阅读说明：本技术 一种聚酰胺多胺-聚醚胺粘缸剂的制备方法 (Preparation method of polyamide polyamine-polyetheramine cylinder sticking agent ) 是由 钱进 梁福根 谢占豪 方黎锋 姚胜 来雷 赵世英 陈文杰 于 2020-04-16 设计创作，主要内容包括：本发明公开了一种聚酰胺多胺-聚醚胺粘缸剂的制备方法。本发明采用的方法为：通氮气保护下,烯基胺衍生物与油脂以及二元酸或对应的二元酯先在常压下进行缩聚反应,然后在真空条件下继续缩聚反应直到分子量不再变大,加水形成聚酰胺多胺中间体的水溶液；在所述的水溶液中加入支化聚醚胺,密闭反应,升温进行交联反应,最后加入有机酸终止反应,加水稀释得到聚酰胺多胺-聚醚胺粘缸剂。本发明制备的粘缸剂具有较好的粘结力、柔软性、水溶性、均匀性和耐久性等,而且避免了环氧氯丙烷的使用。(The invention discloses a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent. The method adopted by the invention comprises the following steps: under the protection of nitrogen, firstly carrying out polycondensation reaction on an alkenyl amine derivative, grease and dibasic acid or corresponding dibasic ester under normal pressure, then continuing the polycondensation reaction under the vacuum condition until the molecular weight is not increased any more, and adding water to form a water solution of a polyamide polyamine intermediate; adding branched polyether amine into the aqueous solution, carrying out a sealing reaction, heating to carry out a crosslinking reaction, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-polyether amine cylinder sticking agent. The cylinder sticking agent prepared by the invention has better adhesive force, flexibility, water solubility, uniformity, durability and the like, and avoids the use of epoxy chloropropane.)

1. A preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent is characterized in that under the protection of nitrogen gas, an alkenyl amine derivative, grease and dibasic acid or corresponding dibasic ester are subjected to polycondensation reaction under normal pressure, then the polycondensation reaction is continued under the vacuum condition until the molecular weight is not increased any more, and water is added to form an aqueous solution of a polyamide polyamine intermediate;

adding branched polyether amine into the aqueous solution, carrying out a sealing reaction, heating to carry out a crosslinking reaction, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-polyether amine cylinder sticking agent.

2. A preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent is characterized in that under the protection of nitrogen, under the conditions of normal pressure and 130-200 ℃ of temperature, a condensation polymerization reaction is carried out on an alkenyl amine derivative, grease and dibasic acid or corresponding dibasic ester, then under the conditions of 150-240 ℃ of temperature and absolute pressure of 1-5000Pa, the condensation polymerization reaction is continued until the molecular weight is not increased any more, and water is added to form a water solution of a polyamide polyamine intermediate; adding branched polyether amine into the aqueous solution, carrying out a closed reaction, heating to 80-140 ℃ for carrying out a crosslinking reaction for 0.5-10 hours, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain a polyamide polyamine-polyether amine cylinder sticking agent with the solid content of 5-30%;

before the grease participates in the reaction, vacuum dehydration is needed, and the pressure is reduced to the absolute pressure of less than 5kPa at the temperature of 100-150 ℃ until the constant weight is achieved.

3. The method of claim 1 or 2, wherein the enamine derivative is selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hydroxyethylethylenediamine, hydroxypropylethylenediamine, aminoethylaminopropylamine, dipropylenetriamine, or a mixture thereof.

4. The method for preparing a polyamidoamine-polyetheramine cylinder stick agent according to claim 1 or 2, wherein the oil is selected from one or a mixture of two or more of rapeseed oil, soybean oil, peanut oil, corn oil, palm kernel oil, coconut oil, rice oil, linseed oil, sunflower seed oil, camellia seed oil, lard oil, and beef tallow.

5. The method for preparing the cylinder sticking agent of polyamide polyamine-polyetheramine as claimed in claim 1, wherein the dibasic acid is one or a mixture of two or more selected from malonic acid, succinic acid, glutaric acid, adipic acid, dodecanedioic acid, succinic acid, isophthalic acid and terephthalic acid; the dibasic ester is one or a mixture of more than two of dimethyl ester, diethyl ester and dibutyl ester.

6. The method for preparing the cylinder sticking agent of polyamide polyamine-polyether amine as claimed in claim 1, wherein the branched polyether amine is polyether amine containing more than 3 terminal amino groups, and the organic acid is one or a mixture of more than two of formic acid, acetic acid, propionic acid and benzoic acid.

7. The process for preparing a polyamidoamine-polyetheramine cylinder adhesive according to claim 6, wherein the branched polyetheramine is a Hunsmet series polyetheramine having 3 terminal amino groups and has the following general formula:

wherein, R is H or alkyl, n is 0 or 1, x, y and z are positive integers, and the value range of x + y + z is 5-85.

8. The process for producing a polyamidoamine-polyetheramine cylinder stick agent according to claim 1 or 2, wherein the molar ratio of the alkenylamine derivative to the oil, the dibasic acid or the dibasic ester is 1.0: 0.001-0.1: 0.9 to 1.1; the molar ratio of the branched polyether amine to hydrogen ions and alkenyl amine derivatives contained in the organic acid is 0.001-0.1: 0.05-0.5: 1.

9. a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent is characterized in that under the protection of nitrogen gas, diethylenetriamine, beef tallow and adipic acid are subjected to polycondensation reaction at normal pressure and at the temperature of 140-180 ℃, then the polycondensation reaction is continued under the conditions of 175-185 ℃ and absolute pressure of 95-105Pa until the molecular weight is not increased any more, and water is added to form a water solution of a polyamide polyamine intermediate; adding branched Henschel Ma polyether amine T3000, carrying out a closed reaction, heating to 105-115 ℃ for carrying out a crosslinking reaction for 3.5-4.5 hours, finally adding formic acid to terminate the reaction, and adding water to dilute to obtain a polyamide polyamine-polyether amine cylinder adhesive with the solid content of 5-30%;

before the beef tallow participates in the reaction, vacuum dehydration is carried out, the pressure is reduced to the absolute pressure below 5kPa at the temperature of 100-150 ℃, and the dehydration is carried out to the constant weight;

the molar ratio of the used diethylenetriamine, the used beef tallow, the used adipic acid, the used polyetheramine T3000 and the used formic acid is 1.5: 0.02: 1.47: 0.06: 0.3.

10. a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent is characterized in that under the protection of nitrogen, diethylenetriamine, triethylene tetramine, palm oil and adipic acid are subjected to polycondensation reaction at normal pressure and the temperature of 140-180 ℃, then the polycondensation reaction is continued under the conditions of 175-185 ℃ and 100Pa absolute pressure until the molecular weight is not increased any more, and water is added to form a water solution of a polyamide polyamine intermediate; adding branched Henschel Ma polyether amine T3000, sealing the reaction kettle, heating to 105-115 ℃ for crosslinking reaction for 3.5-4.5 hours, finally adding formic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-polyether amine cylinder adhesive with the solid content of 5-30%;

before the beef tallow participates in the reaction, vacuum dehydration is carried out, the pressure is reduced to the absolute pressure below 5kPa at the temperature of 100-150 ℃, and the dehydration is carried out to the constant weight;

the molar ratio of diethylenetriamine, triethylene tetramine, palm oil, adipic acid, polyether amine T3000 and formic acid is 1: 0.5: 0.02: 1.47: 0.06: 0.3.

Technical Field

The invention belongs to the technical field of papermaking additives, and relates to a cylinder sticking agent which is sprayed on a drying cylinder to help paper sheet wrinkling during production of crepe paper, in particular to a preparation method of a polyamide polyamine-polyether amine cylinder sticking agent.

Background

When the crepe paper is produced, the paper passes through a drying cylinder for drying, and needs to generate strong impact with a scraper to generate wrinkles so as to improve the properties of softness, water absorption, bulk and the like of the paper and obtain good hand feeling. The creping process requires a suitable bond between the sheet and the dryer, and for paper machines with higher speeds, the natural bond between the sheet and the dryer alone is insufficient to form the desired crepe, requiring adjustment with dryer coating aids (including cylinder stickers, strippers, and modifiers) to achieve flexible control of the creping process. The coating auxiliary agent is improperly used or has poor performance, which not only can cause great influence on the quality of paper, but also can cause the problems of pinholes, dead lines, broken holes and the like, and even can cause the cutter jump to cause the damage of a drying cylinder. Among them, the most critical to the establishment and adjustment of the coating is the cylinder adhesive, but the current cylinder adhesive has the problems of not being compatible in terms of performance, such as adhesion, flexibility, water solubility, uniformity and durability.

Compared with substitutes such as polyvinyl alcohol, polyvinyl acetate, polyacrylamide, polyether and the like, the polyamide polyamine-epichlorohydrin series cylinder-sticking agent has obvious comprehensive performance advantages, and therefore becomes the cylinder-sticking agent which is most widely applied in commerce. The polyamide polyamine-epichlorohydrin cylinder-sticking agent is thermosetting resin which takes polyamide polyamine as a main chain and takes epichlorohydrin as a cross-linking agent, and is also called PAE resin and PAE cylinder-sticking agent. The PAE resin has good flexibility and water solubility; the viscosity is low and the leveling is easy under the water environment, so that the uniformity is realized; one epichlorohydrin molecule can be connected with 2-3 polyamide polyamine molecules, so that the molecular weight of the polymer is increased, the number of terminal groups is increased, and the adhesive force is stronger.

However, the unreacted epichlorohydrin in the PAE resin can be absorbed by human body and is harmful to human health, and the chloropropanol as the hydrolysis product is more harmful. National standard GB5009.191-2016 specifies the allowable content of chloropropanol in food products, including DCP (1, 3-dichloro-2-propanol), MCPD (3-chloro-1, 2-propanediol). The national standard GB/T36420-2018 specifies the limited content of absorbable halides in the paper for daily use and paper products, including epichlorohydrin, DCP and MCPD, but does not provide a detection method.

In addition, the irreversible crosslinking reaction provides good adhesion to the PAE cylinder adhesive, which also results in less than desirable durability. PAE stickers tend to build up on the dryer surface, crosslinking continues to raise the polymer molecular weight indefinitely, the coating hardens over time, causing blade rattle, partial coating may crack and fall off, causing sheet holes and even sheet breaks, and the coating has to be rebuilt.

Many researchers have carried out molecular structure modification or blending based on PAE resins in an attempt to overcome the disadvantage of easy hardening of PAE. For example, CN201180024895 uses reactive assistant modified PAE with strippability formed by reacting polyalkylene polyamine with electrophilic reagent to prepare cylinder sticking agent; patent CN201280003852 prepares a cylinder sticking agent by blending PAE with a polyvinyl alcohol copolymer having a carboxylic ester or sulfonic ester repeating unit; patent CN201610814690 inserts acrylic acid monomer into polyamide polyamine molecule and polymerizes to obtain polyamide polyamine with higher molecular weight, and then cross-links with epichlorohydrin to obtain cylinder sticking agent.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a preparation method of the polyamide polyamine-polyether amine cylinder sticking agent, which avoids using epoxy chloropropane and is used for improving the comprehensive performance of the polyamide polyamine-polyether amine cylinder sticking agent.

Therefore, the invention adopts the following technical scheme: a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent comprises the following steps: under the protection of nitrogen, firstly carrying out polycondensation reaction on an alkenyl amine derivative, grease and dibasic acid or corresponding dibasic ester under normal pressure, then continuing the polycondensation reaction under the vacuum condition until the molecular weight is not increased any more, and adding water to form a water solution of a polyamide polyamine intermediate;

adding branched polyether amine into the aqueous solution, carrying out a sealing reaction, heating to carry out a crosslinking reaction, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-polyether amine cylinder sticking agent.

The cylinder sticking agent prepared by the invention has better adhesive force, flexibility, water solubility, uniformity, durability and the like, and avoids the use of epoxy chloropropane. In the case of the cylinder sticking agent of polyamide polyamine-epichlorohydrin and polyamide polyamine-polyetheramine, the aging process of the coating with time is the process of crosslinking the polymer and hardening from soft, so that the good durability and the good softness are consistent.

The other technical scheme adopted by the invention is as follows: a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent comprises the following steps: under the protection of nitrogen, firstly, the alkenyl amine derivative, the grease and the dibasic acid or the corresponding dibasic ester are subjected to polycondensation reaction at normal pressure and at the temperature of 130-200 ℃, then the polycondensation reaction is continued under the conditions of 150-240 ℃ and the absolute pressure of 1-5000Pa until the molecular weight is not increased any more, and water is added to form the aqueous solution of the polyamide polyamine intermediate; adding branched polyether amine into the aqueous solution, carrying out a closed reaction, heating to 80-140 ℃ for carrying out a crosslinking reaction for 0.5-10 hours, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain a polyamide polyamine-polyether amine cylinder sticking agent with the solid content of 5-30%;

before the grease participates in the reaction, vacuum dehydration is needed, and the pressure is reduced to the absolute pressure of less than 5kPa at the temperature of 100-150 ℃ until the constant weight is achieved.

The enamine derivative is selected from one or a mixture of two of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, amino ethyl aminopropylamine and dipropylenetriamine.

Further, the oil is selected from one or a mixture of more than two of rapeseed oil, soybean oil, peanut oil, corn oil, palm kernel oil, coconut oil, rice oil, linseed oil, sunflower seed oil, camellia seed oil, lard oil and beef tallow. The main component of these fats and oils is triglyceride.

Further, the dibasic acid is selected from one or a mixture of more than two of malonic acid, succinic acid, glutaric acid, adipic acid, dodecanedioic acid, succinic acid, isophthalic acid and terephthalic acid; the dibasic ester is one or a mixture of more than two of dimethyl ester, diethyl ester and dibutyl ester.

Further, the branched polyether amine is polyether amine containing more than 3 terminal amino groups, and the organic acid is one or a mixture of more than two of formic acid, acetic acid, propionic acid and benzoic acid.

Further, the branched polyether amine is a Henschel MiT series polyether amine with 3 terminal amino groups, and the general formula is as follows:

wherein, R is H or alkyl, n is 0 or 1, x, y and z are positive integers, and the value range of x + y + z is 5-85.

Further, the mol ratio of the alkenyl amine derivative to the grease, the dibasic acid or the dibasic ester is 1.0: 0.001-0.1: 0.9-1.1, when the using amount of the dibasic acid is increased, the using amount of the grease needs to be properly reduced, and the adhesive force and the water resistance of a final product are better; the grease can be regarded as monoacid, and when the using amount is increased, the softness and uniformity of the obtained resin are better; the molar ratio of the branched polyether amine to hydrogen ions and alkenyl amine derivatives contained in the organic acid is 0.001-0.1: 0.05-0.5: 1.

the invention adopts another technical scheme that: a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent comprises the following steps: under the protection of nitrogen, performing polycondensation reaction on diethylenetriamine, beef tallow and adipic acid at normal pressure and at the temperature of 140-180 ℃, then continuing the polycondensation reaction at the temperature of 175-185 ℃ and under the absolute pressure of 95-105Pa until the molecular weight is not increased any more, and adding water to form an aqueous solution of a polyamide polyamine intermediate; adding branched Henschel Ma polyether amine T3000, carrying out a closed reaction, heating to 105-115 ℃ for carrying out a crosslinking reaction for 3.5-4.5 hours, finally adding formic acid to terminate the reaction, and adding water to dilute to obtain a polyamide polyamine-polyether amine cylinder adhesive with the solid content of 5-30%;

before the beef tallow participates in the reaction, vacuum dehydration is carried out, the pressure is reduced to the absolute pressure below 5kPa at the temperature of 100-150 ℃, and the dehydration is carried out to the constant weight;

the molar ratio of the used diethylenetriamine, the used beef tallow, the used adipic acid, the used polyetheramine T3000 and the used formic acid is 1.5: 0.02: 1.47: 0.06: 0.3.

the invention adopts another technical scheme that: a preparation method of a polyamide polyamine-polyetheramine cylinder sticking agent comprises the following steps: under the protection of nitrogen, performing polycondensation reaction on diethylenetriamine, triethylenetetramine, palm oil and adipic acid at normal pressure and at the temperature of 140-180 ℃, then continuing the polycondensation reaction at the temperature of 175-185 ℃ and under the absolute pressure of 100Pa until the molecular weight is not increased any more, and adding water to form a water solution of a polyamide polyamine intermediate; adding branched Henschel Ma polyether amine T3000, sealing the reaction kettle, heating to 105-115 ℃ for crosslinking reaction for 3.5-4.5 hours, finally adding formic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-polyether amine cylinder adhesive with the solid content of 5-30%;

before the beef tallow participates in the reaction, vacuum dehydration is carried out, the pressure is reduced to the absolute pressure below 5kPa at the temperature of 100-150 ℃, and the dehydration is carried out to the constant weight;

the molar ratio of diethylenetriamine, triethylene tetramine, palm oil, adipic acid, polyether amine T3000 and formic acid is 1: 0.5: 0.02: 1.47: 0.06: 0.3.

the invention has the beneficial effects that: the polyamide polyamine-polyether amine resin has higher initial molecular weight and good initial adhesive force when being used as a cylinder sticking agent; the branched polyether amine is used as a crosslinking agent, so that the drying cylinder coating can keep a long-time and slow crosslinking speed, the coating cannot become very hard in the period, and the bonding property lasts for a long time; the branched polyether amine has better water solubility than epoxy chloropropane, the obtained polyamide polyamine-polyether amine resin has good water solubility and low viscosity, and a drying cylinder coating formed by spraying has good uniformity; by additionally adding grease, the cylinder sticking agent contains long alkyl chain amide compounds, a non-combination area is formed locally, and the drying cylinder coating still has certain fluidity in the non-combination area even after long-time crosslinking, so that the drying cylinder coating does not become hard as a whole.

Detailed Description

The technology of the present invention will be described in detail below with reference to specific embodiments. It should be understood that the following detailed description is only for the purpose of assisting those skilled in the art in understanding the present invention, and is not intended to limit the present invention.