Anion dispersed rosin size as well as raw material composition and preparation method thereof

Abstract

The invention provides an anionic dispersed rosin size raw material composition which comprises the following raw materials in parts by weight: 100-200 parts of rosin, 5-20 parts of a modifier, 8-15 parts of an anionic emulsifier, 2-8 parts of a stabilizer and / or a proper amount of a functional aid, and the anionic emulsifier is a product obtained by carrying out sulfonation reaction on castor oil or rapeseed oil and concentrated sulfuric acid and then neutralizing with sodium hydroxide. The method for preparing the anionic dispersed rosin size from the raw material composition comprises the following steps: heating and melting rosin, adding a modifier, fully reacting to obtain modified rosin, heating an anionic emulsifier and a stabilizer to 60-90 DEG C, dropwise adding the mixture into the modified rosin in a molten state for pre-emulsification, slowly dropwise adding hot water into the pre-emulsified rosin liquid for phase inversion, and cooling to room temperature to obtain the anionic dispersed rosin size. And cooling and adding a functional additive. Main raw materials of the anionic dispersed rosin size are natural renewable substances, and the anionic dispersed rosin size is environmentally friendly, easy to degrade, narrow in particle size distribution, good in stability, less in foam, free of fiber flocculation and capable of achieving sizing from acidity to neutrality.

Description

Technical Field

[0001] The invention relates to the technical field of papermaking sizing agents, and in particular to an anionic dispersed rosin size and a preparation method thereof. Background Art

[0002] Sizing is an important process in papermaking. Among the numerous paper sizing agents, rosin sizing agents are dominant, accounting for more than 2 / 3 of the total sizing amount. Rosin sizing agents include saponified rosin sizing, reinforced rosin sizing and dispersed rosin sizing. The sizing rate of dispersed rosin sizing is 4 times that of saponified rosin sizing and 2 times that of reinforced rosin sizing. Dispersed rosin sizing can improve the quality of paper and reduce the amount of aluminum sulfate and brightener.

[0003] In the prior art, the preparation method of anionic dispersed rosin glue has problems such as the emulsifier used is usually not easy to degrade, a large amount of organic solvent is used, and the process is complicated. For example, patent CN117779517A discloses an anionic rosin glue and its preparation method, which uses a large amount of acetone as a solvent and the raw material γ-aminopropyltriethoxysilane is difficult to degrade; its preparation is relatively complicated and the production process control is relatively cumbersome. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide an anionic dispersed rosin glue, a raw material composition thereof and a preparation method thereof, so as to improve stability and biodegradability.

[0005] The present invention is achieved by adopting the following technical solutions:

[0006] The first aspect of the present invention is to provide an anionic dispersed rosin glue raw material composition, which comprises the following raw materials in parts by weight: 100-200 parts of rosin, 5-20 parts of modifier, 8-15 parts of anionic emulsifier, 2-8 parts of stabilizer, and / or an appropriate amount of functional additives, wherein the anionic emulsifier is a product of castor oil or rapeseed oil subjected to a sulfonation reaction with concentrated sulfuric acid and then neutralized with sodium hydroxide.

[0007] The anionic emulsifier is specifically prepared by the following method: sulfonating castor oil or rapeseed oil with concentrated sulfuric acid at 40-50°C for 3-5h, heating to 50-60°C for aging for 0.5-2h; after the insulation is completed, lowering the temperature to room temperature below 30°C, and adjusting the pH value to 8-10 with sodium hydroxide solution to obtain the anionic emulsifier.

[0008] Preferably, the amount of concentrated sulfuric acid added is 5-40% by weight of the castor oil or rapeseed oil, more preferably 10-30%.

[0009] The modifier is selected from at least one of butenedioic acid, maleic acid and maleic anhydride.

[0010] The stabilizer is selected from at least one of sodium pyrophosphate, sodium lignin sulfonate and sodium polyacrylate.

[0011] The functional additives mainly play the role of sterilization and defoaming for anionic dispersed rosin glue, including bactericides, defoamers, etc. The functional additives can be added alone or multiple functional additives can be added at the same time, and the specific selection can be based on the actual dispersion and foaming of anionic dispersed rosin glue and the application scenario.

[0012] Furthermore, the fungicide is selected from at least one of Bit, MIT and CMIT.

[0013] Furthermore, the defoaming agent is selected from at least one of emulsified silicone oil, a high-carbon alcohol complex, polyether, and polydimethylsiloxane.

[0014] The preferred addition amounts of the functional additives are: 1-2 parts of bactericide and 1-3 parts of defoamer.

[0015] The second aspect of the present invention is to provide a method for preparing anionic dispersed rosin glue, using the above-mentioned anionic dispersed rosin glue raw material composition, specifically comprising the following steps:

[0016] S1, heating and melting rosin, adding a modifier and reacting the mixture sufficiently to obtain modified rosin;

[0017] S2, heating anionic emulsifier and stabilizer to 60-90° C., and dropping them into the molten modified rosin for pre-emulsification to obtain pre-emulsified rosin liquid;

[0018] S3, slowly dripping 85-95° C. hot water into the pre-emulsified rosin solution to perform phase inversion, cooling, and adding functional additives to obtain the anionic dispersed rosin glue.

[0019] The inventor unexpectedly discovered that the anionic dispersed rosin glue prepared by using the product obtained by sulfonating and neutralizing castor oil or rapeseed oil as an anionic emulsifier has outstanding chemical stability, mechanical stability and storage stability. The specific reason is not very clear. The inventor speculates that it may be due to the following mechanism: taking castor oil as an example, castor oil mainly contains ricinoleic acid glyceride and ricinoleic acid. After adding concentrated sulfuric acid, multiple hydroxyl groups and carbon-carbon double bonds in ricinoleic acid glyceride will be partially sulfonated, and the hydroxyl groups and carbon-carbon double bonds in ricinoleic acid will also be partially sulfonated. After adding sodium hydroxide to neutralize, sodium salt is formed. The sulfonated products of the above complex components constitute a relatively complex anionic emulsification system, thereby providing a very stable dispersion system for rosin glue. The inventor further studied and found that directly using sulfonated castor oil as an emulsifier cannot obtain a dispersed rosin glue with excellent stability. It can be seen that the anionic emulsifier of the present invention has a special stability contribution. Based on the above discovery, the inventor completed the present invention.

[0020] Preferably, in step S2, the reaction temperature of rosin and modifier is 180-200° C., and the reaction time is 1-3 h.

[0021] Preferably, the anionic emulsifier is added dropwise for 5-20 min in step S3, and the shear rate is 800-1200 rpm.

[0022] Preferably, the amount of hot water added in step S4 is 100-200 parts by weight.

[0023] The third aspect of the present invention is to provide an anionic dispersed rosin glue prepared by the above method, which has a solid content of 30%-50%, a viscosity of 15-50mPa.s, a chemical stability of ≤60ppm, a mechanical stability of ≤55ppm, and a storage stability of ≥8 months.

[0024] The anionic dispersed rosin glue of the present invention has a raw material composition in which the main raw materials used are all natural renewable materials, which is environmentally friendly and easy to degrade, has a simple process, is low in cost and is easy to use. The anionic dispersed rosin glue is prepared by a phase inversion method using a homemade anionic emulsifier, has a narrow particle size distribution, good stability, is extremely easy to disperse in cold water, is simple to operate, and does not need to readjust the original process; has a high free rosin content, low viscosity, high whiteness, stable quality, can be placed for a long time, and has a quality shelf life of 8 months at room temperature. The anionic dispersed rosin glue has less foam, does not cause fiber flocculation, and does not affect paper material forming.

[0025] In summary, the anionic dispersed rosin glue of the present invention has the advantages of reduced cost, convenient use, good stability, less foam and strong adaptability, etc., can achieve acidic to neutral sizing, and its preparation process is simple and has low requirements on equipment. When sizing, conventional retention system and sizing process are used, which can achieve the purpose of neutral sizing. DETAILED DESCRIPTION

[0026] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only used as examples, but are not used to limit the scope of the present invention. Those skilled in the art can think of other obvious variations. The basic principles of the present invention defined in the following description can be applied to other embodiments, variations, improvements, equivalent solutions, and other technical solutions that do not deviate from the spirit and scope of the present invention.

[0027] The instruments or raw materials in the present invention that do not indicate the manufacturer are all conventional commercial instruments or raw materials. If the detection indicators involved in the embodiments of the present invention are not mentioned, they are all detected by conventional detection methods in the field. Among them:

[0028] 1. Solid content determination: 2g sample, drying at 150℃ for 30min;

[0029] 2. Viscosity measurement: rotational viscometer;

[0030] 3. Particle size determination: Malvern particle size analyzer;

[0031] 4. Chemical stability determination: Take 100g sample, add 10g 0.5mol / L calcium chloride, stir for 10min, and detect the residue on the 325-mesh filter;

[0032] 5. Mechanical stability determination: Take 100g sample, stir at 5000rpm for 30min, and detect the residue on the 325-mesh filter;

[0033] 6. Storage stability determination: Place at room temperature and observe the stratification.

[0034] Example 1

[0035] (1) Preparation of anionic emulsifier: Weigh 30 g of rapeseed oil, heat to 40° C., add 8 g of sulfuric acid dropwise, react for 4 h, obtain a sulfonated product, age for 1 h, add about 16 g of sodium hydroxide solution (concentration 50%), adjust the pH to 8-10, and obtain anionic emulsifier.

[0036] (2) Rosin modification: Weigh 200 g of rosin, heat it to 170 °C, add 20 g of maleic anhydride, and modify it at 200 °C for 2 h.

[0037] (3) Pre-emulsification: Heat 8 g of sodium pyrophosphate and 15 g of anionic emulsifier to 60° C. and slowly add them to the molten modified rosin over a period of 10 min. Pre-emulsify the mixture under stirring at 800 rpm.

[0038] (4) Phase transition: 200 g of water at 90° C. was slowly dripped into the pre-emulsified rosin solution. As the hot water was added, the viscosity of the pre-emulsion decreased rapidly from a maximum value, and the oil-in-water emulsion was transformed into an anionic rosin glue emulsion of oil-in-water. After cooling, 1 g of an organic silicon defoamer and 2 g of a fungicide BIT were added. Water was added to adjust the solid content to obtain an anionic dispersed rosin glue with a solid content of 40% and a viscosity of 20 mPa.s.

[0039] Example 2

[0040] (1) Preparation of anionic emulsifier: Weigh 30 g of castor oil, heat to 40° C., add 4 g of sulfuric acid dropwise, react for 4 h, obtain a sulfonated product, age for 1 h, add 8 g of sodium hydroxide solution (concentration 50%), adjust the pH to 8-10, and obtain anionic emulsifier.

[0041] (2) Rosin modification: Weigh 100 g of rosin, heat it to 170 °C, add 5 g of maleic anhydride, and modify it at 200 °C for 2 h.

[0042] (3) Pre-emulsification: Heat 8 g of sodium lignin sulfonate and 8 g of anionic emulsifier to 60° C. and slowly add them to the molten modified rosin over a period of 10 min. Pre-emulsify the mixture under stirring at 800 rpm.

[0043] (4) Phase inversion: 100 g of water at a temperature of 90-95° C. is slowly dripped into the pre-emulsified rosin solution. As the hot water is added, the viscosity of the pre-emulsion decreases rapidly from a maximum value, and the oil-in-water emulsion is converted into an anionic rosin glue emulsion of oil-in-water. After cooling, 0.5 g of a polyether defoamer and 1 g of a fungicide MIT are added, and water is added to adjust the solid content to obtain an anionic dispersed rosin glue with a solid content of 40% and a viscosity of 15 mPa.s.

[0044] Example 3

[0045] (1) Preparation of anionic emulsifier: Weigh 60 g of rapeseed oil, heat to 40° C., add 8 g of sulfuric acid dropwise, react for 4 h, obtain a sulfonated product, age for 1 h, add 12 g of sodium hydroxide solution (concentration 50%), adjust the pH to 8-10, and obtain anionic emulsifier.

[0046] (2) Rosin modification: Weigh 100 g of rosin, heat it to 170 °C, add 5 g of maleic anhydride, and modify it at 200 °C for 2 h.

[0047] (3) Pre-emulsification: Heat 8 g of sodium polyacrylate and 8 g of anionic emulsifier to 60° C. and slowly add them to the molten modified rosin over a period of 10 min. Pre-emulsify the mixture under stirring at 1000 rpm.

[0048] (4) Phase inversion: 100 g of water at a temperature of 90-95° C. is slowly dripped into the pre-emulsified rosin solution. As the hot water is added, the viscosity of the pre-emulsion decreases rapidly from a maximum value, and the oil-in-water emulsion is converted into an anionic rosin glue emulsion of water-in-oil. After cooling, 0.5 g of a higher alcohol defoamer and 1 g of a fungicide CMIT are added. Water is added to adjust the solid content to obtain an anionic dispersed rosin glue with a solid content of 30% and a viscosity of 10 mPa.s.

[0049] Example 4

[0050] (1) Preparation of anionic emulsifier: Weigh 60 g of castor oil, heat to 40° C., add 8 g of sulfuric acid dropwise, react for 4 h, and obtain a sulfonated product. After aging for 1 h, add 16 g of sodium hydroxide solution (50%) in water to adjust the pH to 8-10 to obtain anionic emulsifier.

[0051] (2) Rosin modification: Weigh 200 g of rosin, heat it to 170 °C, add 5 g of maleic anhydride, and modify it at 200 °C for 2 h.

[0052] (3) Pre-emulsification: Heat 2 g of sodium lignin sulfonate and 10 g of anionic emulsifier to 60°C, slowly add them to the molten modified rosin, add them over 10 min, and fully pre-emulsify them under stirring at 1200 rpm.

[0053] (4) Phase inversion: 150 g of water at a temperature of 90-95° C. is slowly dripped into the pre-emulsified rosin solution. As the hot water is added, the viscosity of the pre-emulsion decreases rapidly from a maximum value, and the oil-in-water emulsion is converted into an anionic rosin glue emulsion of oil-in-water. After cooling, 0.5 g of an organic silicon defoamer and 2 g of a fungicide BIT are added, and water is added to adjust the solid content to obtain an anionic dispersed rosin glue with a solid content of 50% and a viscosity of 17 mPa.s.

[0054] Comparative Example 1

[0055] The commercially available rosin glue is model NS-801 produced by Arakawa Chemical Industries, Ltd. of Japan.

[0056] Comparative Example 2

[0057] Commercially available sulfonated castor oil (also known as sulfated castor oil, sodium castor oil sulfonate, CAS: 8002-33-3, molecular formula: C 18 H 32 Na2O6S) replaces the anionic emulsifier in Example 1 (the amount used is converted according to the purity to make it roughly equivalent), and the rest is the same as in Example 1. The specific process is as follows:

[0058] (1) Rosin modification: Weigh 200 g of rosin, heat it to 170 °C, add 20 g of maleic anhydride, and modify it at 200 °C for 2 h.

[0059] (2) Pre-emulsification: Heat 8 g of sodium pyrophosphate and 13 g of sulfonated castor oil to 60°C, slowly add them to the molten modified rosin, add them over 10 min, and fully pre-emulsify them under stirring at 800 rpm.

[0060] (3) Phase inversion: 200 g of water at 90° C. was slowly dripped into the pre-emulsified rosin solution. As the hot water was added, the viscosity of the pre-emulsion decreased rapidly from a maximum value, and the oil-in-water emulsion was converted into an anionic rosin glue emulsion of oil-in-water. After cooling, 1 g of an organic silicon defoamer and 2 g of a fungicide BIT were added. Water was added to adjust the solid content to obtain an anionic dispersed rosin glue with a solid content of 40% and a viscosity of 32 mPa.s.

[0061] The indicators and properties of the anionic rosin glue of the above-mentioned embodiments and comparative examples were measured, and the results are shown in Table 1.

[0062] Table 1 Performance indexes of anionic dispersed rosin glue

[0063]

[0064]

[0065] It can be seen from the test results that the chemical stability and mechanical stability of the anionic dispersed rosin glue of the present invention are better than those of the comparative example, and the storage stability reaches 8 months, which is significantly better than the comparative sample, indicating that the emulsifier used in the present invention has a better effect of stabilizing the rosin glue.

[0066] In addition, when the anionic dispersed rosin glue of the present invention was stored at 30°C for 10 months, bacterial growth and corruption were still detected even after the addition of a bactericide component, while the comparative sample showed no bacteria or mold after bacterial and mold culture detection at 10 months, indicating that the present invention has better biodegradability than the comparative product.

[0067] It should be understood by those skilled in the art that the above embodiments are only examples and do not limit the present invention. The purpose of the present invention has been fully and effectively achieved. The functional and structural principles of the present invention have been demonstrated and explained in the embodiments, and the embodiments of the present invention may be deformed or modified in any way without departing from the principles.

Claims

1. An anionic dispersed rosin glue raw material composition, characterized in that: The invention comprises the following raw materials in parts by weight: 100-200 parts of rosin, 5-20 parts of modifier, 8-15 parts of anionic emulsifier, 2-8 parts of stabilizer, and / or an appropriate amount of functional additives. The anionic emulsifier is a product obtained by sulfonation reaction of castor oil or rapeseed oil with concentrated sulfuric acid and then neutralized with sodium hydroxide.

2. The anionic dispersed rosin glue raw material composition according to claim 1, characterized in that: The anionic emulsifier is prepared by the following method: sulfonation reaction of castor oil or rapeseed oil with concentrated sulfuric acid at 40-50°C for 3-5h, heating to 50-60°C for aging for 0.5-2h; after the insulation is completed, the temperature is lowered to room temperature below 30°C, and the pH value is adjusted to 8-10 with sodium hydroxide solution to obtain the anionic emulsifier.

3. The anionic dispersed rosin size raw material composition according to claim 1, characterized in that: The amount of concentrated sulfuric acid added is 5-40% by weight of castor oil or rapeseed oil.

4. The anionic dispersed rosin size raw material composition according to claim 1, characterized in that: The modifier is selected from at least one of butenedioic acid, maleic acid and maleic anhydride.

5. The anionic dispersed rosin size raw material composition according to claim 1, characterized in that: The stabilizer is selected from at least one of sodium pyrophosphate, sodium lignin sulfonate and sodium polyacrylate.

6. The anionic dispersed rosin size raw material composition according to claim 1, characterized in that: The bactericide is selected from at least one of Bit, MIT and CMIT, and the defoamer is selected from at least one of emulsified silicone oil, high-carbon alcohol complex, polyether and polydimethylsiloxane.

7. The anionic dispersed rosin size raw material composition according to claim 1, characterized in that: The added amounts of the functional additives are: 1-2 parts of bactericide and 1-3 parts of defoamer.

8. A method for preparing anionic dispersed rosin glue, using the anionic dispersed rosin glue raw material composition according to any one of claims 1 to 7, specifically comprising the following steps: S1, heating and melting rosin, adding a modifier and reacting the mixture sufficiently to obtain modified rosin; S2, heating anionic emulsifier and stabilizer to 60-90° C., and dropping them into the molten modified rosin for pre-emulsification to obtain pre-emulsified rosin liquid; S3, slowly dripping 85-95° C. hot water into the pre-emulsified rosin solution to perform phase inversion, cooling, and adding functional additives to obtain the anionic dispersed rosin glue.

9. The method according to claim 8, characterized in that In step S2, the reaction temperature of rosin and modifier is 180-200°C, and the reaction time is 1-3h; in step S3, the dropwise addition time of anionic emulsifier is 5-20min, and the shear rate is 800-1200rpm; in step S4, the amount of hot water added is 100-200 parts by weight.

10. Anionic dispersed rosin glue prepared according to the method of claim 8 or 9, characterized in that: The solid content is 30%-50%, the viscosity is 15-50mPa.s, the chemical stability is ≤60ppm, the mechanical stability is ≤55ppm, and the storage stability is ≥8 months.

Images