FI58930B - FOERFARANDE FOER FRAMSTAELLNING AV HARTS AV EN DIELS-ALDER-ADDITIONSPRODUKT OCH ETT BENSENDERIVAT - Google Patents

Description

R3F ^ 1 [B] ^ «CULULATION PUBLICATION.SU 5393 ()

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Patent- och ragirterstyralMn '' Amekm uthgd och uti. »Krift * n pobimrad 30.01.81 (32) (33) (31) ^« ty «Tuoik ·» »* —prloritet 28.02.73 OI.O3.73, 12. II.73 Japan-Japan (JP) 2¾5¾9, 25 ^, 12758¾ (71) Aräkava Rinsan Kagaku Kogyo Kabushiki Kaisha, 21, 1-chome, Hirano-machi, Higashi-ku, Osaka-shi, Japan-Japan (JP) ( (72) Shuhei Ishibe, Nara-ken, Toshiharu Okumichi, Hoyogo-ken, Keizo Matsumoto, Osaka-shi, Katsuhisa Shimizu, Kyoto-fu, Masani Ori,

Osaka-shi, Osamu Oseto, Osaka-fu, Japan-Japan (JP) (7¾) Berggren Oy Ab (5¾) Method for preparing a resin from a Diels-Alder adduct and a benzene derivative - Preparation of a resin from the Diels-Alder addition product This invention relates to a process for preparing novel resins from a Diels-Alder adduct and a benzene derivative. More particularly, the invention relates to a process for preparing resins useful as adhesives and emulsifiers for emulsion polymerization of synthetic rubbers.

Rosin and its derivatives have been known to be used not only in the manufacture of synthetic rubbers as emulsifiers and adhesives in papermaking, but also in versatile use as binders in pressure sensitive adhesives, hot melt adhesives and various rubbers and as resins for coatings and printing inks.

For example, alkali salts of a rosin derivative obtained by disproportionating or hydrogenating rosin to inactivate a conjugated double bond are widely used as emulsifiers in emulsion polymerization in the preparation of styrene-butadiene rubber, acrylonitrile-butadiene-styrene rubber. polymerization and improve the adaptability and adhesion of the resulting synthetic rubbers.

2,58930

In addition, when a small amount of an alkali salt of rosin or a rosin derivative such as fortified rosin is added to a cellulose suspension in a papermaking process, such a compound imparts writability properties and a slip effect to the resulting paper. Thus, colphonium and its derivatives are widely used as main additives in the papermaking industry.

Rosin is further characterized by solubility in a wide variety of solvents and miscibility in many different high polymers. The softening point can be varied as desired and its miscibility with various substances can be improved by modifying it with metal compounds, alcohols, polybasic acids, phenolic resins, etc.

Besides, when rosin is mixed with other substances, it gives these sticky properties. Thus, rosin or its derivatives are widely used as a tackifier for pressure sensitive adhesives, hot melt adhesive preparations and various rubbers and also as a resin for coating compositions, printing inks and floor tiles.

Due to these excellent properties of rosin for many different uses, it is very useful as an industrial material. However, because it is a naturally occurring material, its availability is not stable and there is no scope to increase production. As a result, the synthesis of resins having similar properties to rosin and its derivatives has become an important problem.

The main object of the present invention is to provide a novel rosin-like resin having the same properties and characteristics as rosin and useful as a substitute for rosin and its derivatives.

Another object of the present invention is to provide a process for preparing a rosin-like resin having the above properties and characteristics from materials readily available on a commercial scale.

It is a further object of the invention to provide a preparation containing novel rosin-like resins which can be used for various purposes as substitutes for preparations containing rosin or its derivatives, such as emulsifiers in the manufacture of synthetic rubber by emulsion polymerization, gluing preparations in paper, pressure sensitive adhesives, hot melt adhesives, hot melt adhesives , printing inks, etc.

It is a further object of the invention to provide a paper glue which shows a better gluing effect compared to 3,58930 not only with conventional rosin adhesives but also with reinforced rosin adhesives.

It is a further object of the present invention to provide an emulsifying preparation for producing a synthetic rubber by emulsion polymerization, which preparation is similar to or better than conventional emulsifiers containing disproportionated rosin.

These and other advantages and objects of the present invention will become apparent from the following description.

According to the present invention, the subject resin is prepared by reacting a Diels-Alder adduct in the presence of a Priedel-Crafts catalyst with a benzene derivative of the formula - (R 1) n (I) wherein R 1 is an alkyl group having 1 to 12 carbon atoms and n is an integer 1 or 2, and the invention is characterized in that said addition product is at least one of the compounds a) of formula r6 ϋ R2 (1I) CH. {11) R9 m 2 3 2 | . Wherein each of R, R, R and R is a hydrogen atom or a methyl group, each of R 1, R 2, R and R 9 is a hydrogen atom or a methyl group, each of X and Y is -C00H or -COOR a or X and Y represent an acid anhydride ring, formed by bonding to each other, wherein Ra is an alkyl group having 1 to 4 carbon atoms and m is zero or an integer of 1 or 2, or (b) of formula 4 4 RR R2 ktvVwL, (I CHp CH2 (III), · ς R3 RJ R5 __ _J m 2 3 4 5 wherein R, R, R, R, X, Y and m have the same meaning as above, and “58930 if desired 1) when at least one of X and Y is -C00Ra or X and Y form an anhydride ring wherein Ra is as defined above, hydrolyzing the resulting resin to give rosin acid, 2) when at least one of X and Y is -COOH, neutralizing the resulting resin with an alkali to give a rosin acid salt, or 3) when one of X and Y is -C00R and the other is - COOH or X and Y form an anhydride ring, where R is as defined above, the resulting resin neu is treated with ammonia, a primary amine or a secondary amine to give a rosin acid salt having an acid amide group.

The benzene derivatives used in the invention are those of the above formula (I). Examples are benzene, toluene, xylene, ethylbenzene, methylethylbenzene, cumene, cymene, trimethylbenzene, tetramethylbenzene, butylbenzene, hexylbenzene, octylbenzene, dodecylbenzene, etc. Of these, those of formula (I) wherein n or 1 or 2.

Diels-Alder adducts of formulas (II) and (III) above are known compounds and can be easily prepared. Recommended methods for the preparation of addition products (II) and (III) are as follows: (1) Products of formulas (II) and (III) in which m is zero can be prepared by equimolar Diels-Alder of α, 3 ′ ′ unsaturated dibasic acid derivatives. -addition reactions with conjugated dienes represented by the following equations: R6 6 <j 7 1 yi> ♦ T _> y Yx

r2 / Xr3 rO r8'T ^ S

R9 r9 R

(IV) (V) (II-a) \ / Y rwr5 νγ-χ \ _ /. PCH? 11 / c ~ c \ * V n ^ γΥγ

R2 R3 K5 R

(IV) (VI) (III-a) 5 58930 wherein R 2 -R 1, X and Y are as defined above.

The Diels-Alder reaction of (α) -unsaturated dibasic acid derivatives (IV) with (i) or (ii) conjugated acyclic dienes (V) or conjugated cyclic dienes (VI) is usually carried out in an open or closed reactor at a temperature between 10 and 250 ° C and preferably between 10-200 ° C. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen gas and normal, autogenous or elevated pressure may be used for the reaction. It is recommended to use 0.5 to 2.0 moles per mole of conjugated diene (V) or (VI) of the α, β-unsaturated dibasic acid derivative (IV). If necessary, organic solvents such as benzene, toluene, xylene, n-hexane, cyclohexane, etc. can be used. The reaction is usually completed in 5 minutes to 20 hours according to the reaction conditions used. The resulting 1: 1 molar adduct (II-a) or (III-a) can be separated from the reaction product by distilling off unreacted reagents and solvents, if any. Furthermore, the product (II-a) or (III-a) itself can be isolated by distillation under reduced pressure.

(2) Products of formula (II) in which m is 1 can be prepared by equimolar Diels-Alder addition reaction of the products (III-a) obtained by the above method (1) with conjugated acyclic dienes represented by the following equation: ho R , 6 r6 R4 R2 '7 7 R4 R2, CF0 + * CH9 R5 R3 9 R® R5 \ 3 (III-a) (V) (II-b)

2 Q

wherein R -R, X and Y are as defined above.

The above-mentioned Diels-Alder reaction between the adduct (III-a) and the conjugated acyclic diene (V) is usually carried out in a closed reactor at a temperature between 100 and 300 ° C and preferably between 150 and 250 ° C. An inert gas atmosphere is recommended and auto-genetic or elevated pressure may be used. The conjugated acyclic diene (V) is used in an amount of 0.5 to 2.0 moles per mole of adduct (III-a). If necessary, organic solvents can be used. The reaction is usually completed in 0.5 to 10 hours depending on the reaction conditions used. The resulting Diels-Alder adduct (II-b) can be separated from the reaction mixture by distilling off unreacted 6,58930 reagents and solvents, if any.

(3) Products of formula (III) in which m is 1 can be prepared by a 1: 2 molar Diels-Alder addition reaction between α, β-unsaturated dibasic acid derivatives and conjugated cyclic dienes represented by the following equations: 4 R2 \ / c = \ * r H2 R3 r5 ^ r5 ^ r3 (IV) (VI) (III-b) 2 ς wherein R -R, X and Y are the same as defined above.

In this reaction, a conjugated cyclic diene (VI) is used in an amount of 1> 5-2.5 moles per mole of the α, β-unsaturated dibasic acid derivative (IV). The reaction conditions are the same as described in the above method (2). The obtained adduct (III-b) can be separated from the reaction mixture by distilling off unreacted reagents and solvents, if any.

(4) Products of formula (II) in which m is 2 can be prepared by equimolar Diels-Alder addition reaction of the addition products (III-b) obtained by method (3) with conjugated acyclic dienes represented by the following equation.

NEW, »O .vXSo-rV'- Λ \ \ '' f λ _V CHp CHp 'Λ Awv r5 rd r ^ 9

o R

Ry (Ill-b) (V) (II-c)

2 Q

wherein R -R, X and Y are as defined above.

In this reaction, the conjugated acyclic diene (V) is used in an amount of 0.5 to 1.5 moles per mole of the adduct (III-b). The reaction conditions are the same as described in Method (2) above. The obtained reaction product (II-c) can be separated from the reaction mixture by distilling off unreacted reagents and solvents, if any.

7 58930 (5) Products of formula (III) in which m is 2 can be prepared by a 1: 3 molar Diels-Alder reaction between α, β-unsaturated dibasic acid derivatives (IV) and conjugated cyclic dienes (VI). by an addition reaction described by the following equation: R 4 R 4 R 4 R 2 / -W * R 2 R 3 R 5 R 5 R 5 R 3 (IV) (VI) (III-c) 2 S. .

wherein R -R, X and Y are as defined above.

In this reaction, the conjugated cyclic diene (VI) is usually used in an amount of 2.5 to 3.5 moles per mole of the α, β-unsaturated dibasic acid derivative (IV). The reaction conditions are the same as described in the above method (2). The product (III-c) obtained can be separated from the reaction mixture by distilling off unreacted reagents and solvents, if any.

A mixture containing any of the addition products (II-b), (II-c), (III-b) and (III-c) can be prepared from the Diels-Alder of products (III-a) and / or (III-b). by reaction with the sequence of acyclic dienes (V) and cyclic dienes (III).

Examples of α, β-unsaturated dibasic acid derivatives (IV) for use in the above methods (1) to (5) include, for example, maleic acid, fumaric acid, citraconic acid, and other similar α, β-unsaturated dibasic acids and their mono- or dialkyl esters, and acid anhydrides. Maleic anhydride, dimethyl maleate and dimethyl fumarate are preferred.

Conjugated dienes for use include conjugated acyclic dienes (V) and conjugated cyclic dienes (VI). Examples of the former are butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene (piperylene), 2-methyl-1,3-pentadiene, 1,3-hexadiene, 2, ij-hexadiene and 2, 4-heptadiene. Examples of the latter are cyclopentadiene, methylcyclopentadiene and 1,3-cyclohexadiene. Dimers or codimers of these dienes that produce the corresponding monodienes under the reaction conditions can also be used. Of these, butadiene, isoprene, e 58930 piperylene, cyclopentadiene, methylcyclopentadiene and dicyclopentadiene are preferred. Of these, conjugated dienes can be used alone or in admixture with each other. For example, petroleum fractions obtained by cracking fuel oil and containing these dienes in a mixture can be used for this purpose.

In the Friedel-Crafts reaction, for the preparation of the resin in question, the starting products (II) and (III) can be used in purified form or in impure form obtained simply by removing any unreacted reagents and solvents from the reaction mixture. Preferred addition products are those of the formulas ROtvyZ_R2c ^ ° _ and r4 n1 * / R2 λ !! WCV / - e <_m 2 0.

wherein R -R and m are the same as defined above. The most recommended are those with formulas

O

R9 _ Jm and 9 58930 f ^ _ / ° - Jm ’6 Q ....

wherein R -RJ are the same as defined above and m 'is 0 or 1.

Another starting material, i.e. the benzene derivative (I) is used alone or in a mixture in an amount of at least 0.5 moles per mole of the adduct (II) or (III) to be used. Since the benzene derivative (I) acts as a solvent in the reaction, it can be used in large excesses, e.g., 20 moles per one mole of the adduct (II) or (III). The amount of the benzene derivative (I) is preferably between 3 and 10 moles per one mole of the addition compound.

The reaction between the benzene compound (I) and the addition compound (II) or (III) to prepare the resin of the present invention is carried out in the presence of a Friedel-Crafts catalyst. The Friedel-Crafts catalysts used are those commonly used in the art and include, for example, hydrogen fluoride, phosphoric acid, sulfuric acid, boron trifluoride, boron trifluoride etherate, boron trifluoride diphenolate, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, zinc cyclo are sulfuric acid, boron trifluoride, boron trifluoride etherate, boron trifluoride diphenolate and aluminum trichloride. The amount of the catalyst to be used may vary within wide limits depending on the catalyst, starting materials, reaction conditions and the like, but is usually in the range of 0.5 to 100% by weight based on the weight of the starting adduct (II) or (III).

The Friedel-Crafts reaction used to prepare the resin in question is carried out in an open or closed reactor at a temperature of 0-300 ° C and preferably between 20-200 ° C. If necessary, the reaction can be carried out in an inert gas atmosphere such as nitrogen. Although elevated pressure may be used, the reaction is usually carried out at normal or autogenous pressure. The reaction is usually completed in 1 to 10 hours.

At the end of the reaction, the spent catalyst is inactivated with water, acid or alkali and removed by filtration and / or washing with water. The reaction mixture is then distilled to remove any unreacted substances and solvents to give the resin in question as a residue.

The resin thus obtained is a Friedel-Crafts reaction product of the benzene derivative (I) and the adduct (II) or (III) used as starting materials and has the groups represented by the letters X and Y contained in the latter starting materials, but its exact structure has not yet been determined, for several different reactions take place depending on the starting materials, catalysts, etc. Usually, the alkylation reaction proceeds selectively, but the acylation reaction also takes place under certain conditions. For example, when the addition product (II-a) or (III-a) having an acid anhydride ring formed by X and Y is reacted with the benzene derivative (I) in the presence of an aluminum trihalide, alkylation and / or acylation reactions take place. In fact, it has been found that the resin contains not only a 1: 1 molar reaction product of the benzene derivative (I) and the Diels-Alder adduct (II) or (III), but also a 2: 1 molar reaction product depending on the reaction conditions used. . Further, the resin may contain a small amount of a 1: 2 molar reaction product of the benzene derivative (I) and the adduct (II) or (III), depending on the conditions.

The resin of the invention may be a mixture of the above products, but whether or not the resin obtained by the present invention has such a mixture, it has useful properties similar to rosin and its derivatives, and can be used as a substitute for rosin and its derivatives. It is therefore not necessary to distinguish between these products.

The resin thus obtained is subjected, if necessary, to hydrolysis to form rosin acid or a salt thereof having one or two carboxyl groups neutralized with alkali or unneutralized. The hydrolysis can be carried out in a conventional manner. When a resin derived from an adduct of formula (II) or (III) in which at least one of X and Y is -CN or -COORa (Ra is the same as defined above) or X and Y represents an acid anhydride ring formed when combined, hydrolyzed in the presence or absence of an acid, a rosin acid having one or two carboxyl groups in the molecule can be obtained. The resin acid salt can be obtained by alkali neutralizing the resin acid thus obtained having one or two carboxyl groups in the molecule. In addition, when the hydrolysis is carried out in the presence of an alkali, a resin acid salt can be obtained, one or two of which has one or two carboxyl groups neutralized with alkali. Alkalis used for neutralization include, for example, sodium hydroxide, potassium hydroxide and the like alkali metal hydroxides; ammonia; methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, aniline and other primary amines, dimethylamine, diethylamine, dipropylamine, morpholine, piperidine and other secondary amines; and trimethylamine, triethylamine, pyridine and the like tertiary amines. These alkalis can be used alone or mixed with each other.

In particular, when a resin in which one of X and Y is an ester group and the other is a carboxyl group or has an acid anhydride ring formed by X and Y is treated with ammonia or a primary or secondary amine, neutralization and aminolysis reactions take place simultaneously to form a resin acid salt, having one alkali-neutralized carboxyl group and one acid amide group. The obtained rosin acid salt containing an acid anhydride group has a stronger slipping effect than the rosin acid salt which does not contain an acid amide group when used for hardening in hard water.

The resin in question, which contains one or two carboxyl groups neutralized with alkali or is not neutralized, has similar properties to rosin or its derivatives.

(1) The resin in question having one or two carboxyl groups is easily dispersible in an aqueous alkaline solution to form an alkaline aqueous dispersion which is stable and has both hydrophilic and hydrophobic properties. Therefore, the dispersion has an excellent gluing effect on the paper as well as an emulsifying effect. These properties can be obtained by reacting the adduct (II) or (III) with the benzene derivative (I) in the presence of Friedel-Crafts catalysts. The adduct (II) or (III) itself is poor or insufficient in these properties.

(2) The resin is highly resistant to light and heat because it has essentially no reactive carbon-carbon double bond in the alicyclic ring due to the addition of a benzene derivative. Furthermore, the resin can be easily modified to the desired form by utilizing the reactive groups represented by the letters X and Y contained therein.

i 2 589 30 (3) The resin has the special property of being able to impart tack to various materials and can also be easily modified with alcohols, metal compounds, epoxy compounds or phenyl resins, utilizing the reactive carboxyl groups contained therein according to the desired uses. Therefore, it can be used for various purposes as well as rosin or its derivatives, for example as tackifiers for natural and synthetic rubbers, hot melt adhesive mixtures, etc., and as resins for paints, printing inks, floor tiles, road marking mixtures, etc.

For a better understanding of the invention, examples are given below. Example 1,588 g of maleic anhydride and 990 g of benzene were placed in a three-liter four-necked flask equipped with a reflux condenser, dropping funnel and thermometer. While maintaining the mixture at 30-40 ° C and stirring, 396 g of cyclopentadiene was added dropwise to the mixture over 2 hours. The resulting mixture was then heated to 80 ° C, held at that temperature for 30 minutes, after which it was cooled. Removal of the unreacted substances gave 868 g of a 1: 1 molar adduct of cyclopentadiene and maleic anhydride with an acid number of 668 (theoretical value 684).

280 g of xylene and 56.7 g of anhydrous aluminum chloride were placed in a one-liter four-necked flask equipped with a stirrer and a thermometer. While maintaining the mixture at 50 ° C and stirring, 70 g of adduct was slowly added to maintain a further reaction at 80 ° C for three hours.

The reaction mixture was then cooled, after which dilute hydrochloric acid was added to inactivate the catalyst, which was then removed by filtration and washed with water. The unreacted substances and the solvent were distilled off from the xylene layer under reduced pressure to give 122.7 g of a pasty resin having an acid number of 187.1.

Example 2 100 g of dicyclopentadiene and 246 g of the adduct obtained in Example 1 were placed in a one liter autoclave and the air inside was replaced with nitrogen gas. The reaction system was then allowed to react at 190-200 ° C for 3 hours, after which it was cooled. The distillate was removed under reduced pressure at 154 ° C and 2 mm Hg or less to give 289 g of a 2: 1 molar adduct of cyclopentadiene and maleic anhydride (0Φ - -CO -) f with an acid number of 470 (theoretical value 488 ).

i3 58930 200 g of cumene and 50 g of the above adduct were placed in a one liter four-necked flask. 14.6 g of 97% sulfuric acid was added dropwise to the mixture with stirring while maintaining the mixture at 50 ° C, after which it was heated to 110 ° C to maintain the reaction at this temperature for 3 hours. After completion of the reaction, the reaction mixture was cooled and washed with water to remove the catalyst. The unreacted substances were distilled off under reduced pressure to give 55.6 g of a resin having a softening point of 80 ° C and a saponification number of 286.5.

Example 3 225 g of dicyclopentadiene (3 * 4 mol of cyclopentadiene), 167 g (1.7 mol) of maleic anhydride and 392 g of xylene were placed in a one liter stainless steel autoclave equipped with an electromagnetic stirrer and the air inside was replaced with nitrogen gas. The mixture was then heated to 220 ° C and allowed to react with stirring for 3 hours. After cooling, the xylene was removed by distillation, followed by further distillation under 2 mm Hg until the bottom temperature reached 200 ° C of a 1: 1 molar adduct of unreacted dicyclopentadiene and cyclopentadiene and maleic anhydride / ** 0.

to distill off to give 254 g of distillate at 190-220 ° C and 2 mm Hg, which was found to be a 2: 1 molar adduct of cyclopentadiene and maleic anhydride f ^ ^ \ f || PJ "Vj '^ q \ with an acid number of 470 (theoretical 0 acid number 488).

230 g of the above adduct and 460 g of xylene were placed in a one liter four-necked flask equipped with a stirrer and a thermometer. When the mixture was completely dissolved, 4.6 g of boron trifluoride phenolate was slowly added to the solution, and the resulting mixture was allowed to react at 80 ° C for 3 hours. After the reaction mixture was cooled, 13.8 g of a mixture of water and calcium hydroxide (1: 3 by weight) was added to inactivate the catalyst. The inactivated catalyst was then removed by filtration. The unreacted substances and xylene were distilled off from the filtrate to give 277 g of a resin having a softening point of 38 ° C and an acid number of 327 (theoretical value 334).

14 _ Λ Λ „5 8 9 3 0

Example 4

A one liter autoclave was charged with 280 g of a thermally cracked fuel oil in the range of 20-38 ° C with a distillate fraction having the following composition, and 250 mg of the adduct obtained in Example 1 and the air inside was replaced with nitrogen gas. The mixture was then allowed to react at 250 ° C for 5 hours. After completion of the reaction, the mixture was cooled and distilled under reduced pressure to remove unreacted fraction and the fraction distilling at 150 ° C and 1-2 mm Hg or less to give 301 g of the cyclopentadiene and maleic anhydride adduct 1 obtained in Example 1. : 1 molar adduct. The acid number of the resin thus obtained was 3 ^ 2. Composition of fuel oil used: cyclopentadiene and cis-1,3-pentadiene 15.7% w / w isoprene 14.1% by weight trans-1,3-pentadiene 8.4% by weight others (without conjugated dienes) 6.1.8% by weight 200 g of ethylbenzene and 7.3 g of anhydrous aluminum chloride were placed in a one liter four-necked flask. While the mixture was heated at 50 ° C with stirring, 50 g of the above adduct in the molten state was slowly added to the mixture. After the addition was complete, the resulting mixture was stirred at 80 ° C for three hours. Dilute hydrochloric acid was added to the resulting reaction mixture to decompose the catalyst, followed by filtration and washing with water. The unreacted materials were then distilled off from the ethylbenzene layer to give 53.0 g of a resin having a softening point of 74.5 ° C and an acid number of 272.

Example 5

50 g of conjugated dienes and the adduct of cyclopentadiene and maleic anhydride obtained in Example 4, 200 g of xylene and 1.9 g of boron trifluoride etherate were placed in a one liter autoclave and the air inside was replaced with nitrogen gas. The mixture was stirred at 200 ° C for 3 hours.

After the resulting reaction mixture was cooled, water was added thereto to decompose the catalyst, and the resulting precipitate was filtered off. The filtrate was then washed with water. The xylene layer was distilled off under reduced pressure to remove unreacted substances to give 56.6 g of a resin having a softening point of 77 ° C and an acid number of 271.

Example 6 50 g of an adduct of isoprene and maleic anhydride obtained in the same manner as in Example 1 except that 40 g of isoprene was used instead of cyclopentadiene were slowly placed in a 15,58930 one-liter flask maintained at 50 ° C and containing 200 g of p- cymene and 39.9 g of anhydrous aluminum chloride. The mixture was stirred at 80 ° C for 3 hours.

The same procedure as in Example 1 was then followed to remove the catalyst and unreacted substances to give 58.1 g of a pasty resin having an acid number of 200.

Example 7 55.4 g of a paste-like resin having an acid number of 218 was obtained in the same manner as in Example 6 except that 408 g of piperylene was used instead of isoprene and that p-cymene was replaced by cumene. Example 8

To a 1 liter flask equipped with a stirrer, thermometer and reflux condenser was charged 50 g of the cq> ° 2: 1: 1 molar adduct of cyclopentadiene and maleic anhydride obtained in Example 2 and 200 g of dodecylbenzene and then 3.6 g of boron triflate were added. The mixture was then maintained at 140 ° C.

The mixture was treated in the same manner as in Example 3 to give 79.2 g of a resin having a softening point of 59.0 ° C and an acid number of 221 (theoretical value 236).

Example 9 52.5 g of a resin having a softening point of 8.0 ° C and an acid number of 303 were obtained in the same manner as in Example 8 except that 50 g of cyclopentadiene and maleic acid adduct prepared by hydrolysis of the cyclopentadiene and maleic anhydride adduct of Example 2 were used. 1.9 g of boron trifluoride ether complex.

Example 10 472 g of a 2: 1 molar adduct of cyclopentadiene and maleic anhydride (VRrTTTrZ) were placed in a 1 liter autoclave and the air inside was replaced with nitrogen gas and then heated to 220 ° C. 140 g of isoprene was then added to the system to maintain the reaction for 3 hours. The resulting reaction mixture was distilled to remove unreacted substances and by-products to give 251 g of a fraction distilling between 250-262 ° C and 5 mm Hg, represented by the formula.

/ H ^ C -C '~ "0 j And having an acid number of 371 \ 7 7 16 58930 (theoretical value 376).

50 g co. the adduct and 200 g of xylene were placed in a one liter four-necked flask and distilled. 1.5 g of boron trifluoride phenolate was slowly added to the solution. The resulting mixture was heated to SO 0 and allowed to react at this temperature for 3 hours. The reaction mixture thus prepared was distilled to remove unreacted substances to give 54.2 g of a resin having an acid number of 269 (theoretical value 278).

Example 11

In a one liter flask were placed 200 g of methanol and 50 g of a 2: 1 molar adduct of cyclopentadiene and maleic anhydride obtained in Prime 3, which were allowed to react at reflux temperature for 2 hours. The resulting reaction mixture was distilled to remove methanol to give 56.5 g of the semi-methyl ester of the above adduct, 50 g of the thus obtained half-ester and 200 g of xylene were placed in a four-necked flask and completely dissolved. 8.5 g of boron trifluoride ether complex was then added slowly. The mixture was then allowed to react at 80 ° C for 3 hours. The resulting reaction mixture was cooled and water was added thereto to decompose the catalyst, followed by filtration to remove the precipitate and washing with water. The unreacted substances were distilled off from the xylene layer under reduced pressure to give 46.6 g of a resin having a softening point of 89 ° C and an acid number of 142 (theoretical value 152).

Example 12 In a 100 ml four-necked flask equipped with a stirrer and ammonia gas feed tubes were placed 10 g of the resin obtained in Example 3 and 50 g of benzene, which were dissolved. Feeding ammonia gas at 20-25 ° C immediately produced a white precipitate. After the ammonia was fed for 30 minutes, the reaction mixture was filtered and dried at room temperature under reduced pressure to give 11.0 g of a white powder. The infrared absorption spectrum of the powder showed absorption at 805 and 1600 cm due to the presence of an aromatic ring, at 1400 and 1540 cm 1 due to the presence of a -C00NH1 group and at 1650 and 3200 cm due to the presence of a -CON1 group.

Example 13 In a 100 ml four-necked flask equipped with a stirrer and a dropping funnel were placed 10 g of the resin obtained in Example 3 and 17,58930 50 g of ethyl acetate, which were thoroughly dissolved. 4.5 g of diethylamine was then added dropwise to the solution over 15 minutes, and the mixture was allowed to react further for 1 hour with stirring. After completion of the reaction, the unreacted substances and the solvent were distilled off under reduced pressure to give 14.8 g of a resinous product. Infrared absorption spectral analysis showed the presence of a carboxylate and acid amide group.

Example 14 12.9 g of the resinous product were obtained in the same manner as in Example 3 except that 4.5 g of diethylamine was replaced by 3.4 g of n-propylamine. The infrared absorption spectrum revealed the presence of an acid amide and carboxylate group.

Example 15 A 200 ml flask equipped with a stirrer, reflux condenser and thermometer was charged with 20 g of the resin obtained in Example 3 and 80 g of methanol, which were allowed to react at the boiling point of methanol with stirring for 2 hours. After completion of the reaction, methanol was distilled off to give 20.5 g of a reaction product having an acid number of 207 and a saponification number of 410. (The theoretical acid number of the monomethyl ester is 214 and the saponification number is 428). The infrared absorption spectrum showed absorption at 1705 cm -1 due to the presence of the -COOH group and at 1740 cm -1 due to the presence of the -COOCH 4 group.

A 200 ml autoclave was charged with 62.4 g of a methanol solution containing 10 g of the above-mentioned monomethyl ester and 2.4 g of dimethylamine, and the air inside was replaced with nitrogen gas. The solution was then allowed to react at 150 ° C for 8 hours. After completion of the reaction, methanol and unreacted substances were distilled off under reduced pressure to give 11.2 g of a resin. The infrared absorption spectrum did not show absorption due to the presence of the -COOCH 2 group, but showed absorption due to the presence of the -COON (CH 2) 2 group.

The resins obtained in the above examples were tested for their use as glidants and emulsifiers in the emulsion polymerization of synthetic rubbers according to the following methods with the results shown below.

All the resins of Examples 1-5, rosin and fortified rosin were neutralized with potassium hydroxide in an equimolar amount relative to the acid number of the resin to prepare a 25% by weight aqueous solution thereof. In addition, all the half-amide half-salts obtained in Examples 12-15 were dispersed in water to a concentration of 30% by weight, and the pH of the dispersion was adjusted to 10 with a small amount of sodium hydroxide.

18 58930 1. Molding preparation and molding effect

All of the above preparations were used as glidants in papermaking. A defined amount of lubricant was added to a 1 wt% cellulose additive (LBKP) with a degree of grinding of 30 ° SR. An aqueous solution of aluminum sulfate was then added to the slurry and thoroughly dispersed therein in an amount of 2.5% by weight of dry cellulose and calculated as dry matter. Using a TAPPI standard sheet machine, the resulting slurry was made at 20 ° C into a paper weighing 65-1 g / m 2. The paper was dried at 100 ° C for 5 min and conditioned at 20 ° C and 65% relative humidity. The gluing effect on the paper was determined by the Stöckigt method (JIS P 8122).

The same procedure as above was followed except that calcium chloride was added to the cellulose slurry in an amount to give a German hardness of 15 ° to determine the gluing effect obtained on paper made using hard water. The test results are shown in Table 1.

table 1

Slipping effect ... . .

Slip effect (in seconds)

Molding preparation Water: Soft water Hard water XX) No. Resin Amount used 0.3 0.5 0.3 0.5 (w / w !?) * * 1 Example 1 23.8 27.1 21.5 26.0 2 "2 25.7 29.4 3.3 12.5 3 "3 28.3 33.5 5.4 13.5 4” 4 26.0 31.0 2.0 8.5 5 "5 26.6 33.1 7, 3 14.5 6 "12 25.5 31.2 25.1 30.2 7" 13 26.0 31.1 25.0 29.8 8 "14 26.2 31.5 25.7 30.6 9 "15 27.9 31.2 24.7 30.1 10 lx 27.6 33.1 25.9 31.8 11 Rosin 20.5 27.3 20.0 26.7 12 Confirmed rosin 24.3 29, 2 24.1 28.9 X) ·.

Resin No. 10 is a mixture of rosin having a softening point of 76 ° C and an acid number of 172 and the resin of Example 2 in a weight ratio of 8: 2.

XX), · ·

The amount of leaching preparation is the percentage by weight of dry matter of cellulose.

19 58930

Table 1 shows the following: 1) When soft water is used under papermaking conditions, the sizing preparations of the present invention give better results than the rosin sizing preparation and are as good or better than the reinforced rosin sizing preparation. The resin of Example 2 produces a similar effect to rosin modified in maleic anhydride fortified rosin (No. 12).

2) In papermaking conditions using hard water, a sizing preparation containing a half-amide half-salt gives the same sizing effect as when using soft water. Although the stripping preparation of Example 2 has a lesser effect on hard water, it remains equally effective when used in combination with rosin (No. 10).

2. Emulsifying preparations

All aqueous mixtures of the resin obtained in Examples 3, 12 and 13 were used as emulsifiers in emulsion polymerization according to the cold rubber sulfoxylate recipe shown in Table 2 to obtain SBR rubber. Latex conversion and stability are shown in Tables 3 and 4, respectively.

Table 2 Materials used Materials used Quantities by weight Material names M. ("Butadiene 70

Monomeen [styrene 30

Dispersion Medium Ionized Water 200 (degassed) / Resin of Examples

Emulsifier Ues solution (dry matter) H, 0 ® jNaphthalene-formaldehyde (j-ars sodium sulphonate 0.15

Molecular weight tertiary dodecyl adjusting agent mercaptan 0.1

Polymerization imitator - Oxidizing agent p-menthane hydroperoxide 0.08 - Reducing agent ferrous sulphate (heptahydrate) 0.0125 - Secondary sodium formaldehyde sulphox reducing agent silate 0.15

Chelator EDTA- ^ JNa 0.07

Electrolyte Sodium phosphate 0.8 (dodecahydrate) 20,58930

The polymerization conditions

Polymerization temperature: 5 ° C

Reaction time: 9 hours

Nitrogen Atmosphere Conversion

Table 3 gives the conversions and also shows that obtained in exactly the same manner as above using a commercial dehydrated coophone emulsifier.

Table 3

Emulsifier Conversion (%)

Example 3 58.0

Example 4 53.3

Example 12 6l, 3

Example 13 62.1

Commercial dehydrated rosin emulsifier 61.5

Latex Stability Test 50 g of a 25% by weight aqueous solution of the latex obtained in the above polymerization was placed in a tank and subjected to mechanical shear at 25 ° C for 5 minutes at a load of 5 kg and a speed of 1000 rpm. The resulting coagulation was filtered through an 80 mesh stainless steel screen and dried to determine the amount of coagulation formed.

Amount of coagulation formed _ Weight of dried coagulation (%) ~ Ί0 c x 100

The lower the amount of coagulation formed, the more stable the latex.

Table 4 shows the result compared to that obtained using a commercial dehydrated rosin emulsifier.

Table 4

Emulsifier Amount of coagulate formed (%)

Example 3 1.4

Example 4 1.3

Example 12 1.6

Example 13 2.0

Commercial dehydrated rosin emulsifier 1.5

Claims (5)

58930 A process for preparing a resin by reacting a Diels-Alder adduct in the presence of a Friedel-Crafts catalyst with a benzene derivative of the formula 4- (R1) n wherein R ~ is an alkyl group having 1 to 12 carbon atoms and n is an integer of 1 or 2, characterized in that said adduct is at least one of the compounds a) of formula ov; I CH2 R9 R „m o 3 4. 5 wherein each of R, R, R and R is a hydrogen atom or a methyl group, 678 o each of R 0, R ', R and Ry is a hydrogen atom or a methyl group, each of X and Y is -C00H or -C00Ra or X and Y represent an acid anhydride ring formed by bonding to each other, wherein Ra is an alkyl group having 1 to 4 carbon atoms, and m is zero or an integer of 1 or 2, or b) of the formula r4 H4 r2 wAtA * I CH0 CH, kAA R5 „5 m 2 7 4 R where R, R, R, R, X, Y and m have the same meaning as above, and if desired 22 5 8 9 3 0 1. when at least one of X and Y is -COORa or X and Y form an anhydride ring, wherein Ra is as defined above, hydrolyzing the resulting resin to give rosin acid, 2. when at least one of X and Y is -COOH, neutralizing the resulting resin with alkali to give a rosin acid salt, or 3. when one of X and Y is -COORa and the other is -COOH, or X and Y form an anhydride ring, wherein Ra is as defined above rtsi is neutralized with ammonia, a primary amine or a secondary amine to give a rosin acid salt having an acid amide group. Method according to Claim 1, characterized in that m is zero. Method according to claim 1, characterized in that m is 1. Li. Method according to Claim 1, characterized in that m is 2. Method according to Claim 2, characterized by 2 5. that R 1 -R 2 are hydrogen atoms, X and Y represent an acid anhydride ring and m is zero or 1. 1. A process for the preparation of a genomic resin of a resin with a Friedel-Crafts catalyst in the form of a Diels-Alder addition product with a reagent and a benzene derivative with a formula J— <Rl'n color R ~ är en alkylgrupp med 1- 12 chapters and n 1 or 2, the addition of these addition products to the product a) R6 H i R 2 χ I CH2 RIK RJ R9 R m