A cationic modified rosin anion rosin gum stable to charge reversal and a preparation method and application thereof

Abstract

The application discloses a cationic modified rosin anion rosin size with charge reversal stability and a preparation method and application thereof, and belongs to the technical field of anion rosin size. The rosin size is composed of the following raw materials in parts by mass: rosin 100-200 parts; epichlorohydrin 30-90 parts; trimethylamine 3-7 parts; tetrabutylammonium bromide 0.5-1 part; anion starch emulsifier 5-8 parts, sodium dioctyl sulfosuccinate 5-8 parts; defoaming agent 0.5-2 parts; and water 100-240 parts; wherein the anion starch emulsifier is prepared by reacting cassava starch and sodium chloroacetate under alkaline conditions. The modified rosin liquid and the anion emulsifier are emulsified by using a high-temperature normal-pressure phase inversion method to prepare the cationic modified rosin anion rosin size based on the charge reversal stability, and the cationic modified rosin anion rosin size has the characteristics of no chloropropanol, no organic chlorine and good stability, and can realize acid to neutral sizing.

Description

Technical Field

[0001] This invention belongs to the field of anionic rosin adhesive technology, specifically relating to a charge-reversal-stable cationic modified rosin anionic rosin adhesive, its preparation method, and its application. Background Technology

[0002] Sizing is an indispensable and crucial step in the papermaking industry. Currently, rosin sizing agents still dominate, accounting for more than two-thirds of all sizing agents used. Commercially available rosin sizing agents mainly include saponified rosin gum, reinforced rosin gum, and dispersible rosin gum. Among them, dispersible rosin gum has a sizing efficiency approximately four times that of saponified rosin gum and twice that of reinforced rosin gum, and it can significantly reduce the amount of aluminum sulfate and brighteners used while improving paper strength.

[0003] Currently, widely used rosin sizing agents are mainly anionic or cationic. Cationic rosin gums mostly contain 1,3-dichloro-2-propanol, 3-chloro-1,2-propanediol (collectively known as chloropropanol), or other organochlorine compounds. These substances mainly originate from PAE-type emulsifiers or other chlorinated cationic polymer monomers used in the preparation process. Recent studies have shown that chloropropanol and organochlorine residues pose potential health hazards. On the other hand, anionic rosin gums have significant limitations in practical applications: they are highly dependent on aluminum sulfate, typically only usable under acidic or specific sizing process conditions, and have poor compatibility with common fillers such as calcium carbonate. These shortcomings severely restrict the widespread application of these two types of traditional rosin sizing agents. Summary of the Invention

[0004] To overcome the aforementioned technical problems in the existing technology, this invention provides a charge-reversal-stable cationic modified rosin anionic rosin gum, its preparation method, and its application. To achieve the above objectives, the technical solution adopted by this invention is as follows:

[0005] In one aspect, this invention provides a charge-reversal-stabilized cationic modified rosin anionic rosin gum, composed of the following raw materials in parts by weight:

[0006] Rosin 100-200 parts; epichlorohydrin 30-90 parts; trimethylamine 3-7 parts; tetrabutylammonium bromide 0.5-1 part; anionic starch emulsifier 5-8 parts; sodium dioctyl sulfosuccinate 5-8 parts; defoamer 0.5-2 parts; and water 100-240 parts;

[0007] The anionic starch emulsifier is prepared by reacting cassava starch with sodium chloroacetate under alkaline conditions.

[0008] As a further embodiment of the present invention: the defoamer is at least one of emulsified silicone oil, higher alcohol complex, polyether, and polydimethylsiloxane.

[0009] As a further embodiment of the present invention: the solid content of the cationic modified rosin anionic rosin gum is 30-50%, and the viscosity is 15-50 mPa·s.

[0010] In another aspect, the present invention provides a method for preparing charge-reversal-stabilized cationic modified rosin anionic rosin gum, comprising the following steps:

[0011] (1) Rosin, epichlorohydrin and tetrabutylammonium bromide were reacted at 160°C for 2 hours until the acid value of the reaction system dropped to below 5 mg KOH / g; trimethylamine aqueous solution was added and the reaction was continued at 100°C for 1.5 hours to obtain cationic modified rosin;

[0012] (2) Heat the anionic starch emulsifier and sodium dioctyl sulfosuccinate to 70-90°C respectively, and add them dropwise to the molten cationic modified rosin. Mix for 10 minutes at 110-140°C and a shear rate of 800-1200 rpm to obtain a pre-emulsified rosin liquid.

[0013] (3) Slowly drip water at 90°C into the pre-emulsified rosin liquid, and add defoamer after cooling to obtain the cationic modified rosin anionic rosin gum.

[0014] As a further embodiment of the present invention: the preparation method of the anionic starch emulsifier in step (2) specifically includes: mixing 10-15 parts of sodium chloroacetate, 100-200 parts of cassava starch, 8-16 parts of sodium hydroxide solution with a concentration of 32% and 200-300 parts of water, and heating to 50°C to react for 2-3 hours.

[0015] In a third aspect, the present invention provides the application of the above-mentioned charge-reversal stable cationic modified rosin anionic rosin gum in paper sizing.

[0016] The beneficial effects of this invention are as follows:

[0017] (1) The present invention uses self-made anionic starch emulsifier and sodium dioctyl sulfosuccinate for synergistic phase inversion. The resulting anionic rosin gum has a narrow particle size distribution and is easy to disperse in cold water. When added to a wet cloth, it can be more evenly dispersed in the slurry, significantly improving the sizing degree and exhibiting excellent stability.

[0018] (2) The entire process of this invention is free of organochlorine byproducts such as chloropropanol. The rosin is cationic modified and has low dependence on aluminum sulfate. It can achieve efficient sizing in the acidic to neutral range. The process is simple and can be scaled up without complicated equipment. Detailed Implementation

[0019] The present invention is further illustrated below by way of examples, but these examples do not limit the invention to the scope of the embodiments described. Experimental methods in the following examples, unless otherwise specified, were performed according to conventional methods and conditions, or as selected in the product instructions. Furthermore, all reagents and raw materials used in this invention are commercially available.

[0020] Example 1

[0021] A method for preparing a charge-reversal-stabilized cationic modified rosin anionic rosin gum includes the following steps:

[0022] (1) The preparation method of anionic starch emulsifier includes: 10g sodium chloroacetate, 100g cassava starch, 8g sodium hydroxide solution (concentration 32%), 200g water, heated to 50℃, and stirred for 2h to obtain anionic starch emulsifier;

[0023] (2) React 200g of rosin with 80g of epichlorohydrin and 1g of tetrabutylammonium bromide at 160℃ for 2h until the acid value drops to <5 mg KOH / g; add 20g of 33% trimethylamine aqueous solution and carry out quaternization reaction at 100℃ for 1.5h; heat to 120℃ for later use.

[0024] (3) Heat 7g of anionic starch emulsifier and 6g of sodium dioctyl sulfosuccinate to 90°C, and add them dropwise to molten cationic modified rosin for pre-emulsification. The dropwise temperature is 120°C, the dropwise time is 10 min, and the shear rate is 900 rpm to obtain pre-emulsified rosin liquid.

[0025] (4) Phase inversion: 200g of water at 90℃ is slowly dripped into the pre-emulsified rosin liquid. As hot water is added, the viscosity of the pre-emulsion decreases rapidly from its maximum value, and the oil-in-water emulsion is transformed into an oil-in-water anionic rosin emulsion. After cooling, 1g of emulsified silicone oil defoamer is added, and water is added to adjust the solid content to obtain cationic modified rosin anionic low-chlorine rosin glue.

[0026] Example 2

[0027] A method for preparing a charge-reversal-stabilized cationic modified rosin anionic rosin gum includes the following steps:

[0028] (1) The preparation method of anionic starch emulsifier includes: 15g sodium chloroacetate, 200g cassava starch, 16g sodium hydroxide solution (concentration 32%), 200g water, heated to 50℃, stirred and reacted for 2h to obtain anionic starch emulsifier;

[0029] (2) React 100g of rosin with 30g of epichlorohydrin and 0.5g of tetrabutylammonium bromide at 160℃ for 2h until the acid value drops to <5 mg KOH / g; add 10g of 33% trimethylamine aqueous solution and carry out quaternization reaction at 100℃ for 1.5h; heat to 130℃ for later use.

[0030] (3) Heat 5g of anionic starch emulsifier and 5g of sodium dioctyl sulfosuccinate to 90°C, and add them dropwise to molten cationic modified rosin for pre-emulsification. The dropwise temperature is 125°C, the dropwise time is 10 min, and the shear rate is 1000 rpm to obtain pre-emulsified rosin liquid.

[0031] (4) Phase inversion: 110g of water at 90℃ is slowly dripped into the pre-emulsified rosin liquid. As hot water is added, the viscosity of the pre-emulsion decreases rapidly from its maximum value, and the oil-in-water emulsion is transformed into an oil-in-water anionic rosin emulsion. After cooling, 1g of polyether defoamer is added, and water is added to adjust the solid content to obtain cationic modified rosin anionic low-chlorine rosin glue.

[0032] Example 3

[0033] A method for preparing a charge-reversal-stabilized cationic modified rosin anionic rosin gum includes the following steps:

[0034] (1) The preparation method of anionic starch emulsifier includes: 10g sodium chloroacetate, 200g cassava starch, 16g sodium hydroxide solution (concentration 32%), 200g water, heated to 50℃, stirred and reacted for 3h to obtain anionic starch emulsifier;

[0035] (2) 200g of rosin, 90g of epichlorohydrin, and 0.5g of tetrabutylammonium bromide were reacted at 160℃ for 2h until the acid value dropped to <5 mg KOH / g; 15g of 33% trimethylamine aqueous solution was added and quaternization reaction was carried out at 100℃ for 1.5h; the temperature was raised to 120℃ for later use.

[0036] (3) Heat 5g of anionic starch emulsifier and 8g of sodium dioctyl sulfosuccinate to 80°C, and add them dropwise to molten cationic modified rosin for pre-emulsification. The dropwise temperature is 140°C, the dropwise time is 10 min, and the shear rate is 1200 rpm to obtain pre-emulsified rosin liquid.

[0037] (4) Phase inversion: 230g of water at 90℃ is slowly dripped into the pre-emulsified rosin liquid. As hot water is added, the viscosity of the pre-emulsion decreases rapidly from its maximum value, and the oil-in-water emulsion is transformed into an oil-in-water anionic rosin emulsion. After cooling, 1g of polydimethylsiloxane defoamer is added, and water is added to adjust the solid content to obtain cationic modified rosin anionic low-chlorine rosin glue.

[0038] Example 4

[0039] A method for preparing a charge-reversal-stabilized cationic modified rosin anionic rosin gum includes the following steps:

[0040] (1) The preparation method of anionic starch emulsifier includes: 15g sodium chloroacetate, 200g cassava starch, 12g sodium hydroxide solution (concentration 32%), 300g water, heated to 50℃, stirred and reacted for 2.5h to obtain anionic starch emulsifier;

[0041] (2) 150g of rosin, 70g of epichlorohydrin and 1g of tetrabutylammonium bromide are reacted at 160℃ for 2h until the acid value drops to <5 mg KOH / g; 20g of 33% trimethylamine aqueous solution is added and quaternization reaction is carried out at 100℃ for 1.5h; the temperature is raised to 120℃ for later use.

[0042] (3) Heat 8g of anionic starch emulsifier and 5g of sodium dioctyl sulfosuccinate to 70°C, and add them dropwise to molten cationic modified rosin for pre-emulsification. The dropwise temperature is 110°C, the dropwise time is 10 min, and the shear rate is 800 rpm to obtain pre-emulsified rosin liquid.

[0043] (4) Phase inversion: 160g of water at 90℃ is slowly dripped into the pre-emulsified rosin liquid. As hot water is added, the viscosity of the pre-emulsion decreases rapidly from its maximum value, and the oil-in-water emulsion is transformed into an oil-in-water anionic rosin emulsion. After cooling, 1g of polydimethylsiloxane defoamer is added, and water is added to adjust the solid content to obtain cationic modified rosin anionic low-chlorine rosin glue.

[0044] This application also provides the following comparative examples:

[0045] Comparative Example 1

[0046] The product is anionic rosin adhesive, model NS-801, manufactured by Arakawa Chemical Industry Co., Ltd. of Japan.

[0047] Comparative Example 2

[0048] The product is cationic rosin adhesive with model number CRS35, manufactured by Shanghai Dongsheng New Materials Co., Ltd. (Purchased from the market)

[0049] Comparative Example 3

[0050] The only difference from Example 1 is that the epichlorohydrin in step (2) is replaced with an equal mass of epoxy resin E-44.

[0051] Comparative Example 4

[0052] The only difference from Example 1 is that step (1) is omitted and anionic starch emulsifier is not added in step (3).

[0053] Comparative Example 5

[0054] The only difference from Example 1 is that step (1) is omitted and the anionic starch emulsifier in step (3) is replaced with an equal mass of sodium carboxymethyl starch.

[0055] Comparative Example 6

[0056] The only difference from Example 1 is that zinc acetate is not added in step (3).

[0057] Comparative Example 7

[0058] The only difference from Example 1 is that in step (2), the operation of "adding 20g of 33% trimethylamine aqueous solution and carrying out quaternization reaction at 100°C for 1.5h" is not performed.

[0059] Comparative Example 8

[0060] The only difference from Example 1 is that in step (3), the pre-emulsification dropping temperature is 90°C.

[0061] Effect Example

[0062] The application performance of the products prepared in the embodiments and comparative examples of this application was tested according to the following standards or methods:

[0063] I. Solid content determination: 2g sample, dried at 150℃ for 30min.

[0064] II. Viscosity Measurement: DV-II rotational viscometer manufactured by Bollefeld, USA; testing temperature: 25℃; rotor #1.

[0065] III. Particle size determination: Malvern particle size analyzer

[0066] IV. Chemical stability test: 10g of 0.5mol / L calcium chloride was stirred for 10min and the residue was measured on a 325-mesh filter screen.

[0067] V. Mechanical stability test: 5000 rpm, 30 min to test the residue on the sieve.

[0068] VI. Storage stability test: Observe the stratification when placed at room temperature.

[0069] VII. Comparison of water-resistant application effects, measured using the following methods:

[0070] Experimental design: Design a papermaking quantity of 100g / m³ 2

[0071] Process: 85% pulp + rosin gum + 15% talc + CPAM (200ppm)

[0072] Rosin addition: 14 kg / t paper, 18 kg / t paper (wet / dry, each sample is 35% solids content).

[0073] According to the above process, the pH value of the blank pulp is adjusted to about 6.0-7.0 with a dissolved 30% citric acid solution. Then, the rosin gum prepared in Examples 1-4 or Comparative Examples 1-8 is added. After stirring for 1 minute, talc powder is added. After stirring for 1 minute, retention aid is added. After 1 minute, the prepared pulp is removed, and the pulp is formed into sheets using a 73-62 semi-automatic paper sheet forming machine. After pressing with a 73-50 standard paper sheet press, the paper is dried using a varnishing machine, and the Cobb water absorption value of the paper sample is tested after 1 minute.

[0074] The performance of the samples from Examples 1-4 and Comparative Examples 1-8 was measured, and the results are shown in Tables 1 and 2.

[0075] Table 1

[0076]

[0077] As can be seen from Table 1, the rosin gum prepared in each embodiment of the present invention is significantly superior to all comparative examples in terms of particle size distribution, chemical stability, mechanical stability, and storage stability. When Examples 1-4 were stored in a variable temperature chamber at 20-40℃ for 12 months, the samples remained in a homogeneous and stable emulsion state, while Comparative Example 1 showed demulsification and sedimentation at the bottom after 6 months, and Comparative Example 2 showed demulsification and sedimentation at the bottom after 10 months.

[0078] Table 2

[0079]

[0080] As shown in Table 2, under the same addition amount, the sizing and water resistance performance of the product of the present invention is superior to that of commercially available products and comparative examples. Especially at the addition amount of 14 kg / t paper after folding and at an iso-dry level, the advantages of the present invention are more significant, with a Cobb value of 40.2~44.95 g / m³. 2 It was significantly lower than the comparative sample of 51.4~71.3 g / m 2 .

[0081] It should be noted that, in the embodiments of the present invention, Example 1 is the optimal embodiment, and the sizing effect is significantly superior under low additive conditions.

[0082] Finally, it should be noted that in this invention, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0083] Although this disclosure has been described above through specific embodiments, it should be understood that those skilled in the art can devise various modifications, improvements, or equivalents to this disclosure within the spirit and scope of the appended solutions. Such modifications, improvements, or equivalents should also be considered to be included within the scope of protection claimed in this disclosure.

Claims

1. A charge-reversal-stabilized cationic modified rosin anionic rosin gum, characterized in that, It consists of the following raw materials in parts by weight: Rosin 100-200 parts; epichlorohydrin 30-90 parts; trimethylamine 3-7 parts; tetrabutylammonium bromide 0.5-1 part; anionic starch emulsifier 5-8 parts; sodium dioctyl sulfosuccinate 5-8 parts; defoamer 0.5-2 parts; and water 100-240 parts; The anionic starch emulsifier is prepared by reacting cassava starch with sodium chloroacetate under alkaline conditions.

2. The charge-reversal-stabilized cationic modified rosin anionic rosin gum according to claim 1, characterized in that, The defoamer is at least one of emulsified silicone oil, higher alcohol complex, polyether, and polydimethylsiloxane.

3. The charge-reversal-stabilized cationic modified rosin anionic rosin gum according to claim 1, characterized in that, The cationic modified rosin anionic rosin gum has a solid content of 30-50% and a viscosity of 15-50 mPa·s.

4. A method for preparing charge-reversal-stabilized cationic modified rosin anionic rosin gum as described in claims 1-3, characterized in that, Includes the following steps: (1) Rosin, epichlorohydrin and tetrabutylammonium bromide were reacted at 160°C for 2 hours until the acid value of the reaction system dropped to below 5 mg KOH / g; trimethylamine aqueous solution was added and the reaction was continued at 100°C for 1.5 hours to obtain cationic modified rosin; (2) Heat the anionic starch emulsifier and sodium dioctyl sulfosuccinate to 70-90°C respectively, and add them dropwise to the molten cationic modified rosin. Mix for 10 minutes at 110-140°C and a shear rate of 800-1200 rpm to obtain a pre-emulsified rosin liquid. (3) Slowly drip water at 90°C into the pre-emulsified rosin liquid, and add defoamer after cooling to obtain the cationic modified rosin anionic rosin gum.

5. The method for preparing charge-reversal-stabilized cationic modified rosin anionic rosin gum according to claim 4, characterized in that, The preparation method of the anionic starch emulsifier in step (2) specifically includes: mixing 10-15 parts of sodium chloroacetate, 100-200 parts of cassava starch, 8-16 parts of sodium hydroxide solution with a concentration of 32% and 200-300 parts of water, and heating to 50°C to react for 2-3 hours.

6. The application of the charge-reversal stable cationic modified rosin anionic rosin gum according to any one of claims 1 to 3 in paper sizing.

Images