CN110924222A - Water-resistant oil-resistant dispersed rosin size and preparation method thereof - Google Patents
Water-resistant oil-resistant dispersed rosin size and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- 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
- D21H21/16—Sizing or water-repelling agents
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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
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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
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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
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
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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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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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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- 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
- D21H17/60—Waxes
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/62—Rosin; Derivatives thereof
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- 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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- D—TEXTILES; PAPER
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- 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 discloses a water-resistant oil-resistant dispersed rosin size and a preparation method thereof, and is characterized in that: the rosin sizing agent comprises 50-60% of rosin size, 30-40% of rosin maleic anhydride polyol ester, 20-30% of rosin, 20-30% of anhydride, 9-13% of oligomeric surfactant, 8-12% of reinforced rosin size, 8-10% of petroleum wax, 10-12% of tall oil, 8-10% of oxidized polyethylene wax, 6-8% of emulsifier, 15-25% of tricyclic diterpene oxygen-containing compound, 10-14% of polyacrylamide dispersant, 1-2% of catalyst, 20-30% of polyethylene glycol, 30-40% of alkylene oxide, 10-12% of antioxidant and 6-9% of esterifying agent, and the technical effect of the invention is as follows: the rosin size prepared by the formula and the preparation process has high water resistance, oil resistance and dispersibility.
Description
Technical Field
The invention relates to the technical field of rosin size and preparation technology, in particular to a water-resistant oil-resistant dispersed rosin size and a preparation method thereof.
Background
Sizing refers to a method of treating paper or board. The purpose of sizing paper is to impart the paper with resistance to fluid penetration. Almost all papers, except a few specialty papers, require different degrees of sizing. The sizing methods include internal sizing, also known as internal paper sizing, and surface sizing, which is a common method of sizing by adding sizing agents to the pulp during the wet end. Sizing agents are classified into two major types, rosin type and non-rosin type. Rosin sizing agent uses rosin as main body, mainly including rosin size, reinforced rosin size, paraffin rosin size and dispersed rosin size, etc. due to different glue-making processes and methods, rosin size is divided into brown rosin size, white rosin size and high-freeness rosin size. The non-rosin sizing agent mainly comprises paraffin latex, sodium stearate, polyvinyl alcohol, carboxymethyl cellulose, animal gum, casein, starch, synthetic gum and the like. The rosin sizing agent is mainly used for internal sizing, the non-rosin sizing agent is mainly used for surface sizing, the paper or the paperboard with special requirements also uses the non-rosin sizing agent as the internal sizing agent, the rosin size is a common sizing agent for paper and paperboard, the rosin and alkali are saponified into brown colloid, and the brown colloid is stirred by heating water or sprayed by steam and is diluted into emulsion by cold water for use. When in use, the pulp is added into the pulp after being filtered, alum or aluminum sulfate is used as a precipitating agent to precipitate the sizing material on the fiber, and then the finished product with water resistance is obtained after papermaking and drying.
The rosin size prepared by the existing rosin size formula and the process still has the problems of unsatisfactory water resistance, oil resistance and dispersibility.
Disclosure of Invention
The invention aims to provide a water-resistant oil-resistant dispersed rosin size and a preparation method thereof, so as to solve the problems in the background technology.
In order to realize the purpose, the invention provides the following technical scheme: a water-resistant and oil-resistant dispersed rosin size and a preparation method thereof are disclosed, wherein the water-resistant and oil-resistant dispersed rosin size comprises 50-60% of rosin size, 30-40% of rosin maleic anhydride polyol ester, 20-30% of rosin, 20-30% of anhydride, 9-13% of oligomeric surfactant, 8-12% of reinforced rosin size, 8-10% of petroleum wax, 10-12% of tall oil, 8-10% of oxidized polyethylene wax, 6-8% of emulsifier, 15-25% of tricyclic diterpene oxygen-containing compound, 10-14% of polyacrylamide dispersant, 1-2% of catalyst, 20-30% of polyethylene glycol, 30-40% of alkylene oxide, 10-12% of antioxidant and 6-9% of esterifying agent, and the preparation method specifically comprises the following steps:
the method comprises the following steps: adding the mass of the rosin maleic anhydride polyol ester serving as a reference into a No. 1 thermocouple reaction kettle for heating and melting, adding a catalyst, polyethylene glycol and alkylene oxide into the molten rosin maleic anhydride polyol ester, and reacting at the temperature of 300-340 ℃ for 1-2 hours;
step two: carrying out vacuum-pumping treatment on the No. 1 thermocouple reaction kettle in the step one under reduced pressure, keeping the vacuum degree less than or equal to 1kPa for 40-60 min, and removing low-boiling-point substances;
step three: cooling the No. 1 thermocouple reaction kettle in the step two to 50-100 ℃, adding an antioxidant, a reinforced rosin size and an esterifying agent in batches, wherein the adding time interval is 20-30 min, then reacting for 1-2 h at the temperature of 50-100 ℃, and discharging to obtain a rosin-based surfactant;
step four: adding rosin and acetic anhydride into a No. 2 thermocouple reaction kettle according to the weight ratio of 1:1, adjusting the temperature to 230-250 ℃, heating for 2-3 h, simultaneously removing produced acetic acid and excessive acetic anhydride, and repeating the operation until the acid value of a product is less than 10 to prepare rosin anhydride;
step five: adding petroleum wax and tall oil into a No. 2 thermocouple reaction kettle in the fourth step, mixing, heating to enable the rosin anhydride to reach a molten state, starting a stirrer to stir at the rotating speed of 20-30 revolutions per minute, uniformly mixing the liquid rosin anhydride, the petroleum wax and the tall oil, adding oxidized polyethylene wax, adjusting the temperature to 80-90 ℃, and stirring to react for 1-2 hours;
step six: adding an oligomeric surfactant into the No. 2 thermocouple reaction kettle in the fifth step, continuously stirring, increasing the rotating speed to 150-250 r/min when the solution becomes whitish, adding a proper amount of water and an emulsifier, cooling to normal temperature while stirring, and stopping stirring to obtain a modified rosin sizing agent;
step seven: adding rosin size into a No. 3 thermocouple reaction kettle, heating to 60-90 ℃, stirring for 1-2 hours, adding rosin-based surfactant and modified rosin sizing agent, continuously stirring for 5-9 hours, cooling to room temperature, sequentially adding tricyclic diterpene oxygen-containing compound and polyacrylamide dispersing agent, continuously stirring for 3-4 hours, and discharging to obtain the water-resistant oil-resistant dispersed rosin size.
Preferably, the oligomeric surfactant is one or more of a dimeric surfactant, a trimeric surfactant and a tetrameric surfactant.
Preferably, the reinforced rosin size contains 20-25% of free rosin, and is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and addition of a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by carrying out Diels-Alder reaction on rosin and fumaric acid.
Preferably, the petroleum wax is further added with a polyolefin additive, wherein the polyolefin additive is one or a mixture of polyethylene with the molecular weight of 1500-15000 and polyisobutylene with the molecular weight of 3500-40000, and the addition amount is 0.5-3%.
Preferably, the molecular structure of the tricyclic diterpene oxygen-containing compound contains a hydrogenated phenanthrene nucleus which is well compatible with hydrocarbons, and a highly polar carboxyl group.
Preferably, the oxidized polyethylene wax is a novel excellent polar wax, and the molecular chain of the oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl, has high compatibility with fillers, pigments and polar resins, and also has coupling property.
Preferably, the concentration of the solution of the polyacrylamide dispersant is 0.1-0.3%, namely 1 g-3 g of powder of the polyacrylamide dispersant is added into 1 liter of water.
Compared with the prior art, the invention has the beneficial effects that: the water-resistant oil-resistant dispersed rosin size and the preparation method thereof have the advantage that the rosin size prepared by the formula and the preparation process has higher water resistance, oil resistance and dispersibility.
1. The water-resistant and oil-resistant dispersed rosin size and the preparation method thereof are characterized in that the added oligomeric surfactant is a dimer surfactant, a trimer surfactant and a tetramer surfactant, and is added when the rosin sizing agent is modified, compared with the salt added for improving the surface activity, the temperature is increased or the anionic surfactant and the anionic surfactant are mixed, the ions are ensured to be closely connected when the rosin sizing agent is mixed and stirred, so that the strong interaction between the hydrocarbon chains is easier to generate, namely, the hydrophobic bonding force between the hydrocarbon chains is enhanced, and the repulsion tendency between the ion head groups is greatly weakened due to the chemical bond force, so that the rosin size has high surface activity; on the other hand, the chemical bond linkage between the two ionic head groups does not damage the hydrophilicity, and the surface activity is improved by the chemical bond linkage method to be obviously superior to that of the conventional commonly applied physical method, so that the prepared modified rosin sizing agent is more easily adsorbed on the surface of gas/liquid when being added into the prepared rosin size, thereby more effectively reducing the surface tension of the aqueous solution; the agglomeration is easier to generate micelle; the surface tension tendency is far greater than the tendency of aggregation to generate micelles, and the efficiency of the surface tension of the aqueous solution is reduced; compared with the common surfactant, especially the compound of the common surfactant and the nonionic surfactant, the synergistic effect on the reduction capability and the reduction efficiency of the surface tension of the aqueous solution can be generated, so that the aqueous solution has good calcium soap dispersion property, and the dispersibility of the prepared rosin size is improved.
2. The rosin maleic anhydride polyol ester is prepared by the addition of polyol esterified rosin and maleic anhydride, can improve the dryness of the rosin gum after coating and improve the water resistance and hardness, the added reinforced rosin gum contains 20-25% of free rosin, and the rosin is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and adding a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by performing Diels-Alder reaction on rosin and fumaric acid, can be used with white rosin size due to the fact that the particles of the fumaric rosin are smaller than the white rosin size, can improve the sizing effect, and has the advantages of high softening point, high acid value, high saponification value and strong antioxidant stability, and the antioxidant stability and the oxidant are enhanced, so that the antioxidant property and the water resistance of the prepared rosin size are improved.
3. The water-resistant and oil-resistant dispersed rosin size and the preparation method thereof, the added emulsifier is a surface active substance, the molecules of the emulsifier are provided with hydrophilic groups and lipophilic groups at the same time, the emulsifier is gathered on an oil/water interface, the interfacial tension can be reduced, and the energy required for forming emulsion can be reduced, so that the energy of the emulsion can be improved, the added tricyclic diterpene oxygen-containing compound has a hydrogenated phenanthrene nucleus which can be well dissolved with hydrocarbons in a molecular structure and also contains high-polarity carboxyl, so that the compatibility with rubber and synthetic resin is good, meanwhile, the rosin contains a hydrogenated phenanthrene nucleus with large steric hindrance, so that the tackifying effect is remarkable, and the oil resistance and the water resistance of the rosin size are greatly improved by combining the emulsifier and the tricyclic diterpene oxygen-containing compound.
4. The water-resistant and oil-resistant dispersed rosin size is widely used for producing damp-proof and waterproof wrapping paper, paperboard, surface coatings of certain textiles and candles, and is characterized in that added tall oil, also called paper pulp floating oil, is obtained by skimming soap on the surface of waste liquid of pine pulp produced by sulfate and then acidifying the soap, is dark oily liquid, has the density of 0.950-1.024, the iodine value of 135-216 and the saponification value of 142-185, has hydrophilic groups and hydrophilic oil bases, is combined with tall oil, and has stronger water resistance and oil resistance.
5. The added oxidized polyethylene wax is excellent novel polar wax, and the molecular chain of the oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl, so that the intermiscibility of the oxidized polyethylene wax with filler, pigment and polar resin is obviously improved. The modified rosin maleic anhydride polyether has the advantages that the wettability and the dispersibility in a polar system are superior to those of polyethylene wax, the modified rosin maleic anhydride polyether also has coupling performance, special performances such as low viscosity, high softening point and good hardness, nontoxicity, good thermal stability, low high-temperature volatility, excellent dispersibility on fillers and pigments, excellent external lubricity, strong internal lubrication effect and coupling effect, the production efficiency of rosin size processing can be improved, the production cost is reduced, the modified rosin maleic anhydride polyether polyol has good compatibility with rosin maleic anhydride polyol, and the moisture resistance and the water resistance at normal temperature are good.
Drawings
FIG. 1 is a table showing test results in the examples of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the 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.
Example 1
A water-resistant and oil-resistant dispersed rosin size and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps of 50% of rosin size, 30% of rosin maleic anhydride polyol ester, 20% of rosin, 20% of anhydride, 9% of oligomeric surfactant, 8-12% of reinforced rosin size, 8% of petroleum wax, 10% of tall oil, 8% of oxidized polyethylene wax, 6% of emulsifier, 15% of tricyclic diterpene oxygen-containing compound, 10% of polyacrylamide dispersant, 1% of catalyst, 20% of polyethylene glycol, 30% of alkylene oxide, 10% of antioxidant and 6% of esterifying agent, and the preparation method specifically comprises the following steps:
the method comprises the following steps: adding the mass of the rosin maleic anhydride polyol ester serving as a reference into a No. 1 thermocouple reaction kettle for heating and melting, adding a catalyst, polyethylene glycol and alkylene oxide into the molten rosin maleic anhydride polyol ester, and reacting at the temperature of 300-340 ℃ for 1-2 hours;
step two: carrying out vacuum-pumping treatment on the No. 1 thermocouple reaction kettle in the step one under reduced pressure, keeping the vacuum degree less than or equal to 1kPa for 40-60 min, and removing low-boiling-point substances;
step three: cooling the No. 1 thermocouple reaction kettle in the step two to 50-100 ℃, adding an antioxidant, a reinforced rosin size and an esterifying agent in batches, wherein the adding time interval is 20-30 min, then reacting for 1-2 h at the temperature of 50-100 ℃, and discharging to obtain a rosin-based surfactant;
step four: adding rosin and acetic anhydride into a No. 2 thermocouple reaction kettle according to the weight ratio of 1:1, adjusting the temperature to 230-250 ℃, heating for 2-3 h, simultaneously removing produced acetic acid and excessive acetic anhydride, and repeating the operation until the acid value of a product is less than 10 to prepare rosin anhydride;
step five: adding petroleum wax and tall oil into a No. 2 thermocouple reaction kettle in the fourth step, mixing, heating to enable the rosin anhydride to reach a molten state, starting a stirrer to stir at the rotating speed of 20-30 revolutions per minute, uniformly mixing the liquid rosin anhydride, the petroleum wax and the tall oil, adding oxidized polyethylene wax, adjusting the temperature to 80-90 ℃, and stirring to react for 1-2 hours;
step six: adding an oligomeric surfactant into the No. 2 thermocouple reaction kettle in the fifth step, continuously stirring, increasing the rotating speed to 150-250 r/min when the solution becomes whitish, adding a proper amount of water and an emulsifier, cooling to normal temperature while stirring, and stopping stirring to obtain a modified rosin sizing agent;
step seven: adding rosin size into a No. 3 thermocouple reaction kettle, heating to 60-90 ℃, stirring for 1-2 hours, adding rosin-based surfactant and modified rosin sizing agent, continuously stirring for 5-9 hours, cooling to room temperature, sequentially adding tricyclic diterpene oxygen-containing compound and polyacrylamide dispersing agent, continuously stirring for 3-4 hours, and discharging to obtain the water-resistant oil-resistant dispersed rosin size.
In this embodiment, the oligomeric surfactant is one or more of a dimeric surfactant, a trimeric surfactant and a tetrameric surfactant.
In the embodiment, the reinforced rosin size contains 20-25% of free rosin, and is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and addition of a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by carrying out Diels-Alder reaction on rosin and fumaric acid.
In the embodiment, the petroleum wax is further added with a polyolefin additive, wherein the polyolefin additive is one or two of polyethylene with the molecular weight of 1500-15000 and polyisobutylene with the molecular weight of 3500-40000, and the addition amount is 0.5-3%.
In this example, the molecular structure of the tricyclic diterpene oxygen-containing compound contains a hydrogenated phenanthrene nucleus that is well soluble in hydrocarbons, and a highly polar carboxyl group.
In the embodiment, the oxidized polyethylene wax is an excellent novel polar wax, and the molecular chain of the oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl, has high compatibility with fillers, pigments and polar resins, and also has coupling property.
In this embodiment, the concentration of the solution of the polyacrylamide dispersant is 0.1% to 0.3%, that is, 1g to 3g of powder of the polyacrylamide dispersant is added to 1 liter of water.
Example 2
A water-resistant and oil-resistant dispersed rosin size and a preparation method thereof, wherein the water-resistant and oil-resistant dispersed rosin size comprises 60% of rosin size, 40% of rosin maleic anhydride polyol ester, 30% of rosin, 30% of anhydride, 13% of oligomeric surfactant, 12% of reinforced rosin size, 10% of petroleum wax, 12% of tall oil, 10% of oxidized polyethylene wax, 8% of emulsifier, 25% of tricyclic diterpene oxygen-containing compound, 14% of polyacrylamide dispersant, 2% of catalyst, 30% of polyethylene glycol, 40% of alkylene oxide, 12% of antioxidant and 9% of esterifying agent, and the preparation method specifically comprises the following steps:
the method comprises the following steps: adding the mass of the rosin maleic anhydride polyol ester serving as a reference into a No. 1 thermocouple reaction kettle for heating and melting, adding a catalyst, polyethylene glycol and alkylene oxide into the molten rosin maleic anhydride polyol ester, and reacting at the temperature of 300-340 ℃ for 1-2 hours;
step two: carrying out vacuum-pumping treatment on the No. 1 thermocouple reaction kettle in the step one under reduced pressure, keeping the vacuum degree less than or equal to 1kPa for 40-60 min, and removing low-boiling-point substances;
step three: cooling the No. 1 thermocouple reaction kettle in the step two to 50-100 ℃, adding an antioxidant, a reinforced rosin size and an esterifying agent in batches, wherein the adding time interval is 20-30 min, then reacting for 1-2 h at the temperature of 50-100 ℃, and discharging to obtain a rosin-based surfactant;
step four: adding rosin and acetic anhydride into a No. 2 thermocouple reaction kettle according to the weight ratio of 1:1, adjusting the temperature to 230-250 ℃, heating for 2-3 h, simultaneously removing produced acetic acid and excessive acetic anhydride, and repeating the operation until the acid value of a product is less than 10 to prepare rosin anhydride;
step five: adding petroleum wax and tall oil into a No. 2 thermocouple reaction kettle in the fourth step, mixing, heating to enable the rosin anhydride to reach a molten state, starting a stirrer to stir at the rotating speed of 20-30 revolutions per minute, uniformly mixing the liquid rosin anhydride, the petroleum wax and the tall oil, adding oxidized polyethylene wax, adjusting the temperature to 80-90 ℃, and stirring to react for 1-2 hours;
step six: adding an oligomeric surfactant into the No. 2 thermocouple reaction kettle in the fifth step, continuously stirring, increasing the rotating speed to 150-250 r/min when the solution becomes whitish, adding a proper amount of water and an emulsifier, cooling to normal temperature while stirring, and stopping stirring to obtain a modified rosin sizing agent;
step seven: adding rosin size into a No. 3 thermocouple reaction kettle, heating to 60-90 ℃, stirring for 1-2 hours, adding rosin-based surfactant and modified rosin sizing agent, continuously stirring for 5-9 hours, cooling to room temperature, sequentially adding tricyclic diterpene oxygen-containing compound and polyacrylamide dispersing agent, continuously stirring for 3-4 hours, and discharging to obtain the water-resistant oil-resistant dispersed rosin size.
In this embodiment, the oligomeric surfactant is one or more of a dimeric surfactant, a trimeric surfactant and a tetrameric surfactant.
In the embodiment, the reinforced rosin size contains 20-25% of free rosin, and is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and addition of a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by carrying out Diels-Alder reaction on rosin and fumaric acid.
In the embodiment, the petroleum wax is further added with a polyolefin additive, wherein the polyolefin additive is one or two of polyethylene with the molecular weight of 1500-15000 and polyisobutylene with the molecular weight of 3500-40000, and the addition amount is 0.5-3%.
In this example, the molecular structure of the tricyclic diterpene oxygen-containing compound contains a hydrogenated phenanthrene nucleus that is well soluble in hydrocarbons, and a highly polar carboxyl group.
In the embodiment, the oxidized polyethylene wax is an excellent novel polar wax, and the molecular chain of the oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl, has high compatibility with fillers, pigments and polar resins, and also has coupling property.
In this embodiment, the concentration of the solution of the polyacrylamide dispersant is 0.1% to 0.3%, that is, 1g to 3g of powder of the polyacrylamide dispersant is added to 1 liter of water.
Example 3
A water-resistant and oil-resistant dispersed rosin size and a preparation method thereof, wherein the water-resistant and oil-resistant dispersed rosin size comprises 55% of rosin size, 35% of rosin maleic anhydride polyol ester, 25% of rosin, 25% of anhydride, 11% of oligomeric surfactant, 10% of reinforced rosin size, 9% of petroleum wax, 11% of tall oil, 9% of oxidized polyethylene wax, 7% of emulsifier, 20% of tricyclic diterpene oxygen-containing compound, 12% of polyacrylamide dispersant, 1.5% of catalyst, 25% of polyethylene glycol, 35% of alkylene oxide, 11% of antioxidant and 7.5% of esterifying agent, and the preparation method specifically comprises the following steps:
the method comprises the following steps: adding the mass of the rosin maleic anhydride polyol ester serving as a reference into a No. 1 thermocouple reaction kettle for heating and melting, adding a catalyst, polyethylene glycol and alkylene oxide into the molten rosin maleic anhydride polyol ester, and reacting at the temperature of 300-340 ℃ for 1-2 hours;
step two: carrying out vacuum-pumping treatment on the No. 1 thermocouple reaction kettle in the step one under reduced pressure, keeping the vacuum degree less than or equal to 1kPa for 40-60 min, and removing low-boiling-point substances;
step three: cooling the No. 1 thermocouple reaction kettle in the step two to 50-100 ℃, adding an antioxidant, a reinforced rosin size and an esterifying agent in batches, wherein the adding time interval is 20-30 min, then reacting for 1-2 h at the temperature of 50-100 ℃, and discharging to obtain a rosin-based surfactant;
step four: adding rosin and acetic anhydride into a No. 2 thermocouple reaction kettle according to the weight ratio of 1:1, adjusting the temperature to 230-250 ℃, heating for 2-3 h, simultaneously removing produced acetic acid and excessive acetic anhydride, and repeating the operation until the acid value of a product is less than 10 to prepare rosin anhydride;
step five: adding petroleum wax and tall oil into a No. 2 thermocouple reaction kettle in the fourth step, mixing, heating to enable the rosin anhydride to reach a molten state, starting a stirrer to stir at the rotating speed of 20-30 revolutions per minute, uniformly mixing the liquid rosin anhydride, the petroleum wax and the tall oil, adding oxidized polyethylene wax, adjusting the temperature to 80-90 ℃, and stirring to react for 1-2 hours;
step six: adding an oligomeric surfactant into the No. 2 thermocouple reaction kettle in the fifth step, continuously stirring, increasing the rotating speed to 150-250 r/min when the solution becomes whitish, adding a proper amount of water and an emulsifier, cooling to normal temperature while stirring, and stopping stirring to obtain a modified rosin sizing agent;
step seven: adding rosin size into a No. 3 thermocouple reaction kettle, heating to 60-90 ℃, stirring for 1-2 hours, adding rosin-based surfactant and modified rosin sizing agent, continuously stirring for 5-9 hours, cooling to room temperature, sequentially adding tricyclic diterpene oxygen-containing compound and polyacrylamide dispersing agent, continuously stirring for 3-4 hours, and discharging to obtain the water-resistant oil-resistant dispersed rosin size.
In this embodiment, the oligomeric surfactant is one or more of a dimeric surfactant, a trimeric surfactant and a tetrameric surfactant.
In the embodiment, the reinforced rosin size contains 20-25% of free rosin, and is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and addition of a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by carrying out Diels-Alder reaction on rosin and fumaric acid.
In the embodiment, the petroleum wax is further added with a polyolefin additive, wherein the polyolefin additive is one or two of polyethylene with the molecular weight of 1500-15000 and polyisobutylene with the molecular weight of 3500-40000, and the addition amount is 0.5-3%.
In this example, the molecular structure of the tricyclic diterpene oxygen-containing compound contains a hydrogenated phenanthrene nucleus that is well soluble in hydrocarbons, and a highly polar carboxyl group.
In the embodiment, the oxidized polyethylene wax is an excellent novel polar wax, and the molecular chain of the oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl, has high compatibility with fillers, pigments and polar resins, and also has coupling property.
In this embodiment, the concentration of the solution of the polyacrylamide dispersant is 0.1% to 0.3%, that is, 1g to 3g of powder of the polyacrylamide dispersant is added to 1 liter of water.
Testing and detecting: the rosin glues prepared in example 1, example 2 and example 3 and the rosin glue prepared in the prior art are respectively subjected to test detection on water resistance, oil resistance and dispersion performance, and a specific test data table is shown in fig. 1;
and (3) analyzing a detection result: the water resistance, oil resistance and dispersion performance of the rosin size prepared in example 1, example 2 and example 3 are equivalent and are obviously higher than that of the rosin size prepared in the prior art.
The invention has the beneficial effects that: the water-resistant oil-resistant dispersed rosin size and the preparation method thereof have the advantage that the rosin size prepared by the formula and the preparation process has higher water resistance, oil resistance and dispersibility.
The water-resistant and oil-resistant dispersed rosin size and the preparation method thereof are characterized in that the added oligomeric surfactant is a dimer surfactant, a trimer surfactant and a tetramer surfactant, and is added when the rosin sizing agent is modified, compared with the salt added for improving the surface activity, the temperature is increased or the anionic surfactant and the anionic surfactant are mixed, the ions are ensured to be closely connected when the rosin sizing agent is mixed and stirred, so that the strong interaction between the hydrocarbon chains is easier to generate, namely, the hydrophobic bonding force between the hydrocarbon chains is enhanced, and the repulsion tendency between the ion head groups is greatly weakened due to the chemical bond force, so that the rosin size has high surface activity; on the other hand, the chemical bond linkage between the two ionic head groups does not damage the hydrophilicity, and the surface activity is improved by the chemical bond linkage method to be obviously superior to that of the conventional commonly applied physical method, so that the prepared modified rosin sizing agent is more easily adsorbed on the surface of gas/liquid when being added into the prepared rosin size, thereby more effectively reducing the surface tension of the aqueous solution; the agglomeration is easier to generate micelle; the surface tension tendency is far greater than the tendency of aggregation to generate micelles, and the efficiency of the surface tension of the aqueous solution is reduced; compared with the common surfactant, especially the compound of the common surfactant and the nonionic surfactant, the synergistic effect on the reduction capability and the reduction efficiency of the surface tension of the aqueous solution can be generated, so that the aqueous solution has good calcium soap dispersion property, and the dispersibility of the prepared rosin size is improved. The rosin maleic anhydride polyol ester is prepared by the addition of polyol esterified rosin and maleic anhydride, can improve the dryness of the rosin gum after coating and improve the water resistance and hardness, the added reinforced rosin gum contains 20-25% of free rosin, and the rosin is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and adding a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by performing Diels-Alder reaction on rosin and fumaric acid, can be used with white rosin size due to the fact that the particles of the fumaric rosin are smaller than the white rosin size, can improve the sizing effect, and has the advantages of high softening point, high acid value, high saponification value and strong antioxidant stability, and the antioxidant stability and the oxidant are enhanced, so that the antioxidant property and the water resistance of the prepared rosin size are improved. The water-resistant and oil-resistant dispersed rosin size and the preparation method thereof, the added emulsifier is a surface active substance, the molecules of the emulsifier are provided with hydrophilic groups and lipophilic groups at the same time, the emulsifier is gathered on an oil/water interface, the interfacial tension can be reduced, and the energy required for forming emulsion can be reduced, so that the energy of the emulsion can be improved, the added tricyclic diterpene oxygen-containing compound has a hydrogenated phenanthrene nucleus which can be well dissolved with hydrocarbons in a molecular structure and also contains high-polarity carboxyl, so that the compatibility with rubber and synthetic resin is good, meanwhile, the rosin contains a hydrogenated phenanthrene nucleus with large steric hindrance, so that the tackifying effect is remarkable, and the oil resistance and the water resistance of the rosin size are greatly improved by combining the emulsifier and the tricyclic diterpene oxygen-containing compound. The water-resistant and oil-resistant dispersed rosin size is widely used for producing damp-proof and waterproof wrapping paper, paperboard, surface coatings of certain textiles and candles, and is characterized in that added tall oil, also called paper pulp floating oil, is obtained by skimming soap on the surface of waste liquid of pine pulp produced by sulfate and then acidifying the soap, is dark oily liquid, has the density of 0.950-1.024, the iodine value of 135-216 and the saponification value of 142-185, has hydrophilic groups and hydrophilic oil bases, is combined with tall oil, and has stronger water resistance and oil resistance. The added oxidized polyethylene wax is excellent novel polar wax, and the molecular chain of the oxidized polyethylene wax has a certain amount of carbonyl and hydroxyl, so that the intermiscibility of the oxidized polyethylene wax with filler, pigment and polar resin is obviously improved. The modified rosin maleic anhydride polyether has the advantages that the wettability and the dispersibility in a polar system are superior to those of polyethylene wax, the modified rosin maleic anhydride polyether also has coupling performance, special performances such as low viscosity, high softening point and good hardness, nontoxicity, good thermal stability, low high-temperature volatility, excellent dispersibility on fillers and pigments, excellent external lubricity, strong internal lubrication effect and coupling effect, the production efficiency of rosin size processing can be improved, the production cost is reduced, the modified rosin maleic anhydride polyether polyol has good compatibility with rosin maleic anhydride polyol, and the moisture resistance and the water resistance at normal temperature are good.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A water-resistant oil-resistant dispersion rosin size and a preparation method thereof are characterized in that: the rosin adhesive comprises 50-60% of rosin size, 30-40% of rosin maleic anhydride polyol ester, 20-30% of rosin, 20-30% of anhydride, 9-13% of oligomeric surfactant, 8-12% of reinforced rosin size, 8-10% of petroleum wax, 10-12% of tall oil, 8-10% of oxidized polyethylene wax, 6-8% of emulsifier, 15-25% of tricyclic diterpene oxygen-containing compound, 10-14% of polyacrylamide dispersant, 1-2% of catalyst, 20-30% of polyethylene glycol, 30-40% of alkylene oxide, 10-12% of antioxidant and 6-9% of esterifying agent, and the preparation method specifically comprises the following steps:
the method comprises the following steps: adding the mass of the rosin maleic anhydride polyol ester serving as a reference into a No. 1 thermocouple reaction kettle for heating and melting, adding a catalyst, polyethylene glycol and alkylene oxide into the molten rosin maleic anhydride polyol ester, and reacting at the temperature of 300-340 ℃ for 1-2 hours;
step two: carrying out vacuum-pumping treatment on the No. 1 thermocouple reaction kettle in the step one under reduced pressure, keeping the vacuum degree less than or equal to 1kPa for 40-60 min, and removing low-boiling-point substances;
step three: cooling the No. 1 thermocouple reaction kettle in the step two to 50-100 ℃, adding an antioxidant, a reinforced rosin size and an esterifying agent in batches, wherein the adding time interval is 20-30 min, then reacting for 1-2 h at the temperature of 50-100 ℃, and discharging to obtain a rosin-based surfactant;
step four: adding rosin and acetic anhydride into a No. 2 thermocouple reaction kettle according to the weight ratio of 1:1, adjusting the temperature to 230-250 ℃, heating for 2-3 h, simultaneously removing produced acetic acid and excessive acetic anhydride, and repeating the operation until the acid value of a product is less than 10 to prepare rosin anhydride;
step five: adding petroleum wax and tall oil into a No. 2 thermocouple reaction kettle in the fourth step, mixing, heating to enable the rosin anhydride to reach a molten state, starting a stirrer to stir at the rotating speed of 20-30 revolutions per minute, uniformly mixing the liquid rosin anhydride, the petroleum wax and the tall oil, adding oxidized polyethylene wax, adjusting the temperature to 80-90 ℃, and stirring to react for 1-2 hours;
step six: adding an oligomeric surfactant into the No. 2 thermocouple reaction kettle in the fifth step, continuously stirring, increasing the rotating speed to 150-250 r/min when the solution becomes whitish, adding a proper amount of water and an emulsifier, cooling to normal temperature while stirring, and stopping stirring to obtain a modified rosin sizing agent;
step seven: adding rosin size into a No. 3 thermocouple reaction kettle, heating to 60-90 ℃, stirring for 1-2 hours, adding rosin-based surfactant and modified rosin sizing agent, continuously stirring for 5-9 hours, cooling to room temperature, sequentially adding tricyclic diterpene oxygen-containing compound and polyacrylamide dispersing agent, continuously stirring for 3-4 hours, and discharging to obtain the water-resistant oil-resistant dispersed rosin size.
2. The water-resistant oil-resistant dispersed rosin size and the preparation method thereof according to claim 1, wherein the water-resistant oil-resistant dispersed rosin size is prepared by the following steps: the oligomeric surfactant is one or a mixture of dimer surfactant, trimer surfactant and tetramer surfactant.
3. The water-resistant oil-resistant dispersed rosin size and the preparation method thereof according to claim 1, wherein the water-resistant oil-resistant dispersed rosin size is prepared by the following steps: the reinforced rosin size contains 20-25% of free rosin, and is prepared by alkali saponification of maleic rosin or fumaric rosin and natural rosin and addition of a small amount of paraffin; the maleated rosin is prepared by carrying out Diels-Alder reaction on rosin and maleic acid; the fumaric rosin is prepared by carrying out Diels-Alder reaction on rosin and fumaric acid.
4. The water-resistant oil-resistant dispersed rosin size and the preparation method thereof according to claim 1, wherein the water-resistant oil-resistant dispersed rosin size is prepared by the following steps: the petroleum wax is further added with a polyolefin additive, wherein the polyolefin additive is one or a mixture of polyethylene with the molecular weight of 1500-15000 and polyisobutylene with the molecular weight of 3500-40000, and the addition amount is 0.5-3%.
5. The water-resistant oil-resistant dispersed rosin size and the preparation method thereof according to claim 1, wherein the water-resistant oil-resistant dispersed rosin size is prepared by the following steps: the molecular structure of the tricyclic diterpene oxygen-containing compound not only has hydrogenated phenanthrene nucleus which can be well dissolved with hydrocarbon, but also contains high-polarity carboxyl.
6. The water-resistant oil-resistant dispersed rosin size and the preparation method thereof according to claim 1, wherein the water-resistant oil-resistant dispersed rosin size is prepared by the following steps: the oxidized polyethylene wax is excellent novel polar wax, has a certain amount of carbonyl and hydroxyl on a molecular chain, has high intermiscibility with filler, pigment and polar resin, and also has coupling property.
7. The water-resistant oil-resistant dispersed rosin size and the preparation method thereof according to claim 1, wherein the water-resistant oil-resistant dispersed rosin size is prepared by the following steps: the solution concentration of the polyacrylamide dispersant is 0.1-0.3%, namely 1-3 g of polyacrylamide dispersant powder is added into 1 liter of water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443785A (en) * | 2002-03-12 | 2003-09-24 | 牛华 | Preparation method of high-molecular emulsifer for making rosen polyester sizing agent |
| CN103469684A (en) * | 2012-06-09 | 2013-12-25 | 江苏五洲纸业有限公司 | Method for producing modified rosin sizing agent |
| CN105017860A (en) * | 2015-08-09 | 2015-11-04 | 吴房文 | Technology for preparing ink by adding rosin maleic anhydride polyol ester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1443785A (en) * | 2002-03-12 | 2003-09-24 | 牛华 | Preparation method of high-molecular emulsifer for making rosen polyester sizing agent |
| CN103469684A (en) * | 2012-06-09 | 2013-12-25 | 江苏五洲纸业有限公司 | Method for producing modified rosin sizing agent |
| CN105017860A (en) * | 2015-08-09 | 2015-11-04 | 吴房文 | Technology for preparing ink by adding rosin maleic anhydride polyol ester |
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