JPS5851932B2 - Hydride of isoprene/propylene alternating oligomer and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydride of alternating isoprene-propylene oligomers having one unit of propylene monomer at both ends, which hydride is a useful new saturated hydrocarbon.

The present invention also relates to a method for producing the above-mentioned hydride.

With the progress of polymerization technology, alternating copolymerization methods, in which different types of monomers are regularly and alternately polymerized, have recently been rapidly developed.
Among these, many patents have been granted, including Japanese Patent Publication No. 43088/1983, regarding the method for producing alternating copolymers of olefins and diolefins.

As a result of research into the uses of these new alternating copolymers, the present inventors found that they are not only excellent as raw materials for synthetic rubber, but also that due to their regular structure, they have traditionally been obtained only from living organisms. Focusing on its high potential as a resource substitute, we succeeded in synthesizing and utilizing a new compound, an alternating copolymer hydride.

That is, the present invention provides a hydride of a propylene/isoprene alternating copolymer having one unit of propylene monomer at both ends of the polymer chain and having carbon numbers of 27.35 and 43, and a hydride of a propylene/isoprene alternating copolymer having one unit of propylene monomer at both ends of the polymer chain and having carbon numbers of 27.35 and 43. 27.35
The present invention also relates to a method for producing the above-mentioned hydride, which comprises hydrogenating the propylene/isograne alternating copolymer of No. 43 with molecular hydrogen in the presence of a reducing catalyst.

The propylene/isoprene alternating copolymer, which is a starting material for the method of the present invention and whose polymer chain has one unit of propylene monomer at both ends, is known as disclosed in, for example, Japanese Patent Publication No. 49-41115.

The fact that the end ends with one propylene monomer unit means that in the alternating copolymerization reaction in Japanese Patent Publication No. 49-41115 etc., propylene and isoprene always react as a pair; therefore, this alternating copolymerization reaction The combination has a molecular weight of 110, i.e. propylene (42)+
It means that it is a mixture of molecules having a stepwise distribution of molecular weights with isoprene (68) as one step.

This means that ordinary polymers, for example polypropylene, have a molecular weight distribution step of 42, while isoprene has a step of 68.
This means that it is extremely easy to separate isoprene-propylene alternating copolymers by distillation, chromatography, etc. to separate substances with specific molecular weights or mixtures within specific molecular weight ranges.

In the field of polymeric materials such as synthetic rubber and synthetic resins, the need to separate products in a specific molecular weight range is not so high, and even if it is desired to separate products in a specific range, Contamination with out-of-range products is not severely restricted.

However, in synthetic lubricating oils, cosmetic bases, pharmaceutical bases, etc., which are the applications of the hydrogenated imprene/propylene alternating copolymer, which is the compound of the present invention, compounds having molecular weights outside the desired range may be mixed into the lubricating oil. In the case of cosmetic bases, absorption into the human body, rash, texture, etc. are generally greatly affected, and whether or not it is easy to separate the desired compound is a serious issue.

C2□, C35 or C4 as the starting material for the process of the invention
The propylene/isoprene alternating copolymer of No. 3 can be easily isolated by vacuum distillation and/or molecular distillation of the alternating copolymerization reaction product.

Hydrogenation is carried out using molecular hydrogen in the presence of a reducing catalyst.

The type of catalyst to be used is not particularly restricted, and reduction catalysts such as metal catalysts, sulfide metal catalysts, and carbonyl catalysts can be used; however, metal catalysts,
Particularly preferred is the use of nickel catalysts.

The reaction pressure is arbitrary, but usually 20 to 150 kg/c
It is carried out under hydrogen pressure of about rA, and the reaction temperature is room temperature to 200℃.
℃ range, generally 50 to 150℃ range is adopted.

The reaction time varies depending on the conditions used, but generally 1 to 24 hours, and usually 2 to 10 hours is sufficient.

It is desirable to carry out the reaction while stirring the system in order to promote the reaction.

Once the reaction is complete, the catalyst is removed by centrifugation or filtration to obtain the product.

If there is a possibility that some hydrogenolysis has occurred during the hydrogenation reaction and a by-reactant with a small molecular weight is produced, it is preferable to subject the product to reduced pressure or molecular distillation again.

As shown in the examples, the structure of the product is a hydride of a propylene/imprene alternating copolymer in which both ends of C2□, C35, and C43 are propylene groups, as shown in the examples, and it was confirmed by gel permeation chromatography that It showed one peak and was confirmed by gas chromatography/mass spectroscopy, ultraviolet absorption spectroscopy, iodine value measurement, and elemental analysis.

In the product obtained in this way, for example, taking the case of C2□, one propylene monomer unit at one end, probably the end where polymerization was initiated,
It is a mixture of hexamethylheneicosane bonded in the form of a propyl group and heptamethyleicosane bonded as an i-propyl group, and both are the first half of two closely spaced peaks or one broad peak in gas chromatography. The latter half can be separated by fractionation, but in normal applications, the two are used as a mixture.

Identification of isomers with different bonding forms of these terminal groups was performed by nuclear magnetic resonance absorption spectroscopy (NMR) and infrared absorption spectroscopy (IR).

In addition, the bonding form between one unit of isoprene monomer and one unit of propylene monomer in the chain of the raw material copolymer is mostly regular head-to-tail bonding, but some are head-to-head bonding and tail-to-tail bonding. Therefore, the structure of the hydrogenated product is considered to be a mixture of isomers corresponding to the structure of these raw materials, but these fine structures can be specified to some extent by oxidative decomposition of the raw materials. However, with the hydrogenated products of the present invention, this measure is no longer applicable;
Further separation or structural determination is currently not possible using other separation means or measurement techniques.

Further, further separation is considered to be industrially meaningless.

On average, the compounds of the invention contain 1 carbon atom for every 3 main chain carbon atoms.
It is a hydrocarbon having methyl groups.

It has been known that hydrocarbons having branched chains are not only more suitable as lubricating oils than n-paraffin, but also preferred as bases for cosmetics or pharmaceuticals. .

Some of the reasons for this are that branched hydrocarbons have lower melting points, water-air permeability, and better texture than n-paraffins.Hydrocarbons are used as cosmetic bases and pharmaceutical bases. is required to have appropriate diffusion permeability, solubility, flexibility, lubricity, and gloss, and in general, branched-chain hydrocarbons meet these objectives better than straight-chain hydrocarbons. .

Until now, squalane has been particularly preferred as a base for pharmaceuticals or cosmetics, and it is a special compound corresponding to a hydrogenated compound of two head-to-tail trimers of isoprene bonded back to back. Traditionally, shark liver oil is saponified, the unsaponified portion is distilled under reduced pressure, hydrogenated with Raney nickel, etc., the product is further purified with metallic sodium, and then re-distilled under reduced pressure. .

As described above, natural shark liver oil, which is a raw material for squalane production, is not easily available, and there has been a desire to develop an inexpensive industrial product that can be stably supplied.

Recently, it has been reported that it has become possible to synthesize squalane, but the details are unknown and the process is considered to be complicated, so it has not yet been possible to produce squalane at a low cost.

From these points of view, C
It has been proposed to use a hydride of an oligomer having 8 pendant groups in place of squalane, but in the latter case, it is not easy to obtain higher olefins as raw materials, and the number of side chains per number of carbon atoms in the main chain is small. In addition, since the isoprene oligomer hydride uses only isoprene compared to the isoprene/propylene alternating oligomer hydride of the present invention, the raw material is more expensive and it is difficult to separate a product having a desired specific molecular weight. .

The contamination of low molecular weight components is harmful to cosmetics and products due to their odor and irritating properties.
Not preferred as a pharmaceutical base.

Although there are reports that oligomers of isobutylene can be used for similar purposes, it is quite difficult to produce a purified product with a molecular weight range suitable for the purpose in good yield.

As shown in Reference Examples 2 to 4, the compounds of the present invention have the same quality as Sufwan, which is currently considered to be the best base for cosmetics and pharmaceuticals, and can be used equally.

The present invention will be explained in more detail by showing Examples and Reference Examples below.

Reference example 1 (A) Propylene of C2□, C35 and C43
Synthesis of infrene alternating copolymer 2001 n-hexane and 25 oz of isoprene were added to a nitrogen-substituted autoclave with a capacity of 31 and equipped with a stirrer. After cooling it to -50°C, 800 y of liquefied propylene was added and the whole was homogenized. The temperature was maintained at -50°C while stirring.

Separately, 4 mmol of n-hexa750i1 vanadyl trichloride (vOC13) and 1 mmol of aluminum tri-n-butoxide (AI (OnBu)s) were added one after another to a 200 mA eggplant flask at room temperature and left at room temperature for about 10 minutes. did.

Thereafter, it was cooled to -30°C and 20 mmol of triisobutylaluminum (AliBu3) was added to prepare a catalyst solution.

This solution was injected into the autoclave while being maintained at -30°C.

After the catalyst was injected, polymerization was carried out for 2 hours with stirring at a temperature of 0°C to -10°C.

Polymerization was stopped by adding a small amount of methanol, and the residual catalyst produced was removed by centrifugation to obtain a colorless and transparent polymer solution.

This solution was treated at room temperature under reduced pressure of about 200 mmHg to completely remove the solvent, yielding an oily polymer of 270f.

The obtained polymer was subjected to vacuum distillation and molecular distillation to separate it into the following six fractions.

Furthermore, by molecular distillation of the oily polymer, the above C,
Obtaining a volume corresponding to a mixture of D and E fractions,
When this was subjected to gel permeation chromatography, it showed three distinct peaks as shown in Figure 1.

(B) Structure determination of fractions C, D and E (1
) Structure of Fraction C Fraction C had a nearly constant boiling point (160~b).Permeation chromatography gave a single peak corresponding to the C2□ peak shown in FIG.

From the following experimental facts, this fraction is propylene 4
molecule and three molecules of isoprene.
It was confirmed that it was an alternating isofrene heptamer.

1 Determination of Molecular Formula The molecular weight is 372 by glass chromatography/mass spectroscopy, the amount of double bonds is 4 per molecule by bromine number measurement, and C27H48 by direct elemental analysis (C86, 98%; HI 3.00%).
It turned out to be.

This corresponds to a structure whose constituent units are four molecules of propylene and three molecules of isoprene.

i c13 Nuclear magnetic resonance absorption spectrum and infrared absorption spectrum Based on propylene continuous bond structure CH3CH3 (-CH-CH2-CH-CH2-) <115
The absorption of 5CIrL-1 and the methylene group of the above structure (
-CH2-) is easily absorbed by the carbon (46, lppm
) was not observed in the infrared absorption spectrum and C13 nuclear magnetic resonance absorption spectrum.

In addition, in the infrared absorption spectrum, the impropenyl group H3 (-C=CH2) has a very sharp absorption at 889cfrL', and the vinyl group (-CH-C
H2) based absorption (910cIrL'990CIn
−〇 was not recognized.

Out H1 Nuclear Magnetic Resonance Absorption Spectrum 4- The methylene group hydrogen adjacent to the double bond of the isoprene unit derived from the alternating bonds of bonded isoprene and propylene is present at δ-2, Oppm,
■・Methylene group hydrogen adjacent to double bond derived from 4-bonded isoprene continuous bond (δ = 2.1 ppm)
was not recognized.

Further, as a result of H1 nuclear magnetic resonance absorption spectrum, it was found that this fraction was composed of the following structural group.

Raction is a propylene/isoprene alternating copolymer consisting of 4 molecules of propylene represented by C2□H48 and 3 molecules of isogrene combined at 1.4%, and one end is an isoproH3 benyl group (-C=CH2). It was proved that the other end consists of an n-propyl group (CH3CH2CH2CH3 or isopropyl group (>CH-)).

(2) Structure of Fraction D Fraction D has a nearly constant boiling point (160~b). The gel permeation chromatography results showed a single peak corresponding to the C35 peak in Figure 1.

As described for fraction C, molecular weight measurement by gas chromatography/mass spectrum, bromine number, elemental analysis, C1
From the values obtained by 3NMR, JR and H' NMR, this fraction is an alternating propylene-isoprene copolymer consisting of 5 molecules of propylene with the molecular formula of C35H62 and 4 molecules of 1,4-bonded isoprene; It was shown that the terminal of is an inpropenyl group, and the other end is an n-propyl group or an i-propyl group.

(3) Structure of Fraction E Fraction E had an almost constant boiling point (170~b).The results of gel permeation chromatography showed a single peak corresponding to the peak of C43 in Figure 1.

As described for fraction C, molecular weight measurement by gas chromatography/mass spectrum, bromine number, elemental analysis, C1
From the values obtained by C13N, IR and H' NMR, this fraction is an alternating propylene-isoprene copolymer consisting of 6 molecules of propylene with the molecular formula of C43H76 and 5 molecules of 1,4-bonded isoprene; It was shown that the terminal of is an inpropenyl group, and the other end is an n-propyl group or an i-propyl group.

Example 1 Synthesis of hydrides of C2□, C35 and C43 propylene-isoglene alternating copolymers (A) Hydrogenation was carried out using reduced nickel in a mixed portion of the C, D and E fractions obtained in Reference Example 1. ,
A hydride of the above mixture was obtained.

Hydrogenation was carried out as follows.

Reduced nickel N-111 manufactured by JGC Chemical Co., Ltd. was treated in advance at 120 to 150° C. in a hydrogen stream to activate the catalyst.

The above activated catalyst 2 (l) and the above mixed portion 8M' were added into a nitrogen-substituted autoclave with a capacity of 11,
100℃ with stirring and hydrogen pressure of 50kg/crAG
, and reacted for 55 hours.

After the reaction, the catalyst was removed by centrifugation to obtain a colorless and transparent liquid.

When the hydrogenated product thus obtained was subjected to gel permeation chromatography, it showed three distinct peaks as shown in FIG.

(B) Hydrogenation of C2□ propylene/isoprene alternating copolymer (synthesis of hexamethylheneicosane and heptamethyleicosane) The C fraction obtained in Reference Example 1, that is, the C2□ propylene/isoprene alternating copolymer described above The hydride of the C fraction was obtained by treatment in exactly the same manner as described above.

After the reaction, the catalyst was removed by centrifugation to obtain a colorless and transparent liquid.

When this liquid was distilled under reduced pressure, most of it was distilled out with a substantially constant boiling point (160-180°C, 101 mmHg).

Gel permeation chromatography of the distillate gave a single peak corresponding to the C2□ peak in FIG.

The distillate was confirmed to be a mixture of hexamethylheneicosane and heptamethyleicosane from the following experimental facts.

1 Determination of molecular formula Molecular weight 380 by gas chromatography/mass spectroscopy, results of ultraviolet absorption spectrometry and iodine value measurement, hydrogenation rate 99.7%, and elemental analysis value (cg5.t
o%; Hl 491%), it was found to be C2□H56.

This corresponds to a hydride of C2□ propylene/isoprene alternating copolymer.

11 Separated hydrides of hexamethylheneicosane and heptamethyleicosane were separated using a silicon OV-i7 column (column length Im).
) at 195° C., one broad peak was obtained (the first half is designated as a, and the second half is designated as a).

These were fractionated.

111 Identification of hexamethylheneicosane and heptamethyleicosane The H1 nuclear magnetic resonance absorption spectrum and infrared absorption spectrum of the above peak a component are shown in Figures 3a and 4, respectively.
Shown in a.

δ=0.8-0.9pp in nuclear magnetic resonance spectrum
The peak area of the methyl group (-CH3) in m and the methylene group (-CH2-) and methine group (-CH-
) and the peak area was 27:29, indicating that each molecule contained nine methyl groups.

Therefore, this component was identified as heptamethylicosane, which is a hydrogenated product of a C2□ propylene/isoprene alternating copolymer having an isopropyl terminal group.

The nl nuclear magnetic resonance absorption spectrum and infrared absorption spectrum of the gas chromatogram peak b component are shown in FIG. 3b and FIG. 4b, respectively.

The same analysis as above was performed on the nuclear magnetic resonance spectrum, and the ratio of the peak area of methyl groups to the peak areas of methylene and methine groups was found to be 24:32, which means that each molecule contains 8 methyl groups. It was shown that

Therefore, this component was fixed with hexamethylheneicosane, which is a hydrogenated product of a C2□ propylene/isoprene alternating copolymer having an n-propyl terminal group.

Comparing the incisions of the methyl group at 13706rfl' in the infrared absorption spectra of both, the a component has a sharper incision than the b component, indicating that the a component has more isopropyl groups, and this fact is consistent with the above-mentioned nucleus. This is consistent with the magnetic resonance spectrum analysis results.

'C) Hydrogenation of C35 propylene/isoprene alternating copolymer (synthesis of octamethyl hebutacosane and nonamethyl hexacosane) The D-flank John obtained in Reference Example 1, that is, the C35 propylene/imprene alternating copolymer, was subjected to the above (4) The hydride of the D fraction was obtained by treatment in exactly the same manner as described in .

After the reaction, the catalyst was removed by centrifugation to obtain a colorless and transparent liquid.

This product was subjected to chikel permeation chromatography by removing low-boiling substances that may be present due to side reactions by distillation under reduced pressure.
A single peak corresponding to the peak was shown.

The molecular weight according to gas chromatography/mass spectroscopy is 493, the hydrogenation rate determined from ultraviolet absorption spectrometry and iodine value is 99.7%, and the elemental analysis value is C85.29%.
The HI was 3.82%.

This result corresponds to the molecular formula C35H72, which is consistent with the molecular formula of the hydride of C35 propylene/isoprene alternating copolymer.

When this hydride was similarly subjected to gas chromatography analysis using a silicon 0V-17 column (column length 1 m), one broad peak was obtained.

The first half was separated into the A tank, and the second half was separated into the B tank.

Hl NMR and IR of the a reservoir are shown in Figures 5a and 6a.

From NMR, absorption based on -CH3 and -CH2- and -C
The area ratio of absorption based on H- was found to be approximately 33:39, indicating the presence of 11 methyl groups, and was recognized as nonamethyl hexacosane.

A similar analysis of HlNMR of the b reservoir revealed that the ratio of the absorption areas of -CH3 and (-CH2- and -sumi-) was approximately 30:4.
2 showed the presence of 10 methyl groups and was identified as octamethylhebutacosane.

The NMR and IR of the b reservoir are shown in Figures 5b and 6b, respectively.

Q)) Hydrogenation of 043 propylene/isoprene alternating copolymer (synthesis of decamethyl tritriacontane and undecamethyl tritriacontane) The E fraction obtained in Reference Example 1, that is, the C43 propylene/isoprene alternating copolymer, was Treat it exactly as described in (4) and
A fraction of hydride was obtained.

After the reaction, the catalyst was removed by centrifugation to obtain a colorless and transparent liquid.

This product was distilled under reduced pressure to remove low-boiling substances that may be present due to side reactions, and then subjected to gel permeation chromatography.
A single peak corresponding to the peak was shown.

The molecular weight according to gas chromatography/mass spectroscopy is 605, the hydrogenation rate determined from ultraviolet absorption spectrometry and iodine value is 99.6%, and the elemental analysis value is C85.36%.
The HI was 3.70%.

This result corresponds to the molecular formula C43H88, which is consistent with the molecular formula of water trinide of C propylene/isoprene alternating copolymer.

When this hydride was similarly subjected to gas chromatography analysis using a silicon 0V-17 column (column length 1 m), one broad peak was obtained.

The first half was divided into a tank and the second half was separated into a tank b.

H' NMR and IR of the a reservoir are shown in Figures 7a and 8a.

From NMR, absorption based on -CH3 and -CH2- and -C
When the area ratio of absorption based on H- was determined, it was approximately 39:49, indicating the presence of 13 methyl groups, and was recognized as undecamethyltodriacontane.

Similar analysis of H' NMR of the b reservoir revealed -CH
The absorption area ratio of 3 and (-CH2- and -CH-) is approximately 3
6:52 showed the presence of 12 methyl groups and was identified as decamethyltritriacontane.

The NMR and IR of the b reservoir are shown in Figures 7b and 8b, respectively.

Reference example 2 Nutritional cream (4) Polyoxyethylene glycerin Vegetable oil fatty acid varnish 2% Tilturbitane sesquiolate Myristine 1 C27/C35/C43 (4:3:2) Propylene/isoprene alternating copolymer hydrogenated product 0% Setanol 5 Paraffin wax, (57℃, below 135) 3 Whale wax
6 Beeswax
6 tt preservative
0.2 (B) Borax 0.
4,/Propylene glycol 3 H I00 〃 Total amount with purified water, Sou (C) Fragrance 0.3-0.5%
Heat (A) to 80°C and (season) to 82°C or higher to uniformly dissolve.

Once dissolved, add (B) to (A) while stirring (N) and emulsify with stirring.

Once the addition is complete, check the temperature.

Next, continue stirring and cooling until the temperature reaches 60-65°C.
was added, stirred to 45°C, left to stand, and defoamed to prepare a nutritional cream.

When comparing this formulation with one in which the hydrogenated alternating copolymer was replaced with suffuran, the two had almost the same color, odor, long-term stability, non-irritability, spreadability, stiffness, and texture. showed that.

Reference example 3 Cold cream (A) Polyoxyethylene mono 2% Stearate sorbitan monopalmite 3N Monobutyl isostearate 0, 7 Inglovir myristyrate Liquid paraffin (#70) 1 C2 Propylene/isoprene alternating copolymer water Additives 2 Stearic acid 3, 5 Setanol beeswax 4% Lanolin paraffin wax (57℃, 135'P) Preservative (B) Polyethanolamine 70 Pyrene glycol 0.211 0.4 Total amount with purified water 100" (q Fragrance: 0.3-0.5%) A cold cream was prepared by treating the above composition in the same manner as in Reference Example 2. It exhibited almost the same color, odor, long-term stability, non-irritation, spreadability, stiffness, and texture as the one it replaced.

Reference example 4 External drug base (hydrophilic Nanko base) C27HSC35H% C43H (3:2:1) 30%
Glycerol triisostearate 35 Glycerol monostearate 22 Glycerol tristearate 5 Hydrogenated castor oil 5% P, O, E, Sorbitan monostearate 3//
- The above components were added and mixed, heated and stirred to a temperature of 82° C. or higher, and left to defoam to form a product.

The product's oral coloring test and skin cumulative irritation test showed that it had the same oral stability and safety as the above formulation in which the alternating oligomer hydrogenated fluoropylene and isoprene was replaced with squalane.

[Brief explanation of the drawing]

Figure 1 is a gel permeation chromatograph of a portion corresponding to the mixture of C, D and E fractions obtained in Reference Example 1 (A!); Figure 2 is a gel permeation chromatograph of the product obtained in Example 1 (A). Figures 3a and 4a are NMR and IR of hexamethylheneicosane; Figures 3b and 4b are NMR and IR of hexamethylheneicosane; Figures 5a and 6a are gel permeation chromatographs; Figures 5b and 6b are the NMR and IR of octamethylhepcosane; Figures 7a and 8a are the NMR and IR of undecamethyltodo'J T contane; and Figure 7b is the NMR and IR of nonamethyl hexacosane. and Figure 8b
are the M and IR of decamethyltritriacontane.

Claims (1)

[Scope of Claims] 1. A hydride of a propylene/isoprene alternating copolymer having one propylene monomer unit at both ends of the polymer chain and having 27.35 or 43 carbon atoms. 2. The compound according to claim 1, wherein the hydride is hexamethylheneicosane. 3. The compound according to claim 1, wherein the hydride is hebutamethyleicosane. 4. The compound according to claim 1, wherein the hydride is octamethylhebutacosane. 5. The compound according to claim 1, wherein the hydride is nonamethyl hexacosane. 6. The compound according to claim 1, wherein the hydride is decamethyltritriacontane. 7. The compound according to claim 1, wherein the hydride is undecamethyltodriacontane. 8 Both ends of the polymer chain are obtained by hydrogenating a propylene/isoprene alternating copolymer having one unit of propylene monomer and having 27.35 or 43 carbon atoms with molecular hydrogen in the presence of a hydrogenation catalyst. is one unit of propylene monomer and has 27.35 or 43 carbon atoms.