JPH03247604A - Hydrogenation of polymer - Google Patents

Abstract

PURPOSE:To obtain in high efficiency a hydrogenated polymer excellent in resistance to heat, ozone and low temperature, weatherability, etc., by hydrogenating a polymer having carbon-carbon unsaturated double bond in the presence of a nitrogen-contg. compound using a catalyst with noble metal(s) on a carrier. CONSTITUTION:A polymer having carbon-carbon unsaturated double bond (e.g. polymer of 1,3-butadiene, isoprene etc.) is hydrogenated in the presence of a nitrogen-contg. compound (pref. monoethanolamine, diethanolamine or triethanolamine) using a noble metal-based catalyst where at least one metal selected from palladium, rhodium, ruthenium and platinum is carried on a carrier. It is preferable that the amount of the nitrogen-contg. compound to be used be such as to be, based on the amount of the catalytically active metal in the catalyst, (0.07:1)-(1: 1) in the molar ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for hydrogenating a polymer or copolymer having carbon-carbon unsaturated bonds.

[Prior Art] In recent years, carbon-carbon unsaturated bonds in polymers, for example, styrene/butadiene copolymers, acrylonitrile/butadiene copolymers, and ring-opening polymers of compounds having norbornene rings, have been hydrogenated. Many attempts have been made to improve its heat resistance and weather resistance.

In particular, hydrogenated ring-opening polymers of compounds with norbornene rings have recently been proposed as transparent resins with excellent optical properties and heat resistance, and various (co)polymers and their production methods have been proposed due to their usefulness. ing.

For example, a monodentate selected from norbornene, dicyclopentadiene, tetracyclo[4,4,0,12''', 17°10co3-dodecene and their derivatives can be WS
A polymerization catalyst selected from transition metal compounds such as MoSReXTi or those transition metals, Li, Mg, AI,
Polymers obtained by ring-opening polymerization using a catalyst in combination with an organometallic compound such as Sn are known. and,
It is also well known to hydrogenate these ring-opened polymers in order to improve their thermal stability and weather resistance.

As a method for hydrogenating a (co)polymer having such a carbon-carbon unsaturated bond, ■ combining an organic acid salt such as Ti, Co, or Ni or an acetylacetone salt with an organometallic compound such as Li, Mg, AI, or Sn; In addition, a method of carrying out a hydrogenation reaction in the presence of a so-called Ziegler type homogeneous catalyst, ■
A method in which hydrogenation is carried out in the presence of a supported noble metal catalyst in which noble metals such as palladium, platinum, ruthenium, and rhodium are supported on a carrier such as carbon, alumina, silica/alumina, and diatomaceous earth; A method of carrying out a hydrogenation reaction in the presence of a solid catalyst used, ■R
A method using a noble metal complex catalyst such as h, Ru, etc. is well known.

[Problems to be improved by the invention] As mentioned above, various methods are known for hydrogenating polymers, but none of them is definitive from an industrial standpoint. Currently, various methods are selected depending on the properties of the polymer.

That is, method (2) uses expensive precious metals, but the activity is not so high, and the catalyst is difficult to recover and reuse, resulting in a very high catalyst cost.

Although the catalyst itself is inexpensive in method (2), it has the disadvantage that the hydrogenation rate cannot be increased sufficiently in reactions where hydrogenation is relatively slow, such as the hydrogenation of polymers.

Compared to method (2), which is a heterogeneous reaction, method (2) has the characteristic that the reaction proceeds under mild hydrogenation conditions with a relatively small amount of catalyst, low reaction temperature, and low hydrogen pressure. Because it is sensitive to other polar compounds and easily deactivates, it is difficult to handle as it is necessary to remove the substances that cause these deactivations before the reaction, and to carry out the hydrogenation reaction itself with sufficient exclusion of air and water. In addition to this drawback, if the solvent used is highly polar, the hydrogenation reaction activity decreases, so there are restrictions on the range of solvent selection. For polymers with polar groups, such as ring-opening polymers of norbornene ring compounds with groups, there is only an extremely narrow range of choices depending on the solubility and hydrogenation activity of the polymer.

Method (2) can obtain a high hydrogenation rate even if polar substituents are present in the polymer, and even if water is present in the hydrogenation reaction system, the activity is not substantially affected, and the used catalyst can be recovered. This is preferable because it has the advantage that it can be easily done by simply filtering. In particular, in the case of a catalyst using a support made of silica and an oxide of an element of Group ⅠA of the periodic table, which was proposed by the present inventors as mentioned above, the catalyst has extremely high activity and long life. - This is a preferred method for hydrogenating a (co)polymer having carbon unsaturated bonds. However, even with this method, the supported catalyst becomes fine during the hydrogenation reaction, although it is a small amount, and the catalyst cannot be sufficiently removed from the polymer solution using the catalyst separation and removal methods commonly used in industry, such as sedimentation, centrifugation, and filtration. There was a major industrial defect. this is,
Not only is the catalyst lost, but the catalyst remains in the polymer, which worsens the hue and accelerates the deterioration of the polymer, resulting in a loss of commercial value when used as a transparent resin. For this reason, there has been a strong desire to develop a catalyst that does not become pulverized during the hydrogenation reaction, or to develop a hydrogenation reaction method.

Means for Solving the Problems] Under such circumstances, the inventors of the present invention have conducted extensive studies and have found that
The inventors have discovered that if a hydrogenation reaction using a supported noble metal catalyst is carried out in the presence of a nitrogen-containing compound, it is possible to prevent the catalyst from becoming finer, thereby achieving the present invention.

That is, the present invention provides hydrogenation of a polymer having carbon-carbon unsaturated bonds in the presence of a supported noble metal catalyst in which one or more metals selected from palladium, rhodium, ruthenium, and platinum are supported on a carrier. , provides a method for producing a hydrogenated polymer, characterized in that hydrogenation is carried out in the presence of a nitrogen-containing compound.

The present invention will be explained in detail below.

[Detailed Description of the Invention] The polymer having a carbon-carbon unsaturated bond as used in the present invention is not particularly limited as long as it has a carbon-carbon unsaturated bond in the main chain and side chain, but for example, Polymers containing at least one component of conjugated dienes such as 1,3-butadiene and isoprene (hereinafter referred to as diene polymers), polymers obtained by metathesis polymerization of cyclic olefins (
(hereinafter referred to as metathesis polymers), and polymers with aromatic rings such as polystyrene and polycarbonate (hereinafter referred to as metathesis polymers).
Hereinafter, there are aromatic ring-containing polymers).

In the diene polymer, the conjugated diene monomer is one or more monomers selected from 1゜3-butadiene, isoprene, 1,3-pentadiene, etc., and 10 to 100% by weight of the total monomers, together with conjugated diene monomers. Polymerizable ethylenically unsaturated monomers include unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.), monovinyl aromatic hydrocarbons [e.g., styrene, alkylstyrenes (Om
- and p-methylstyrene, ethylstyrene), α-
methylstyrene, etc.], unsaturated carboxylic acids or their esters (e.g., acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid) One or more monomers selected from methyl, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc.), vinylpyridine, and vinyl esters (e.g., vinyl acetate, etc.), in an amount of 0 to 90% by weight of all monomers. It is a conjugated diene-based polymer composed of

Typical diene polymers include polybutadiene, polyisoprene, butadiene-styrene random and block copolymers, acrylonitrile-butadiene random and alternating copolymers, acrylic ester-butadiene copolymers, and acrylic ester-acrylonitrile. −
Mention may be made of butadiene copolymers.

A metathesis polymer is a polymer obtained by ring-opening polymerization of a cyclic olefin using a metathesis catalyst. Monomers used in the polymerization include, for example, monocyclic olefins such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene, as well as compounds having a norbornene structure represented by the following structural formula (I).

Structural formula (I) (However, A and B are hydrogen or hydrocarbon groups, and may be the same or independent, and in the case of hydrocarbon groups, they may be connected to each other to form a ring) .

X and Y are hydrogen, a hydrocarbon group, and a polar substituent, and n is 0
is an integer from 2 to 2. ) As a specific example of the compound represented by structural formula (I), bicyclo[2,2,1]hept-2
-Eng 2.5 7. t.

Tetracyclo[4,4,0,1,113-dodecene, Hexacyclo[6,6,1°3.6 2.7 9
．． 14 1. 0. 0]-]4-heptadecentric tricyclo[5,2,1,02°6]-8-dese3.6
2.7 N, Pentacyclo[6,5,1,1,009'13]
4-pentadecene, heptacyclo [8°2.9
4,7 11,17 3.87.0.1
．． 1. 1. 012.16 0 ]-]5-icocentric cyclo[4,4°0.
1”6]-3-decene, 5-methoxycarbonylbicyclo[2,2,1]hept-2-ene, 5-methyl-5-
Methoxycarbonylbicyclo[2,2,1]hept-2
-ene, 5-cyanobicyclo[2,2,1]hept-2
-ene, 8-methoxycarbonyltetracyclo[4,4
,0°2.5 7. LO 1,1co-3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo[4,4°2.5 7. t.

O,1,1]-]3-dodecene9-methyl-8-methoxycarbonyltetracyclo[4°4.0.12″5.1
7°103 3-dodecene is mentioned.

These monomers do not necessarily need to be used alone, and two or more compounds can also be copolymerized.

In addition, metathesis polymerization is applied to unsaturated hydrocarbons containing carbon-carbon double bonds in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-nonconjugated diene copolymer, and polynorbornene. Polymerization can also be carried out in the presence of a polymer, in which case the impact resistance of the resin is generally improved. Among these unsaturated hydrocarbon polymers, butadiene-styrene copolymer and isoprene-styrene copolymer can easily be used to obtain copolymers of the present invention with good transparency by changing the ratio of diene and styrene. This is preferable because it allows In this case, the copolymer of diene and styrene may be a random copolymer or a block copolymer. During polymerization in the presence of an unsaturated hydrocarbon polymer, the polymer has the structural formula (I
), preferably 3% to 90%, preferably 3% to the compound represented by
~70%, more preferably 5-40%.

The metathesis polymerization catalyst used in ring-opening polymerization is a platinum group compound such as ruthenium, rhodium, palladium, iridium, or platinum. Also, (a) W, Mo
and (b) at least one compound selected from the compounds of the periodic table IA, IIA, IIB, II[B
, at least one compound of group IVA or IVB elements
The catalyst may be a catalyst consisting of at least one combination selected from those having the element-carbon bond or the element-hydrogen bond, and in this case, an additive (C) that increases the catalytic activity is added. It may be something.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl6, ~1°C15, Re0C
13, but the compounds shown in Japanese Patent Application No. 63-65817 can be used.

Specific examples of component (b) include n-BuLi, (
C2H5) 3A 1, (C2H5)2AICI, Li
H, etc., but the one shown in Japanese Patent Application No. 63-65817 can also be used.

As representative examples of component (C), alcohols, aldehydes, ketones, amines, etc. can be suitably used, but other compounds shown in Japanese Patent Application No. 63-65817 can also be used.

The usage ratio of component (a) and component (b) is 1:1 to 1:50 in terms of metal atomic ratio (a):(b), preferably 1
:2 to 1:30.

The usage ratio of component (c) and component (a) is the molar ratio of (c)
)+ (a) is used in a range of 0.005:1 to 10:1, preferably 0.05:1 to 2:1.

The molecular weight of the polymer can also be adjusted by the polymerization temperature, type of catalyst, and type of solvent, but more preferably ethylene,
It is preferable to make α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene coexist in the reaction system and adjust the amount by changing the amount.

Examples of aromatic ring-containing polymers include polymers containing at least one component of a vinyl aromatic compound such as styrene, aromatic polyesters, aromatic polycarbonates, polyarylates, and specific examples include polystyrene, styrene-methacrylate, etc. acid methyl copolymer, polycarbonate,
Examples include boary arylate.

The polymer used in the present invention has a molecular weight of ηinh and 0.
A range of 2 to 5.0 can be applied, but as the molecular weight increases, it becomes difficult to obtain a high hydrogenation rate.

The catalyst used in the present invention has one or more metals selected from the group consisting of palladium, rhodium, ruthenium, and platinum supported on a carrier.

Among these metals, palladium is optimal in terms of catalytic activity and metal price. In addition, hydrogenation activity is mentioned,
If it is necessary to achieve hydrogenation selectivity, other metal components may be added to these metals, and examples of these added metal components include tellurium, antimony,
Bismuth, lead, etc. The solid support used may be a commonly used support such as activated carbon, silica, alumina, diatomaceous earth, or silica alumina, but from the viewpoint of catalytic activity and life, it is preferable to use a support made of silica and an oxide of Group IIA element of the periodic table. preferable. Here, examples of oxides of Group UA elements of the periodic table include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. Silica and these oxides may be a simple mixture as long as they are intimately mixed, but preferably they are in a so-called composite form. Among these supports, silica magnesia is the most suitable in terms of hydrogenation activity and catalyst life, and as a supported catalyst, a catalyst in which palladium is supported on a silica magnesia support is optimal in terms of catalyst activity, life, and catalyst cost. be.

The loading rate of one or more metals selected from the group consisting of palladium, rhodium, ruthenium and platinum on the carrier also varies depending on whether the catalyst is a powder catalyst for suspended beds or a granular catalyst for fixed beds. However, it is usually 0.01 to 20%, preferably 0.1 to 10%, more preferably 0.01 to 10%.
It is 3-8%.

The catalyst preparation method is not particularly limited, and for example, it can be produced by impregnating a carrier with an aqueous solution or an organic solvent solution of a compound containing one or more metals selected from the group consisting of palladium, rhodium, ruthenium, and platinum. Although the catalyst may be reduced or added to the reaction system in an unreduced state, it is preferable to reduce the catalyst before adding it to the hydrogenation reaction system in terms of catalytic activity. Methods for reducing the catalyst include reducing a solid catalyst with hydrogen gas, and reducing the catalyst suspended in a solvent with hydrogen or formalin, Li
The method of reducing with A I H4 etc. is not particularly limited.

The hydrogenation reaction of the present invention is usually carried out using a suspended bed using a powder catalyst, a moving bed using a granular catalyst, or a fixed bed.The shape and size of the catalyst used vary depending on the method of the hydrogenation reaction. When the hydrogenation reaction is carried out in a suspended bed, the average particle size is usually 1 to 1000μ, preferably 3 to 500μ, more preferably 5 to 100μ.If the particle size is too small, the catalyst and polymer solution Separation becomes difficult, and conversely, if the particle size is too large, the hydrogenation activity decreases.The shape of the catalyst used in the suspended bed is not particularly limited, but a spherical shape is preferable from the viewpoint of wear resistance.Hydrogenation reaction When carried out in a fixed bed, the shape of the catalyst used is not particularly limited as long as it is granular, such as cylindrical or spherical.In this case, the particle size is as follows:
0.3 to 30 mmφ, preferably 0.5 to 20 mmφ,
More preferably, the diameter is 0°7 to 10°. If the particle size is too small, the pressure loss during the hydrogenation reaction will be too large, which is undesirable, and if the particle size is too large, the hydrogenation activity will decrease.

The hydrogenation reaction can be carried out without a solvent if the polymer is liquid or dissolves at a relatively low temperature.
- Boat fishing is carried out by dissolving the polymer in a solvent. Since the catalyst of the present invention has no effect on hydrogenation activity due to the solvent,
Any solvent may be used as long as it dissolves the polymer and is not itself hydrogenated.

When using a solvent, the concentration of the polymer is not particularly limited,
For example, it is 1 to 80%, preferably 5 to 50%, and more preferably 5 to 30%. Economic efficiency is compromised at low concentrations;
If the concentration is too high, the viscosity of the solution increases too much, which not only reduces the reaction rate but also makes it difficult to remove the catalyst.

The amount of catalyst used varies greatly depending on the molecular weight of the polymer, the type of metal component supported on the catalyst, the loading rate, the reaction format, and the desired hydrogenation rate, but in the case of a batch reaction, it is usually 0.1 to 0.1 to the amount of hydrogen per polymer. 60% by weight, preferably 0.3-40% by weight
, more preferably 0.5 to 30% by weight.

The temperature of the hydrogenation reaction is from 0°C to 300°C, preferably 20°C.
℃ to 250℃, more preferably 30℃ to 200℃
It will be held in If the temperature is too low, the hydrogenation reaction rate will not be sufficient, and if the temperature is too high, the polymer will deteriorate, which is not preferable.

The pressure of the hydrogenation reaction is 1 to 200 kg/coy, preferably 2 to 150 kg/cJ, more preferably 5 to 120 kg/coy.
kg/ctB. If the pressure is too low, the hydrogenation reaction rate will not be sufficient; if the pressure is too high, the reaction rate will be high, but the equipment will be expensive and uneconomical.

The time required for the hydrogenation reaction is not necessarily limited as it is related to the concentration of the polymer and the hydrogenation pressure, but it is usually 10 minutes to 10 minutes.
Selected within the range of 0 hours.

In the present invention, the presence of a nitrogen-containing compound during the hydrogenation reaction is essential. In the absence of a nitrogen-containing compound, the catalyst becomes finer due to the hydrogenation reaction, making it economically impossible to completely remove the catalyst from the polymer solution after the reaction.

The nitrogen-containing compounds used in the present invention include aliphatic amines,
Aromatic amines, nitrogen-containing cyclic compounds, amides, carbamic acids, imides, and the like can be used.

Examples of aliphatic amines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, 5ec-butylamine, amylamine, 5ec-amylamine, 5ec-hexylamine, 2-ethylbutylamine, heptylamine, 2-ethylhexylamine. , dimethylamine, diethylamine,
Dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, cyamylamine, dioctylamine, trimethylamine, triethylamine, triisopropylamine, triisopropylamine, tributylamine, triisobutylamine, tri-sec-butylamine, Triamylamine, cyclohexylamine, dicyclohexylamine, ethylenediamine, propylenediamine, diaminobutane, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, NNN'N'-tetramethylethylenediamine, monoethanolamine, jetanolamine, triethanolamine, Ethyl monoethanolamine, n-butyl monoethanolamine,
Examples include dimethylethanolamine, diethylethanolamine, ethylgetanolamine, n-butylgetanolamine, di-n-butylethanolamine, and isopropanolamine.

Aromatic amines include aniline, monomethylaniline, dimethylaniline, diethylaniline, N-mono-n
-butylaniline, N, N-di-n-butylaniline, N
-monoamylaniline, ptert-amylaniline,
Examples include N,N-cyamylaniline, N,N-di-tert-amylaniline, 0-toluidine, diethylbenzylamine, and p-phenylenediamine.

Examples of amides include formamide, N,N-dimethylformamide, acetamide, and the like.

Examples of nitriles include acetonitrile.

The oil-containing nitrogen cyclic compounds include morpholine, ethylmorpholine, phenylmorpholine, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine,
2,6-lutidine, quinoline, isoquinoline, pyrrolidine, pyrrole, pyrrolidine, pyrazole, imidazole, triazole, oxazole, isoxazole, picoline, pyrimidine, indole, etc. can be used.

Among these, aliphatic amines are preferred because they are highly effective in preventing the catalyst from becoming fine, and monoethanolamine, jetanolamine, and triethanolamine are particularly preferred.

The amount of the nitrogen-containing compound used is in a molar ratio of 0.01:1 to 10:1, preferably 0.05:1 to 5:1, more preferably 0.05:1 to 5:1, relative to the amount of catalytically active metal in the catalyst. 0.0
The ratio is 7:1 to 1:1. If the amount of the nitrogen-containing compound used is too small, the catalyst will become fine during the hydrogenation reaction, whereas if it is too large, the catalytic activity will decrease, which is not preferable.

The nitrogen-containing compound may be added to the hydrogenation reaction system separately from the catalyst, or some or all of the nitrogen-containing compound to be added and the hydrogenation catalyst may be mixed in advance in the hydrogenation reaction. May be added to the system.

When a powdered catalyst is used for the hydrogenation reaction in the presence of a nitrogen-containing compound, the catalyst is prevented from becoming fine, so in order to recover and separate the catalyst from the polymer solution after the hydrogenation reaction, This can be easily carried out by appropriately combining filtration, sedimentation, centrifugation, etc., which are usually carried out industrially.

The separated supported catalyst can be used again in the hydrogenation reaction as it is. In addition, known filter aids can also be used for filtration.

In the case of the present invention, catalyst separation is not necessary in the case of the fixed bed reaction since the catalyst is not substantially refined. , filtration, sedimentation, centrifugation, etc. may be carried out in appropriate combination.

To separate and recover the hydrogenated polymer from the reaction solution from which the catalyst has been removed, the method normally used to recover the polymer from the polymer solution can be used as is. A method in which the polymer is precipitated by adding a poor solvent to the polymer solution, a method in which the polymer solution is heated in a container and the solvent is distilled off, and a method in which the solvent is removed using a vented extruder. Depending on the properties of the polymer and solvent, a method including pelletization can be adopted as appropriate.

Depending on the purpose, the hydrogenated polymer of the present invention may contain antioxidants,
Ultraviolet absorbers, lubricants, colorants, and pigments can also be added. Methods for adding antioxidants and the like to the hydrogenated polymer include methods of adding to the polymer solution after hydrogenation, methods of adding at the time of pelletization, etc., and are not particularly limited.

The hydrogenated polymer obtained by the present invention has significantly improved heat resistance, weather resistance, ozone resistance, and cold resistance compared to the polymer before hydrogenation. Furthermore, since there is no coloration due to trace amounts of residual catalyst, it can be used in a wide range of applications. For example, the hydrogenated norbornene resin obtained in the present invention can be used in the production of various molded products as optical materials such as lenses, optical disk substrates, and optical fibers, as well as window glass, automobile glass, films, sheets, and general molding materials. I can do it. Moreover, hydrogenated acrylic ester-butadiene rubber is a high-performance rubber with excellent cold resistance and strength, and can be used under a wider range of conditions than ever before.

4. Example Hereinafter, the present invention will be specifically explained with reference to Examples.

The hydrogenation rate was measured by 60MHz NMR, and δ = 4.5 to 6.
It was calculated from the reduction of the peak in the 0 ppm range due to the hydrogenation reaction. The amount of catalyst metal in the hydrogenated polymer was measured by atomic absorption spectrometry after incinerating the polymer by a conventional method and dissolving it in hydrochloric acid. Further, in the examples, % represents weight % unless otherwise specified.

Reference Example 1 (Production of Metathesis Polymer-1) In a nitrogen atmosphere, a norbornene ring-containing monomer, 8-methyl-8-methoxycarbonyltetracyclo[4°2.5 7. 10 4.0.1. 1] -]3-dodecene 500
And toluene 1? 00011, 83 g of 1-hexene as a molecular weight regulator, and WC16 as a catalyst at a concentration of 0.
．． 8.5 ml of a chlorobenzene solution of 0.05M/, Q and a concentration of paraldehyde of 0.05M/. 1. 4.3 ml of a 1° 2-dichloroethane solution of M/(l) and 11 ml of a toluene solution of diethylaluminium chloride with a concentration of 0.8 M/(l were added and reacted at 60°C for 4 hours. The polymer is precipitated by pouring it into methanol, and is then filtered, washed, and dried to determine its intrinsic viscosity (η
inh) 0.45cl/gc in chloroform, 3
480 g of a polymer (metathesis polymer-1) was obtained at 0°C and at a concentration of 0.5 g/a.

Reference Example 2 (Production of Metathesis Polymer-2) In a nitrogen atmosphere, a norbornene ring-containing monomer Te2.5 7.10 tracyclo[4,4,0,1,1 ]-3 dodecene 350
g and pentacyclo[6,5°3.6 2.7 9
．． 13 1.1. 0. 0]-]4-pentadecene, 2000+r+1 toluene, 7.5ml of 1-hexene as a molecular weight regulator, and T as a catalyst.
i C14 concentration 1.0M/! Q toluene solution 15ml
1 and triethylamine 0. 20 ml of a toluene solution of IJi/, Q and a concentration of triethylaluminum of 1. O
80 ml of a toluene solution of M/(l) was added and reacted at 25°C for 2.5 hours. A polymer was recovered from this polymer solution in the same manner as in Reference Example 1, and the intrinsic viscosity (ηin
h) 0.47 rinses/g (in chloroform, 30°C,
Concentration 0. 5g/dff) of 260g of a polymer (metathesis polymer-2) was obtained.

Reference Example 3 (Preparation of Si02/MgO carrier) While vigorously stirring a 0.2N-sodium silicate aqueous solution to 6N, a 4N-MgC12 aqueous solution 300K was added dropwise. After completion of the dropwise addition, the mixture was aged for 30 minutes while stirring. The resulting precipitate was diluted with dilute aqueous MgCl2 solution (approximately 0.01 mo
l/Ω), washed several times by the declination method, finally washed and filtered with distilled water, dried at 110°C, calcined at 450°C for 2 hours, and sieved to obtain the 5i02 MgO carrier ( Specific surface area = 450rr?/g, average particle size = 10μ)
I got it.

(Preparation of hydrogenation catalyst) Add 120 ml of pure water and 7 ml of 1.36% concentrated hydrochloric acid to 2.5 g of palladium chloride and dissolve by heating. Add pure water to this to make the total volume 1.22. 5i02 prepared earlier as carrier
・MgO2 (specific surface area -450d1g, average particle size = 1
0μ) was placed in an evaporating dish, and while heating in a water bath, the palladium chloride solution prepared earlier was added little by little to the entire amount.

After that, it was heated in a hot water bath for 2 hours, then evaporated to dryness, then calcined under nitrogen at 500℃ for 5 hours, and then reduced under a hydrogen stream at 450℃ for 3 hours to catalyze hydrogenation. was prepared.

Example 1 A polymer solution in which 40 g of the polymer obtained in Reference Example 1 and 0.12 g of triethanolamine were dissolved in 360 g of tetrahydrofuran was charged into a high-pressure autoclave equipped with an electromagnetic induction stirrer, and 4 g of the hydrogenation catalyst prepared in Reference Example 3 was added. was added. After introducing hydrogen into the autoclave, under stirring 1
The temperature was raised to 50°C. The pressure was 35 kg/cd when the temperature reached 150 °C. After maintaining this temperature for 5 hours, the temperature was returned to room temperature, hydrogen was released, and the reaction solution was suction-filtered through 5C paper. The P solution was completely colorless and transparent without any turbidity. A portion of this P solution was taken and added to a large amount of methanol with stirring to precipitate a polymer. After drying the obtained polymer, the hydrogenation rate was measured by NMR.

The peak attributed to olefin completely disappeared due to the hydrogenation reaction, and the hydrogenation rate was 100%. Also, the P obtained earlier
A portion of the liquid was taken, heated to remove the solvent, and after ashing, the amount of palladium was measured by atomic absorption spectrometry. The amount of palladium remaining in the polymer was 80 ppb based on the polymer.

(Repeated hydrogenation reaction) Except for using the hydrogenation catalyst collected on 5CF paper,
The same operation as the first hydrogenation reaction conducted previously was performed. The hydrogenation rate this time was also 100%. Moreover, the amount of palladium contained was also 4Clppb.

Comparative Example 1 The same hydrogenation reaction as in Example 1 was carried out except that triethanolamine was not used. 5
C? Table 1 shows the filterability with paper, the turbidity and coloration of the P liquid, the hydrogenation rate, and the palladium content in the hydrogenated polymer.

Examples 2 to 7 Examples 2 to 7 except that the polymer obtained in Reference Example 1 was used, and the nitrogen-containing compounds shown in Table 1 were used in the amounts shown in Table 1 instead of triethanolamine. A hydrogenated polymer was obtained in the same manner as in Example 1. Table 1 shows the filterability with SCP paper, the turbidity and coloration of the P solution, the hydrogenation rate, and the palladium content in the hydrogenated polymer.

Example 8 An experiment was conducted in the same manner as in Example 1, except that the polymer was changed to Metathesis Polymer 2 obtained in Reference Example 2. 5C? Table 1 shows the filterability through paper, the turbidity and coloring of the P solution, the hydrogenation rate, and the palladium content in the hydrogenated polymer.

Examples 9 to 12 In Example 1, the hydrogenation catalyst was
5% Palladium/Silica Catalyst from Chemcat, 2%
Rhodium/alumina catalyst, 2% Platinum/activated carbon catalyst, 5%
An experiment was conducted in the same manner as in Example 1, except that the ruthenium/activated carbon catalyst was used. Table 1 shows the filtration performance with 50P paper, the turbidity and coloration of the P solution, the hydrogenation rate, and the content of each metal in the hydrogenated polymer.

Comparative Examples 2 to 6 Example 8, except that no nitrogen-containing compound was added
The experiment was conducted in the same manner as in 12.

5C? Table 1 shows the filterability with paper, the turbidity and coloration of the solution, the hydrogenation rate, and the content of each metal in the hydrogenated polymer.

Examples 13 to 17 Methyl methacrylate-styrene copolymer (styrene content -85, hereinafter abbreviated as MS) as the polymer to be hydrogenated
, acrylonitrile-butadiene copolymer (acrylonitrile content -39%, MLl+4.100°c -5
0, hereinafter abbreviated as NBR), methyl acrylate-butadiene copolymer (methyl acrylate content = 57.4%
, MLl+4.100'c=109, hereinafter abbreviated as ABR), butadiene rubber (cis 1.4 content -98%, M
Ll+4.100'C=37, hereinafter abbreviated as BR),
Styrene-butadiene rubber (styrene content = 15%, vinyl content = 49, MLl + 4.100'c'' 54,
Table 1 shows the hydrogenation reaction of styrene-butadiene-styrene block copolymer (styrene content = 40%, vinyl content = 19%, MI = 2, hereinafter abbreviated as SBS). The post-treatment was performed in the same manner as in Example-1. Table 1 shows the transient properties of the SCP paper, the turbidity and coloring of the P solution, the hydrogenation rate, and the content of each metal in the hydrogenated polymer.

Comparative Examples 7 to 9 Example 1 except that no nitrogen-containing compound was added
The experiment was conducted in the same manner as in 3.14.16. 5C
Filtration performance with paper, turbidity and coloring of P solution, hydrogenation rate,
Table 1 shows the content of each metal in the hydrogenated polymer.

Blank space below [Effects of the Invention] Thus, according to the present invention, even when a known noble metal catalyst is used, it is possible to prevent the catalyst from becoming fine just by the presence of a nitrogen-containing compound when carrying out a hydrogenation reaction. Therefore, it is possible to easily produce a polymer that is free from coloration due to residual catalyst.

Claims (1)

[Claims] When hydrogenating a polymer having carbon-carbon unsaturated bonds in the presence of a supported noble metal catalyst in which one or more metals selected from palladium, rhodium, ruthenium, and platinum are supported on a carrier, the nitrogen-containing compound is hydrogenated. A method for producing a hydrogenated polymer, comprising hydrogenation in the presence of hydrogen.