阅读说明：本技术 一种阳离子分散松香胶及其制备方法 (Cation dispersed rosin size and preparation method thereof ) 是由 施晓旦 段鹏真 沈安成 于 2020-04-23 设计创作，主要内容包括：本发明公开了一种阳离子分散松香胶,其组分包括改性松香、有效量的复合乳化剂和稳定剂,所述复合乳化剂由阳离子丙烯酸酯类乳化剂和聚酰胺环氧树脂组成。其制备方法是将松香加热熔融,搅拌下加入改性剂充分反应,得到改性松香液；将复合乳化剂通入改性松香液,充分预乳化后通入高压均质机均质,冷却后加入稳定剂即得到所述阳离子分散松香胶。本发明利用阳离子丙烯酸酯类乳化剂和聚酰胺环氧树脂作为复合乳化剂,采用连续型高温预乳化和高压均质乳化工艺,得到低粘、低泡、低氯含量的乳白色阳离子松香胶,其稳定性好,冷水中分散性良好,贮存稳定性好,常温放置六个月不分层、不沉淀,无漂浮物。(The invention discloses a cation dispersed rosin size, which comprises modified rosin, an effective amount of composite emulsifier and a stabilizer, wherein the composite emulsifier is composed of a cation acrylate emulsifier and polyamide epoxy resin. The preparation method comprises heating and melting rosin, adding modifier under stirring, and reacting to obtain modified rosin solution; and introducing the compound emulsifier into the modified rosin solution, fully pre-emulsifying, introducing into a high-pressure homogenizer for homogenizing, cooling, and adding the stabilizer to obtain the cation dispersed rosin size. The invention uses cationic acrylate emulsifier and polyamide epoxy resin as composite emulsifier, and adopts continuous high-temperature pre-emulsification and high-pressure homogeneous emulsification processes to obtain the milky cationic rosin size with low viscosity, low foam and low chlorine content, and the milky cationic rosin size has the advantages of good stability, good dispersibility in cold water, good storage stability, no layering and precipitation after being placed for six months at normal temperature, and no floating matter.)

1. The cation dispersed rosin size is characterized by comprising modified rosin, an effective amount of composite emulsifier and a stabilizer, wherein the composite emulsifier is composed of a cation acrylate emulsifier and polyamide epoxy resin.

2. The cationic dispersion rosin size of claim 1, wherein said cationic acrylate emulsifier is prepared by radical polymerization of styrene, butyl acrylate, dimethylaminoethyl methacrylate, acrylamide; the polyamide epoxy resin is prepared by condensing adipic acid, diethylenetriamine, glycerol and epichlorohydrin.

3. The cationic dispersion rosin size of claim 1, wherein the weight ratio of the cationic acrylate emulsifier to the polyamide epoxy resin in the composite emulsifier is 1.5-2.0: 1.

4. The cationically dispersed rosin size as in claim 1, wherein said modified rosin is prepared by reacting a rosin with at least one of fumaric acid, maleic acid, and maleic anhydride as a modifier.

5. The cationic dispersion rosin size of claim 4, wherein the weight ratio of rosin to modifier is 5-20: 1.

6. the cationic dispersion rosin size of claim 4, wherein the weight ratio of rosin to compound emulsifier is 1: 1-4.

7. The cationic dispersion rosin size of claim 4, wherein said stabilizer is at least one selected from the group consisting of polydiallyldimethylammonium chloride and cetyltrimethylammonium chloride, and is added in an amount of 0.1-1.0% by weight of rosin.

8. A process for the preparation of a cationically dispersed rosin size according to any one of claims 1 to 7, characterized in that it comprises the following steps:

heating and melting rosin, adding a modifier while stirring, and fully reacting to obtain modified rosin liquid;

mixing a cationic acrylate emulsifier and polyamide epoxy resin to prepare a composite emulsifier;

step three, introducing the compound emulsifier into the modified rosin solution, and fully pre-emulsifying to obtain pre-emulsified rosin solution;

and step four, introducing the pre-emulsified rosin solution into a high-pressure homogenizer, homogenizing, cooling, adding a stabilizer, and adjusting solid content to obtain the cationic dispersion rosin size.

9. The method of claim 8, wherein the weight ratio of each component is as follows:

10. the method as claimed in claim 8, wherein the first step comprises a heating and melting temperature of 120-; in the second step, the composite emulsifier is mixed and heated to 120-130 ℃; in the third step, the full pre-emulsification is carried out under the action of a dispersion machine, the pre-emulsification temperature is 150-: 8000-10000 r/min; the homogenizing pressure of the homogenizer in the fourth step is controlled as follows: low pressure 8-10MPa and high pressure 25-30 MPa.

Technical Field

The invention relates to the field of rosin size preparation, in particular to a cationic dispersion rosin size and a preparation method thereof.

Background

Sizing is an important process for papermaking, rosin sizing agent is dominant in a plurality of paper sizing agents, and the most domestic sizing agent in the stock is the rosin sizing agent, and the dosage of the rosin sizing agent accounts for more than 2/3 of the total sizing amount. The glue applying rate of the dispersive rosin size is 4 times that of the common rosin size, the glue applying rate of the dispersive rosin size is 2 times that of the reinforced rosin size, the quality of paper can be improved, the using amount of aluminum sulfate and a whitening agent is reduced, and the dispersive rosin size is a replacement product of saponified rosin size.

Cationic dispersion rosin size has numerous advantages and has been one of the main sizing agents for internal sizing of papermaking pulps. At present, the production process of cationic rosin size is mostly an intermittent normal pressure reverse phase method, the requirement on the emulsification process condition is higher, the stability of the produced rosin size is slightly poor, and the phase transformation is easy to occur to form brown precipitate on the liquid surface; the emulsifier is a single high molecular polymer, a large amount of foam is generated in use or the chlorine content of a finished product is higher, and the emulsifier is complex in production process and higher in cost.

Disclosure of Invention

The invention aims to provide a cation dispersed rosin size and a preparation method thereof, so as to solve the defects in the background technology.

The invention is realized by the following technical scheme:

the cationic dispersion rosin size comprises modified rosin, an effective amount of composite emulsifier and a stabilizer, wherein the composite emulsifier is composed of cationic acrylate emulsifier and polyamide epoxy resin.

The cationic acrylate emulsifier is prepared by polymerizing styrene, butyl acrylate, dimethylaminoethyl methacrylate and acrylamide through free radicals. Can be prepared by methods conventional in the art, for example, by the following method: adding pure water, dilute sulfuric acid (20%), styrene, butyl acrylate and dimethylaminoethyl methacrylate into a reaction kettle in sequence, starting stirring and heating, respectively preparing acrylamide and sodium persulfate into aqueous solutions, starting dropwise adding the acrylamide solution and the sodium persulfate solution at the same time when the temperature of the kettle material rises to 78 ℃, dropwise adding for 1 hour, and continuing to keep the temperature for 4 hours after the dropwise adding is finished, thereby obtaining the cationic acrylate emulsifier.

The polyamide epoxy resin is prepared by condensing adipic acid, diethylenetriamine, glycerol and epichlorohydrin. Can be prepared by methods conventional in the art, for example, by the following method: adding adipic acid and glycerol into the kettle bottom, stirring, slowly adding diethylenetriamine, heating to 150 ℃, keeping the temperature, reacting for 3 hours, cooling to 40 ℃, dropwise adding epoxy chloropropane, heating to 50 ℃, keeping the temperature, reacting for 4 hours, discharging and cooling to obtain the polyamide epoxy resin.

The weight ratio of the cationic acrylate emulsifier to the polyamide epoxy resin in the composite emulsifier can be adjusted according to the practical application condition of the cationic dispersed rosin size product, but in order to obtain a product with good stability and less foam, the weight ratio of the cationic acrylate emulsifier to the polyamide epoxy resin in the composite emulsifier is preferably 1.5-2.0:1, and the solid content of the composite emulsifier is preferably 6.0-6.5%.

The modified rosin may be a modified rosin commonly used in the art, such as polymerized rosin, disproportionated rosin, and the like. Preferably, the modified rosin is prepared by reacting at least one of fumaric acid, maleic acid and maleic anhydride as a modifier with rosin. The preferable weight ratio of the rosin to the modifier is 5-20: 1. the preferred reaction conditions are 190 ℃ and 195 ℃ for 2 h.

In the invention, the addition amount of the composite emulsifier can be adjusted according to the actual use requirement, and preferably, the weight ratio of the rosin to the composite emulsifier is 1: 1-4.

Preferably, the stabilizer is at least one selected from polydiallyl dimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride. The addition amount of the stabilizer is 0.1-1.0% of the weight of the rosin.

The invention further provides a preparation method of the cation dispersed rosin size, which comprises the following steps:

heating and melting rosin, adding a modifier while stirring, and fully reacting to obtain modified rosin liquid;

mixing a cationic acrylate emulsifier and polyamide epoxy resin to prepare a composite emulsifier;

step three, introducing the compound emulsifier into the modified rosin solution, and fully pre-emulsifying to obtain pre-emulsified rosin solution;

and step four, introducing the pre-emulsified rosin solution into a high-pressure homogenizer, homogenizing, cooling, adding a stabilizer, and adjusting solid content to obtain the cationic dispersion rosin size.

As a preferred technical scheme, the weight ratio of each component is as follows:

and a proper amount of water.

The weight parts of the components are calculated according to the effective content of the raw materials as 100 percent, and the actual dosage needs to be converted according to the effective content of the raw materials.

Preferably, the modifier is selected from at least one of fumaric acid, maleic acid and maleic anhydride.

Preferably, the stabilizer is at least one selected from polydiallyl dimethyl ammonium chloride and hexadecyl trimethyl ammonium chloride.

Preferably, the heating and melting temperature in the first step is 120-130 ℃, the modification reaction temperature is 180-195 ℃, and the reaction time is 2-3 hours.

Preferably, in the second step, the composite emulsifier is mixed and heated to 120-130 ℃; in the third step, the full pre-emulsification is carried out under the action of a dispersion machine, the pre-emulsification temperature is 150-: 8000-10000 r/min.

The homogenizing pressure of the homogenizer in the fourth step is controlled as follows: low pressure 8-10MPa and high pressure 25-30 MPa.

Wherein the solid content of the composite emulsifier is 6.0-6.5 wt%.

The cationic rosin size with low viscosity, low foam and low chlorine content is obtained by using a cationic acrylate emulsifier and polyamide epoxy resin as composite emulsifiers and adopting continuous high-temperature pre-emulsification and high-pressure homogenizing emulsification processes. The cation dispersed rosin size has the advantages of milky appearance, good stability, solid content of 30-40%, viscosity of 15mPa.s, good dispersibility in cold water, good storage stability, no delamination, no precipitation and no floating objects after being placed for six months at normal temperature.

Detailed Description

The invention is illustrated below by means of specific examples, without being restricted thereto. The components in the examples are conventional commercial products unless otherwise specified.

Wherein, the cationic acrylate emulsifier is prepared by the following method: adding pure water, dilute sulfuric acid (20%), styrene, butyl acrylate and dimethylaminoethyl methacrylate into a reaction kettle in sequence, starting stirring and heating, respectively preparing acrylamide and sodium persulfate into aqueous solutions, starting dropwise adding the acrylamide solution and the sodium persulfate solution at the same time when the temperature of the kettle material rises to 78 ℃, dropwise adding for 1 hour, and continuing to keep the temperature for 4 hours after the dropwise adding is finished, thereby obtaining the cationic acrylate emulsifier.

The polyamide epoxy resin is prepared by the following method: adding adipic acid and glycerol into the kettle bottom, stirring, slowly adding diethylenetriamine, heating to 150 ℃, keeping the temperature, reacting for 3 hours, cooling to 40 ℃, dropwise adding epoxy chloropropane, heating to 50 ℃, keeping the temperature, reacting for 4 hours, discharging and cooling to obtain the polyamide epoxy resin.