JPS6243418A - Reactive high polymer composition - Google Patents

Abstract

PURPOSE:A reactive high polymer composition useful as a raw material for producing a dehydrating agent for organic sludge treatment, having improved dehydrating properties, obtained by reacting an epihalohydrin with a dialkylamine and a (meth)acrylic acid aminoalkyl ester. CONSTITUTION:(A) An epihalohydrin, preferably epichlorohydrin, is blenced with (B) a dialkylamine, preferably dimethylamine, etc., and (C) a (meth)acrylic acid aminoalkyl ester (preferably dimthylaminoethyl acrylate, etc.,) while keeping the reaction system preferably at <=304oC and reacted at 60-95 deg.C for 2-10hr, to give the aimed composition. A molar ratio of the component A to the component B to the component C used is preferably 1.0:1.8-1.1:0.0005-0.2. USE:Providing a high polymer material such as coating compound, etc., with function such as electrical conductivity, mildewproofing effects, etc.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a reactive organic polymer composition, and in particular to a reactive polymer composition for producing a dehydrating agent for treating organic sludge such as surplus sludge generated in sewage treatment plants. A reactive polymer composition useful as a giant polymer commonly referred to as a macromer, and more generally a reactive polymer composition useful for imparting functionality to polymer compositions. relating to things. (Conventional technology) Mixed sludge generated at sewage treatment plants and human waste treatment plants. Digested sludge, surplus sludge, etc. consist of colloidal particles containing a large amount of organic matter, are fine and highly compressible, and have a hydrophilic surface and are extremely difficult to dehydrate. For these organic sludges that are difficult to dewater, various efforts have been made to improve dewatering properties and dewatering efficiency using chemical and physical methods. For the former, inorganic iron salts such as ferric chloride and ferrous sulfate, lime, basic aluminum chloride, etc. have been used for a long time, and for organic systems, cationic modified products of polyacrylamide, chitosan, dimethylamino Water-soluble polymers such as copolymers of hexagenized salts or quaternized salts of ethyl methacrylate and acrylamide, and condensation-based cationic polymers have been used. For the latter, methods such as deep dehydration, belt press dehydration, compression dehydration, pressure dehydration, vacuum dehydration, screen dehydration, etc. have been used, depending on the chemicals used and the type of sludge, and improvements have been made. However, the current situation is that a sufficient dehydration effect has not yet been obtained. (Problems to be Solved by the Invention) In view of the current situation, the inventors of the present invention have repeatedly conducted research to develop an excellent dehydrating agent. A composition obtained by reacting with an acid aminoalkyl ester has reactivity, and this reactive composition can be used alone or by reaction with a monomer, such as acrylamide, to be used in the production of a general organic polymer flocculant. It was discovered that the resulting polymer had better dehydration properties than conventionally known cationic organic polymer flocculants. Further, as a result of further research by the present inventors, a composition having a susceptor reactivity for reacting epihalohydrin, dialkylamine, and acrylic acid aminoalkyl ester or methacrylic acid aminoalkyl ester has been widely used as a polymer composition. We discovered that it is effective in adding functionality,
This has led to the completion of the present invention. (Means for Solving the Problems) That is, the present invention relates to a reactive polymer composition obtained by reacting an epihalohydrin, a dialkylamine, and an amine alkyl acrylate or an aminoalkyl methacrylate. To explain the reactive polymer composition of the present invention in more detail, the reaction between epihalohydrin, dialkylamine, and aminoalkyl acrylate or aminoalkyl methacrylate is as shown in the following formula, and the extended product has a molecular weight of The composition of about 1,000 to several thousand leaves unsaturated bond sites at the ends, which easily react with other vinyl monomers. However, R1: carbon t & 1-4 alkyl group RI H or CH. General Fulkylene having 1 to 4 carbon atoms R1 Alkyl group having 1 to 2 carbon atoms By carrying out the copolymerization reaction, a polymer having a high molecular weight and high cationic strength can be obtained, and excellent dehydration properties are imparted. (Function) To further explain the reactive polymer composition of the present invention in detail,
Examples of epichlorhydrin used in the present invention include epichlorohydrin, epibromohydrin, and ebrohydrin, and examples of dialkylamines include dimethylamine, diethylamine, dialkylamine, diptylamine, and the like. In addition, as acrylic acid amino()V-kyl ester,
Dimethylaminoethyl acrylate. Dimethylaminoethyl acrylate, dimethylamitsuno I remalderopyl acrylate, diethylamino normalpropylacrylate, dinotylaminoisopropylacrylate, dinotylaminoisopropylacrylate, diethylaminonormalpropylacrylate, diethylaminonormalbutyl acrylate, dimethylaminoisobutyl acrylate , dimethylaminoisobutyl acrylate and the like. In addition, as methacrylic acid aminoalkyl ester,
Dimethylaminoethyl methacrylate, diethylamine ethyl methacrylate, dimethylamino normal propyl methacrylate. Examples include zenalamino normal propino dimethacrylate, diethylaminoisobutyl methacrylate, diethylaminoisobutyl methacrylate, trimethylamino normal butyl methacrylate, diethylamine normal butyl methacrylate, dimethylaminoisobutyl methacrylate, diethylaminoisobutyl methacrylate. However, from the viewpoints of reactivity, stability of the reaction product, and safety (9) price, among these, epichlorohydrin is used for epihalohydrin, diethylamine or diethylamine is used for dialkylamine, and acrylic acid amino is used. Among the alkyl esters or aminoalkyl methacrylates, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and zenalaminoethyl methacrylate are preferably used. Regarding manufacturing method 1 of the composition of the present invention, first, predetermined amounts of epihalohydrin and one or more of acrylic acid aminoalkyl ester or methacrylic acid aminoalkyl ester are charged into a reaction vessel, and while stirring and cooling, A predetermined amount of dialkylamine is added dropwise to this. There is no particular limitation on the addition order of epihalohydrin, dialkylamine, and aminoalkyl acrylate or aminoalkyl methacrylate, but in any addition order, the temperature of the reaction solution increases when added. Therefore, it is necessary to keep the temperature of the reaction solution at 50°C or lower, preferably at 50°C or lower. That is, if the temperature of the reaction solution at this time exceeds 50°C, the reactive polymer composition becomes a low molecular weight composition, which is not preferable. The addition time is usually 1 to 3 hours. The usage ratio of these 1 is the molar ratio of Ebino-rohydrin, dialkylamine and aminoalkyl ester of acrylate or aminoalkyl methacrylate +! 1.0: 0.8~1.1: 0.005~0
Use within the range of 2. Ill H. When the molar ratio of epihalohydrin and acrylic acid aminoalkyl ester or methacrylic acid aminoalkyl ester is less than 10005, or when the molar ratio of epihalohydrin and dialkylamine is 1:11.
If it exceeds 100%, the number of reactive unsaturated bond sites in the composition of the present invention is too small, the reaction activity is low, and the effects of the reactive composition of the present invention cannot be obtained. In addition, when the molar ratio of epihalohydrin and acrylic acid aminoalkyl diester or methacrylic acid aminoalkyl diester/l/l/exceeds 0.2, or when the molar ratio of epihalohydrin and dialkylamine exceeds 1.08 If the molecular weight is less than 20%, the molecular weight of the composition of the present invention decreases, which is not preferable. After predetermined amounts of epihalohydrin, dialkylamine, and acrylic acid aminoalkyl ester or methacrylic acid aminoalkyl ester are added, the reaction system is heated to 60 to 90%
The mixture is heated to 5° C. and the reaction is carried out for about 2 to 10 hours. If the reaction temperature is lower than 60°C, the reaction will not proceed, and if it is higher than 95°C, the reactive unsaturated bond sites of the composition of the present invention will be cleaved, resulting in loss of reactivity, which is not preferred. (Effects of the Invention) The reactive polymer composition of the present invention that can be obtained by these methods leaves an unsaturated bond site at the end, which easily reacts with other vinyl monomers, etc.
A polymer composition can be obtained. For example, when using a sludge dehydrating agent, as mentioned above, 1
By widening the degree of copolymerization with a vinyl monomer such as acrylamide having another hydrophilic group, a polymer having a high molecular weight and high kanaonic strength can be obtained, and excellent dehydration properties can be obtained. In addition, since the composition of the present invention has conductivity, it can be used as a paint, #
When producing fibers, fibers, etc., tetraelectricity is imparted by reacting this composition as a part of the constituent components.
Functions such as antistatic effect are exhibited. Moreover, since the composition of the present invention has bactericidal properties. Same as i1? It also has an anti-mold effect on paints and films. Depending on the manufacturing conditions, the composition of the present invention can also be useful as a crosslinking agent because the main chain portion, which accounts for most of the composition, has a partially branched structure. For example, when used in paints and adhesives. A polymer composition having high structural properties can be obtained, and it is also effective in increasing the strength of the coated surface and the strength of the adhesive. That is, the reactive polymer composition of the present invention is thus effective in imparting functionality to polymer PlIt structures, and has a wide range of uses depending on its purpose. (Examples) In order to explain the present invention in more detail, the present invention will be described below with reference to Examples, but the present invention is not limited thereto. Example 1 5 equipped with a thermometer, stirrer, reflux condenser and dropping rotor
00me 1 four-bottle flask, 19 epichlorohydrin
L59 (2,07 mo)v) and dimethylaminoethyl methacrylate 4.71 (o, o 5 mole) were mixed and introduced, while +80P (2,00 mole) was added to the dropping funnel.
Add a 1% aqueous solution of dimethylamine to 1% aqueous solution, cool the flask from the outside, and adjust the dropping rate so that the temperature of the reaction system is below 60°C while stirring the reaction solution. The amine was reacted dropwise. After the dropwise addition of dimethylamine was completed, heating was started from outside the flask, and the reaction was carried out at 80°C for 6 hours with stirring to obtain a pale yellow transparent viscous liquid (composition of the present invention). This composition was water-soluble and had a cation value of 6.5 meq/9 as determined by colloid titration. In addition, bromine addition method t
As a result of measuring the amount of unsaturated bonds derived from dimethylaminoethyl meth/J-rate using this unsaturated bond (double bond) quantitative injection method 1), the amount of remaining unsaturated bonds was 9546% of the charged amount. It was 0051. As is clear from these results, the composition of the present invention has unsaturated bond sites remaining, and due to these unsaturated bonds, the composition of the present invention has high reactivity. Note 1) Unsaturated bond (double bond) determination method by bromine addition method. Bromine is added to the unsaturated bond site of a composition having unsaturated bonds in the presence of excess bromine, and the remaining bromine is converted into potassium iodide. The iodine liberated by the reaction is titrated with sodium chloride sulfate using starch as an indicator. Calculate from the titration value to determine the amount of unsaturated bonds. Example 2 Similarly to Example 1, 20 moles of various shrimp halohydrins and various acrylic acids (methacrylic acids) as shown in Table 1 were added.
1.17 moles of various dialkylamines were added dropwise from a dropping funnel to a mixture of 0.005 moles of aminoalkyl ester to carry out a reaction. After the heating reaction was completed, the molecular weight of the obtained composition was determined by the limiting viscosity method at 50°C in a 2N sodium chloride solution. Table 1 ff1L, ECH Epichlorohydrin ,
EBH Epibromohydrin EIH: Epibromohydrin DMA Dimethylamine, DEA Nidiethylamine DPA Schiff Chi'/L'7min, DBA
Diptylamine DMAEM: Dimethino V7 Minoethyl methacrylate DMAEA Dimethylaminoethyl acrylate DEAEM Diethylaminoethyl methacrylate DEAEA: Dimethino V Amine Ethino V
Acrylate DMAPM Dimethylaminofucypyl methacrylate DMABM Dimethylaminobunal methacrylate Example 5 Same as Example 1. The reaction was carried out. After the reaction was completed, the intrinsic viscosity and unsaturated bond content of the resulting composition were measured, and the results are shown in Table 2-10. Table 2 However, the monomer type abbreviations are the same as those used in Table 1 Note 2) The amount of unsaturated bonds refers to the unsaturation at the time of preparation derived from Acrylic acid (methacrylic acid) aminoalkyl ester. It refers to the residual rate of unsaturated bonds remaining in the composition after the completion of the reaction, relative to the amount of bonds. As is clear from the results in Table 2, when the molar ratio of epichlorohydrin and diptylamine is outside the range of 1.08 to 11, the molecular weight of the composition decreases, and epichlorohydrin and dimethylaminoethyl acrylate It can be seen that when the molar ratio is less than 1-0005, the amount of unsaturated bonds decreases, and when the molar ratio is 1:02, both the molecular weight and the amount of unsaturated bonds decrease by 1. Example 4 Using the same reactor as in Example 1, epichlorohydrin 1
85.09 (2.0 mol) and diethylaminoethyl methacrylate 25.6 p (0.+5 mo/Ll) were mixed and added to the dropping funnel.
Add a 50% by weight aqueous solution of dimethylamine (mol), stir the reaction solution while cooling the flask from the outside, and adjust the dropping rate so that the temperature of the refrigerant system is below 30°C. was reacted dropwise. After the dropwise addition of dimethylamine was completed, heating was started from outside the flask, and the reaction was carried out at 65°C for 6 hours while stirring to obtain a pale yellow, slightly opaque viscous liquid (composition of the present invention). This composition was water-soluble and had a cation value of 5.9 meq/P as determined by colloid titration. In addition, as a result of measuring the amount of unsaturated bonds derived from diethylaminoethyl methacrylate, the amount of remaining unsaturated bonds was 8
It was 26%. Example 5 The reactive polymer composition of the present invention obtained in Example 1 and Example 4 was used alone or as β-methacryloy/reoxyethyltrimethinocyanmonium chlorite. Alternatively, a polymerization reaction was performed with acrylamide. The reaction method was as follows: First, each composition was placed alone or mixed in the proportions shown in Table 3 in a stainless steel bag 1 (surface thickness: 5 + nm), and 2.2'-aZo was added as a photosensitizer.
℃is (2-amidinc propane) by
drc:i+1. )ride was added in an amount of 01% by weight. This was irradiated with ultraviolet light using a 400 high pressure mercury lamp from a position 251 above the liquid level. Table 5 shows the viscosity and solubility of the polymer in 05% water after being exposed to irradiation for about 50 minutes. Table 3 Note-3) B71!ノ3'已turtle+j"l ('shi July and 5
0'(:Ht11) Table 5 It is clear from Table 5 that the composition of Example 4 of the present invention acts as a crosslinking agent. Also, '-)! :The first components of Examples 1 and 4 react alone, but their molecular weight is low (
The aqueous solution has a low viscosity), and a high molecular weight polymer can be obtained by reacting this with β-methacryloyloxoethyltrimenal ammonium chloride or acrylamide. Example 6 Surplus sludge from sewage treatment plant (SS [1,76%, I) +
Example 5 as shown in Table 4.
A pressure dehydration test was conducted using the obtained polymer, commercially available Cation M, and a single molecule flocculant. The test method is 200% of sludge. +7 was placed in a 500-capacity stoppered bone scalpel syringe, and each of the drugs listed in Table 4 was added thereto in the proportions shown in Table 5. After stirring this graduated syringe 20 times, a transparent acrylic syringe with a total volume of 350 mm (inner diameter somm) was used.
a) Scrub the bottom of 1)

Place it in a container with [Kobinun] Uno 8 Go] attached, and after gravity dehydration for 1 minute, use a piston from the top to heat it at 05 and 97- for 1 minute, then 1.0 k.
Perform pressure dehydration for 1 minute at q/crd. After completion of pressure dehydration, the cake was taken out from the container and the water content of the cake was measured. The results are shown in Table 5. Table 4 Table 5 Note 4) The amount added is expressed as the amount added per SS of sludge. Example 7 Into a flask with the same volume as in Example 1, υ styrene 302. Butyl acrylate, itaconic acid 159
．． β-Hydroxyethino V methacrylate 10y, isopropano-/l/+002 as a solvent, and benzoyl peroxide 102 as a catalyst were mixed. To this was added 2y, a composition obtained by drying the viscous liquid of the reactive composition of the present invention obtained in Example 4 by freeze-drying, and a reaction was carried out at a temperature of 95° C. for 6 hours. This was cooled, and 100 P of 5% ammonium hydroxide solution was gradually added with stirring, and then the isopropanol was collected and removed at about 45° C. under reduced pressure. The highly viscous liquid thus obtained becomes an acrylic water-soluble baking paint. For comparison, the same coating material was obtained in the same manner as above without adding the reactive composition of the present invention. When these paints were applied to a glass plate, pre-dried at 70°C for 2 hours, and then baked at 130°C, the coated surface of the paint using the composition of the present invention was uniform and good. However, in the case where the composition of the present invention was not used, the coated surface was slightly uneven and some sagging phenomenon was observed.

Claims (2)

[Claims] (1) A reactive polymer composition obtained by reacting epihalohydrin, dialkylamine, and one or more of acrylic acid aminoalkyl ester or methacrylic acid aminoalkyl ester. (2) The molar ratio of epihalohydrin, dialkylamine, and acrylic acid aminoalkyl ester or methacrylic acid aminoalkyl ester is 1.0:0.8 to 1.1:
The composition according to claim 1, which is reacted in a range of 0.005 to 0.2.