JPH0948749A - New n-allyl-substituted oligoisobutenlysuccinic acid half amide compound, its copolymer and paper additive containing the copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a polymerizable surfactant and a paper additive. SOLUTION: This N-monoallyl-substituted oligoisobutenylsuccinic acid half amide compound is expressed by formula I, formula II (R1 and R2 are each H or a group of formula III; (n) is 0-6; M is H, an alkali metal, an alkaline earth metal, ammonium or an organic base), etc. The compound is a hydrophobic compound soluble in organic solvents and is also an amphiphatic compound exhibiting water-solubility or water-dispersibility according to the pH, temperature conditions, etc., owing to carbonyl group and amide group existing in the molecule. It is polymerizable with various vinyl compounds and useful as a raw material for synthetic resins. Especially a copolymer with (meth) acrylamide is soluble or dispersible in water and useful as a paper additive having excellent paper-strengthening property and sizing performance. The compound of formula I or formula II can be produced by using an oligoisobutenylsuccinic anhydride as a raw material and reacting with allylamine or diallylamine in the absence of solvent or in an organic solvent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel allyl compound having an oligoisobutenyl succinic acid half amide structure, a copolymer of a vinyl compound copolymerizable with the novel allyl compound, and a copolymer thereof. The present invention relates to a water-soluble or dispersible copolymer of a novel allyl compound and (meth) acrylamide, and a papermaking additive (hereinafter abbreviated as PAM sizing agent) containing the copolymer as an active ingredient. The compounds according to the present invention and the copolymers of these compounds are novel compounds which have never been reported.

[0002]

2. Description of the Related Art Most conventional sizing agents have reduced paper strength due to their use, and some surface sizing agents are known to have the ability to improve the strength. Wasn't enough.

[0003]

The object of the present invention is to provide a novel N-monoallyl-substituted oligoisobutenyl succinic acid half amide compound (hereinafter abbreviated as BSA-MA) or N, N-diallyl-substituted oligoisobutenyl. It is intended to provide a succinic acid half amide compound (hereinafter abbreviated as BSA-DA) and a copolymer of these compounds. Furthermore, it is a water-soluble or dispersible additive for papermaking, which has the ability to significantly improve the paper strength and the size performance, which is produced by copolymerizing acrylamide with BSA-MA or BSA-DA. Regarding agents.

[0004]

That is, the present invention provides an N-monoallyl-substituted oligoisobutenylsuccinic acid half amide compound represented by the formulas (1) to (4) [Chemical Formula 3].

[0005]

Embedded image A mixture of N-monoallyl-substituted oligoisobutenyl succinic acid half amide compounds represented by the formulas (1) to (4). N, N-diallyl-substituted oligoisobutenyl succinic acid half amide compounds represented by formulas (5) to (8) [Chemical Formula 4].

[0006]

Embedded image A mixture of N, N-diallyl-substituted oligoisobutenyl succinic acid half amide compounds represented by formulas (5) to (8). Oligoisobutenyl obtained by copolymerizing 0.1-90.0% by weight of the compound represented by the formulas (1) to (4) or a mixture thereof with 10.0-99.9% by weight of a copolymerizable vinyl compound. A polymer compound with a succinic acid half amide structure in the side chain. Oligoisobutenyl obtained by copolymerizing 0.1-90.0% by weight of the compound represented by the formulas (5) to (8) or a mixture thereof with 10.0-99.9% by weight of a copolymerizable vinyl compound. A polymer compound with a succinic acid half amide structure in the side chain. Soluble or dispersed in water, which is obtained by copolymerizing 0.1-90.0% by weight of the compound represented by the formulas (1) to (4) or a mixture thereof with 10.0-99.9% by weight of (meth) acrylamide. Possible copolymer compounds. An additive for papermaking containing the water-soluble or dispersible copolymeric compound as an active ingredient. Soluble or dispersed in water, obtained by copolymerizing 0.1-90.0% by weight of the compound represented by the formulas (5) to (8) or a mixture thereof with 10.0-99.9% by weight of (meth) acrylamide. Possible copolymer compounds. The present invention relates to a papermaking additive containing a water-soluble or dispersible copolymer compound as an active ingredient.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The novel allyl compound having an oligoisobutenyl succinic acid half amide structure of the present invention is a hydrophobic compound soluble in organic solvents, but has a carboxyl group and an amide group in the molecule. Therefore, it is an amphipathic compound which is water-soluble or water-dispersible depending on pH, temperature conditions and the like. Further, since this compound has a double bond in the molecule, it can be polymerized with various vinyl compounds in a solvent-free system, an aqueous system or an organic solvent system, and is a compound useful as a synthetic resin raw material.

Specific uses of the N-allyl-substituted oligoisobutenyl succinic acid half amide compound and its copolymer of the present invention include plasticizers, heat-resistant resins, lubricants, antistatic agents, paints and adhesives. , Dispersants, polymerizable surfactants, cement admixtures and the like. Above all,
The copolymer of the N-allyl-substituted oligoisobutenyl succinic acid half amide compound of the present invention and (meth) acrylamide is soluble or dispersible in water, and is capable of significantly improving paper strength performance. It has been found that it has high utility value as a sizing agent.

BSA-MA or BSA-D of the present invention
A is oligoisobutenyl succinic anhydride (hereinafter BSA
Is abbreviated) as a raw material and is reacted with allylamine or diallylamine in a solventless system or an organic solvent system.

The BSA used in the present invention is produced by reacting an oligomer of isobutene with maleic anhydride. Oligomers of isobutene are those obtained by polymerizing isobutene in the presence of an acid catalyst such as solid phosphoric acid or liquid phosphoric acid or a Friedel-Crafts catalyst such as aluminum chloride to obtain a branched olefin mixture. Fractional distillation is carried out by pressure distillation or vacuum distillation, and those having 6 to 60 carbon atoms are preferable. When the number of carbon atoms of the isobutene oligomer is less than 6 or more than 60, the amphipathic properties of BSA-MA and BSA-DA are not remarkable, which is not suitable for the purpose of the present invention and is not preferable. For the production of BSA, a mixture having different carbon numbers may be used, or a mixture having different internal olefin double bond positions may be used. The reaction between the oligomer of isobutene and maleic anhydride is non-catalytic, and preferably according to a known technique such as heating at 180 to 250 ° C. under normal pressure or pressure in an inert atmosphere, and if necessary, distillation is carried out. It is desirable to remove unreacted substances and by-products.

The reaction of BSA with allylamine or diallylamine is usually carried out by dropwise addition of allylamine or diallylamine while stirring a solution of BSA in an organic solvent. As an example of the organic solvent that can be used as the reaction solvent, any solvent that can dissolve both BSA and allylamines may be used, and acetone, 2-butanone, benzene, toluene, xylene, pentane, hexane, cyclohexane, DMF, DMSO, THF, Examples include diethyl ether, dioxane, dichloromethane, dichloroethane, chloroform and the like. Methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve,
Alcohol-based solvents such as 2-ethylhexanol and cyclohexanol may cause an esterification reaction with some succinic anhydrides, but the reactivity between succinic anhydrides and allylamines is generally high and esterification is generally performed. Since the production amount of is small, it is also possible to use an alcohol solvent for applications where the physical properties of the resin are not greatly affected even if the esterified product is mixed.

It should be noted that BSA which has a short carbon number such as trimer and tetramer of isobutene and which is liquid at room temperature can be reacted in a solventless system. As in the case of using BSA-MA or BSA-DA in a water system,
When it is necessary to remove the reaction solvent, it is preferable to carry out the reaction in a solventless system.

The amount of allylamine or diallylamine used is such that an equimolar amount is reacted with the succinic anhydride group of BSA. If it is less than equimolar, unreacted BSA remains, and if it exceeds equimolar, allylamines form a salt with the carboxyl group of BSA-MA or BSA-DA, which is not preferable. Since allylamines are highly volatile compounds, it is preferable to use a closed reaction vessel. When carrying out the reaction in an open system, it is necessary to trap the volatilized allylamines with a cooling pipe, but in such a case, the reaction should be performed by adding an excessive amount of allylamines trapped in advance. To complete.

The reaction is carried out at 0 ° C. to 15 ° C. under normal pressure or pressure.
0 ° C, preferably 5 to 130 ° C, more preferably 10
The desired BSA-MA or BSA-DA can be obtained in high yield by reacting for 30 minutes to 10 hours in the temperature range of 100 ° C to 100 ° C. It is not necessary to keep the temperature constant during the reaction, and the reaction temperature may be changed for the purpose of controlling the reaction rate or adjusting the viscosity of the reaction solution.

The N-allyl-substituted oligoisobutenylsuccinic acid half-amide compound of the present invention can be produced by an amidation reaction of oligoisobutenylsuccinic acid, which is a hydrolyzate of BSA, with allylamine and diallylamine. It is more preferable to use BSA as a raw material from the viewpoint of reactivity.

Since BSA is an asymmetric compound, there are two positional isomers in the reaction product with allylamine and diallylamine, and they are a mixture of two kinds under normal reaction conditions.
The presence of each isomer was determined by ¹ H-NMR and ¹³ C-NM.
Using the R analysis method, it can be proved by the detection of two corresponding carboxamide groups. Allylamine,
Diallylamine has a high rate of forming an amide bond on carbon to which an oligoisobutenyl group is not bonded,
This tendency is remarkably recognized in diallylamine and oligoisobutenyl groups having a large number of carbon atoms as compared with allylamine. The abundance ratio of these is considered to be determined by the chain length of the oligoisobutenyl group of BSA, the reaction conditions such as the reaction solvent, the reaction temperature, the reaction concentration, etc. But there is no problem.

In the present invention, examples of vinyl compounds copolymerizable with the above BSA-MA and BSA-DA include aromatic vinyl compounds, vinyl cyanide compounds, diene compounds, unsaturated carboxylic acid ester compounds, and unsaturated compounds. It is one or more compounds selected from the group consisting of carboxylic acid compounds, unsaturated carboxylic acid amide compounds, alkyl vinyl ether compounds, and other vinyl compounds.

As the aromatic vinyl compound, styrene,
α-methylstyrene, α-chlorostyrene, p-ter
Examples thereof include t-butylstyrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, divinylbenzene and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Examples of the diene compound include diolefin compounds such as allene, butadiene and isoprene, and chloroprene.

Examples of unsaturated carboxylic acid ester compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate and lauryl. Methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3
-Hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethacrylic acid-1,3-butylene glycol, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol ( Meta)
Examples thereof include acrylates, propoxy polyethylene glycol (meth) acrylates, isopropoxy polyethylene glycol (meth) acrylates, phenoxy polyethylene glycol (meth) acrylates, and divinyl compounds such as epoxy acrylates and urethane acrylates.

As the unsaturated carboxylic acid compound, acrylic acid, methacrylic acid, crotonic acid, angelic acid, tiglic acid, 2-pentenoic acid, β-methylcrotonic acid, β-
Methyl tiglic acid, α-methyl-2-pentenoic acid, β-
Methyl-2-pentenoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid,
Glutaconic acid, α-dihydromuconic acid, 2,3-dimethylmaleic acid, 2-methylglutaconic acid, 3-methylglutaconic acid, 2-methyl-α-dihydromuconic acid, 2,
Examples thereof include acids such as 3-dimethyl-α-dihydromuconic acid and their alkali metal salts, ammonium salts, organic amine salts and the like.

As the unsaturated carboxylic acid amide compound,
Acrylamide, methacrylamide, diacetone acrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl acrylamide, N,
N-dimethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide,
N-propylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorpholine, N, N-di-n-propylacrylamide, Nn-butylacrylamide, Nn-hexylacrylamide, Nn-hexyl Methacrylamide,
N-n-octyl acrylamide, N-n-octyl methacrylamide, N-tert-octyl acrylamide,
N-dodecyl acrylamide, Nn-dodecyl methacrylamide, N, N-diglycidyl acrylamide,
N, N-diglycidylmethacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6 -Glycidoxyhexyl) acrylamide, methylenebisacrylamide, N, N'-ethylenebisacrylamide, N,
Examples thereof include N'-hexamethylene bisacrylamide and N-methylol acrylamide.

As the alkyl vinyl ether compound,
Examples thereof include vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether, vinyl isobutyl ether, vinyl-2-ethylhexyl ether and vinyl-n-octadecyl ether. Other vinyl compounds include vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, isoprene, N-vinyl-2.
-Pyrrolidone, N-vinylformamide, N-vinylacetamide, divinyl adipate, divinyl sebacate, and other divinyl esters, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and vinylsulfonic acid, styrenesulfonic acid, 2-acrylamide Examples thereof include sulfonic acids such as 2-phenylpropanesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, and their alkali metal salts, ammonium salts, organic amine salts and the like.

In addition to the above vinyl compounds, allylamines such as allylamine, N-methylallylamine, 2-methylallylamine, diallylamine, and dimethyldiallylammonium chloride and their salts, allylsulfonic acid, methallylsulfonic acid, and other allylamines. It is also possible to copolymerize sulfonic acids and their salts, allyl compounds such as allyl alcohol, diallyl isophthalate, diallyl terephthalate, diethylene glycol diallyl carbonate and triallyl cyanurate.

BSA-MA or BSA-D of the present invention
The copolymerization ratio of A and the above-mentioned copolymerizable vinyl compound is about 0.1 to 90.0 for BSA-MA or BSA-DA.
% By weight, 10.0-99.9% by weight of copolymerizable vinyl compound
In the range. The copolymerization ratio with the copolymerizable allyl compound is the same as that of the vinyl compound, and the vinyl compound and the allyl compound may be used in combination.

BSA-MA or BSA-DA of the present invention
There is no particular limitation on the copolymerization method of the above-mentioned vinyl compound, and the copolymerization can be carried out by a known method. Usually, polymerization is carried out by maintaining a predetermined temperature in the presence of a radical polymerization initiator. It is not necessary to maintain the same temperature during the polymerization, and the temperature may be changed appropriately as the polymerization progresses. The heating is performed or the heat is removed as necessary. The polymerization temperature varies depending on the type of monomer used and the type of polymerization initiator, and is generally in the range of 30 to 200 ° C. in the case of a single initiator, lower in the case of a redox type polymerization initiator, and collectively. The temperature is generally -5 to 50 ° C when polymerization is performed, and is generally 30 to 90 ° C when sequentially added. At a high temperature of 100 ° C or higher, an imide cyclization reaction due to a dehydration reaction may occur,
There is no particular problem when it is intended for use as a heat-resistant resin. The atmosphere in the polymerization vessel is not particularly limited, but it is preferable to replace with an inert gas such as nitrogen gas in order to carry out the polymerization rapidly. The polymerization time is not particularly limited, but is generally 1 to 4
0 hours.

The above-mentioned vinyl compound and B are used as the polymerization solvent.
Any solvent capable of uniformly dissolving SA-MA or BSA-DA may be used, and examples of the organic solvent include hexane, cyclohexane, decalin, tetralin, dioxane, carbon tetrachloride, toluene, xylene, cumene, ethylbenzene,
Carbon disulfide, chloroform, ethyl acetate, acetic acid, morpholine, benzene, tetrahydrofuran, pyridine, methyl ethyl ketone, acetone, methanol, ethanol,
Examples include alcohols such as propanol, butanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and ethylene glycol, formamide, dimethylformamide, dimethyl sulfoxide, and the like.

For a vinyl compound which is compatible with BSA-MA or BSA-DA and requires desolvation, copolymerization in a solventless system may be preferable for the purpose of simplifying the process. BSA-MA or BSA
-DA becomes soluble in water when the carboxyl group in the molecule is neutralized with alkali. The pH at which water becomes soluble varies depending on the chain length of the oligoisobutenyl group, but for example, when the oligoisobutenyl group has 16 carbon atoms, it is possible to carry out homogeneous polymerization using water as the solvent at a pH of 8 or higher. Is. It is also possible to carry out emulsion polymerization in the presence of a surfactant even under pH conditions insoluble in water.

A general polymerization initiator can be used as the polymerization initiator. In the peroxide system, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 1,1,3,3,
-Tetramethylbutyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, tert-butylperbenzoate, te
rt-butyl peracetate, tert-butyl perphenylacetate, tert-butyl peroxylaurate, cumyl perbivalate Further, as the azo compound, azobisisobutyronitrile, 2,2'-azobis (4-methoxy- 2,4
-Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2 -Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2 '-Azobis (2-methylpropionate) or the like can be used. Furthermore, the above-mentioned polymerization initiator 2
More than one species can be used in combination.

The polymerization initiator when water is used as a solvent is not particularly limited as long as it is water-soluble. Specifically, examples of the peroxide type include ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl peroxide. In this case, although it can be used alone, it can also be used as a redox polymerizing agent in combination with a reducing agent.
Examples of the reducing agent include sulfite, bisulfite, iron,
Salts of lower ions such as copper and cobalt, hypophosphorous acid, hypophosphite, organic amines such as N, N, N ', N'-tetramethylethylenediamine, and reducing sugars such as aldose and ketose. And so on. Further, as the azo compound, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2 '
-Azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleic acid and salts thereof can be used. Further, two or more of the above-mentioned polymerization initiators may be used in combination.

The amount of the polymerization initiator added is 0.00 based on the monomer.
The range is 01 to 10% by weight, preferably 0.01 to 8% by weight
It is. In the case of redox type, the amount of the reducing agent added to the polymerization initiator is 0.1 to 100%, preferably 0.2 to 80% on a molar basis. Further, if necessary, a chain transfer agent such as isopropyl alcohol, α-thioglycerol, mercaptosuccinic acid, thioglycolic acid, triethylamine, sodium hypophosphite can be appropriately used. For the purpose of adjusting the polymerization rate, sodium ethylenediamine tetraacetate (EDTA-Na), citric acid, tartaric acid, urea, thiourea, L-ascorbic acid,
Compounds such as ethylene trithiocarbonate, phenothiazine, nicotinamide may be used. The amount of the chain transfer agent, the regulator of the polymerization rate, or the like used varies depending on the purpose of use of the copolymer, but is generally 0.01% with respect to the total amount of the monomers.
It is in the range of ppm to 5.0%.

The monomers, the polymerization initiator, the solvent, the chain transfer agent and the like to be used for the polymerization may be charged into the reaction vessel at a time when the polymerization is started, but one or more components may be added depending on the progress of the polymerization. , May be added individually or as a mixture with a solvent.

The thus obtained copolymer of the present invention (a polymer compound having an oligoisobutenyl succinic acid half amide structure in the side chain) is generally a plasticizer, a heat resistant resin,
It is used as an antistatic agent, lubricant, paint, adhesive, dispersant, surfactant, admixture for cement, etc. In particular, it can be suitably used as a papermaking additive containing the compound as an active ingredient. Among them, the N-allyl-substituted oligoisobutenyl succinic acid half amide compound of the present invention and (meth)
A copolymer with acrylamide is soluble or dispersible in water and is highly useful as a new sizing agent (PAM-based sizing agent) capable of significantly improving paper strength performance. Although its function is not always clear, the amide group of the copolymer forms a hydrogen bond with the cellulose fiber in the drying process after coating, which significantly improves the paper strength and, at the same time, increases the oligo-strength. It is considered that the size performance is exhibited by the aggregation of the isobutenyl groups and the orientation of the isobutenyl groups on the surface side of the paper.

Specifically, BSA-MA and BSA-D
The copolymer of A and (meth) acrylamide has a viscosity of 0.01 to 500 at 25 ° C. at a concentration of 5 to 30% by weight.
Within the range of poise. Unlike the starting material BSA, the PAM-based sizing agent of the present invention is water-dispersible by itself, so that it is not necessary to emulsify using a surfactant and can be used as it is. When the PAM-based sizing agent is applied (externally added) to the surface of the paper, the sizing property is imparted to the paper and the strength of the paper strength is significantly improved. The concentration of the coating solution used for coating the paper is 0.01 to 10.0%, preferably 0.10 to 8.0%. The coating amount is 0.001 to 5.0 g / m ² , preferably 0.
It is in the range of 005 to 1.0 g / m ² .

For coating the paper, general methods such as impregnation, size press, gate roll coater, calender, blade coater and spray are used. The drying temperature after coating may be a temperature at which water evaporates, and preferably 100
It is in the range of ℃ to 180 ℃. Furthermore, the PAM-based sizing agent of the present invention is further improved in surface strength and internal strength by combining with conventionally known chemicals for surface coating such as starch-based, carboxymethylcellulose-based, PVA-based, PAM-based and the like. You can also let it.

BSA-MA or BSA-DA
Is an anionic hydrophobic monomer having a carboxyl group and therefore imparts an anionic property to the acrylamide polymer (PAM). Therefore, PAM-based sizing agents are widely used as fixing agents for improving the yield of sizing agents, such as aluminum sulfate, aluminum chloride, sodium aluminate, polyethyleneimine, Mannich modified products of polyacrylamide and Hoffmann modified products, and polyalkylenepolyamines. , Can be fixed to pulp by interaction with water-soluble polymers having cationic groups such as cationized starch, and can be used as an internal sizing agent for acidic papermaking. In this case, among the above-mentioned copolymerizable vinyl compounds, unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc. It is also possible to enhance the same effect by copolymerizing the unsaturated sulfonic acid compound.

Further, N, N-dimethylaminoethyl acrylate (DA), N, N-dimethylaminoethyl methacrylate (DM), N, N-dimethylaminopropyl acrylamide (DMAPAA), N, N-dimethylaminopropyl methacrylamide. By using a vinyl compound and an allyl compound which show a cationic property under acidic to weakly acidic conditions such as (DMAPMA), allylamine and diallylamine as copolymerization components, the fixability to pulp can be further improved.

Further, DA, DM, DMAPAA, DM
APMA, etc., with dimethylsulfate, halogenated alkyls such as methyl chloride and methyl bromide, allyl chloride, halogenated benzyls such as benzyl chloride and benzyl bromide, epihalohydrins such as epiclohydrin and epibromohydrin, propylene oxide and styrene oxide, etc. When a vinyl compound quaternized with the epoxy compounds and an allyl compound such as dimethyldiallylammonium chloride are used as copolymerization components, they can be fixed on the pulp even under neutral to weakly alkaline conditions. It can also be used as an agent.

At this time, a fixing agent for a sizing agent such as aluminum sulfate as exemplified above may be used in combination. When the PAM-based sizing agent is used as an internally added sizing agent, it is added in an amount of 0.01 to 4.0% by weight, preferably 0.05 to 2.0% by weight, based on the weight of the pulp, and it is an ordinary internally added sizing agent such as a seed box or a machine chest. It may be added at the same place as. The PAM-based sizing agent of the present invention may be mixed with an antifoaming agent, an antiseptic agent, an anticorrosive agent, an antislip agent, or the like, or may be used together when used.

[0040]

The present invention will be described in detail below with reference to Examples.
The present invention is not limited to these examples. In the following,% is based on weight and viscosity is B at 25 ° C.
It is a value measured by a viscometer. The molecular weight was determined by GPC analysis using a ShodexOH-pak SB-80M + SB-804 (Showa Denko) column and an eluent Na ₂ HPO ₄ -KH ₂ PO ₄ (50 mM) -NaNO.
_The measurements were carried out using ₃ (0.1 M) (pH 6.5). For NMR analysis, a sample was uniformly dissolved in deuterated chloroform to a concentration of about 10 to 20% w / v, and an NMR with an outer diameter of 5 mmφ was used.
Put in a sample tube for spectrum measurement, 500MHz NMR
Using a spectrum measuring device A500 (made by JEOL Ltd.)
¹ H- and ¹³ C-NMR spectra were measured. IR
The analysis uses the window plate of KRS-5 or the KBr tablet method,
The infrared analyzer used was FT / IR-8900 (manufactured by JASCO Corporation). For elemental analysis, CHN analyzer Model 2400 (manufactured by Perkin-Elmer) was used.

[Example 1] BSA (manufactured by Nippon Petrochemical Co., C ₂₄ type, LV) was placed in a 1-liter four-neck separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel.
-7M) After adding 470.0 g of acetone to 200.0 g and dissolving,
Allylamine 25.4g from dropping funnel while stirring at 20 ℃
Was dropped in 30 minutes. After the addition, the temperature was raised to 40 ° C. for 1 hour at 20 ° C., and the stirring was continued for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure to obtain 225.4 g of a dark brown highly viscous substance. Elemental analysis value; C: 75.71%, H: 11.68%, N: 2.85% (calculated value: C ₃₁ H ₅₇ NO ₃ ) C: 75.99%, H: 11.58%, N: 2.89% (actual measurement value) IR analysis ( Fig. 1) shows that the raw material BSA is 1780 cm.
^-1 and characteristic absorption bands of the acid anhydride group found in 1860 cm ^-1 (C = O stretch) disappears, behalf and 1705 cm ^-1 to the carboxylic acid (C = O stretching), amide 1640 cm ^-1 (C = O stretch, N-
Absorption bands derived from H bending angle) and 3300 cm ^-1 (N-H stretching) were observed.

2 and 3 show the ¹ H-N of BSA-MA.
The MR spectrum and ¹³ C-NMR spectrum are shown. The magnetic field strength on the horizontal axis is based on tetramethylsilane (0p
pm) in ppm. BSA-obtained above
MA is soluble in water in the form of a carboxylate salt, and in the following examples 40.0 g of BSA-MA was added to a 40% aqueous solution of caustic soda 8.6.
g, and 351.4 g of distilled water were added and uniformly dissolved (pH 8.
97) was used.

Example 2 A BSA (manufactured by Nippon Petrochemical Co., C ₂₄ type, LV) was placed in a 1-liter four-neck separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel.
-7M) After adding 470.0 g of acetone to 200.0 g and dissolving,
Diallylamine from the dropping funnel while stirring at 20 ° C 43.
3 g was added dropwise in 37 minutes. After the addition, the temperature was raised to 40 ° C. for 1 hour at 20 ° C., and the stirring was continued for 2 hours. The solvent of the reaction solution was distilled off under reduced pressure to obtain 242.5 g of a dark brown highly viscous substance. Elemental analysis value; C: 76.78%, H: 11.56%, N: 2.63% (calculated value: C ₃₄ H ₆₁ NO ₃ ) C: 77.29%, H: 12.05%, N: 2.80% (actual value) IR analysis ( in Figure 4), the carboxylic acid (C = O stretch in the 1710 cm ^-1), an absorption band derived from an amide (C = O stretch) was observed in 1650 cm ^-1.

5 and 6 show the ¹ H-N of BSA-DA.
The MR spectrum and ¹³ C-NMR spectrum are shown. The BSA-DA obtained above was dissolved in water in the form of a carboxylic acid salt, and 40.0 g of BSA-DA was used in the following examples.
An aqueous solution (pH 8.99) in which 7.9 g of 40% aqueous sodium hydroxide solution and 352.1 g of distilled water were added and uniformly dissolved was used.

[Example 3] A 10% aqueous solution of BSA-MA obtained in Example 1 was added to a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube.
Distilled water (29.7 g) and sodium hypophosphite (0.30 g) were added to 0.0 g, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. Using a microtube pump, a mixture of 54.0 g of 50% aqueous acrylamide solution, 185.7 g of distilled water, and 0.30 g of ammonium persulfate (APS) 0.30 g (cooled on an ice bath) was added to this solution.
Dropped at 0 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a uniform yellow colored aqueous solution. The nonvolatile content of the obtained aqueous solution was 10.5%, the pH was 7.19, the viscosity was 8.4 cp, and the weight average molecular weight was 30,300.

Example 4 A 10% aqueous solution of BSA-MA obtained in Example 1 was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube.
Sodium hypophosphite (0.60 g) was added to 0.0 g, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. A 50% acrylamide aqueous solution 48.0
A mixed solution of g, distilled water 191.1 g, and APS 0.30 g (cooled on an ice bath) was added dropwise over 120 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a uniform yellow colored aqueous solution. The nonvolatile content of the obtained aqueous solution was 10.7%, the pH was 7.72, the viscosity was 5.3 cp, and the weight average molecular weight was 35,000.

Example 5 A 10% aqueous solution of BSA-MA obtained in Example 1 was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube.
Sodium hypophosphite (0.90 g) was added to 0.0 g, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. A 50% acrylamide aqueous solution 42.0
A mixed solution of g, 166.8 g of distilled water and 0.30 g of APS (cooled on an ice bath) was added dropwise over 120 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a uniform yellow colored aqueous solution. The nonvolatile content of the obtained aqueous solution was 10.8%, the pH was 7.91, the viscosity was 3.7 cp, and the weight average molecular weight was 30,400.

[Example 6] A 10% aqueous solution of BSA-DA obtained in Example 2 in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube 3
Distilled water (29.7 g) and sodium hypophosphite (0.30 g) were added to 0.0 g, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. Using a microtube pump, a mixed solution of 54.0 g of 50% acrylamide aqueous solution, 185.7 g of distilled water and 0.30 g of APS (cooled on an ice bath) was added dropwise to this solution in 120 minutes. 1 at 80 ℃
Stirring was continued for 80 minutes to obtain a homogeneous aqueous solution which was lightly colored yellow. The nonvolatile content of the obtained aqueous solution is 10.7%, the pH is 7.06,
The viscosity was 7.28 cp and the weight average molecular weight was 29,000.

Example 7 A 10% aqueous solution of BSA-DA obtained in Example 2 was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube.
Sodium hypophosphite (0.60 g) was added to 0.0 g, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. A 50% acrylamide aqueous solution 48.0
A mixed solution of g, distilled water 191.1 g, and APS 0.30 g (cooled on an ice bath) was added dropwise over 120 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a uniform yellow colored aqueous solution. The resulting aqueous solution had a nonvolatile content of 10.6%, a pH of 7.50, a viscosity of 5.0 cp, and a weight average molecular weight of 49,600.

Example 8 A 10% aqueous solution of BSA-DA obtained in Example 2 was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube.
Sodium hypophosphite (0.90 g) was added to 0.0 g, and the mixture was heated to 80 ° C while stirring under a nitrogen stream. A 50% acrylamide aqueous solution 42.0
A mixed solution of g, 166.8 g of distilled water and 0.30 g of APS (cooled on an ice bath) was added dropwise over 120 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a uniform yellow colored aqueous solution. The nonvolatile content of the obtained aqueous solution was 10.8%, the pH was 7.76, the viscosity was 4.4 cp, and the weight average molecular weight was 29,500.

Comparative Example 1 60.0 g of distilled water and 0.05 g of sodium hypophosphite were added to a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introducing tube and a feed tube, and the mixture was stirred under a nitrogen stream. While heating to 80 ° C. Using a microtube pump, a mixed solution of 150.0 g of a 40% acrylamide aqueous solution, 89.7 g of distilled water and 0.30 g of APS (cooled on an ice bath) was added dropwise to this solution in 120 minutes. 180 at 80 ℃
Stirring was continued for a minute to obtain a transparent homogeneous aqueous solution. The viscosity of the obtained aqueous solution was 2,680 cp and the weight average molecular weight was 189,00.
It was 0.

In each of the following coating examples and coating comparative examples, newspaper base paper (basis weight: 50 g / m ² ) was used. The sizing degree is measured according to the Steckigt size test method of JIS P8122, and the surface strength is R using a RI-3 type (manufactured by Ming Seisakusho).
The I-pick was measured using a 10-point method (the higher the score, the higher the surface strength), and the Z-axis strength was measured using an internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd.).

[Coating Examples 1 to 6] The base paper to be coated was dipped in the polymer solutions obtained in Examples 1 to 1 for 1 second, squeezed by two rolls, and the amount of the absorbed liquid was measured. Then, the coating amount was obtained. The coating amount was adjusted in advance so that the nonvolatile content of the polymer was 1.2 g / m ² (polymer concentration: 2.2 to 2.4
wt%). The pH of the coating solution was adjusted to 7.3 to 7.5. Immediately after coating, it was dried for 50 seconds with a drum dryer whose surface temperature was set to 120 ° C., and after being conditioned for 24 hours in a constant temperature and constant humidity chamber (20 ° C., humidity 65%), sizing degree and paper strength were measured. The results are shown in Table 1.

[Comparative Coating Example 1] A coated paper was prepared in the same manner as in Coating Examples 1 to 6 except that the polymer prepared in Comparative Example 1 was used instead of the polymer. The strength of the force was measured. The results are shown in Table 1.

[0055]

[Table 1]

[0056]

INDUSTRIAL APPLICABILITY The N-allyl-substituted oligoisobutenylsuccinic acid half amide compound of the present invention is soluble in an organic solvent, but it is also an amphipathic compound excellent in water solubility depending on pH and temperature conditions. Is. Since this compound has a polymerizable double bond in the molecule, it can be used for various purposes as a polymerizable surfactant. Further, since it has a half amide structure, it forms an imide ring by heat treatment before and after polymerization, and thus can be applied to applications requiring heat resistance or water resistance. Further, when used as a copolymerization component of an acrylamide polymer, it is useful as an additive for papermaking having not only paper strength performance but also size performance as is clear from the examples.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the novel compound obtained in Example 1.

FIG. 2 ¹ H-NMR of the novel compound obtained in Example 1.
Spectral diagram

FIG. 3 ¹³ C-NMR of the novel compound obtained in Example 1.
Spectral diagram

FIG. 4 is an infrared absorption spectrum diagram of the novel compound obtained in Example 2.

FIG. 5 ¹ H-NMR of the novel compound obtained in Example 2.
Spectral diagram

6] ¹³ C-NMR of the novel compound obtained in Example 2
Spectral diagram

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 39/02 LJY C08L 39/02 LJY D21H 17/34 D21H 3/38 (72) Inventor Masayuki Yanagi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kyoyoshi Watanabe 1-6 Takasago, Takaishi-shi, Osaka Mitsui Toatsu Chemical Co., Ltd.

Claims (10)

[Claims] 1. An N-monoallyl-substituted oligoisobutenyl succinic acid half amide compound represented by formulas (1) to (4) [Chemical formula 1]. Embedded image 2. A mixture of N-monoallyl-substituted oligoisobutenyl succinic acid half amide compounds represented by formulas (1) to (4) according to claim 1. 3. An N, N-diallyl-substituted oligoisobutenyl succinic acid half amide compound represented by formulas (5) to (8) [Chemical Formula 2]. Embedded image 4. A mixture of N, N-diallyl-substituted oligoisobutenylsuccinic acid half amide compounds represented by formulas (5) to (8) according to claim 3. 5. A compound represented by formula (1) to (4) or a mixture thereof according to claim 1, 0.1-90.0% by weight.
A polymer compound having an oligoisobutenyl succinic acid half amide structure as a side chain, which is obtained by copolymerizing a copolymerizable vinyl compound with 10.0 to 99.9% by weight. 6. A compound represented by formula (5) to (8) or a mixture thereof according to claim 3, 0.1-90.0% by weight.
A polymer compound having an oligoisobutenyl succinic acid half amide structure as a side chain, which is obtained by copolymerizing a copolymerizable vinyl compound with 10.0 to 99.9% by weight. 7. A compound represented by formula (1) to (4) or a mixture thereof according to claim 1, 0.1-90.0% by weight.
And a (meth) acrylamide 10.0 to 99.9 wt% copolymerizable compound that is soluble or dispersible in water. 8. A papermaking additive containing the water-soluble or dispersible copolymer compound according to claim 7 as an active ingredient. 9. A compound represented by formulas (5) to (8) or a mixture thereof according to claim 3, 0.1-90.0% by weight.
And a (meth) acrylamide 10.0 to 99.9 wt% copolymerizable compound that is soluble or dispersible in water. 10. A papermaking additive containing the water-soluble or dispersible copolymer compound according to claim 9 as an active ingredient.