阅读说明：本技术 一种聚酰胺多胺-缩水甘油醚树脂粘缸剂及其制备方法和应用 (Polyamide polyamine-glycidyl ether resin cylinder-sticking agent and preparation method and application thereof ) 是由 钱进 梁福根 谢占豪 俞晗 肖鹏 陈文杰 张勇 钟俊汉 于 2021-01-20 设计创作，主要内容包括：本发明公开了一种聚酰胺多胺-缩水甘油醚树脂粘缸剂及其制备方法和应用。本发明的聚酰胺多胺-缩水甘油醚树脂粘缸剂是烯基胺衍生物与二元酸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。降温加入缩水甘油醚类物质,密闭反应釜,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-缩水甘油醚树脂粘缸剂。本发明的聚酰胺多胺-缩水甘油醚树脂粘缸剂具有良好的水溶性,粘度低,喷涂形成的烘缸涂层具有良好的均匀性。(The invention discloses a polyamide polyamine-glycidyl ether resin cylinder-sticking agent, a preparation method and application thereof. The cylinder sticking agent of polyamide polyamine-glycidyl ether resin is prepared by the steps of firstly carrying out polycondensation reaction on alkenyl amine derivatives and dibasic acid 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 an aqueous solution of a polyamide polyamine intermediate. Cooling, adding glycidyl ether substances, sealing the reaction kettle, heating to carry out crosslinking reaction, adding organic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-glycidyl ether resin cylinder-sticking agent. The polyamide polyamine-glycidyl ether resin cylinder adhesive has good water solubility and low viscosity, and a drying cylinder coating formed by spraying has good uniformity.)

1. A method for preparing polyamide polyamine-glycidyl ether resin cylinder-sticking agent is characterized in that,

firstly, performing polycondensation reaction on an alkenyl amine derivative and dibasic acid at normal pressure and at the temperature of 130-200 ℃, then continuing the polycondensation reaction at the temperature of 150-240 ℃ and under the absolute pressure of 1-5000Pa until the molecular weight is not increased any more, and adding water to form an aqueous solution of a polyamide polyamine intermediate;

cooling the aqueous solution of the polyamide polyamine intermediate to 0-20 ℃, adding glycidyl ether, sealing the reaction kettle, heating to 10-70 ℃ for crosslinking reaction for 1-10 hours, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-glycidyl ether resin cylinder sticking agent with the solid content of 5-30%.

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

3. The method for preparing a polyamide polyamine-glycidyl ether resin cylinder adhesive as claimed in claim 1, wherein the dibasic acid is one or more selected from malonic acid, succinic acid, glutaric acid, adipic acid, dodecanedioic acid, succinic acid, isophthalic acid and terephthalic acid.

4. The method for preparing a polyamide polyamine-glycidyl ether resin cylinder adhesive according to claim 1, wherein the glycidyl ether is selected from one or a mixture of more than two of 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether and ethylene glycol diglycidyl ether.

5. The method for preparing a polyamide polyamine-glycidyl ether resin cylinder-sticking agent according to claim 1, wherein the organic acid is one or a mixture of more than two of formic acid, acetic acid, propionic acid and benzoic acid.

6. The method for preparing a polyamide polyamine-glycidyl ether resin cylinder adhesive according to claim 1, wherein the molar ratio of the alkenyl amine derivative to the dibasic acid to the glycidyl ether is 1.0: 0.9-1.1: 0.01-0.8.

7. The process for preparing a cylinder stick of polyamide polyamine-glycidyl ether resin according to claim 1 or 6, wherein the molar ratio of the alkenyl amine derivative to the dibasic acid to the glycidyl ether is 1.0: 0.9-1.1: 0.2-0.6.

8. A polyamide polyamine-glycidyl ether resin cylinder adhesive characterized by being prepared by the method of any one of claims 1 to 7.

9. Use of a polyamidoamine-glycidyl ether resin cylinder adhesive for creping paper, characterized in that the polyamidoamine-glycidyl ether resin cylinder adhesive prepared by the method of any one of claims 1 to 7 is sprayed on a drying cylinder to help the creping of the paper sheet.

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 polyamide polyamine-glycidyl ether resin cylinder sticking agent, and a preparation method and application thereof.

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.

The irreversible crosslinking reaction provides good adhesion to the PAE cylinder adhesive and also results in less than ideal 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, patent CN201180024895 uses reactive auxiliary agent with stripping property formed by reaction of polyalkylene polyamine and electrophilic reagent to modify PAE to prepare the cylinder sticking agent, patent CN201280003852 mixes PAE and polyvinyl alcohol copolymer with carboxylic ester or sulfonic ester repeating units to prepare the cylinder sticking agent, patent CN201610814690 inserts acrylic acid monomer into polyamide polyamine molecules and polymerizes to obtain polyamide polyamine with higher molecular weight, and then crosslinks with epichlorohydrin to obtain the cylinder sticking agent.

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 paper and paper products for daily use, 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.

Furthermore, because the PAE has certain crosslinking property at normal temperature, the higher the solid content is, the more easily the PAE is gelled due to crosslinking, the solid content of the commercially available jar-sticking agent is generally below 15 percent and not more than 40 percent at most, and the packaging, storage and transportation cost is higher.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a polyamide polyamine-glycidyl ether resin cylinder sticking agent which has high solid content and is easy to stably store, and a preparation method and application thereof.

Therefore, the invention adopts the following technical scheme: a method for preparing a polyamide polyamine-glycidyl ether resin cylinder-sticking agent comprises the following steps:

firstly, performing polycondensation reaction on an alkenyl amine derivative and dibasic acid at normal pressure and at the temperature of 130-200 ℃, then continuing the polycondensation reaction at the temperature of 150-240 ℃ and under the absolute pressure of 1-5000Pa until the molecular weight is not increased any more, and adding water to form an aqueous solution of a polyamide polyamine intermediate;

cooling the aqueous solution of the polyamide polyamine intermediate to 0-20 ℃, adding glycidyl ether, sealing the reaction kettle, heating to 10-70 ℃ for crosslinking reaction for 1-10 hours, finally adding organic acid to terminate the reaction, and adding water to dilute to obtain the polyamide polyamine-glycidyl ether resin cylinder sticking agent with the solid content of 5-30%.

The invention avoids the use of epoxy chloropropane.

The enamine derivative is selected from one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hydroxyethyl ethylenediamine, hydroxypropyl ethylenediamine, aminoethyl aminopropylamine and dipropylenetriamine.

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.

Further, the glycidyl ether is selected from one or a mixture of more than two of 1, 4-butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, resorcinol diglycidyl ether, cyclohexanediol diglycidyl ether, neopentyl glycol diglycidyl ether and ethylene glycol diglycidyl ether.

Further, the organic acid is selected from one or a mixture of more than two of formic acid, acetic acid, propionic acid and benzoic acid.

Further, the mol ratio of the alkenyl amine derivative to the dibasic acid to the glycidyl ether is 1.0: 0.9-1.1: 0.01-0.8.

Further, the mol ratio of the alkenyl amine derivative to the dibasic acid to the glycidyl ether is 1.0: 0.9-1.1: 0.2-0.6.

The invention also provides the polyamide polyamine-glycidyl ether resin cylinder adhesive prepared by the preparation method.

The invention also provides application of the polyamide polyamine-glycidyl ether resin cylinder adhesive, and the polyamide polyamine-glycidyl ether resin cylinder adhesive is sprayed on a drying cylinder to help paper sheet wrinkling when crepe paper is produced.

The invention has the following beneficial effects: the polyamide polyamine-glycidyl ether resin has higher initial molecular weight and good initial adhesive force when being used as a cylinder sticking agent; the glycidyl ether is used as a cross-linking agent, so that the drying cylinder coating can keep a long-time and slow cross-linking speed, the coating cannot become very hard in the period, and the bonding property lasts for a long time; the glycidyl ether has better water solubility than epoxy chloropropane, the obtained polyamide polyamine-glycidyl ether resin cylinder bonding agent has good water solubility and low viscosity, and a drying cylinder coating formed by spraying has good uniformity; the molecular chain length of the glycidyl ether compared to epichlorohydrin makes the polyamide polyamine-glycidyl ether resin much softer than the polyamide polyamine-epichlorohydrin resin.

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.

Example 1

In a stainless steel reaction kettle with the conditions of weighing, jacket heating, temperature reduction, nitrogen protection, stirring, temperature indication, pressure indication, feeding and the like, nitrogen is replaced, stirring is started, the temperature is increased to 140 ℃, and the vacuum is pumped to 5kPa and kept for 15 minutes. Adding 146g (1mol) of adipic acid, charging nitrogen to slight positive pressure, dropwise adding 113.3g (1.1mol) of diethylenetriamine, heating to 140 ℃, stirring and mixing for 2 hours, then heating to 10 ℃ per hour until 180 ℃, and preserving heat for 2 hours. Starting a vacuum system, gradually vacuumizing to the absolute pressure of 100Pa, and keeping the temperature for 2 hours. Stopping heating, filling nitrogen to micro positive pressure, adding 453.4g of hot deionized water to dilute the reaction materials until the solid content is 33 percent, namely the aqueous solution of the polyamide polyamine intermediate. Cooling the aqueous solution of the polyamide polyamine intermediate to 10 ℃, dropwise adding 70g (0.4mol) of ethylene glycol diglycidyl ether, sealing the reactor, heating to 15 ℃, reacting for 3 hours, adding 4.6g (0.1mol) of formic acid to terminate the reaction, and adding 2155g of deionized water to obtain the polyamide polyamine-glycidyl ether resin cylinder sticking agent A with the solid content of 10%.

Example 2

In a stainless steel reaction kettle with the conditions of weighing, jacket heating, temperature reduction, nitrogen protection, stirring, temperature indication, pressure indication, feeding and the like, nitrogen is replaced, stirring is started, the temperature is increased to 140 ℃, and the vacuum is pumped to 5kPa and kept for 15 minutes. Adding 146g (1mol) of adipic acid, charging nitrogen to slight positive pressure, dropwise adding 113.3g (1.1mol) of diethylenetriamine, heating to 140 ℃, stirring and mixing for 2 hours, then heating to 10 ℃ per hour until 180 ℃, and preserving heat for 2 hours. Starting a vacuum system, gradually vacuumizing to the absolute pressure of 100Pa, and keeping the temperature for 2 hours. Stopping heating, filling nitrogen to micro positive pressure, adding 453.4g of hot deionized water to dilute the reaction materials until the solid content is 33 percent, namely the aqueous solution of the polyamide polyamine intermediate. Cooling the aqueous solution of the polyamide polyamine intermediate to 10 ℃, dropwise adding 8.7g (0.05mol) of ethylene glycol diglycidyl ether, sealing the reactor, heating to 15 ℃, reacting for 5 hours, adding 6g (0.15mol) of formic acid to terminate the reaction, and adding 2070g of deionized water to obtain the polyamide polyamine-glycidyl ether resin cylinder sticking agent B with the solid content of 10%.

Example 3

In a stainless steel reaction kettle with the conditions of weighing, jacket heating, temperature reduction, nitrogen protection, stirring, temperature indication, pressure indication, feeding and the like, nitrogen is replaced, stirring is started, the temperature is increased to 140 ℃, and the vacuum is pumped to 5kPa and kept for 15 minutes. Adding 146g (1mol) of adipic acid, charging nitrogen to slight positive pressure, dropwise adding 113.3g (1.1mol) of diethylenetriamine, heating to 140 ℃, stirring and mixing for 2 hours, then heating to 10 ℃ per hour until 180 ℃, and preserving heat for 2 hours. Starting a vacuum system, gradually vacuumizing to the absolute pressure of 100Pa, and keeping the temperature for 2 hours. Stopping heating, filling nitrogen to micro positive pressure, adding 453.4g of hot deionized water to dilute the reaction materials until the solid content is 33 percent, namely the aqueous solution of the polyamide polyamine intermediate. Cooling the aqueous solution of the polyamide polyamine intermediate to 10 ℃, dropwise adding 136g (0.4mol) of bisphenol A diglycidyl ether, sealing the reactor, heating to 15 ℃, reacting for 5 hours, adding 4.6g (0.1mol) of formic acid to terminate the reaction, and adding 3200g of deionized water to obtain the polyamide polyamine-glycidyl ether resin cylinder sticking agent C with the solid content of 10%.

Comparative example 1

In a stainless steel reaction kettle with the conditions of weighing, jacket heating, temperature reduction, nitrogen protection, stirring, temperature indication, pressure indication, feeding and the like, nitrogen replacement is carried out, 146g (1mol) of adipic acid is added, nitrogen is filled to the micro positive pressure, 113.3g (1.1mol) of diethylenetriamine is dropwise added, the temperature is increased to 140 ℃, stirring and mixing are carried out for 2 hours, then the temperature is increased to 10 ℃ per hour until 180 ℃, and the temperature is kept for 2 hours. Starting a vacuum system, gradually vacuumizing to the absolute pressure of 100Pa, and keeping the temperature for 2 hours. Stopping heating, filling nitrogen to micro positive pressure, adding 453.4g of hot deionized water to dilute the reaction materials until the solid content is 33 percent, namely the aqueous solution of the polyamide polyamine intermediate. Cooling the aqueous solution of the polyamide polyamine intermediate to 25 ℃, dropwise adding 27.8g (0.3mol) of epichlorohydrin, sealing the reactor, heating to 30 ℃ for reaction for 3 hours, heating to 70 ℃ again for reaction for 2 hours, adding 4.6g (0.1mol) of formic acid to terminate the reaction, and adding 3200g of deionized water to obtain the polyamide polyamine-epichlorohydrin resin cylinder adhesive D with the solid content of 10%.

Comparative example 2

Selecting a commercially available polyamide polyamine-epichlorohydrin resin cylinder sticking agent E.

Test method

Molecular weight-viscosity. The viscosity of each cylinder-sticking agent was measured in cP at room temperature at 20 ℃ using a rotary viscometer, spindle No. 3, at 30 RPM. The higher the viscosity, the higher the molecular weight.

Adhesion-tensile strength. A polytetrafluoroethylene channel plate with a groove with the size of 50mm multiplied by 100mm is prepared by adding 5g of wood short fiber into the groove, uniformly spreading, dripping 10g of cylinder sticking agent prepared by the invention, placing in a 105 ℃ oven for drying for 30 minutes, taking out the channel plate, carefully taking down the whole coating when the coating is hot, standing and cooling to room temperature of 20 ℃, cutting out a sample strip with the width of 15mm by a cutter, and testing the tensile strength with a tensile machine with the unit of gf. The greater the tensile strength, the greater the adhesion.

Durability-adhesion rating. The stainless steel channel plate with 50mm 100mm groove is dropped with 10g of the cylinder sticking agent prepared by the invention, and then the channel plate is dried in a 105 ℃ oven for 120 minutes, taken out and cooled to room temperature of 20 ℃. The adhesion of the coating was tested with a hundred grid knife, see GB/T9286-98. The adhesive force is divided into 6 grades of 0-5, the incision of 0 grade is the smoothest, and the adhesive force is the best.

Durability-bond retention. A stainless steel cell plate having a groove of 50mm X100 mm in size, weighed WA at room temperature, WAs dropped with 10g of the jar-bonding agent prepared according to the present invention into the groove, and then dried in an oven at 105 ℃ for 60 minutes. 5g of wood staple fibers were scattered and spread evenly in the grooves in an oven and pressed for 1 minute with a stainless steel block weighing 1kg and having a bottom dimension of 48mm by 98 mm. And removing the steel block, turning the groove plate and slightly shaking to enable the unbonded wood short fibers to fall off fully. The trough plate was taken out, cooled to room temperature of 20 ℃ and weighed as WB. WB-WA is the total weight of the coating in g, the larger the value, the better the retention of the adhesion of the coating.

TABLE 1 Cylinder sticking agent test results

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.