JPH0967415A - New oligoisobutenylsuccinic acid half ester compound and its copolymer and additive containing the copolymer and used for paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new oligoisobutenylsuccinic acid half ester compound having an amphiphatic property and useful for paper additives, polymerizable surfactants, etc. SOLUTION: A compound of formula I or II [R1 , R2 , are each H, a group of formula (n is 0-6); R3 is H, methyl; M is H, an alkali (ne earth) metal, ammonium, an organic base]. The compound of formula I or II is obtained e.g. by reacting the oligomer of isobutene with maleic anhydride and subsequently reacting the obtained oligoisobutenylsuccinic anhydride with allyl alcohol or methallyl alcohol in a solvent-free system or in an organic solvent system. 0.01-90.0wt.% of the compound (mixture) of formula I or II is copolymerized with 10.0-99.9wt.% of a vinylic compound such as (meth)acrylamide to obtain the polymeric compound having the oligoisobutenylsuccinic acid half ester structures in the side chains.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel allyl compound having an oligoisobutenyl succinic acid half ester structure, a copolymer of a vinyl compound copolymerizable with these novel allyl compounds, 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 oligoisobutenyl succinic acid half allyl ester compound (hereinafter abbreviated as BSA-AL) or an oligoisobutenyl succinic acid half methallyl ester compound (hereinafter BSA). -ML) and a copolymer of this compound. Furthermore, it is a water-soluble or dispersible papermaking machine that has both the ability to significantly improve paper strength and size performance, produced by copolymerizing BSA-AL or BSA-ML with (meth) acrylamide. For additives.

[0004]

Means for Solving the Problems That is, the present invention provides an oligoisobutenyl succinic acid half ester compound represented by the formula (1), (2), (3) or (4)

[0005]

Embedded image A mixture of oligoisobutenyl succinic acid half ester compounds represented by the formulas (1) to (4), a compound represented by the formulas (1) to (4) or a mixture thereof in an amount of 0.1 to 90.0% by weight; A polymer compound having an oligoisobutenyl succinic acid half ester structure in the side chain, obtained by copolymerizing with a copolymerizable vinyl compound 10.0 to 99.9% by weight, represented by the formulas (1) to (4) Soluble compound or a water-soluble copolymer compound obtained by copolymerizing 0.1 to 90.0% by weight of a compound or a mixture thereof with 10.0 to 99.9% by weight of (meth) acrylamide. Alternatively, the present invention relates to a papermaking additive containing a dispersible copolymer compound as an active ingredient.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The novel allyl compound having an oligoisobutenyl succinic acid half ester structure of the present invention is a hydrophobic compound soluble in organic solvents, but since it has a carboxyl group in the molecule, , An amphipathic compound that is water-soluble or water-dispersible depending on 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 oligoisobutenyl succinic acid half ester compound and its copolymer of the present invention include plasticizers, heat resistant resins, lubricants, antistatic agents, paints, adhesives, dispersants, Examples thereof include use as a polymerizable surfactant and an admixture for cement. Among them, the copolymer of the oligoisobutenyl succinic acid half ester compound of the present invention and (meth) acrylamide is soluble or dispersible in water, and has a novel size capable of significantly improving paper strength performance. It has been found that it has high utility value as an agent.

BSA-AL or BSA-M of the present invention
L is oligoisobutenyl succinic anhydride (hereinafter BSA
Is abbreviated) as a raw material and is reacted with allyl alcohol or methallyl alcohol 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. The oligomer of isobutene is 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. It is one obtained by fractional distillation by pressure distillation or reduced pressure distillation, and it is preferable that the number of carbon atoms is 8 or more and 60 or less, but it may be a mixture of those having different carbon numbers, and those having different double bond positions of internal olefins. It may be a mixture. 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. If the isobutene oligomer has less than 8 carbon atoms and more than 60 carbon atoms, BS
Since the amphipathic properties of A-AL and BSA-ML are not remarkable, they are not suitable for the purpose of the present invention and are not so preferable.

The reaction between BSA and allyl alcohol or methallyl alcohol is usually carried out by dropwise addition of allyl alcohol or methallyl alcohol while stirring the organic solvent solution of BSA. As an example of the organic solvent which can be used as the reaction solvent, any solvent capable of dissolving both BSA and allyl alcohol may be used, and acetone, 2-butanone, benzene, toluene, xylene, pentane, hexane, cyclohexane, DMF, DMSO, THF. , Diethyl ether, dioxane, dichloromethane, dichloroethane, chloroform and the like. Alcohol solvents such as methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve, 2-ethylhexanol, and cyclohexanol are not preferable because they cause an esterification reaction with succinic anhydride.

BSA which is liquid at room temperature, such as BSA having a short carbon number, such as isobutene trimer and tetramer.
With respect to, it is also possible to react in a solventless system. BSA
When it is necessary to remove the reaction solvent, such as when using -AL or BSA-ML in an aqueous system, it is preferable to carry out the reaction in a solventless system.

Although the reaction proceeds without a catalyst, it is preferable to use a catalyst in order to accelerate the reaction. The catalyst used in this reaction is not particularly limited, and the catalyst used in this type of reaction can be used. Specifically, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, or those supporting these on an inorganic carrier such as silica, organic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid, acidic ion exchange resins Examples thereof include solid acids such as Zinc, zinc chloride, sodium acetate, pyridine, and the like, and one or more of these can be used. The amount used depends on the catalyst used, so it cannot be specified unconditionally, but it is usually 0.001% by weight to 300% by weight relative to the raw material BSA.
%, Preferably 0.01% to 30% by weight.

The amount of allyl alcohol or methallyl alcohol used is such that an equimolar amount (that is, 1 mol of alcohol per 1 mol of acid anhydride in this case) is reacted with the succinic anhydride group of BSA. If it is less than equimolar, unreacted BSA remains. If the amount exceeds the equimolar amount, allyl alcohol remains, and further, in the presence of a catalyst, allyl alcohol may react with the carboxyl group of BSA-AL or BSA-ML to form a diester compound, which is not preferable.

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-AL or BSA-ML can be obtained in high yield by reacting for 30 minutes to 20 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 oligoisobutenyl succinic acid half ester compound of the present invention can also be produced by an esterification reaction of oligoisobutenyl succinic acid which is a hydrolyzate of BSA with allyl alcohol or methallyl alcohol. It is more preferable to use BSA as a raw material from the viewpoint of reactivity.

BSA synthesized from an oligomer of isobutene and maleic anhydride has two structural isomers having different double bond positions depending on the reaction conditions. Also, BS
Since A is an asymmetric compound, in the reaction product with allyl alcohol and methallyl alcohol, an ester is bonded to the carbon side to which the oligoisobutenyl group is bonded (1),
(3) and an ester bonded to the opposite side (2),
(4) exists and becomes a mixture thereof under normal reaction conditions. That is, a mixture of up to 4 kinds can be obtained under normal reaction conditions. Presence of positional isomer of ester is ¹ H-NM
This can be proved by the detection of two corresponding carboxylic acid ester groups using R and ¹³ C-NMR analysis methods. Allyl alcohol and methallyl alcohol have a high rate of forming an ester bond on a carbon to which an oligoisobutenyl group is not bonded, and this tendency is remarkably recognized in the oligoisobutenyl group having a large number of carbon atoms. The abundance ratio of these is considered to be determined by the reaction conditions such as the chain length of the oligoisobutenyl group of BSA, the reaction solvent, the reaction temperature, and the reaction concentration, but for normal use, the two are used without separation. But there is no problem.

Examples of vinyl compounds copolymerizable with the above BSA-AL and BSA-ML include aromatic vinyl compounds, vinyl cyanide compounds, diene compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid compounds, It is one or more compounds selected from the group consisting of 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.

The vinyl cyanide compound may, for example, be acrylonitrile or 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 and methallylsulfonic acid allyl. It is also possible to copolymerize sulfonic acids and their salts, allyl compounds such as allyl alcohol, methallyl alcohol, diallyl isophthalate, diallyl terephthalate, diethylene glycol diallyl carbonate and triallyl cyanurate.

BSA-AL or BSA-ML of the present invention
The copolymerization ratio of the above-mentioned copolymerizable vinyl compound is generally in the range of 0.1 to 90.0% by weight of BSA-AL or BSA-ML and 10.0 to 99.9% by weight of the copolymerizable vinyl compound. The copolymerization ratio with the copolymerizable allyl compound is similar to that of the vinyl compound, and the vinyl compound and the allyl compound may be used in combination.

BSA-AL or BSA-ML 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. 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 40 hours.

The above-mentioned vinyl compound and B are used as the polymerization solvent.
Any solvent capable of uniformly dissolving SA-AL or BSA-ML 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 compatible with BSA-AL or BSA-ML and requiring desolvation, solvent-free copolymerization may be preferable for the purpose of simplifying the process. BSA-AL or BSA
-ML 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) can be used. Furthermore, the above-mentioned polymerization initiator 2
More than one species can be used in combination.

The polymerization initiator in the case of using water 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 polymerization initiator in combination with a reducing agent. Examples of the reducing agent include sulfite, bisulfite,
Iron, copper, cobalt, etc., low ionic salts, hypophosphorous acid,
Examples thereof include organic amines such as hypophosphite and N, N, N ′, N′-tetramethylethylenediamine, and reducing sugars such as aldose and ketose. Further, as the azo compound, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2-amidinopropane hydrochloride,
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 addition amount of the polymerization initiator is 0.00 with respect to the monomer.
The range is 01 to 10% by weight, preferably 0.01 to 8% by weight
It is. In the case of a redox system, 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 used as appropriate. 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 (polymer compound having oligoisobutenyl succinic acid half ester structure in the side chain) is a plasticizer, heat resistant resin, antistatic agent, lubricant, paint, adhesive. Used as agents, dispersants, surfactants, cement admixtures, etc. Among them, the novel PAM that can dissolve or disperse in water the copolymer of the oligoisobutenyl succinic acid half ester compound of the present invention and (meth) acrylamide and can significantly improve the paper strength performance. Highly useful as a system sizing agent.
Although its action is not always clear,
In the drying process after coating, the amide group of the copolymer forms a hydrogen bond with the cellulose fiber, which significantly improves the strength of the paper, and at the same time, the oligoisobutenyl group aggregates to the surface side of the paper. It is considered that the size performance is exhibited by the orientation.

Specifically, BSA-AL and BSA-
The copolymer of ML and (meth) acrylamide is 5 to 30.
The viscosity at 25 [deg.] C. in the concentration by weight is 0.01 to 50.
It is in the range of 0 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-AL or BSA-ML
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.

[0041]

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, the column was ShodexOH-pak SB-80M + SB-804 (Showa Denko KK), and the eluent was Na ₂ HPO ₄ -KH ₂ PO ₄ (50 mM) -NaNO.
_The measurements were performed using ₃ (0.1M) (pH 6.5). For NMR analysis, a sample is uniformly dissolved in deuterated chloroform to a concentration of about 20% w / v, put into a sample tube for measuring an NMR spectrum having an outer diameter of 5 mmφ, and a 500 MHz NMR spectrum measuring apparatus A500 (JEOL Ltd.) is used. Ltd.) using ¹ H
-And ¹³ C-NMR spectra were measured. For IR analysis, a KRS-5 window plate or KBr tablet method was used, and for an infrared analyzer, FT / IR-300 (manufactured by JASCO Corporation) was used. CHN analyzer Model 2400 (Perkin
-Elmer) was used.

Example 1 BSA (manufactured by Nippon Petrochemical Co., C ₂₄ type, LV-7M) was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel.
After adding 100.0 g, a mixed solution of 12.9 g of allyl alcohol and 0.22 g of sulfuric acid was added dropwise from a dropping funnel over 30 minutes while stirring.
During the dropping, the reaction temperature was adjusted to 40 ° C. with a water bath, and after the dropping was completed, stirring was continued at 40 ° C. for another 4 hours to obtain 113.1 g of an amber highly viscous liquid. The viscosity of BSA before the reaction was 4020 cp, but the viscosity of the reaction product (BSA-AL) was 3070 cp. Elemental analysis value; C: 75.56%, H: 11.45% (calculated value: C ₃₁ H ₅₆ O ₄ ) C: 75.47%, H: 12.12% (actual value) When IR analysis (Fig. 1) was performed, the raw material BSA was obtained. 1780 cm
^-1 and 1860cm characteristic absorption band anhydride groups found in ^-1 (C = O stretch) disappears, behalf and carboxylic acid 1700 cm ^-1 (C = O stretching), ester 1740 cm ^-1 (C = An absorption band due to O stretching was observed.

2 and 3 show the ¹ H-N of BSA-AL.
The MR spectrum and ¹³ C-NMR spectrum are shown. The magnetic field strength on the horizontal axis is based on tetramethylsilane (0
ppm). In the following examples, a yellow cloudy aqueous solution (pH 8.73) was used in which 40.0 g of BSA-AL obtained above, 7.9 g of a 40% aqueous solution of caustic soda, and 352.1 g of distilled water were mixed by stirring.

[Example 2] A 10% aqueous solution of BSA-AL 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.
0.09 g, distilled water 29.9 g and sodium hypophosphite 0.15 g
Was added and heated to 80 ° C. with stirring under a nitrogen stream. Using a microtube pump, a mixture of 54.0 g of 50% acrylamide aqueous solution, 185.7 g of distilled water, and 0.30 g of ammonium persulfate (APS) (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 slightly turbid aqueous solution which was colored pale yellow. The resulting aqueous solution has a non-volatile content of 10.7%, a pH of 6.90, and a viscosity of 17.3 cp.
And the weight average molecular weight was 152,700.

[Example 3] A 10% aqueous solution of BSA-AL 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 (0.30 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 was added to this solution using a microtube pump.
A mixed solution of 8.0 g, distilled water 191.4 g and APS 0.30 g (cooled on an ice bath) was added dropwise in 120 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a slightly turbid aqueous solution which was colored pale yellow. The nonvolatile content of the obtained aqueous solution is 10.7%, the pH is 7.32,
The viscosity was 7.7 cp and the weight average molecular weight was 163,500.

Example 4 A 10% aqueous solution of BSA-AL 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 (0.38 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 was added to this solution using a microtube pump.
A mixed solution of 2.0 g, distilled water 167.3 g and APS 0.30 g (cooled on an ice bath) was added dropwise in 120 minutes. Further, stirring was continued at 80 ° C. for 180 minutes to obtain a slightly turbid aqueous solution which was colored pale yellow. The nonvolatile content of the obtained aqueous solution is 10.8%, the pH is 7.58,
The viscosity was 7.1 cp and the weight average molecular weight was 34,900.

The following coating examples were all carried out using newspaper base paper (basis weight 50 g / m ² ). Size degree is JIS P8122
The surface strength was measured by using the RI-3 type (manufactured by Akira Seisakusho Co., Ltd.) according to the Steckigt size test method of (1).
The higher the score in the 0-point method relative evaluation, the higher the surface strength),
The Z-axis strength was measured using an internal bond tester (Kumagaya Riki Kogyo Co., Ltd.).

[Coating Examples 1 to 3] The base paper to be coated was dipped in the polymer solutions obtained in Examples 2 to 4 for 1 second, squeezed by two rolls, and the amount of the absorbed liquid was measured. Then, the coating amount was obtained. The concentration of the coating solution was adjusted in advance so that the coating amount was 1.0 g / m ^{2 as} the nonvolatile content of the polymer (polymer concentration: 2.5 wt
%). The pH of the coating solution was adjusted to 4.5 to 5.0. Immediately after coating, dry for 50 seconds with a drum dryer whose surface temperature is set to 120 ° C, and store in a constant temperature and constant humidity chamber (20 ° C, humidity 65 ° C).
%), The sizing degree and the paper strength were measured after conditioning for 24 hours. The results are shown in Table 1.

[0049]

[Table 1]

[0050]

INDUSTRIAL APPLICABILITY The oligoisobutenyl succinic acid half ester compound of the present invention is an amphipathic compound which is soluble in an organic solvent but is also highly soluble in water depending on pH and temperature conditions. Since this compound has a polymerizable double bond in the molecule, it can be used for various purposes as a polymerizable surfactant. 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

Front page continued (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, Osaka

Claims (5)

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