JPS5827257B2 - Takashiki carbon sun mataha sonokinzokuen no seizouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing carboxylic acid derivatives of special polycyclic olefins.

The present inventors have previously discovered an alicyclic carboxylic acid or a metal salt thereof having a unique function by carboxylating the endocyclic unsaturated group of a 3- and/or 4-mer of cyclopentadiene (hereinafter referred to as CPD). Invented a method for manufacturing (Patent Applications 1987-95517, 1986-452, 1983-1999)
453).

CPD trimers and/or tetramers have a chemical structure in which one or two molecules of CPD are added to dicyclopentadiene.

The present inventors have recently discovered that, in place of the above-mentioned dicyclopentadiene, tetra- or hexa-hydroindene or their alkyl substituted products are used as starting materials, and 1 to 2
Endomethylene polycyclic olefins such as those shown below, obtained by adding CPD molecules, can also be carboxylated to produce polycyclic carboxylic acids that have specific effects similar to the case of the above patent application. or its metal salt can be obtained.

It has been well known that carboxyl groups can be introduced into various olefins, and it is also known that dicyclopentadiene and norbornene can be carboxylated.

However, such bicyclic olefins (however, the rings formed by endomethylene groups are not counted).

Carboxylic acids derived from carboxylic acids (the same applies hereinafter) cannot provide the specific effects aimed at by the present invention.

However, when a carboxyl group was introduced into various polycyclic olefins having a bone core and their properties were investigated, an example of carboxylation of a polycyclic olefin having three or more rings was found. It has been found that carboxylic acids are distantly related to the object of the present invention.

The unique action and effect aimed at by the present invention are that in the carboxylic acid state, it can become resinous, and in the alkali metal salt state, it exhibits excellent surface activity in water.

This unique property can only be found in rosin (a tricyclic monocarboxylic acid with an alicyclic structure) extracted from natural pine trees, which is currently available industrially.

In addition, the present invention provides a method for synthesizing a substance having the same efficacy as rosin.

The present invention uses a polycyclic olefin (hereinafter simply referred to as polycyclic olefin) having a nucleus obtained by adding one or two molecules of cyclopentadiene to tetra- or hexa-hydroindene, and the bone nucleus derived from the polycyclic olefin is used. It has been found that the polycyclic carboxylic acid (hereinafter simply referred to as polycyclic carboxylic acid) or its metal salt is a new substance and exhibits the same effect as rosin.

Moreover, according to the method of the present invention, monocarboxylic acids can be synthesized with higher selectivity than when using CPD trimers or tetramers as starting materials.

This is because tri- or tetramers of CPD tend to contain olefins with two norbornene rings, but when CPD is added to tetra- or hexa-hydroindene, only one norbornene ring is formed; - Another unsaturated group formed when hydroindene is used is a cyclopentene or cyclohexene ring, which has low reactivity.

However, under strong carboxylation conditions it can also be a dicarboxylic acid.

As is clear from the above, the present invention provides tetra- or hexa-hydroindene or an alkyl substituted product thereof with 1
A polycyclic carboxylic acid or a metal salt thereof characterized in that a polycyclic olefin obtained by adding one or two molecules of CPD is reacted with a suitable reagent to introduce a carboxyl group into an unsaturated group in the ring. This is a manufacturing method, and the method for introducing a carboxyl group is: ■ React with a carbon monoxide donor ■ React with a cyanide ion donor, with or without halogenation, cyanate and then hydrolyze ■...Rogen After being treated with metallic magnesium,
There is a method of reacting carbon dioxide.

3a.4.7 7a-Tetrahydroindene, which is the most easily obtained tetrahydroindene, is represented by the following structural formula, and can be easily synthesized by heating CPD and 1.3-butadiene to 200° C. or higher.

Further, when CPD and isoprene are subjected to a thermal addition reaction, an alkyl-substituted 3a.4.7.7a-tetrahydroindene with a methyl group attached at the 5th or 6th position is obtained.

Similarly, various alkyl-substituted products can be synthesized by thermal addition reactions between 1.3-butadiene alkyl-substituted products and CPD alkyl-substituted products.

Substituted alkyl groups include methyl group, ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Examples include butyl group, t-butyl group, etc., and the number of substituents may be two or more.

Tetrahydroindene can also be obtained by partially hydrogenating indene.

Further hydrogenation yields hexahydroindene.

Hexahydroindene is also cyclopentene and 1,3-
It can also be obtained by thermal addition reaction with butadiene.

One or two molecules of CPD can be added to tetra- or hexa-hydroindene or an alkyl substituted product thereof by adding CPD or dicyclopentadiene to the hydroindene and carrying out a thermal addition reaction.

The thermal addition reaction proceeds at a temperature of 160°C or higher, especially 200°C or higher, but when the temperature reaches 250°C or higher, a higher order adduct with three or more molecules of CPD added or a polymer that proceeds by a different reaction mechanism. The amount of produced increases, making it difficult to obtain the desired adduct.

Since CPD further undergoes an addition reaction with the CPD adduct, the CPD addition reaction takes on polymolecular properties even when the reaction is carried out at an appropriate temperature range (2000 to 230°C).

Therefore, in order to obtain adducts with only 1 and/or 2 CPD molecules, the reaction should be stopped when an appropriate reaction rate is reached, and after collecting unreacted products, the desired addition product should be removed from the raw acid. It is best to separate only the substances by distillation.

However, even if hydroindene or an adduct of three or more molecules of CPD is mixed in the starting material of the present invention, it does not seriously impede the purpose of the present invention, and is therefore acceptable depending on the application. The addition operation need not be limited to the above method.

For example, when synthesizing tetrahydroindene by thermal addition reaction of CPD and 1,3-butadiene, if the reaction temperature is raised (around 230°C) or if CPD is blended in excess, CPD will be added together with tetrahydroindene. It also produces a lot of things, so you can get them in one step.

In order to introduce a carboxyl group into the polycyclic olefin thus obtained, well-known methods and reaction conditions can be applied.

The first method of carboxylation reaction employed in the present invention is carried out by reacting a carbon monoxide donor, but of course a method in which carbon monoxide itself is reacted can also be adopted.

Among these, a representative method is the addition reaction of carbon monoxide, which is called oxo synthesis or the Retzpe reaction in which olefins are chopped.

The polycyclic olefin is treated with a metal catalyst of group Ⅰ of the periodic table, such as a cobalt salt such as cobalt carbonate or cobalt acetate, or a cobalt carbonyl derived from these, and if necessary with a hydrogen donor such as an amine. When carbon monoxide is applied under pressure in the presence of a promoter such as water, alcohol, or hydrogen, a hydrocarbonyl addition reaction first occurs to the unsaturated group of the norbornene ring.

In addition to cobalt, nickel, iron, palladium, rhodium, etc. can also be used as a catalyst.

In the presence of water, a hydroxyl group enters the added carbonyl, and a carboxyl group is introduced into the carbon of the norbornene unsaturated group of the polycyclic olefin.

Further, in the presence of alcohol, a carboxylic acid ester is similarly introduced, and further in the presence of hydrogen, an aldehyde group is introduced.

The esters and aldehydes obtained here can be used as they are as new resins, but when they are hydrolyzed and oxidized, they become carboxylic acids or alkali metal salts of carboxylic acids.

Needless to say, even when a carboxylic acid is obtained directly, a metal salt of the carboxylic acid is obtained when this is treated with an alkali hydroxide, an alkali carbonate, an alkaline earth metal hydroxide, or other metal compound.

According to this method, the introduction rate of carboxyl groups into polycyclic olefins can be adjusted by monitoring the amount of carbon monoxide absorbed, and in some cases, the reaction rate can be reduced to control side reactions. Or, conversely, when tetrahydroindene is used, by allowing the reaction to proceed excessively, a carboxyl group is introduced only into the norbornene ring, resulting in a monocarboxylic acid and a carboxyl group is also introduced into the cyclopentene ring or cyclohexene ring. The resulting dicarboxylic acid can be synthesized in any ratio.

In addition, carbon monoxide can also be carbonylated by reacting with an acid catalyst by a Kotsuzo type reaction, and can be converted into a carboxyl group by subsequent addition of water.

As the acid catalyst, sulfuric acid, phosphoric acid, hydrogen fluoride, fluorine trifluoride, etc. can be used, and carbon monoxide is applied under pressure.

Under acid catalysis, carbonyl compounds capable of generating carbon monoxide, such as formic acid, can be used instead of carbon monoxide.

When using formic acid, peroxides can also be used as catalysts.

The second method of the carboxylation reaction employed in the present invention is to react a cyanide ion donor such as hydrogen cyanide or metal cyanide to form an IJ compound, which is then hydrolyzed to give a carboxylic acid or its metal salt. It's something you get.

A complex compound of a polycyclic olefin and a metal from group II of the periodic table,
For example, when hydrogen cyanide acts as a catalyst on palladium or nickel triphenylphosphine complexes, cobalt carbonyl, nickel carbonyl, etc., an addition reaction progresses to form monocyanate even if the ring is an unsaturated group that does not have an electron-withdrawing group. can get.

Dicyanate can also be obtained from a polycyclic olefin obtained by adding CPD to tetrahydroindene by applying strong reaction conditions.

In order to synthesize a monocyanate, the norbornene ring unsaturated group of a polycyclic olefin may be reacted with a halogenating reagent in advance to form a halide, and the halide may be substituted with a cyanide ion donor.

Examples of the halogenating reagent include hydrogen chloride and hydrogen bromide.

In addition, as a cyanide ion donor, sodium cyanide,
Alkali metal cyanides such as potassium cyanide and metal cyanides such as copper cyanide are suitable.

When using alkali cyanide, the substitution reaction is 100
Although it may proceed at temperatures around 0.degree. C., it is preferred to use a polar solvent such as dimethyl sulfoxide.

Alternatively, according to the method described in Journal of the American Chemical Society Vol. 93, p. It is also possible to adopt a method of transporting cyanide ions from water to the organic layer by intervening a quaternary ammonium salt having a higher alkyl group such as phosphonium salts such as hexadecyltributylphosphonium bromide.

The third method of carboxylation reaction adopted in the present invention is to first convert a polycyclic olefin into a halide, as in the above method, and
This is treated with metallic magnesium to form a Grignard reagent, and then carbon dioxide is blown into it to cause a Grignard reaction, followed by carboxylation by adding water.

The purpose of the present invention can be achieved by employing any of the methods described above, but the reaction time, reaction temperature, pressure conditions, type of solvent, type of catalyst, etc. are determined as appropriate, and these can be arbitrarily determined. Even if this is selected, it does not depart from the technical scope of the present invention.

The polycyclic carboxylic acid obtained by the present invention can be used in the same applications as rosin or its derivatives, as described above, to bring about excellent effects.

When used as a compounding agent for paints, inks, adhesives, etc., the carboxylic acid can be used as it is, but it can be esterified with a polyhydric alcohol or monohydric alcohol, or as a metal salt of group Ⅰ of the periodic table. It is more effective to lower the molecular weight and increase the molecular weight.

When esterifying, the carboxylic acid obtained in the present invention is subjected to a condensation reaction with alcohol using a conventional method, or a polycyclic olefin is reacted with carbon monoxide in the presence of alcohol to directly produce an ester, or If the obtained ester is an ester of a monohydric alcohol, it can be obtained by further transesterifying this with a polyhydric alcohol.

When used as an alkaline earth metal salt, a polycyclic carboxylic acid is reacted with a metal oxide or metal hydroxide, or metathesized between an alkali metal salt of the carboxylic acid and a water-soluble inorganic alkaline earth metal salt. This can be obtained by

□ When used with a high molecular weight as described above, it contains a large amount of polymer products such as dicarboxylic acid by-produced or dimerized by-produced by other reaction mechanisms during the carboxylation reaction. It is rather advantageous to do so.

On the other hand, the metal salts obtained by the present invention, especially the alkali salts, exhibit a surfactant effect in water and are therefore useful as detergents and emulsifiers.In particular, the metal salts obtained by the present invention are useful as detergents and emulsifiers. It also has industrial value if used as an emulsifier in the emulsion polymerization of synthetic rubbers and synthetic resins.

In this case, monocarboxylic acid salts are preferred.

In addition, as mentioned above, when using a high molecular weight product, a material containing a considerable amount of a polycyclic olefin in which three or more molecules of CPD are added to tetra- or hexa-hydroindene should be used as a starting material. You can also do it.

Furthermore, the carboxylic acid of the present invention derived from hexahydroindene has the advantage of being chemically stable since no unsaturated group is present in the polycyclic hydrophobic group.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 3a.4.7.7a tetrahydroindene with a purity of 90% was prepared by precision fractional distillation from the product obtained by reacting an equimolar mixture of butadiene and CPD at 230° C. for 1 hour under autogenous pressure.

The impurities were coordination isomers formed by codimerization of butadiene and CPD, consisting primarily of vinylnorbornene, dicyclopentadiene, and vinylcyclohexene.

10 moles of the thus obtained rectified product were stirred while keeping the temperature at 230°C, and 3 moles of dicyclopentadiene was added dropwise thereto over 6 hours.

After completion of dropping, fractional distillation is carried out at 90℃~110℃/10mmH.
A fraction with a boiling point range of 110° to 140°C/10 rtanHg was collected.

A gas chromatogram was obtained, and the structure of each component separated by a preparative gas chromatograph was confirmed by NMR. The result was that the first fraction of the former was a co-trimer formed by adding one molecule of CPD (a small amount of The second fraction of the latter contains 70% co-trimer and 20% co-tetramer (one molecule of CPD added to the co-trimer). and other coordination isomers at 10%.

130g of the cotrimer obtained as the first fraction was mixed with benzene 13
0 gr, dicobalt octacarbonyl 6.5 gr,
Put 65 gr of water and 35 gr of pyridine into a 21 autoclave, seal it, pressurize carbon monoxide and keep it at a pressure of 180 kg/crA1 temperature of 160°C.
I stirred for hours.

After the reaction was completed, the contents were taken out, the catalyst was decomposed with dilute sulfuric acid, washed with water, dried, and then benzene and unreacted substances were distilled off to obtain 121 gr of a hydrocarboxylic compound as a residue.

The infrared absorption spectrum (hereinafter referred to as IR) of this product showed the presence of carboxylic acid and the disappearance of the norbornene ring double bond, and it was a pale yellow resin with a ring and ball softening point of 82°C and an acid value of 241.

This acid value is g equal to the value calculated from the formula (CI) (molecular weight 232), but from the Kölpermutation chromatogram, in addition to the main component corresponding to the molecular weight of the formula [■], there are also components equivalent to twice that amount. (approximately 30%), and it is estimated that it also contains a small amount of dicarboxylic acid.

Example 2 200 gr of the cotrimer mixture obtained as the second fraction in the first half of Example 1 was mixed with 200 gr of xylene, 5 gr of dicobalt octacarbonyl, and 128 gr of methyl alcohol.
, and 50g of pyridine into a 21 autoclave, sealed, and pressurized with carbon monoxide to bring the pressure to 180g.
kg/cst, the temperature was maintained at 145° C., and the mixture was stirred for 3 hours.

After the reaction is complete, the contents are taken out, the catalyst is decomposed with dilute sulfuric acid, washed with water, dried, and transferred to a distillation vessel to recover methyl alcohol, xylene, and unreacted substances by distillation.
A fraction of 10° C./1 mvtHg was distilled under reduced pressure.

This product showed absorption of ester groups by IR, absorption of norbornene ring double bonds disappeared, no acid value, and a saponification value of 210, indicating that it was a methyl ester of the corresponding polycyclic monocarboxylic acid. It appears to be.

This was saponified with sodium hydroxide to give the corresponding sodium salt.

A part of it is taken and made acidic, and the precipitated resin is extracted with benzene to recover the benzene, which has a softening point of 98°C and an acid value of 221.
A pale yellow transparent resin was obtained.

Example 3 1030 grams of isoprene, 100 grams of CPD, and 21 grams of methyl alcohol were charged into a 101 autoclave.
The mixture was stirred at 270°C under autogenous pressure for 1 hour.

Post-reaction distillation yielded a fraction of 992 gr at 50° to 75°C/20 mm Hg.

This contained 72% of 5-methyl or 6-methyltetrahydroindene as determined by gas chromatography, with the remainder being a mixture of coordination isomers of various dimers.

670 gr of this fraction was stirred while keeping it at 240°C.
PD200gr was added dropwise over 3 hours, and the reaction was continued for 1 hour.

After distilling and recovering unreacted substances from the reaction product, vacuum distillation was subsequently carried out to separate a fraction with a boiling point of 151 nr/LHg at 80° to 130°C.

When this product was analyzed for composition by a conventional method, it was found that the main component was polycyclic olefins such as na and -b obtained by addition of CPDI molecules.

100 gr of this stuff, 100 gr of benzene.

Hydrogen cyanide 5 grlPd (P (C6H=, O)
s ] 48gr・and P (C6H50) 340
Pour into 11 autoclaves with gr and heat to 140°C.
heated to.

The temperature was maintained for a total of 20 hours while adding 5 gr of hydrogen cyanogen every 4 hours.

The reaction product was washed with dilute alkali and dilute hydrochloric acid, washed with water, dried, and then distilled to separate 65 gr of a fraction with a boiling point of 1300 to 140°C/1 vtrrtHg.

This product was confirmed to be the corresponding polycyclic cyano compound based on the results of elemental analysis and IR1 molecular weight measurement.

50f of the obtained cyano compound was heated to 170°C in a stainless steel flask equipped with a strong stirrer, and then
Add 25g of 8% caustic potassium aqueous solution dropwise over 1 hour, make the whole into a paste, and then add 50g of warm water for another 1 hour. Obtained 150 gr.

This soap was a potassium salt of the corresponding monocarboxylic acid.

This soap solution was made acidic, and the precipitated resin was extracted with benzene. When the benzene was recovered, a pale yellow transparent resinous substance was obtained.

This resin is a monocarboxylic acid with an acid value of 218 and a softening point of 79.
℃ was shown.

Example 4 Same 3a, 4, 7, 7a as used in Example 1
- Tetrahydroindene was subjected to a mild hydrogen reaction under a palladium carbon catalyst, and
A mixture consisting of - and 3a,4,5,6,7,7a-hexahydroindene and a small amount of 3a,4,7,7a-tetrahydroindene was obtained.

600 gr of this mixture was stirred while keeping it warm at 240°C, and 260 gr of hedicyclopentadiene was added dropwise thereto over 6 hours.

After the completion of the dropwise addition, the reaction was continued for 1 hour, and then fractional distillation was carried out to remove unreacted substances, and then a fraction with a boiling point of 70 DEG to 150 DEG C. and 15 zmHg was collected.

This product had a number average molecular weight of 214, and a norbornene ring double bond was clearly recognized by IR, but only a small number of cyclohexene ring and cyclopentene ring double bonds were present.

From this, it was estimated that the main components of the mixture obtained here consisted of about 60% of hexahydroindene with one molecule of CPD added and about 40% of hexahydroindene with two molecules of CPD added.

Take 200g of this and add 200g of benzene.

21 autoclave with 20 gr of dicobalt octacarbonyl, CO,/H2=1. /
The mixed gas of i was injected under pressure to 160 kg/ctA, and the temperature was raised while stirring to react at 150° C. for 3 hours.

After the reaction, the catalyst was removed by a conventional method, and benzene and unreacted substances were removed by distillation.
A fraction of ~210°C/lmmHg was obtained.

This fraction showed IR absorption of aldehyde, and was oxidized by a conventional method to obtain a pale yellow transparent resin.

this. The resin was a polycyclic monocarboxylic acid having a soft f point of 120° C. and an acid value of 206.

Example 5 100g of second fraction prepared in the same manner as in the first half of Example 1
into 11 flasks, add 35% hydrochloric acid under the
00 gr was added thereto, and the mixture was kept warm at 80° C. for 5 hours.

100g of xylene was added to the reaction solution to separate the xylene layer and water layer, and the xylene layer was washed with water, dehydrated, and then distilled to reduce the boiling point to 1.
A fraction of 15° to 196°C/0.6 mrnHg was collected.

This substance was estimated to be monochloride based on IR.

Next, 50 (Cyan f Hisoda 30 in Jml flask)
gr and 150 ml of dimethyl sulfoxide were heated to 90°C while stirring, and the above monochloride 130
gr was added dropwise.

Although the reaction temperature rose due to exothermic heat, it was controlled not to exceed 160°C.

After the dropwise addition was completed, the temperature was maintained at 160°C for 3 hours.

After cooling, the reaction solution is poured into water, the product is extracted from the water with ether, and the boiling point is 130° to 220°C by distillation under reduced pressure.
/0.7 mmHg was fractionated.

The nitrile obtained here was stirred at 200°C with an aqueous solution of hicalmium hydroxide in an autoclave to saponify it,
A carboxylic acid potassium salt was obtained.

The free carboxylic acid obtained from this soap by a conventional method was a yellow transparent resin-like substance with a softening point of 96° C. and an acid value of 218.

Example 6 A flask of 5007711 containing 100 gr of ethyl ether and 5 gr of ribbon metal magnesium was placed in a dry state without air, and at 25° to 30°C the odor f 0.5 ethyl was added.
gr was added dropwise to initiate the Grignard reaction.

There, 50 g of monochloride obtained in the first half of Example 5
The solution was added dropwise over 2 hours while keeping the temperature at 30° C., and then stirred for 30 minutes to dissolve and react most of the magnesium.

Next, 100 gr of ethyl ether was added, the mixture was kept cool at 50° C., and 15 J of carbon dioxide was blown into the mixture over 30 minutes.

Finally, 100g of 3% hydrochloric acid was added dropwise and stirred for 10 minutes.

After removing the aqueous layer from the reaction solution, it was washed with water, dried, and distilled to remove the fraction up to 130° C./1.2 mmHg to obtain a pale yellow transparent resinous substance as a residue.

This is the corresponding monocarboxylic acid with a softening point of 89.
℃ and an acid value of 217.

Soaps obtained in each of the above Examples (Examples 2.3 and 5)
All of these exhibited excellent effects as paper-making sizing material 1].

It also has a good milk effect, similar to rosin soap,
It could be used as an emulsion agent in the emulsion polymerization of synthetic rubber.

Carboxylic acids were also good tackifiers for natural rubber and SBR, giving them their unique tackiness.

The carboxylic acid obtained in Example 4 exhibited properties similar to those of polymerized rosin, and its triglyceride or calcium salt showed softening points of 135°C and 160°C, respectively, and was excellent as a resin for printing ink. Indicated.

Claims (1)

[Scope of Claims] 1. A carbon monoxide donor is reacted with a molecular terminal fin obtained by adding one or two molecules of cyclopentadiene to tetra- or hexa-hydroindene or an alkyl substituted product thereof, 1. A method for producing a polycyclic carboxylic acid or a metal salt thereof, which comprises carboxylating an unsaturated group in a ring. 2. A cyanide ion donor is reacted with a molecular terminal fin obtained by adding one or two molecules of cyclopentadiene to tetra- or hexa-hydroindene or an alkyl substituted product thereof, with or without halogenation. 1. A method for producing a polycyclic carboxylic acid having a bone core or a metal salt thereof, which comprises cyanizing an unsaturated group in the ring and then hydrolyzing it. 3 Obtained by adding 1 to 2 molecules of cyclopentadiene to tetra- or hexa-hydroindene or an alkyl substituted product thereof. 1. A method for producing a carboxylic acid having the formula formula or a metal salt thereof at a molecular end, the method comprising halogenating an unsaturated group in the ring of a fin at the end of the molecule, then reacting with metallic magnesium, and then reacting with carbon dioxide.