CN112500532A - Multifunctional lubricant, and preparation method and application thereof - Google Patents
Multifunctional lubricant, and preparation method and application thereof Download PDFInfo
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- CN112500532A CN112500532A CN202011464129.XA CN202011464129A CN112500532A CN 112500532 A CN112500532 A CN 112500532A CN 202011464129 A CN202011464129 A CN 202011464129A CN 112500532 A CN112500532 A CN 112500532A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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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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- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a multifunctional lubricant, a preparation method and an application thereof, wherein the multifunctional lubricant comprises the following raw materials in parts by weight: 100 parts of oxidized polyethylene wax, 5-30 parts of active monomer, 0.1-2 parts of initiator, 5-25 parts of alkali, 0-15 parts of composite emulsifier and 400 parts of water, wherein the active monomer comprises a first monomer and a second monomer, the first monomer is at least one of sodium allylsulfonate, sodium methallyl sulfonate and sodium styrene sulfonate, and the second monomer is at least one of itaconic acid, citraconic acid, acrylic acid, methacrylic acid, maleic anhydride, acrylamide and styrene. Also disclosed are methods of making the multifunctional lubricant and its use in papermaking. The introduction of sulfonic group and carboxyl group enhances the dispersibility of the sulfonic group and carboxyl group to filler and pigment, so that the product has excellent external lubricity and strong internal dispersion lubrication effect, the smoothness, glossiness and the like of paper are improved, meanwhile, the particle size is small, the specific surface area is large, paper scratches caused by overlarge particle size in the coating are avoided, and a better effect can be exerted.
Description
Technical Field
The invention relates to the field of papermaking, in particular to a multifunctional lubricant for papermaking industry and a preparation method and application thereof.
Background
Paper making, an ancient technology, has a long history in China, and since the east Han Chuan Lun improved paper making technology, paper is widely used, and is known as four major inventions in China. The development of the technology has been advanced to the present, the demand of paper is increasing, and the demand of paper is also increasing, and therefore, many special chemicals including various types of paper making coating lubricants, such as calcium stearate and oxidized polyethylene wax series products, are developed.
However, the oxidized polyethylene wax products on the market lack good wettability, so that the smoothness and the glossiness of the paper are not enough, and the requirements of people on the paper cannot be met. The anionic or nonionic modified oxidized polyethylene wax emulsion described in domestic literature and patents is obtained by improving water solubility for polymerization of oxidized polyethylene wax and acrylic monomers, and then saponifying and emulsifying. The Caochlore patent 'a preparation method of self-emulsifying wax' is that wax and acrylic acid monomer are polymerized, and then the self-emulsifying wax is obtained through saponification and vacuum dehydration, and the solid form is convenient for transportation, and when the self-emulsifying wax is used, the wax is directly melted and then heated and stirred without adding an emulsifier. However, the obtained emulsion has large particle size of 500-4000nm and poor stability, and the large particle size generally causes streaks on the surface of paper.
Therefore, the present inventors, aiming at the above technical problems, aim to invent a multifunctional lubricant, and a preparation method and application thereof.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a multifunctional lubricant, and a preparation method and application thereof.
In order to achieve the above purposes, the invention adopts the technical scheme that: the multifunctional lubricant comprises the following raw materials in parts by weight: 100 parts of oxidized polyethylene wax, 5-30 parts of active monomer, 0.1-2 parts of initiator, 5-25 parts of alkali, 0-15 parts of composite emulsifier and 400 parts of water, wherein the active monomer comprises a first monomer and a second monomer, the first monomer is at least one of sodium allylsulfonate, sodium methallyl sulfonate and sodium styrene sulfonate, and the second monomer is at least one of itaconic acid, citraconic acid, acrylic acid, methacrylic acid, maleic anhydride, acrylamide and styrene.
Preferably, the acid value of the oxidized polyethylene wax is 10-40mg KOH/g, and the molecular weight is 1000-4000 g/mol.
Preferably, the initiator is dibenzoyl peroxide. Dibenzoyl peroxide, also known as benzoyl peroxide, is commonly known as initiator BPO, a commonly used initiator.
Preferably, the base is at least one of an inorganic base and an organic base. The inorganic base is generally sodium hydroxide, potassium hydroxide, etc., and the organic base is generally diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hydroxyethylethylenediamine, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, methylethanolamine, dimethylethanolamine, etc., and when used, one kind may be selected, or two kinds may be mixed.
Preferably, the complex emulsifier is at least one of a nonionic surfactant and an anionic surfactant. The nonionic surfactant includes isotridecanol polyoxyethylene ether, AEO series, SPAN, TWEEN, fatty amine polyoxyethylene ether, etc., and the anionic surfactant is generally K12.
A preparation method of the multifunctional lubricant comprises the following steps:
firstly, graft polymerization, introducing nitrogen into a reaction kettle, then adding oxidized polyethylene wax, a first monomer and a solid second monomer, simultaneously uniformly mixing a liquid second monomer and an initiator, then adding the mixture into a dropwise adding tank, starting a stirrer in the reaction kettle, simultaneously heating the oxidized polyethylene wax to a molten state, starting the dropwise adding tank to dropwise add the second monomer and the initiator into the reaction kettle, and preserving heat at the temperature of 130 ℃ under the condition of 100 ℃ plus materials after dropwise adding;
secondly, neutralizing and emulsifying, namely mixing alkali and water according to the proportion, or mixing alkali, water and a composite emulsifier, uniformly stirring, heating to 80-100 ℃, adding the heat-preserved substances in the first step into the alkali water mixed solution under the stirring condition of 500 plus materials at 1000rpm, and uniformly stirring;
thirdly, discharging, and cooling the substances in the second step to 45 ℃ to obtain the multifunctional lubricant.
In general operation, nitrogen is introduced into a reaction kettle with a stirrer, a dropping tank, a condenser, a thermometer and a nitrogen interface for nitrogen protection, oxidized polyethylene wax, a first monomer and a solid second monomer are added, and simultaneously, a liquid second monomer and an initiator are uniformly mixed and added into the dropping tank for later use. Heating oxidized polyethylene wax to 90-130 ℃ for melting under the stirring condition, dropwise adding into a dropwise adding tank for 1-4h, and then preserving heat at 100-130 ℃ for 1-4 h. Preparing mixed solution of alkali and water, or mixed solution of alkali, water and composite emulsifier, stirring, and keeping the temperature at 80-100 deg.C for use. And (3) under stirring at 1000rpm for 500-. And obtaining the coating lubricant. Cooling to below 45 deg.C, and discharging.
Preferably, the invention also discloses the application of the multifunctional lubricant in papermaking.
Compared with similar products, the multifunctional lubricant has the advantages that the polarity and water solubility of the polyethylene wax are increased by grafting the functional monomer containing sulfonic acid groups and carboxyl groups, so that the polyethylene wax is easier to emulsify, and the emulsion with high stability can be prepared by using little or no emulsifier. Meanwhile, the prepared finished product has small grain diameter of about 50-500 nm. The introduction of sulfonic group and carboxyl group strengthens the dispersibility of the sulfonic group and carboxyl group to the filler and pigment, so that the product has excellent external lubricity and stronger internal dispersion lubrication effect, and the smoothness, the glossiness and the like of the paper are improved. Meanwhile, the particle size is small, the specific surface area is large, paper scratches caused by overlarge particle size in the coating can be avoided, and a better effect can be exerted.
The preparation method of the multifunctional lubricant has the beneficial effects that the commercially available oxidized polyethylene wax and the sulfonic group-containing active monomer are subjected to graft polymerization under the action of the initiator to increase the hydrophilic structure. Then adding the mixture into a mixed solution of alkali and water or a mixed solution of alkali, water and a compound emulsifier, and preparing a finished product by one step. The emulsifying dispersivity, the stability and the wettability are improved, and the high-efficiency and high-stability coating lubricant is obtained.
The multifunctional lubricant has the beneficial effects that the multifunctional lubricant is used in papermaking, so that paper has excellent external lubricity and strong internal dispersion lubrication effect, and the smoothness, the glossiness and the like of the paper are improved.
Detailed Description
The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention, and to clearly and unequivocally define the scope of the present invention.
Example 1
Introducing nitrogen into a 250ml flask with a stirrer, a dropping tank, a condenser, a thermometer and a nitrogen interface, and adding 100g of oxidized polyethylene wax, 30g of water, 8g of sodium allylsulfonate and 4g of itaconic acid for later use. 12g of acrylic acid and 0.25g of BPO are uniformly mixed and added into a dripping tank for standby. Heating the oxidized polyethylene wax material to 100 ℃ for melting, dropwise adding the oxidized polyethylene wax material for 1.5h, and then preserving the temperature for 2h at 110 ℃.
And (3) preparing alkaline water mixed solution, uniformly stirring 177g of water and 25g of diethanol amine, heating to 90 ℃, and keeping the temperature for later use. And (3) under stirring at 1000rpm for 500-. Cooling to below 45 deg.C, and discharging. The obtained coating lubricant is light yellow semitransparent liquid with the content of about 40 percent and the particle size of about 200nm and 300 nm.
Example 2
A250 ml flask with a stirrer, a dropping tank, a condenser, a thermometer and a nitrogen interface is filled with nitrogen, and 100g of oxidized polyethylene wax, 30g of water, 2.5g of sodium styrene sulfonate, 4.5g of sodium allyl sulfonate and 3g of citraconic acid are added for later use. 5g of acrylic acid, 5g of methacrylic acid and 1g of BPO are uniformly mixed and added into a dropwise adding tank for later use. Heating the oxidized polyethylene wax material to 100 ℃ for melting, dropwise adding the oxidized polyethylene wax material for 1h, and then preserving the temperature for 2h at 110 ℃.
Preparing alkaline water mixed solution, uniformly stirring 268g of water and 25g of triethanolamine, heating to 90 ℃, and keeping the temperature for later use. And (3) under stirring at 1000rpm for 500-. Cooling to below 45 deg.C, and discharging. The coating lubricant is obtained and is a light yellow semitransparent liquid with the content of about 35 percent and the particle size of about 200 nm.
Example 3
Introducing nitrogen into a 250ml flask with a stirrer, a dropping tank, a condenser, a thermometer and a nitrogen interface, adding 100g of oxidized polyethylene wax, 30g of water and 6g of sodium methallyl sulfonate, uniformly mixing 10g of acrylic acid, 5g of styrene and 0.5g of BPO, and adding the mixture into the dropping tank for later use. Heating the oxidized polyethylene wax material to 110 ℃ for melting, dropwise adding the oxidized polyethylene wax material for 2 hours, and then preserving the temperature at 110 ℃ for 2 hours.
Preparing alkaline water mixed solution, uniformly stirring 215g of water and 17g of diethanol amine, heating to 90 ℃, and keeping the temperature for later use. And (3) under stirring at 1000rpm for 500-. Cooling to below 45 deg.C, and discharging. The coating lubricant was obtained as a pale yellow translucent liquid with a content of about 35% and a particle size of about 200 nm.
Example 4
Introducing nitrogen into a 250ml flask with a stirrer, a dropping tank, a condenser, a thermometer and a nitrogen interface, and adding 100g of oxidized polyethylene wax, 30g of water, 7g of sodium allylsulfonate and 3g of maleic anhydride for later use. Mixing acrylic acid 15g and BPO 0.4g uniformly, and adding into a dripping tank for later use. Heating the oxidized polyethylene wax material to 110 ℃ for melting, dropwise adding the oxidized polyethylene wax material for 1.5h, and then preserving the temperature at 110 ℃ for 2 h.
Preparing emulsifier liquid, uniformly stirring 150g of water, 5g and 3g of isomeric tridecanol polyoxyethylene ether and fatty amine polyoxyethylene ether respectively and 24g of dimethylethanolamine, and heating to 90 ℃ for heat preservation for later use. And (3) under stirring at 1000rpm for 500-. Cooling to below 45 deg.C, and discharging. The coating lubricant is obtained, and is a light yellow semitransparent liquid with the content of about 45 percent and the particle size of about 100-400 nm.
Example 5
A250 ml flask with a stirrer, a dropping tank, a condenser, a thermometer and a nitrogen interface is filled with nitrogen, and 100g of oxidized polyethylene wax, 5g of citraconic acid, 7g of sodium styrene sulfonate and 6g of maleic anhydride are added for standby. BPO 0.6g was charged. Stirring and heating to 120 ℃ for melting, and keeping the temperature for 4 h.
Preparing emulsifier liquid, mixing 187g of water, AEO-9, 3g, 6g and 5g of fatty amine polyoxyethylene ether, K12 and 5g of sodium hydroxide uniformly, heating to 90 ℃, and keeping the temperature for later use. And (3) under stirring at 1000rpm for 500-. The coating lubricant is obtained, and is a light yellow semitransparent liquid with the content of about 40 percent and the particle size of about 100-200 nm.
Example 6
A250 ml flask equipped with a stirrer, a dropping tank, a condenser, a thermometer, and a nitrogen interface was purged with nitrogen, and 100g of oxidized polyethylene wax, 4g of citraconic acid, and 4.5g of sodium allylsulfonate were added thereto for use. 10.5g of methacrylic acid, 5g of styrene and 1.25g of BPO are uniformly mixed and added into a dropwise adding tank for later use. Heating the oxidized polyethylene wax material to 110 ℃ for melting under stirring, dropwise adding the monomer, finishing dropwise adding for 2h, and then preserving heat at 110 ℃ for 2 h.
Preparing emulsifier liquid, uniformly stirring 2g, 2g and 8g of water 355g, SPAN80, TWEEN80, fatty amine polyoxyethylene ether and 25g of triethanolamine, heating to 95 ℃, and keeping the temperature for later use. And (3) under stirring at 1000rpm for 500-. The coating lubricant is obtained as a yellowish translucent liquid with a content of about 30% and a particle size of about 50-150 nm.
The finished products prepared in examples 1-6 were tested. The properties of the resulting coated papers were measured by coating with the same coating formulation as a commercial control. The coating formulation is shown in table 1 and the coated paper properties are shown in table 2.
TABLE 1 coating formulations
GCC is ground calcium carbonate. Coating the coating on the copper plate base paper by using a No. 1 coating rod, wherein the coating weight is 15g/m2And then standby.
Calendering conditions are as follows: the coated paper samples were each calendered twice (4.5MPa,80 ℃) using a small calender. And (5) standby. And (5) adopting a national standard method to carry out performance test on the paper.
And (3) judging standard: the larger the smoothness and gloss, the better the effect.
TABLE 2 paper surface Properties
From the above application results, it can be seen that: compared with a comparative example, the lubricant prepared by the lubricant prepared in the embodiment 1-6 is applied to a coating formula, and the smoothness and the glossiness of the coated paper can be obviously improved.
In conclusion, compared with the coating lubricant prepared by the prior art, the coating lubricant prepared by the invention has the following characteristics and advantages: by grafting functional monomers containing sulfonic acid groups and carboxyl groups, the polarity and water solubility of the polyethylene wax are increased, so that the polyethylene wax is easier to emulsify, and the emulsion with high stability can be prepared by using less or no emulsifier. Meanwhile, the prepared finished product has small grain diameter of about 50-500 nm. The introduction of sulfonic group and carboxyl group strengthens the dispersibility of the sulfonic group and carboxyl group to the filler and pigment, so that the product has excellent external lubricity and stronger internal dispersion lubrication effect, and the smoothness, the glossiness and the like of the paper are improved. Meanwhile, the particle size is small, the specific surface area is large, paper scratches caused by overlarge particle size in the coating can be avoided, and a better effect can be exerted.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. A multifunctional lubricant characterized by: the material comprises the following components by weight: 100 parts of oxidized polyethylene wax, 5-30 parts of active monomer, 0.1-2 parts of initiator, 5-25 parts of alkali, 0-15 parts of composite emulsifier and 400 parts of water, wherein the active monomer comprises a first monomer and a second monomer, the first monomer is at least one of sodium allylsulfonate, sodium methallyl sulfonate and sodium styrene sulfonate, and the second monomer is at least one of itaconic acid, citraconic acid, acrylic acid, methacrylic acid, maleic anhydride, acrylamide and styrene.
2. The multifunctional lubricant of claim 1, wherein: the acid value of the oxidized polyethylene wax is 10-40mg KOH/g, and the molecular weight is 1000-4000 g/mol.
3. The multifunctional lubricant of claim 1, wherein: the initiator is dibenzoyl peroxide.
4. The multifunctional lubricant of claim 1, wherein: the alkali is at least one of inorganic alkali and organic alkali.
5. The multifunctional lubricant of claim 1, wherein: the compound emulsifier is at least one of nonionic surfactant and anionic surfactant.
6. The method for preparing the multifunctional lubricant according to any one of claims 1 to 5, characterized by comprising the steps of:
firstly, graft polymerization, introducing nitrogen into a reaction kettle, then adding oxidized polyethylene wax, a first monomer and a solid second monomer, simultaneously uniformly mixing a liquid second monomer and an initiator, then adding the mixture into a dropwise adding tank, starting a stirrer in the reaction kettle, simultaneously heating the oxidized polyethylene wax to a molten state, starting the dropwise adding tank to dropwise add the second monomer and the initiator into the reaction kettle, and preserving heat at the temperature of 130 ℃ under the condition of 100 ℃ plus materials after dropwise adding;
secondly, neutralizing and emulsifying, namely mixing alkali and water according to the proportion, or mixing alkali, water and a composite emulsifier, uniformly stirring, heating to 80-100 ℃, adding the heat-preserved substances in the first step into the alkali water mixed solution under the stirring condition of 500 plus materials at 1000rpm, and uniformly stirring;
thirdly, discharging, and cooling the substances in the second step to 45 ℃ to obtain the multifunctional lubricant.
7. Use of the multifunctional lubricant according to any one of claims 1 to 6 in papermaking.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116948328A (en) * | 2023-09-20 | 2023-10-27 | 山东宏福化学有限公司 | PVC lubricant and preparation method thereof |
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