KR20140018697A - Preparation eco-frendly dry strength agent of paper making industry - Google Patents

Abstract

The purpose of the present invention is to provide a method for producing a dry strength agent for eco-friendly paper which manufactures a polyacrylamide (PAM) powder by applying a W/O emulsion radical polymerization/recrystallization method to acrylamide and enables the production of a strong ionic dry strength agent which an existing polyacrylamide (PAM) dry strength agent (DSA) hardly has by changing and improving properties with a NaOCl/NaOH formula using the same. The present invention includes a step of producing first solution by dissolving a mixture containing a non-ionic water-soluble monomer and a cross-bonding agent in deionized water; a step of inputting the first solution into an aliphatic solvent of an oil form and polymerizing those by heating and mixing; a step of producing a non-ionic emulsion polymer by inputting surfactants and removing monomer remaining after polymerization; a step of producing non-ionic polyacrylamide powder by drying the non-ionic emulsion polymer after diluting and filtering; and a step of producing polyvinylamine by changing and improving properties by dissolving the non-ionic polyacrylamide powder into the solution and reacting the non-ionic polyacrylamide powder with the solution.

Description

[0001] The present invention relates to a method for manufacturing an eco-friendly paper strength enhancer,

More particularly, the present invention relates to a nonionic polyacrylamide powder prepared by emulsion polymerization of an oil-in-water (W / O) type emulsion polymer by Hoffman rearrangement Hoffman rearrangement (DSA), which is capable of producing a polyvinylamine type dry strength agent (DSA) by chemical modification.

In general, the dry strength agent (DSA) is divided into a natural polymer and a synthetic polymer, and natural starch and vegetable gum are widely used as synthetic polymers. Acrylamide ) Are mainly used.

Polyacrylamide (PAM) has been developed as a water-soluble polymer in the early 1950's. Polyacrylamide (PAM) is used not only as a dry strength agent (DSA) in the paper industry, Dehydration accelerator and wastewater treatment agent.

Here, since polyacrylamide (PAM) is not a natural high molecular substance such as amphoteric starch or vegetable gum, it can be prepared arbitrarily so as to have a desired molecular weight and charge characteristic, and is very usefully used.

Such polyacrylamide (PAM) is often used after being copolymerized with other monomers having ionic properties, or after being polymerized singly and then having a charge.

At this time, the dry strength agent (DSA) generally used is copolymerized with 5 to 10 mol% of an ionic monomer and is supplied in a solution phase having a solid content of 10 to 20%.

Here, the dry strength agent (DSA) has a molecular weight of 100,000 to 500,000 daltons, which is lower than the molecular weight of the retention improver, in the polyacrylamide (PAM) used.

On the other hand, the retention enhancer, glidency enhancer or dispersant has properties depending on the molecular weight and ionic strength of the polymer.

That is, Polyacrylamide (PAM) forms a hydrogen bond with the hydroxyl group of cellulose, thereby increasing the dry strength of the paper. The polyacrylamide (PAM) has an amide group between the amide group of polyacrylamide (PAM) and a hydroxyl group of cellulose The formed hydrogen bond has a strong binding strength as compared with the hydrogen bond between the hydroxyl groups of cellulose and thus has a very strong effect of strengthening the paper.

The cationic polyacrylamide (PAM) has been used since 1967 as a polymeric material having a characteristic that it has an effect of enhancing the drying force of paper by being fixed on fibers even when it is used singly, and cationic polyacrylamide Polyacrylamide (PAM) is a copolymer of acrylamide and 2-aminoethyl methacrylate, diallyldimethylammonium chloride, trimethylbenzylammonium chloride, Or 2 to 10 mol% of the monomer, or converting the amide group of the prepared polyacrylamide (PAM) into cationic by Mannich reaction.

This has the advantage of not requiring an alarm, not only being effective over a wide pH range, but also adding to all natural pulp and high-grade pulp to provide a strengthening effect.

On the other hand, the synthetic polymer strength enhancer has been imparted with ionic properties depending on the content of ionic monomers by using a nonionic monomer, such as acrylamide, as a skeleton. However, as environmental regulations for polyacrylamide (PAM) The countermeasures are becoming the biggest problem.

In addition, the dry strength agent (DSA) of the PAM type has a problem that the use range is limited when the strong ionicity is required, since the ionic strength is 0.7 meq / g or less.

As a result of the above-described problems, it is desired to develop a product having a higher ionicity that can take measures against environmental regulation, and it is required to develop an environmentally friendly paper strength enhancer Agent: DSA) is required to be developed.

On the other hand, research on the development of polyvinylamine (PVAm) type papermaking additive drugs is proceeding in various ways due to social issues. The development of polyvinylamine (Vinyl formamide) monomers and poly Polyacrylamide (PAM) can be classified into the development of polyvinylamine (PVAm) modification by chemical reaction.

Here, BASF Corporation (Coporation), the most advanced technology with the use of Vinylformamide (Vinylformamide) development method has been around since 2005.

In particular, only BASF Corporation, Mitsubishi Chemical, and Air Products are able to mass-produce vinylformamide, and produce and sell related products exclusively.

Therefore, the development of a polyvinylamine (PVAm) type product modified in polyacrylamide (PAM) has been studied in various fields.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a process for producing a polyacrylamide polymer by applying W / O emulsion radical polymerization / recrystallization process from acrylamide to W / : PAM Powder was modified and modified by NaOCl / NaOH chemical formula using it. Thus, it was found that the strength of PAM (PAM) Powder was improved by using PAM (Dry Strength Agent) which is difficult to obtain in conventional Polyacrylamide (PAM) And an object of the present invention is to provide a method for manufacturing an environmentally-friendly paper strength enhancer capable of producing a paper strength enhancer.

The present invention also relates to a process for preparing a polyvinylamine (PVAm) type dry strength agent (DSA) by chemically modifying a nonionic polyacrylamide powder with a Hoffman rearrangement, The present invention provides a method for manufacturing an environmentally friendly paper strength enhancing agent for paper.

According to an aspect of the present invention, there is provided a method for producing a water-soluble polymer, which comprises dissolving a mixture containing a nonionic water-soluble monomer and a cross-linking agent in deionized water to prepare a first solution; Introducing the first solution into an aliphatic solvent in an oil phase, and heating and stirring to polymerize; Adding a surfactant and removing the remaining monomers after polymerization to prepare a nonionic emulsion polymer; Diluting, filtering, filtering and drying the nonionic emulsion polymer to prepare a nonionic polyacrylamide powder; And a nonionic polyacrylamide powder dissolved in an aqueous solution to react and modify the polyacrylamide powder to prepare polyvinylamine; .

Here, the nonionic water-soluble monomer is composed of at least one selected from acrylamide, methacrylamide, N, N-diethylacrylamide, N-isopropylamide and N-t-butyl acrylamide.

In the production of the first solution, at least one selected from methylene bisacrylamide as a cross-linking agent and sodium formate as a molecular weight modifier is added.

On the other hand, in order to remove the monomer remaining in the first solution, ammonium sulfate and sodium bisulfate are added and reacted.

Here, the surfactant is at least one selected from a sorbitan monooleate surfactant, a sorbitan monosterate surfactant, and a polyethylene alkyl ester surfactant.

At least one selected from the group consisting of sodium hypochlorite and sodium hydroxide is added during modification of the nonionic polyacrylamide powder.

Here, sodium molybdate and sodium hydroxide have a molar ratio of 1: 2, and the conversion ratio and ionicity of the polyvinylamine are controlled by the ratio of the added amount.

As described above, the present invention having the above-described structure can be applied to a polyacrylamide (PAM) powder which is chemically modified and modified with a polyvinylamine type dry strength agent (DSA ) Can be extended to a range of 4.0 meq / g of CD measured in a range of 0.2 to 0.78 meq / g in a conventional polyacrylamide (PAM) dry strength agent (DSA) (DSA), which is difficult to obtain from conventional Polyacrylamide (PAM) Dry Strength Agents (DSA), and to have a higher ionic strength It can be used in a wide range of fields and it is possible to take measures against environmental regulations.

The present invention also relates to a process for producing a polyacrylamide (PAM) powder which is not a Hoffmann reaction using a conventional polyacrylamide (PAM) 10 to 40% solution base (PVAm) dry strength agent (DSA) was added to NaOCl / NaOH aqueous solution to prepare polyvinylamine (DSA) having a higher molecular weight than the conventional dry strength agent (DSA) Polyvinylamine (PVAm), a dry strength agent (DSA), and a content of polyvinylamine (PVAm) of 12 to 15% or more.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is not limited to the scope of the present invention, but is merely an example, and various modifications can be made without departing from the technical spirit of the present invention.

The present invention relates to a method for converting a polyacrylamide (PAM) polymer to a polyvinylamine (PVAm) polymer, and more particularly to a method of converting a polyacrylamide (PVAm) polymer in the form of a powder obtained from a W / O type nonionic emulsion polymer (Polyacrylamide: PAM) was transformed into a polyvinylamine (PVAm) by the Hoffman rearrangement reaction and converted to a dry strength agent (DSA) according to the conversion ratio. ≪ / RTI >

Hereinafter, a method for manufacturing an environment-friendly paper strengthening agent for paper according to the present invention will be described.

The process according to the present invention comprises the steps of preparing a first solution by dissolving a mixture containing a nonionic water-soluble monomer and a cross-linking agent in deionized water, introducing the first solution into an aliphatic solvent in an oil phase, heating and stirring to polymerize .

Here, the nonionic water soluble monomer includes acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylamide, Nt-butyl acrylamide and the like.

On the other hand, in the polymer according to the present invention, it is possible to use a small amount of anionic monomer. In this case, there is an advantage that the reaction rate and the polymer dispersibility are increased. Examples of negative unacceptable monomers which can be suitably used in the present invention include acrylic acid and its salts such as sodium acrylate and ammonium acrylate, methacrylic acid and its salts such as sodium methacrylate and ammonium methacrylate, 2-acrylamido- (Including sodium salt, ammonium salt and the like), sulfonate itaconate, sulfopropyl acrylate, sulfopropyl methacrylate (hereinafter referred to as " sulfonate " , Sulfomethylated acrylamide, allylsulfonate, sodium vinylsulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid, sulfomethylated acrylamide and phosphonomethylated acrylamide have.

Here, in the production of the first solution, methylene bisacrylamide as a crosslinking agent and sodium formate as a molecular weight regulator are added.

In this case, the amount of the methylene bisacrylamide is 0.001 to 0.003 g, and the amount of the sodium formate is 0.1 to 0.3 g.

In order to remove the monomer remaining in the first solution, ammonium sulfate and sodium bisulfate are added and reacted.

Meanwhile, the production method according to the present invention includes a step of adding a surfactant and preparing a nonionic emulsion polymer to remove the monomer remaining after polymerization. Here, in order to remove the monomer remaining after polymerization, ammonium sulfate and sodium bisulfate are added and reacted.

Here, the surfactant may be a sorbitan monooleate surfactant, a sorbitan monosterate surfactant, or a polyethylene alkyl ester surfactant.

At this time, the sorbitan monooleate type surfactant is added in an amount of 1.1 to 1.2 wt%, the sorbitan monostearate type surfactant is in the amount of 1.6 to 1.8 wt%, and the polyethylene alkyl ester surfactant is in the amount of 2.2 to 2.6 wt%.

Meanwhile, the production method according to the present invention comprises the step of diluting, filtering, filtering and drying the nonionic emulsion polymer to prepare a nonionic polyacrylamide powder.

In addition, the production method according to the present invention comprises the step of preparing a polyvinylamine by dissolving and reforming the nonionic polyacrylamide powder in an aqueous solution to react.

Here, sodium chloride and sodium hydroxide are added during denaturation reforming of the nonionic polyacrylamide powder.

At this time, the sodium hypochlorite and sodium hydroxide have a molar ratio of 1: 2, and the conversion rate and ionicity of the polyvinylamine are controlled by the addition amount ratio.

Hereinafter, the method for producing the paper strengthening agent for paper of the present invention will be described in detail by way of examples. However, the technical details of the present invention are not limited by the following embodiments.

Preparation of nonionic emulsion coagulant

Example 1

First, 624.32 g of acrylamide (50%) as a water-soluble monomer and 17.42 g of adipic acid as a cross-linking agent are mixed and completely dissolved to prepare a first solution.

291.11 g of an oily aliphatic solvent is charged to the reactor and the temperature is raised to 54 to 57 ° C. Upon completion of the addition, 11.53 g of a sorbitan monooleate surfactant (HLB = 4.0 to 6.0) and 17.55 g of a sorbitan monostearate surfactant (HLB = 9.0 to 15.0) were added while vigorously stirring, . The first solution is injected while stirring at 1200 rpm. When the injection is completed, the speed of the stirrer is reduced to 600 rpm, the temperature of the reactor is maintained at 45 ° C, and nitrogen is purged for 1 hour. After the elapse of the time, 0.35 g of 2,2-azobis (isobutyronitrile) and 0.04 g of 2,2-azobis (2,4-dimethylvaleronitrile) were introduced in a nitrogen atmosphere, Was heated to 65 DEG C and reacted for 1 hour. When the time has elapsed, 12.93 g of ammonium thiosulfate is injected, and the temperature of the reaction tank is lowered to 30 캜 or lower. When the temperature is reached, 24.67 g of a polyethylene alkyl ester surfactant (HLB = 10 to 13) is added to ensure the stability of the nonionic emulsion polymer prepared. The nonionic emulsion polymer is diluted with xylene, added dropwise to acetone, and the resulting white solid compound is filtered / filtered and dried to produce a polyacrylamide powder compound.

Example 2

First, 624.32 g of acrylamide (50%) as a water-soluble monomer, 0.001 g of methylene bisacrylamide as a crosslinking agent, 17.42 g of adipic acid and 0.10 g of sodium formate were mixed and completely dissolved to prepare a first solution.

291.11 g of an oily aliphatic solvent is charged to the reactor and the temperature is raised to 54 to 57 ° C. Upon completion of the addition, 11.53 g of a sorbitan monooleate surfactant (HLB = 4.0 to 6.0) and 17.55 g of a sorbitan monostearate surfactant (HLB = 9.0 to 15.0) were added while vigorously stirring, . The first solution is injected while stirring at 1200 rpm. When the injection is completed, the speed of the stirrer is reduced to 600 rpm, the temperature of the reactor is maintained at 45 ° C, and nitrogen is purged for 1 hour. After the elapse of the time, 0.35 g of 2,2-azobis (isobutyronitrile) and 0.04 g of 2,2-azobis (2,4-dimethylvaleronitrile) were introduced in a nitrogen atmosphere, Was heated to 65 DEG C and reacted for 1 hour. When the time has elapsed, 12.93 g of ammonium thiosulfate is injected, and the temperature of the reaction tank is lowered to 30 캜 or lower. When the temperature is reached, 24.67 g of a polyethylene alkyl ester surfactant (HLB = 10 to 13) is added to ensure the stability of the nonionic emulsion polymer prepared. The nonionic emulsion polymer is diluted with xylene, added dropwise to acetone, and the resulting white solid compound is filtered / filtered and dried to produce a polyacrylamide powder compound.

Example 3

First, 624.32 g of acrylamide (50%) as a water-soluble monomer, 0.002 g of methylene bisacrylamide as a cross-linking agent, 17.42 g of adipic acid and 0.20 g of sodium formate were mixed and completely dissolved to prepare a first solution.

291.11 g of an oily aliphatic solvent is charged to the reactor and the temperature is raised to 54 to 57 ° C. Upon completion of the addition, 11.53 g of a sorbitan monooleate surfactant (HLB = 4.0 to 6.0) and 17.55 g of a sorbitan monostearate surfactant (HLB = 9.0 to 15.0) were added while vigorously stirring, . The first solution is injected while stirring at 1200 rpm. When the injection is completed, the speed of the stirrer is reduced to 600 rpm, the temperature of the reactor is maintained at 45 ° C, and nitrogen is purged for 1 hour. After the elapse of the time, 0.35 g of 2,2-azobis (isobutyronitrile) and 0.04 g of 2,2-azobis (2,4-dimethylvaleronitrile) were introduced in a nitrogen atmosphere, Was heated to 65 DEG C and reacted for 1 hour. When the time has elapsed, 12.93 g of ammonium thiosulfate is injected, and the temperature of the reaction tank is lowered to 30 캜 or lower. When the temperature is reached, 24.67 g of a polyethylene alkyl ester surfactant (HLB = 10 to 13) is added to ensure the stability of the nonionic emulsion polymer prepared. The nonionic emulsion polymer is diluted with xylene, added dropwise to acetone, and the resulting white solid compound is filtered / filtered and dried to produce a polyacrylamide powder compound.

Example 4

First, 624.32 g of acrylamide (50%) as a water-soluble monomer, 0.003 g of methylene bisacrylamide as a cross-linking agent, 17.42 g of adipic acid and 0.30 g of sodium formate were mixed and completely dissolved to prepare a first solution.

291.11 g of an oily aliphatic solvent is charged to the reactor and the temperature is raised to 54 to 57 ° C. Upon completion of the addition, 11.53 g of a sorbitan monooleate surfactant (HLB = 4.0 to 6.0) and 17.55 g of a sorbitan monostearate surfactant (HLB = 9.0 to 15.0) were added while vigorously stirring, . The first solution is injected while stirring at 1200 rpm. When the injection is completed, the speed of the stirrer is reduced to 600 rpm, the temperature of the reactor is maintained at 45 ° C, and nitrogen is purged for 1 hour. After the elapse of the time, 0.35 g of 2,2-azobis (isobutyronitrile) and 0.04 g of 2,2-azobis (2,4-dimethylvaleronitrile) were introduced in a nitrogen atmosphere, Was heated to 65 DEG C and reacted for 1 hour. When the time has elapsed, 12.93 g of ammonium thiosulfate is injected, and the temperature of the reaction tank is lowered to 30 캜 or lower. When the temperature is reached, 24.67 g of a polyethylene alkyl ester surfactant (HLB = 10 to 13) is added to ensure the stability of the nonionic emulsion polymer prepared. The nonionic emulsion polymer is diluted with xylene, added dropwise to acetone, and the resulting white solid compound is filtered / filtered and dried to produce a polyacrylamide powder compound.

The results of the emulsion polymers obtained in Examples 1 to 4 are shown in Table 1 below.

Experimental results of nonionic emulsion polymer Classification Cross-linking agent
(ppm) Molecular weight regulator
(ppm) Solids
(%) pH Salt viscosity
(cps) Yield
(%) Ionic
(meq / g) Example 1 0 0 39.4 4.6 194 31.2 0.02 Example 2 One 100 39.3 4.5 170 31.1 0.01 Example 3 2 200 39.4 4.6 157 31.1 0.01 Example 4 3 300 39.3 4.5 135 31.2 0.02

 * Dry solid at 105 ℃ for 3 hours in drydoven

 * Salt viscosity 1.5% in sample of ammonium sulfate 2% solution Viscosity after complete dissolution

* Ionicity: 0.0025N PVS-K, 0.0025N DADMAC standard titrant, reverse titration test with toludine blue indicator

Example 5

To prepare a polymer having a Hoffmann rearrangement conversion rate = 35 mol%.

5 g of the powder obtained in Example 1 was dissolved in 95 g of deionized water by stirring and then heated to maintain a temperature of 70 캜. A mixed solution of 14.66 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.07 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0. The powder obtained in the experiment is not limited to 5 wt% when it is dissolved in deionized water by stirring, and it is possible to reduce the dissolution concentration at one time depending on the solubility viscosity. Further, in Hoffman rearrangement conversion in Examples 1 to 4, it is not limited to a nonionic polyacrylamide powder, and it is also applicable to a polyacrylamide powder of a cationic emulsion polymer It is possible.

Example 6

To prepare a polymer having a Hoffmann rearrangement conversion rate = 35 mol%.

5 g of the powder obtained in Example 2 was dissolved in 95 g of deionized water by stirring and then heated to maintain the temperature at 70 캜. A mixed solution of 14.66 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.07 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0. The powder obtained in the experiment is not limited to 5 wt% when it is dissolved in deionized water by stirring, and it is possible to reduce the dissolution concentration at one time depending on the solubility viscosity. Further, in Hoffman rearrangement conversion in Examples 1 to 4, it is not limited to a nonionic polyacrylamide powder, and it is also applicable to a polyacrylamide powder of a cationic emulsion polymer It is possible.

Example 7

To prepare a polymer having a Hoffmann rearrangement conversion rate = 35 mol%.

5 g of the powder obtained in Example 3 was dissolved in 95 g of deionized water by stirring and then heated to maintain a temperature of 70 캜. A mixed solution of 14.66 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.07 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0. The powder obtained in the experiment is not limited to 5 wt% when it is dissolved in deionized water by stirring, and it is possible to reduce the dissolution concentration at one time depending on the solubility viscosity. Further, in Hoffman rearrangement conversion in Examples 1 to 4, it is not limited to a nonionic polyacrylamide powder, and it is also applicable to a polyacrylamide powder of a cationic emulsion polymer It is possible.

Example 8

To prepare a polymer having a Hoffmann rearrangement conversion rate = 35 mol%.

5 g of the powder obtained in Example 4 was dissolved in 95 g of deionized water with stirring, followed by heat bath to maintain the temperature at 70 캜. A mixed solution of 14.66 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.07 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0. The powder obtained in the experiment is not limited to 5 wt% when it is dissolved in deionized water by stirring, and it is possible to reduce the dissolution concentration at one time depending on the solubility viscosity. Further, in Hoffman rearrangement conversion in Examples 1 to 4, it is not limited to a nonionic polyacrylamide powder, and it is also applicable to a polyacrylamide powder of a cationic emulsion polymer It is possible.

Conversion rate 35 mol% Experimental results Classification Cross-linking agent
(ppm) Molecular weight regulator
(ppm) Solids
(%) pH Ionic
(meq / g) Example 5 0 0 21.0 2.3 2.78 Example 6 One 100 21.0 2.3 2.78 Example 7 2 200 21.1 2.2 2.79 Example 8 3 300 21.0 2.3 2.78

Example 9

To prepare a polymer having a Hoffman rearrangement conversion rate = 50 mol%.

5 g of the powder obtained in Example 1 was dissolved in 95 g of deionized water by stirring and then heated to maintain a temperature of 70 캜. The reaction is carried out by adding a mixed solution of 20.95 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.96 g of sodium hydroxide (95%) and then adjusting the pH to 2.0 to 3.0 by adding hydrochloric acid.

Example 10

To prepare a polymer having a Hoffman rearrangement conversion rate = 50 mol%.

5 g of the powder obtained in Example 2 was dissolved in 95 g of deionized water by stirring and then heated to maintain the temperature at 70 캜. The reaction is carried out by adding a mixed solution of 20.95 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.96 g of sodium hydroxide (95%) and then adjusting the pH to 2.0 to 3.0 by adding hydrochloric acid.

Example 11

To prepare a polymer having a Hoffman rearrangement conversion rate = 50 mol%.

5 g of the powder obtained in Example 3 was dissolved in 95 g of deionized water by stirring and then heated to maintain a temperature of 70 캜. The reaction is carried out by adding a mixed solution of 20.95 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.96 g of sodium hydroxide (95%) and then adjusting the pH to 2.0 to 3.0 by adding hydrochloric acid.

Example 12

To prepare a polymer having a Hoffman rearrangement conversion rate = 50 mol%.

5 g of the powder obtained in Example 4 was dissolved in 95 g of deionized water with stirring, followed by heat bath to maintain the temperature at 70 캜. The reaction is carried out by adding a mixed solution of 20.95 g of an aqueous solution of sodium hypochlorite (12.5%) and 2.96 g of sodium hydroxide (95%) and then adjusting the pH to 2.0 to 3.0 by adding hydrochloric acid.

Conversion rate 50 mol% Experimental results Classification Cross-linking agent
(ppm) Molecular weight regulator
(ppm) Solids
(%) pH Ionic
(meq / g) Example 9 0 0 21.3 2.3 3.37 Example 10 One 100 21.3 2.3 3.37 Example 11 2 200 21.1 2.2 3.38 Example 12 3 300 21.3 2.3 3.37

Example 13

To prepare a polymer having a Hoffmann rearrangement conversion rate = 75 mol%.

5 g of the powder obtained in Example 1 was dissolved in 95 g of deionized water and stirred, followed by heating to maintain a temperature of 70 캜. A mixed solution of 31.42 g of an aqueous solution of sodium hypochlorite (12.5%) and 4.44 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0.

Example 14

To prepare a polymer having a Hoffmann rearrangement conversion rate = 75 mol%.

5 g of the powder obtained in Example 2 was dissolved in 95 g of deionized water with stirring, and then heated at 70 캜. A mixed solution of 31.42 g of an aqueous solution of sodium hypochlorite (12.5%) and 4.44 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0.

Example 15

To prepare a polymer having a Hoffmann rearrangement conversion rate = 75 mol%.

5 g of the powder obtained in Example 3 was dissolved in 95 g of deionized water to dissolve it, and heat bath was performed to maintain the temperature at 70 캜. A mixed solution of 31.42 g of an aqueous solution of sodium hypochlorite (12.5%) and 4.44 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0.

Example 16

To prepare a polymer having a Hoffmann rearrangement conversion rate = 75 mol%.

5 g of the powder obtained in Example 4 was dissolved in 95 g of deionized water with stirring, followed by heating to maintain a temperature of 70 ° C. A mixed solution of 31.42 g of an aqueous solution of sodium hypochlorite (12.5%) and 4.44 g of sodium hydroxide (95%) is added and reacted, followed by the addition of hydrochloric acid to adjust the pH to 2.0 to 3.0.

Conversion rate 75mol% Experimental results Classification Cross-linking agent
(ppm) Molecular weight regulator
(ppm) Solids
(%) pH Ionic
(meq / g) Example 13 0 0 21.6 2.3 4.01 Example 14 One 100 21.6 2.3 4.02 Example 15 2 200 21.6 2.2 4.02 Example 16 3 300 21.6 2.3 4.01

Comparative Example 1

Paper was prepared by a conventional method using the dry strength agent (DSA) prepared in Examples 5 to 16. Table 5 shows the compressive strength, shear modulus, dehydration speed and turbidity of paper. Here, the normal method means the following test conditions.

Compressive Strength, Shrinkage Measurement Condition

1) Target Base paper: 100 gsm

2) Furnish: UKP 100%

3) Hand sheet: square 20cm x 20cm (Dry BP - 4g)

4) Dosage: PVam (+) 0.8%, 1.2% [Pvam (+): Pvam (-) ratio = 1: 1.5]

5) Program: 0 -> 10sec (-) PVam -> 20sec (+) PVam -> 30sec

6) Press: 3.5Bar - 1 pass

7) Dry: Drum dryer

Comparison of compressive strength and bending strength division 0.8% input At 1.2% input Basis weight Compressive strength Non-abrasive My theft
(1.5 kg) Basis weight Compressive strength Non-abrasive My theft
(1.5 kg) Blank 95.5 15.2 15.9 161.8 95.5 15.2 15.9 161.8 Example 5 100.0 15.7 15.7 165.0 98.0 15.2 15.5 182.2 Example 6 102.8 16.4 16.5 232.2 98.5 15.8 16.1 293.4 Example 7 97.8 14.5 16.9 226.0 101.3 16.4 16.2 259.8 Example 8 102.5 15.6 16.1 182.8 98.5 14.5 14.7 187.6 Example 9 101.0 15.8 15.7 166.8 98.8 15.1 15.3 188.2 Example 10 101.8 15.6 15.4 211.6 100.8 15.4 15.3 273.4 Example 11 103.0 16.4 15.9 284.4 100.5 15.9 15.8 393.4 Example 12 100.3 16.3 16.3 178.6 101.0 17.1 16.9 218.6 Example 13 101.0 15.8 15.7 176.8 101.8 16.4 16.1  192.5 Example 14 103.5 14.2 16.7 206.8 103.2 17.0 16.4 256.0 Example 15 99.5 16.6 16.6 286.6 103.5 17.1 16.5  396.6 Example 16 100.3 16.3 16.3 179.7 105.0 17.5 16.7 222.5

Dehydration rate, turbidity measurement condition

1) Furnish: KOCC

2) Furnishcons: Concentration correction with KOCC (1.4%)

3) DDT: 1000 mL, 1500 rpm

4) Dosage: 0.5%, 1%

5) Program: 0 -> 15 sec Drug injection -> 30sec shutdown

6) Drainage Time: 200 mL, 300 mL, 500 mL time check (filtrate turbidity measurement)

7) Chemicals Dilution: 200 times dilution

Comparison of dehydration speed and turbidity The input cost of dry matter is 1.0% The input cost of dry matter is 1.0% Furnish Input rate of dry matter 0.5% Dehydration time check (sec) Turbidity Dehydration time check (sec) Turbidity 200 mL 300 mL 400 mL NTU 200 mL 300 mL 400 mL NTU





KOCC Blank 6.70 10.50 23.46 906 6.70 10.50 23.46 906 Example 5 6.50 11.31 24.10 356 6.39 10.34 21.49 268 Example 6 6.38 11.06 24.74 448 6.24 10.32 22.03 333 Example 7 6.22 10.34 23.20 385 5.91 10.13 21.55 309 Example 8 6.11 10.70 22.94 349 5.94 9.69 19.52 263 Example 9 6.38 10.85 22.98 434 6.27 10.56 21.78 288 Example 10 6.43 10.71 23.51 455 6.38 10.63 21.58 276 Example 11 6.27 10.45 21.96 278 6.10 10.25 20.91 228 Example 12 6.35 10.88 22.43 339 6.02 9.80 19.45 238 Example 13 6.52 10.97 24.45 547 6.38 11.21 25.06 275 Example 14 6.41 10.43 21.59 300 6.31 10.81 20.42 239 Example 15 6.31 10.54 22.01 264 5.98 10.05 20.11 231 Example 16 6.28 10.61 21.42 299 5.89 9.71 21.22 234

While the present invention has been particularly shown and described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. It will be easy for anyone to know.

Claims (7)

Dissolving the mixture containing the nonionic water soluble monomer and the crosslinker in deionized water to prepare a first solution;
Introducing the first solution into an aliphatic solvent in an oil phase, and heating and stirring to polymerize the first solution;
Adding a surfactant and removing the remaining monomers after polymerization to prepare a nonionic emulsion polymer;
Diluting, filtering and filtering the nonionic emulsion polymer, followed by drying to produce a nonionic polyacrylamide powder; And
Dissolving and reacting the nonionic polyacrylamide powder in an aqueous solution to produce a polyvinylamine;
The method of manufacturing an earth-friendly paper strengthening agent for paper according to claim 1,
The method according to claim 1,
The nonionic water-soluble monomer is an environmentally friendly paper strength enhancer, characterized in that one or two or more selected from acrylamide, methacrylamide, N, N-diethylacrylamide, N-isopropylamide and Nt-butylacrylamide. Manufacturing method.
The method according to claim 1,
Methylene bisacrylamide cross-linking agent or sodium formate molecular weight control agent is added during the preparation of the first solution, the manufacturing method of environmentally-friendly papermaking enhancer for paper.
The method according to claim 1,
In order to remove the remaining monomers in the first solution ammonium sulphate and sodium bisulfate is added to the reaction method of manufacturing an environmentally friendly papermaking enhancer, characterized in that the reaction.
The method according to claim 1,
Wherein the surfactant is one or two or more selected from sorbitan monooleate-based surfactants, sorbitan monoesterate-based surfactants and polyethylene alkyl ester surfactants.
The method according to claim 1,
Wherein the nonionic polyacrylamide powder is modified with sodium hypochlorite or sodium hydroxide. The present invention also provides a method for producing an environmentally-friendly paper strengthening agent for papermaking.
The method of claim 6,
Wherein the sodium hypochlorite and sodium hydroxide have a molar ratio of 1: 2, and the conversion ratio and ionicity of the polyvinylamine are controlled by the addition amount ratio.