JPS6220214B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a cationic polymer with strong hydrophobicity. Currently, fine suspended particles contained in various industrial wastewaters,
Various coagulants are used in the removal of colloidal particles or in the papermaking process, and most of them are inorganic coagulants such as aluminum sulfate, polyaluminum chloride, and ferric chloride. However, in wastewater treatment, although these inorganic coagulants are low-priced, they require the use of large quantities, and the volume of sludge after concentration and dewatering is large, and new methods such as the treatment of ash generated by incineration, etc. are required. I'm having a problem. Furthermore, in the papermaking process, the use of inorganic coagulants makes the paper acidic, which has a negative effect on the strength and durability of the paper. Many organic cationic polymers are being studied to improve these points. For example, epichlorohydrin/ammonia polycondensate
26794), polycondensates of polyalkylenepolyamines and epihalohydrin (Tokuko Shou 38-20741), polycondensates of secondary amines and epichlorohydrin (Tokuko Sho 38-20741),
49-37440, Special Publication No. 51-22471), etc. Furthermore, the present inventors have provided cationic polymers with excellent coagulating properties, such as a polycondensate of a Mannitz reaction product of lower alkyl monovalent phenols and epihalohydrin (Japanese Patent Publication No. 1983-37844). . However, although these polymers are excellent in the coagulation effect of various colloidal particles due to their cationic functional groups, their strong hydrophilicity makes it difficult to use hydrophobic inorganic and organic fine particles suspended in wastewater such as emulsion wastewater and dyeing wastewater. When these polymers are used as a fixing agent for various processing agents such as paper sizing agents, their hydrophilic properties may reduce the water resistance of the paper. This had a negative impact on size, water repellency, etc. In order to improve these drawbacks, the present inventors conducted research aimed at developing a cationic polymer with strong hydrophobicity, and as a result, they arrived at the present invention. That is, the gist of the present invention includes the following (a) and (b), and the molar ratio thereof is (a):(b) = 70:30 ~
The present invention relates to a method for producing a cationic polymer comprising a polycondensate of a 30:70 mixture and epihalohydrin. (a) Reaction product of bisphenol with formaldehyde and dialkylamine (b) General formula (In the formula, R represents an alkyl group having 5 or more carbon atoms) Reaction product of higher alkyl monovalent phenols (hereinafter abbreviated as monovalent phenols) with formaldehyde and dialkylamine The present invention will be explained in detail. In addition, as the bisphenol which is the raw material of the present invention, 2,2-bis(4-
hydroxyphenyl) propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)
Examples include butane (bisphenol B), but
Preferably bisphenol A is used. Examples of monovalent phenols represented by the general formula (1) include higher alkylphenols such as amylphenol, octylphenol, and nonylphenol, and preferably octylphenol and nonylphenol are used. Octylphenol and nonylphenol are produced in large quantities as raw materials for surfactants, and are very advantageous in terms of price. In order to obtain a composition with a predetermined molar ratio of the Mannitz reaction product of bisphenol and monovalent phenols represented by general formula (1), bisphenol and monovalent phenols as raw materials are used in a predetermined molar ratio, It may be reacted with formaldehyde and dialkylamine according to the known Mannitz reaction method. The order of addition of bisphenol and monovalent phenols and formaldehyde and dialkylamine is arbitrary; they may be mixed after performing Mannitz reaction separately, or formaldehyde and dialkylamine may be reacted with a mixture of bisphenol and monovalent phenols. may be allowed to form a Mannich reactant at the same time. Further, formaldehyde and dialkylamine may be used after reacting in advance, or may be added simultaneously or sequentially. Since bisphenol has a maximum of 4 active hydrogen atoms, a Mannich reaction of up to 4 mol of formaldehyde and dialkylamine occurs per 1 mol of bisphenol. In addition, monovalent phenols represented by general formula (1) have a maximum of 3 active hydrogens, so 1
A Mannich reaction of up to 3 moles of formaldehyde and dialkylamines takes place per mole of phenols. The amounts of formaldehyde and dialkylamine to be charged during the Mannitz reaction may be in any range from equimolar to 4 times the mole for bisphenols, and from equimolar to 3 times the mole for monovalent phenols, but the subsequent polycondensation reaction with epihalohydrin Considering the ease of preparation and the stability of the polycondensation product, it is preferable to charge at least 3 times the molar amount of bisphenol and at least 2 times the molar amount of formaldehyde for the monohydric phenols. Formaldehyde and dialkylamine are used in approximately equimolar ratio, but amine or formaldehyde may be used in slightly excess. Further, instead of formaldehyde, a substance that generates formaldehyde such as paraformaldehyde may be used. As the dialkylamine, amines having a lower alkyl group having 1 to 3 carbon atoms are suitable, and dimethylamine, diethylamine, methylethylamine, etc. are particularly preferred from the viewpoint of reactivity, and two or more of these amines may be used in combination. is also possible. The molar ratio of bisphenol and monovalent phenol represented by general formula (1) is preferably in the range of 70:30 to 30:70; if the monovalent phenol is less than 30 mol%, hydrophobicity is insufficient; If it exceeds mol%, the polycondensate will separate, which is not preferable. The temperature during the Mannitz reaction is selected from the range of 10 to 80°C, but at low temperatures it is necessary to lengthen the reaction time, and at high temperatures the dialkylamine is likely to volatilize and by-products are generated, so it is usually 30 to 60°C. 3 to 10
It is preferable to react for a period of time. After the Mannitz reaction, bisphenols and dialkylaminomethylated monohydric phenols can be isolated, but usually they are polycondensed with epihalohydrin without being isolated. As epihalohydrin, epichlorohydrin is usually used. The amount of epihalohydrin used is preferably in the range of 0.7 to 2 moles of the sum of the moles of bisphenol and monohydric phenols; if it is less than 0.7 times the mole, a high molecular weight polymer will not be obtained, and if it exceeds 2 times the mole, three-dimensional polymer will not be obtained. It is easy to create a mesh structure,
Undesirable. The reaction temperature during polycondensation is selected from a range of 10 to 90°C, and a controllable temperature range is selected depending on the reactivity of the Mannitz reactant to be reacted with epihalohydrin. Since the polycondensation reaction is accompanied by heat generation, it is preferable to perform external cooling or to control the reaction temperature by controlling the addition rate of epihalohydrin. Although the solvent used in the Mannitz reaction and polycondensation reaction is not particularly limited, the reaction is usually carried out in an aqueous solvent. In an aqueous solvent, the Mannitz reaction product becomes resinous at low temperatures, so the reaction temperature during polycondensation with epihalohydrin is preferably 45° C. or higher. The reaction is stopped by adding an acid, and the acid may be added at a time when a desired viscosity is obtained depending on the purpose of use. Although the type of acid is not particularly limited, it is preferable to use mineral acids such as hydrochloric acid and sulfuric acid. Further, the amount used is sufficient as long as the pH of the reaction system is 7 or less, but it is preferably PH4 or less. The viscosity of the final product is determined depending on the intended use, but it is preferable that the Bruckfield viscosity at a polymer concentration of 50% is 100 cp or more. The cationic polymer of the present invention can be used to remove and clarify fine particles from emulsion wastewater, dyeing wastewater, pulp wastewater, etc., and as a fixing agent for dyes and various processing agents such as sizing agents in papermaking processes, and as dye fixing agents for textile materials. At the same time, it can be used for clarification, sedimentation promotion, dehydration, and clarification of various wastewaters in which conventional organic cationic coagulants are used. In addition, when using it, it is also possible to use it together with other inorganic or organic coagulants.
It is also possible to use it in combination with acrylamide-based anionic and cationic polymer flocculants. Furthermore, as is clear from the structure of the monovalent phenols used as raw materials, the polymer molecules of the present invention have an ionic group and a long-chain alkyl group, and therefore have surface-active properties and are cationic polymers. It is useful as a surfactant for emulsifying, suspending, and solubilizing ordinary oil phases. Next, the present invention will be explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist of the present invention is exceeded. Example 1 68.4g of bisphenol A in a separable flask
(0.3 mol) and P-nonylphenol 44.1 g (0.2
Take 144 moles of 50% dimethylamine aqueous solution.
g (1.6 mol) and 37% formalin aqueous solution.
129.7 g (1.6 mol) was added dropwise, and the Mannitz reaction was carried out for 8 hours while stirring and keeping the reaction system at 50°C. 46.3 g (0.5 mol) of epichlorohydrin was added dropwise to this Mannitz reaction product solution over 30 minutes with stirring while maintaining the reaction system at 45°C. After the dropwise addition was completed, the reaction solution gradually thickened, and when the Bruckfield viscosity reached 7000 cp after 1 hour, 114.7 g (1.1 mol) of 35% hydrochloric acid was added to stop the polycondensation reaction. The viscosity of this polycondensate at 25°C was 2000 cp using a Bruckfield viscometer. Example 2 57.0% bisphenol A in a separable flask
g (0.25 mol) was added, 90 g (1.0 mol) of 50% dimethylamine aqueous solution was added, and then 81.1 g (1.0 mol) of 37% formalin aqueous solution was added dropwise, and the reaction system was heated to 55°C.
The Mannitz reaction was carried out for 5 hours while stirring and maintaining the temperature. In another separable flask, P-
Take 55.1g (0.25 mol) of nonylphenol and
Add 45g (0.5 mol) of % dimethylamine aqueous solution and 40.5 g (0.5 mol) of 37% formalin aqueous solution.
In addition, the Mannitz reaction was similarly carried out at 55°C for 5 hours. The Mannitz reaction product solution of bisphenol A and P-nonylphenol was mixed, and 55.5 g (0.6 mol) of epichlorohydrin was added dropwise to the mixture over 40 minutes with stirring while maintaining the reaction system at 45°C. After completion of the dropwise addition, the reaction solution gradually started to increase in viscosity, and when the Bruckfield viscosity reached 8000 cp after 1 hour and 30 minutes, 93.9 g (0.9 mol) of 35% hydrochloric acid was added to stop the polycondensation reaction. 25℃ of this polycondensate
The viscosity at
It was 4200 cp. Example 3 41.3g (0.2 mol) of P-octylphenol was placed in a separable flask, 144g (1.6 mol) of 50% dimethylamine aqueous solution and 129.7g (1.6 mol) of 37% formalin aqueous solution were added, and the system was heated to 55°C. The Mannitz reaction was carried out for 3 hours while maintaining and stirring.
To this was added 68.4 g (0.3 mol) of bisphenol A, and the Mannitz reaction was further carried out for 5 hours. In order to moderate the reaction during the subsequent polycondensation, 15.6 g (0.15 mol) of 35% hydrochloric acid was added to the Mannitz reaction product solution, and then 55.5 g (0.6 mol) of epichlorohydrin was added.
was added dropwise over 40 minutes with stirring while keeping the reaction system at 45°C. After the dropwise addition was completed, the reaction solution gradually thickened, and when the Bruckfield viscosity reached 6000 cp after 1 hour, 119 g (0.85 mol) of 70% sulfuric acid was added to stop the polycondensation reaction. This polycondensate had a viscosity of 1500 cp on a Bruckfield viscometer at 25°C. Example 4 When the product of the present invention was used as a fixing agent for a petroleum resin sizing agent, it exhibited superior effects compared to commercially available cationic polymers. Pulp type: LBKP100% Paper PH: 7.1 tsubo Weight: 70 g/m ² Using TAPPI hand paper machine Drying: Drum drying at 120°C for 2 minutes After conditioning for 24 hours at 20°C and relative humidity of 65%, size was determined by Steckhist method. was measured. In addition, petroleum resin sizing agent is added at 1% to the pulp.
The cationic polymers were added in an amount of 0.3, 0.5, and 1.0%, respectively.

[Table] Example 5 Artificial dyeing wastewater (Direct First Scarlet 300 ppm solution) was prepared and bentonite
A clear supernatant liquid (residual color rate 1% or less) could be obtained by processing in combination with 200 ppm and 1 ppm of a polymeric anionic polymer. The minimum addition amount of each sample at that time was as follows.

【table】

Claims (1)

[Claims] 1. A mixture containing the following formulas (a) and (b) and having a molar ratio of (a):(b)=70:30 to 30:70, and epihalohydrin. A method for producing a cationic polymer consisting of a condensate. (a) A reaction product between bisphenol and formaldehyde and dialkylamine in an equimolar to four times the molar amount of bisphenol. (b) General formula (In the formula, R represents an alkyl group having 5 or more carbon atoms)
Higher alkyl monovalent phenols represented by
A reaction product with formaldehyde and dialkylamine in an equimolar to 3-fold molar amount relative to the number of moles thereof.