is known to be a liquid with a lower boiling point when the carbon atom number is increased to 6, so that the alkane containing vinyl is not suitable for being used as a reactant in hydrosilylation reaction at higher temperature. Therefore, l is preferably 7 or more, and in the following examples, vinyl-containing alkanes are all exemplified by 1-dodecene.
Performance detection method
The centrifugal stability test was carried out using an 80-1 electric centrifuge manufactured by jinfeng instruments ltd. And (3) putting 10ml of the emulsion into a 10ml centrifuge tube, centrifuging for 15min in a centrifuge at the rotating speed of 3000r/min, then taking out, and observing whether the state of the emulsion in the centrifuge tube is stable or not and whether the phenomenon of water outlet or oil floating occurs or not. If unstable, record how many milliliters of water are coming out from the bottom and how many milliliters of floating oil are coming out from the top.
Emulsion particle size test Using an Oumec LS-909 laser particle sizer to test the particle size distribution of the emulsion dispersed in water, record D50
The dispersion speed in water 1L of purified water was poured into a 1L peeling beaker, then a drop of the emulsion was sucked up with a 2.5ml pipette, dropped into the water from a height of 50cm, the dispersion speed of the emulsion in the water was observed, and the time required from the start of dropping the emulsion to the uniform distribution of the emulsion particles throughout the beaker was recorded, the longer the time, the slower the dispersion speed.
Oil spots are observed by visual inspection and recorded on 1 square meter paper sheets, and dark oil spots with a diameter greater than 0.2cm
Synthesis example 1
The hydrogen-containing silicone oil RH-H138, Si-H0.170-185% (Si-H0.170-185% means the percentage of H atomic mass in the whole formula 2), the viscosity is 90-130 cst, the number average molecular weight is 10532 by GPC test, and the molecular weight distribution coefficient PDI is 2.3.
Adding hydrogenpolysiloxane RH-H138150 g and 45.4g of 1-dodecene into a 250ml three-neck bottle respectively, then putting the three-neck bottle into a 75 ℃ oil bath pot, starting stirring, adding 0.4g of Carsterdt catalyst (model CSAT-F50050, Pt content 5000ppm) when the temperature of the material is raised to 70 ℃, reacting for 4 hours in the oil bath pot, discharging, collecting the product, namely the alkane modified organosiloxane, and testing the viscosity and the molecular weight of the product. The product has viscosity 480cst, molecular weight distribution coefficient PDI 2.8 and number average molecular weight 15200. The molar mass of the alkane in relation to the molar mass of the molecule was 23.2%.
Emulsification example 1
1. Oil-soluble emulsifier AEO-31.84 g, organic silicon super wetting agent SF-3370.35 g and alkane modified organic siloxane 36.6g synthesized in synthesis example 1 were mixed and stirred in a stirrer.
2. Dissolving 2.1g LAURETH-23 and 2.5g PEG200 in pure water to obtain 30% water solution, dripping into the mixed solution obtained in step 1, and stirring while dripping to obtain viscous white paste; LAURETH-23 is L-23 is polyoxyethylene lauryl ether.
3. Then, 45.9g of pure water was added to the paste obtained in step 2, and it was observed that the viscosity of the paste became thin and phase inversion occurred to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
Synthesis example 2
The hydrogen-containing silicone oil RH-H135, Si-H0.140-150%, viscosity 80-110 cst, number average molecular weight 9800 and molecular weight distribution coefficient PDI 2.3 tested by GPC.
Adding hydrogen-containing polysiloxane RH-H135150 g and 36.4g of 1-dodecene into a 250ml three-neck bottle respectively, then putting the three-neck bottle into an oil bath pan with the temperature of 75 ℃, starting stirring, adding 0.4g of Carsterdt catalyst (model CSAT-F50050, Pt content 5000ppm) when the temperature of the materials is raised to 70 ℃, reacting for 4 hours in the oil bath pan, discharging, collecting the product, namely the alkane modified organosiloxane, and testing the viscosity and the molecular weight of the product. The product has a viscosity of 400cst, a molecular weight distribution coefficient PDI of 2.4 and a number average molecular weight of 13200. The molar mass of the alkane in relation to the molar mass of the molecule was 18.0%.
Emulsification example 2
1. Oil-soluble emulsifier AEO-31.6 g, organic silicon super wetting agent SF-3370.5 g and alkane modified organic siloxane 38g synthesized in synthesis example 2 were mixed and stirred in a stirrer.
2. Dissolving LAURETH-23 1.5g and glycerol 2.0g in pure water to obtain 30% water solution, dripping into the mixed solution obtained in step 1, and stirring while dripping to obtain viscous white paste
3. Then, 48.2g of pure water was added to the paste obtained in step 2, and it was observed that the paste viscosity became thin and phase inversion occurred to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
Synthesis example 3
The hydrogen-containing silicone oil RH-H130, Si-H0.080-0.090%, viscosity of 80-110 cst, number average molecular weight of 9850 and molecular weight distribution coefficient PDI 2.2 in GPC test.
Adding hydrogen-containing polysiloxane RH-H130150 g and 24.4g of 1-dodecene into a 250ml three-neck bottle respectively, then putting the three-neck bottle into an oil bath pan with the temperature of 75 ℃, starting stirring, adding 0.4g of Carsterdt catalyst (model CSAT-F50050, Pt content 5000ppm) when the temperature of the materials is raised to 70 ℃, reacting for 4 hours in the oil bath pan, discharging, collecting the product, namely the alkane modified organosiloxane, and testing the viscosity and the molecular weight of the product. The product has a viscosity of 280cst, a molecular weight distribution coefficient PDI 2.3, and a number average molecular weight of 11200. The molar mass of the alkane in relation to the molar mass of the molecule was 13.8%.
Emulsification example 3
1. Oil-soluble emulsifier AEO-43.5 g, wetting agent dioctyl sulfosuccinate sodium salt OT-750.3 g and alkane modified organosiloxane 32.1g of synthesis example 3 were mixed and stirred in a stirrer.
2. Dissolving 6.0g AEO-12 and 2.0g propylene glycol methyl ether in pure water to obtain 30% aqueous solution, dripping into the mixed solution obtained in step 1, and stirring while dripping to obtain white paste
3. Then, 40.8g of pure water was added to the paste obtained in step 2, and it was observed that the paste viscosity became thin to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
Synthesis comparative example 1
The hydrogen-containing silicone oil RH-H3, Si-H0.28%, viscosity 90-110cst, number average molecular weight 9830 measured by GPC, molecular weight distribution coefficient PDI 2.4.
Adding hydrogenpolysiloxane RH-H3150 g and 70.7g of 1-dodecene into a 250ml three-neck bottle respectively, then putting the three-neck bottle into a 75 ℃ oil bath pot, starting stirring, adding 0.4g of Carsterdt catalyst (model CSAT-F50050, Pt content 5000ppm) when the temperature of the material is raised to 70 ℃, reacting for 4 hours in the oil bath pot, discharging, collecting the product, namely the alkane modified organosiloxane, and testing the viscosity and the molecular weight of the product. The product has high viscosity, 5000cst viscosity, molecular weight distribution coefficient PDI 4.1 and number average molecular weight 30500. The molar mass of the alkane in relation to the molar mass of the molecule was 32.0%. The high viscosity of the product is caused by side reaction, and the hydrogen-containing silicone oil generates crosslinking reaction, so that the molecular structure generates branching and the viscosity is increased sharply.
Emulsification comparative example 1
1. Oil-soluble emulsifier AEO-31.84 g, organosilicon super wetting agent SF-3370.35 g and synthetic comparative example 1 high viscosity alkane modified organic siloxane 36.6g are blended and stirred in a stirrer.
2. Dissolving 2.1g LAURETH-23 and 2.5g PEG200 in pure water to obtain 30% water solution, dripping into the mixed solution obtained in step 1, stirring while dripping to obtain white paste
3. Then, 45.9g of pure water was added to the paste obtained in step 2, and it was observed that the paste viscosity became thin to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
The emulsion centrifugation test gave 2ml of water, particle size 0.95 nm.
Comparative emulsification example 2
1. Oil-soluble emulsifier AEO-31.5 g, wetting agent dioctyl sulfosuccinate sodium salt OT-750.5 g and synthetic comparative example 1 high viscosity alkane modified organosiloxane 36.6g are blended and stirred in a stirrer.
2. Dissolving 2.5g LAURETH-23 and 2.5g PEG200 in pure water to obtain 30% water solution, dripping into the mixed solution obtained in step 1, stirring while dripping to obtain white paste
3. Then, 44.7g of pure water was added to the paste obtained in step 2, and it was observed that the paste viscosity became thin to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
The emulsion is stable, the particle size is 0.65nm, but the diffusion speed of the emulsion in water is very slow, and the compatibility with a water-soluble cylinder sticking agent such as PAE (polyamide epichlorohydrin resin) is poor.
Synthesis comparative example 2
The hydrogen-containing silicone oil RH-H8 has Si-H content of 0.06%, viscosity of 50-70cst, number average molecular weight 3200 and molecular weight distribution coefficient PDI 2.2 measured by GPC. Adding hydrogenpolysiloxane RH-H3150 g and 15.1g of 1-dodecene into a 250ml three-neck bottle respectively, then putting the three-neck bottle into a 75 ℃ oil bath pot, starting stirring, adding 0.4g of Carsterdt catalyst (model CSAT-F50050, Pt content 5000ppm) when the temperature of the material is raised to 70 ℃, reacting for 4 hours in the oil bath pot, discharging, collecting the product, namely the alkane modified organosiloxane, and testing the viscosity and the molecular weight of the product. The product has low viscosity of 85cst, molecular weight distribution coefficient PDI 2.5 and number average molecular weight 3540. The molar mass of the alkane in relation to the molar mass of the molecule was 9.1%.
Emulsification comparative example 3
1. Oil-soluble emulsifier AEO-31.84 g, organosilicon super wetting agent SF-3370.35 g and alkane modified organosiloxane 36.6g of synthetic comparative example 2 were blended and stirred in a stirrer.
2. Dissolving 2.1g LAURETH-23 and 2.5g PEG200 in pure water to obtain 30% water solution, dripping into the mixed solution obtained in step 1, stirring while dripping to obtain viscous white paste
3. Then, 45.9g of pure water was added to the paste obtained in step 2, and it was observed that the viscosity of the paste became thin and phase inversion occurred to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
The emulsion was unstable and 0.5ml of the floating oil was tested by centrifugation.
Emulsification comparative example 4
1. Oil-soluble emulsifier AEO-31.5 g, dioctyl sulfosuccinate sodium salt OT-750.5 g and alkane modified organosiloxane 36.6g of synthetic comparative example 2 were mixed and stirred in a stirrer.
2. Dissolving 2.5g LAURETH-23 and 2.5g PEG200 in pure water to obtain 30% water solution, dripping into the mixed solution obtained in step 1, stirring while dripping to obtain white paste
3. Then, 44.7g of pure water was added to the paste obtained in step 2, and it was observed that the paste viscosity became thin to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
The emulsion is unstable, 1ml of water is discharged by centrifugal test, and 0.2ml of floating oil is discharged.
Comparative emulsification example 5
1. Oil-soluble emulsifier AEO-43.8 g, wetting agent dioctyl sulfosuccinate sodium salt OT-750.5 g and alkane modified organosiloxane 31.6g of synthetic comparative example 2 were blended and stirred in a stirrer.
2. Dissolving 5.5g AEO-12 and 1.5g propylene glycol methyl ether in pure water to obtain 30% aqueous solution, dripping into the mixed solution obtained in step 1, and stirring while dripping to obtain white paste
3. Then, 40.8g of pure water was added to the paste obtained in step 2, and it was observed that the paste viscosity became thin to obtain a white emulsion
4. The prepared emulsion was passed through a high pressure homogenizer and homogenized at 40MPa for 2 times.
The emulsion was stable, particle size 0.46nm. when tested on the customer line, significant oil spotting on the paper sheet was observed.
TABLE 1 results of the experiment
In conclusion, the emulsion type dryer peeling agent has the characteristic of low emulsifier consumption, the produced finished paper has the advantages of low smell and no yellowing, the organosilicon modified oil endows the paper with unique soft hand feeling, the compatibility of the organosilicon modified oil and a cylinder sticking agent is very good, the high-speed operation of a paper machine is not influenced, and the produced paper has no oil spots.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. An organosilicon modified oil, characterized by the following formula 1:
wherein m, n and l are positive integers;
m is more than or equal to 50, n is more than or equal to 10, and l is more than or equal to 7; alkane- (CH)2)l-CH3The molar mass of the organic silicon modified oil is 10 to 35 percent of the molar mass of the organic silicon modified oil.
2. The silicone-modified oil of claim 1, wherein l is 11, alkane- (CH)2)l-CH3The molar mass of (b) is 13.9-23.23% of the molar mass of the silicone modified oil.
3. The silicone-modified oil of claim 1, having a viscosity in the range of 5 to 2000 mpa.s.
4. The silicone-modified oil of claim 1, having a viscosity in the range of 100 to 1000 mpa.s.
5. A process for the preparation of the silicone-modified oil as claimed in any of claims 1 to 4, which is prepared by a one-step reaction of a hydrogenpolysiloxane and a vinyl-containing alkane in the presence of a catalyst;
the structural formula of the hydrogenpolysiloxane is shown as formula 2:
the vinyl-containing alkane has a carbon number greater than or equal to 8.
6. The method for preparing silicone-modified oil according to claim 5, wherein the mass ratio of the hydrogenpolysiloxane to the vinyl-containing alkane is 65-90: 10-35; the catalyst is one of chloroplatinic acid, Speier catalyst and Karstedt catalyst.
7. The emulsion type drying cylinder stripping agent for papermaking is characterized by comprising the following materials:
20-50 parts of the organic silicon modified oil as described in any one of claims 1 to 4;
2-10 parts of surfactant
2-5 parts of solubilizer
40-70 parts of deionized water.
8. An emulsion dryer stripper as set forth in claim 7 wherein said surfactant comprises one or more mixtures of linear or branched fatty alcohol polyoxyethylene ethers, super wetting agents.
9. An emulsion dryer stripper for papermaking according to claim 7, wherein the solubilizer is one or more of propylene glycol, glycerol, polyethylene glycol, polyglycerol and polypropylene glycol methyl ether.
10. The preparation method of the emulsion type drying cylinder stripping agent for papermaking according to claim 8, characterized by comprising the following steps:
step 1: mixing oil-soluble surfactant and organic silicon modified oil uniformly to obtain an oil phase;
step 2: dissolving water-soluble surfactant and solubilizer in water to obtain emulsifier aqueous solution with certain solubility;
and (3) slowly adding the emulsifier aqueous solution in the step (2) into the oil phase in the step (1), stirring the emulsifier aqueous solution into a water-in-oil paste while adding the emulsifier aqueous solution, and finally adding deionized water to ensure that the paste is converted into a stable emulsion of the water-in-oil.
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