JP2620180B2 - Cationic polyelectrolyte copolymer and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The water-soluble polyol cationic derivative-olefin monomer graft copolymer of the present invention is a cationic derivative of a polyol having a hydroxyl group, and if it is water-soluble, all of the olefin monomer in water can be used. It suggests that the polymer can be graft-polymerized to produce a latex polymerization product useful as an immunoassay material.

[0002]

2. Description of the Related Art Conventionally, a method for producing a latex polymerization product as an immunoassay material is mostly a product obtained by emulsion polymerization in an aqueous solution in the presence of a surfactant, and is a soapless product without a surfactant. Is desired. This is because the surfactant present in the aqueous solution affects the action as a latex diagnostic agent.

[0003]

[Means for Solving the Problems] The water-soluble polyol cationic derivative-olefin monomer graft copolymer of the present invention is prepared by suspending an olefin monomer in water with a cationic derivative of a water-soluble polyol having a hydroxyl group. Graft polymerization by a turbidity polymerization method or an emulsion polymerization method is to produce a latex polymerization product useful as an immunoassay material,
The water-soluble polyol cationic derivative-olefin monomer graft copolymer latex of the present invention is used for an antibody-adsorbed latex diagnostic according to the claim, which is a latex diagnostic. Emulsion polymerization is a polymerization method in which an olefin monomer is suspended in an aqueous solution and usually emulsified using a surfactant or the like. To be more specific, hydrogen bonding, Coulomb force, charge transfer This is a polymerization method in which a polymer chain is polymerized and grows to form fine particles in an aqueous solution by interaction at an aqueous solvent interface by action, Van der Waals force, or the like. Usually, the polymerization product is present as a mixture of the polymerized monomer and the surfactant. Surfactants considered as impurities may interfere with the use of the latex diagnostic agent when used in the antibody-adsorbed latex diagnostic agent described in the claims.

[0004]

The present invention is a product obtained by graft-polymerizing an olefin monomer in water with a cationic derivative of a water-soluble polyol having a hydroxyl group. The structures of the growing olefin monomer chain and the resulting copolymer chain are described as chemical structural formulas (Chemical Formula 3) and (Chemical Formula 1), respectively. Each bonding relationship is a covalent bond due to chain transfer of an olefin monomer double bond resulting from radical generation by abstraction of a hydrogen atom of a hydroxyl group (as a proton by oxidation of an initiator) of a water-soluble polyol cationic derivative. That is clear. This is carried out by using tetravalent cerium ion or the like as an initiator and does not use any surfactant, so that it is very useful without being hindered when used as a diagnostic agent for antibody-adsorbed latex. It is claimed that the water-soluble polyol cationic derivative-olefin monomer graft copolymer latex of the present invention is intended to be used as an antibody-adsorbed latex diagnostic according to the claim, which is a latex diagnostic. Is clearer than the description format of the range. That hydroxyl olefin monomer is graft polymerized in water in the water-soluble polymer having a, b
The production of a latex polymerization product useful as a munoassay material is a major part of the essential features of the present invention, and an olefin monomer graft copolymer such as a polysaccharide can also achieve the same object. Such a graft copolymer which grows at an interface between a solvent and a solute, which is called soap-free, is a useful substance having a wide variety of uses.
In particular, attention has been paid to filtration membranes and biomaterials in addition to immunoassay materials. Focusing on its hydrophilicity, it can be applied to artificial kidney membranes, components, blood vessels substitutes, and contact lenses.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyol cationic derivative-olefin monomer graft copolymer of the present invention will be described in detail below. The polyol cationic derivative-olefin monomer graft copolymer has the following 2
Get through these steps. I. Preparation of the polyol cationic derivative The formula of the unit of the cationic derivative of the polyol is

## STR2 ## A cation represented by X in the above (Chemical Formula 2) to a product in which the hydroxyl group of this polyol is partially substituted by an acidic group such as a carboxymethyl group or a sulfate group by an ether bond or partially substituted by an alkyl group. It may have a functional group. Usually, these polyol cationic derivatives are composed of the hydroxyl group of the polyol and XC1.
Is obtained by a Schotten-Baumann reaction in an alkaline solution with a chlorine compound of the above cation substituent. The polyol referred to here may be polyvinyl alcohol, partially saponified vinyl acetate, polyethylene glycol, polypropylene glycol, poly (2-hydroxyethyl methacrylate), or the like. As the olefin monomer to be graft-polymerized, one having a general formula represented by the following formula can be considered.

Embedded image Specifically, acrylic acid, such as methacrylic acid alpha, alkyl esters of β- unsaturated acids, lower alkyl-substituted cyclohexyl esters such as cyclohexyl ester, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 2-hydroxybutyl ester; acrylamide, methacrylamide, acrylamide, acryl- or methacryl-dimethylamide,
The alpha, beta-amino alkyl esters of C ₁ -C ₃ unsaturated acids, dialkylaminoalkyl esters of C ₁ -C _3, glycidyl ester, tetrahydrofurfuryl ester, benzyl ester, polyethylene glycol monoesters, acrylonitrile, methacryl Nitrile groups of α, β-unsaturated acids such as lonitrile : vinyl alcohol, methyl vinyl alcohol, dimethyl vinyl alcohol; C _1-of vinyl alcohol such as vinyl acetate, vinyl propionate, vinyl butyrate and its methyl-substituted vinyl alcohol C ₃ alkyl esters; styrene;
Vinyltoluene; vinylpyrrolidone: vinylmethylpyrrolidone, and the like. II. The adjustment reaction of the graft copolymer is usually performed in an aqueous solution. That is, the above-mentioned olefin monomer is added to an aqueous solution of a cationic derivative of a polyol, and an initiator is added to react. As the initiator, a tetravalent cerium salt, a tetravalent manganese salt, a ferric salt-hydrogen peroxide are usually used, and potassium persulfate (KP
S), azobisisobutylnitrile (AIBN), benzoyl peroxide (BPO) and other radical initiators are also used. The reaction temperature can be widely selected from room temperature to 80 ° C. If necessary, the reaction is continued by replacing with nitrogen. Each binding relationship is based on the hydrogen atom of the hydroxyl group of the cationic derivative of the water-soluble linear polysaccharide (oxidized and
(In tons) , and is a covalent bond due to chain transfer of olefin monomer double bonds due to radical generation by abstraction . In this reaction, the product occurs in latex. This latex polymer is generally insoluble in water, alcohol, or an organic solvent such as acetone or tetrahydrofuran, but can be easily formed into a film by a casting method or the like. Alternatively, an excessively insoluble solvent such as alcohol is added to obtain a precipitate, and then a molded product can be easily formed by a hot press method or the like. For the above purpose, the ratio of the backbone polymer to the graft polymer or the degree of polymerization in the graft polymer can be selected variously according to the purpose. In the graft polymerization, the polymerization rate is determined by the graft rate (%). This is defined as graft ratio (%) = (amount of graft-polymerized monomer / amount of backbone polymer in graft copolymer) × 100. In the present invention, the olefin compound is formed as a graft chain, and a graft ratio in the range of 2% to 5000% is considered appropriate. The invention of the present application repeatedly states that the olefin monomer is graft-polymerized in water with a cationic derivative of a water-soluble polymer having a hydroxyl group, but the structure of the resulting copolymer chain is defined in the claims. It is represented by the following ( Chemical Formula 1) consisting of ( Chemical Formula 2) and ( Chemical Formula 3) as described in the range as a chemical structural formula.

## STR1 ## Each bonding relationship is based on the hydrogen atom of the hydroxyl group of the water-soluble polyol cationic derivative (oxidized proton
) Is a covalent bond due to chain transfer of an olefin monomer double bond due to radical generation by abstraction.

[0006]

EXAMPLES Example 1 Polyvinyl alcohol having an average molecular weight of MW 300,000 (PV
2 g of TEAE (triethylaminoethyl) -polyvinyl alcohol hydrochloride having a nitrogen content of 2% based on A) was dissolved in 50 ml of water, and then 10 ml of methanol and 15 ml of methyl acrylate (MA) were added.
After replacing the air in the reaction vessel with nitrogen gas, 250 mg of ceric ammonium nitrate nitrate dissolved in 15 ml of 0.1 N nitric acid is added with sufficient stirring to start the reaction. The reaction is carried out at 25 ° C. for 1 hour to produce a latex. At the end of the reaction, 3 ml of a 1% hydroquinone solution was used as a terminator. Thereafter, the reaction solution was poured into three times the amount of methanol to obtain a precipitate. The precipitate was sufficiently washed with hot water, centrifuged, and dried at 50 ° C. under reduced pressure. Then, the dried product was placed in a Soxhlet extractor and subjected to acetone extraction for 10 hours, and 2 g of a hydrochloride of TEAE polyvinyl alcohol-MA copolymer was obtained. Obtained. Nitrogen content 0.67% Graft rate 300% vs TEAE-polyvinyl alcohol yield 33% This is insoluble in water, which is a good solvent for TEAE polyvinyl alcohol hydrochloride, and acetone, which is a good solvent for methyl polyacrylate. . Looking at the infrared absorption spectrum of this product, absorption of a carbonyl group, which is not observed in TEAE polyvinyl alcohol hydrochloride, is observed at around 1730 cm ⁻¹ . Example 2 After the same reaction as in Example 1 was performed, the latex reaction completion solution was not poured into methanol, but the mixture was folded in water to remove unreacted substances and initiator, and the homopolymer was mixed. A TEAE polyvinyl alcohol-MA copolymer latex was obtained. This is useful as a reagent for detecting rheumatoid factor and shows the test results. Test Method An equal amount of antibody, [ie 2
Glycine-Nac so as to become 0 μg / mg latex
1 buffer (GB) (0.05 mol / l, PH8.
2) is added dropwise while stirring.
After stirring at room temperature for 2 hours (30 minutes at 4000 rpm if necessary)
Centrifuge for 5 min and repeat resuspension in GB)
It is stored at 4 ° C as a 1% suspension in GB with% BSA (bovine albumin). One drop of the above-mentioned sensitized latex solution of the present invention is dropped on a cleaned glass plate with a capillary tube, and 0.05 ml of a rheumatoid factor-positive serum previously diluted 1/20 in GB is added to the latex solution on a glass plate with a capillary tube. And the mixture was stirred, and the glass plate was shaken. After about 3 minutes, the presence or absence of aggregation was visually determined. When a similar operation was performed using a known rheumatoid factor-negative serum diluted 1/20, no aggregate was observed.

Claims (2)

(57) [Claims] 1. A compound of the general formula In the formula of the unit of the cationic derivative of the water-soluble polyol, Wherein the unit of the polymer of the olefin compound is represented by the following formula: Wherein a cationic derivative of a water-soluble polyol is used as a trunk polymer, its hydroxyl group is used as a binding site by abstraction of a hydrogen atom, and an olefin compound is used as a graft chain. The graft ratio ranges from 2% to 5000%. )
Represented by the above (Chemical Formula 1)
A copolymer obtained by grafting an olefin monomer to a cationic partially substituted water-soluble polyol in water. 2. The formula of the unit of the cationic derivative of the water-soluble polyol in the general formula is represented by the following formula: wherein the formula of the polymer unit of the olefin compound is: Wherein a cationic derivative of a water-soluble polyol is used as a trunk polymer, its hydroxyl group is used as a binding site by abstraction of a hydrogen atom, and an olefin compound is used as a graft chain. The graft ratio is in the range of 2% to 5000%. 2) and an antibody using a copolymer obtained by grafting an olefin monomer in water to a cationically-substituted water-soluble polyol represented by the above formula (1), which is represented by the above formula (1). Adsorbed latex diagnostics.