TW499452B - A method of hydrogenating aromatic polymers in the presence of branched hydrocarbons - Google Patents

Abstract

A method of hydrogenating aromatic polymers, optionally in the presence of catalysts, wherein branched hydrocarbons are used as solvents, which branched hydrocarbons possess at most one hydrogen atom at the branching location, a boiling temperature higher than 45 DEG C and an ignition temperature (DIN51794) above 280 DEG C, or a mixture is used of hydrocarbons such as these with solvents which are suitable for hydrogenation reactions.

Description

A7 B7 V. Description of the invention (1) = Invented a method for hydrogenating aromatic polymers, which is characterized by using branched saturated smoke as a solvent, and branched saturated hydrocarbons having at most one hydrogen atom at the branch, boiling The temperature is above 45. 〇And the ignition temperature (_N51794) is still at or below 280 C, or a solvent mixture is used, which includes some hydrocarbons and solvents commonly used in hydrogenation reactions. The invention also relates to polymers made in this way. The halogenation of aromatic polymers is known. DE_AS1 131885 describes the hydrogenation of polystyrene in the presence of catalysts and catalysts. Generally mentioned are aliphatic and cycloaliphatic hydrocarbons, ethers, alcohols and aromatic hydrocarbons as solvents. A mixture of cyclohexane and tetrahydrofuran is preferred. W096 / 34896 (= US_A_5612422) describes a method for hydrogenating aromatic polymers, such as in which the hydrogenation reaction is performed in the presence of a metal coated on a silica carrier as a hydrogenation catalyst, where the silica has a certain pore size The distribution 无 None or% 爿 group smoke is mentioned as a solvent and isoprene (2-methylbutane) is used as a branched saturated hydrocarbon. Diethylene glycol dimethyl ether and tetrahydrofuran are used as ethers. EP-A-322731 describes a manufacturing method mainly for syndurtacdc polymers based on vinylcyclohexane, in which polymers based on styrene are argonized in the presence of hydrogenation catalysts and solvents. Cycloaliphatic and aromatic hydrocarbons are mentioned as solvents. (Please read the notes on the back before filling out this page) ·-| Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7

In addition to pentane, in the foregoing article (please read the precautions on the back before filling this page) at 26 (TC's work on the fire field chopping has a lower or lower than the agent. Engineering chapter side: ,, in the industrial method is Not easy to fool

0MN5i794), because, & have enough people with the same fire temperature Z, six s ^ ^ and hydrogenated polystyrene in the solvent Γ to divide: at temperature T can reach or exceed 24, for example. . . . There are fires and explosions in households; ^ Maintain a sufficient temperature difference 'No 1 ^ Replacing the solvent before the granulation forming step is costly and labor intensive. I == The compound formation step becomes inert and prevents solvent / air contact. ;

The method is expensive and practically impossible in large-scale operations. For example, because the entire device must be shrouded in an inert gas. k In addition to Iso-Institute, printed clothing for the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs from the aforementioned article (WO ·· 6; still in its infancy) The strong Rongzhou has no precautionary measures or other complex and expensive Solvents that could catch fire and pose a significant security threat. However, for example, terracotta is not used as a solvent for polystyrene, so this solvent is not suitable for the lice reaction of this polymer. However, isoprene as a solvent has the disadvantage of boiling at 溶剂 28 ° C ’. First, it makes the solution difficult to handle, and second, the formation step must be -4-

499452 A7 V. Description of the invention (3) The result of cooling results in expensive cooling and condensation devices. The purpose of the present invention is that the solvent used should be dissolved in the polymer starting material, and the product should be dissolved so that the aromatic unit actually completely maintains the temperature difference between the reverse = rr degrees (relative to the photo = 15 /.). A system that can be fed directly to the forming step. == One chlorination reaction with an aromatic polymer = square: r branched smoke, so it can obviously simplify its polymer shape, / The method is characterized by the ability to directly order the hydrogenated polymer solution into the formation step And does not require uncomplicated technical methods to avoid dissolution / airborne contact at the surface at a temperature south of or equal to the ignition temperature. Another advantage of using some special branched hydrocarbons is that the solvent can be separated from the polymer at higher temperatures, which results in lower solvent residues and higher polymer material throughput. The method of printing the Maoyueguan Lili Hydrogenated Aromatic Polymers by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Online Economy There is at most one hydrogen atom, its boiling temperature is higher than 45r and the ignition μ degree (DIN51794) is higher than 280 ° C, or a mixture of hydrocarbons such as these and a solvent suitable for the hydrogenation reaction is used. The reaction is generally 0.01% to 100% relative to the total solvent, preferably 1% to 80%. The best is the branched saturated hydrocarbon volume concentration of 5% -70 ° / 〇. The paper size applies the Chinese National Standard (CNS) A4 specification (21 × x297 mm) A7 B7 V. Description of the invention (4 ) Row. General: Second, the method according to the present invention 3 actually results in complete hydrogen of the aromatic unit. The degree of privacy is > 80%, preferably > 90 ° /. The best is 299%, especially 100%. The degree of hydrogenation can be measured, for example, by R or UV spectroscopy. : The aromatic polymer used as the starting material is selected from, for example, polystyrene, which is substituted on the vinyl or ethyl group, or is selected from the poly-to-Ganzao progenitor with the monomer is selected from the group containing dilute Hydrocarbons, (meth) acrylic acid esters, or mixtures thereof. Other suitable polymers include aromatic polyethers, especially polyphenylene oxides, aromatic polyesters, aromatic polyesters, aromatics. Polyamine, polyphenylene, polyxylene,? Long phenylene phenylene, polyphenylene phenylene, polyphenylene sulfide, polyaryl _ homologous, aromatic polystone wind, aromatic poly _ stone wind and aromatic polyimide 'and mixtures thereof and Copolymers, optionally copolymers with aliphatic compounds. Suitable substituents in the benzene ring include C1_C4 filaments, such as methyl and ethyl, C1f4f ° oxygen, such as methoxy or ethoxy, and aromatic compounds, where the square compounds are substituted by condensation and passed through One smoke atom or two carbon atoms are bonded to the benzene ring, which includes phenyl 'diphenyl, theophyl. Suitable substituents on vinyl include CVC4, such as methyl, ethyl and n- or iso-propyl, especially methyl in the cardiac position. 6-'Paper size applies Chinese National Standards (CNS) ^^ i ^ x 2 公公 (-(Please read the notes on the back before filling this page) J ^ T · Line · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives Preparation 499452 A7 B7 V. Description of the invention (5) Suitable olefin comonomers include butylene, butylene, isoprene, butylene, butadiene, cyclohexadiene, cyclohexene, cyclopentene Diene, orthobornene, which may be substituted as appropriate, dicyclopentadiene, which may be substituted, tetracyclododecene, which may be substituted as appropriate, or dihydrocyclopentadiene Alkenes, which can be substituted as appropriate, C ^ Cs of (meth) acrylic acid, preferably cKC4 alkyl esters, preferably methyl or vinyl esters, CVC8 of vinyl alcohol, preferably Cl_C4 alkyl Base esters, preferably methyl or ethyl esters, vinyl alcohol cvc8, preferably Cl_C4 silk vinegar, preferably vinyl acetate (please read the notes on the back before filling This page) Order _ _ Printed agricultural maleic acid derivatives by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, preferably maleic acid And derivatives of propylene situation, the preferred system acrylonitrile and methacrylonitrile. Aromatic polymer-molecular weight Mw A surface to% _, 00 () ′, generally measured by light scattering, preferably 60, _ to! Gangca, the best is 70,000 to 600,000 '. The polymer has a linear structure, or it can include branches due to common units (if this paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297) (Centimeter) thread_ A7 B7 V. Description of the invention (6) Graft copolymer). In the branch-level, level two, level three: depending on whether the Γ contains a star polymer, or may contain a morphology. Other geometric copolymers of the quaternary / quaternary polymer structure may exist in the form of an irregular polymer. Or, it can be block copolymerized. Block copolymers include diblocks, glycine I copolymers. _ Segments, multi-blocks, and stellate 5 starting materials are generally known (eg W094 / 21694). The second most used solvent is branched hydrocarbon of formula ⑴, whose boiling temperature is higher than valence and the ignition temperature (DIN5H94) is higher than or equal to 28 (rc. R1 RC—R2 R3 (Please read the precautions on the back before filling this page) )

T where

R, R, R3, and R4 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs represent linear or branched Ci-C ^ Q ^ Wenji, and at most one of R1, R2, R3, and R4 can represent hydrogen. The following compounds: 2,2,3-trimethylbutane; 2,2-dimethylbutane; 2,3-dimethylbutane; basic paper size applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (7) Cyclopentane; 2-methylpentane; 3-methylpentane; 3,3-diethylpyrane ; 2,4-dimethylpentane; 2,2-dimethylpentane; 2,3-dimethylpentane; 2,4-dimethyl-3-ethylpentane; 2,2,3 _Tri-methylpentane; 2,3,3-trimethylpentane; 2,2,4-dimethylpyrene (isooctane); 2,2,3,3-tetramethylpyrene ; 2,2,3,4-tetramethylpentane; 2,3,3,4-tetramethylpentane; 2-methylhexane; 3-methylhexane; 2-methyl-4- Ethyl hexane; third butyl cyclohexane; 2-methylheptane; 2,5,5-trimethylheptane; 3,3-difluorenyl-heptane; 2,2,5-tri Methylheptane. The best solvent for hydrogenating polystyrene and its derivatives is methylcyclopentane, which is a good solvent and has a boiling temperature of 72 ° C and The ignition temperature is 315 ° C. The amount of catalyst used is described, for example, in W096 / 34896. V. The amount of catalyst used depends on the method used. This method can be performed continuously, semi-continuously, or in batches. '' In a continuous system, the response time is significantly shorter and is affected by the size of the response. In a continuous process, the operating time of both the fixed catalyst: the flow system and the reactor bottom system is as long as possible, for example, as long as the system contains circulating suspended catalyst. The fixed catalyst may exist in a protruding form. 3 Relative to the total weight of solvent and polymer, the range of polymer concentration — this paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page )

Fifth, the description of the invention (8) is generally from 80 to 1, preferably from 50 to 10, especially from 15 to 15% by weight. The starting materials are hydrogenated according to generally known methods (eg WO94 / 2i694, W096 / 34895, EP_A-322,731). Many known hydrogenation catalysts are used as catalysts. Preferred catalysts are, for example, those cited in W094 / 21694 or WO96 / 34896. As the catalyst, any known catalyst for the nitriding reaction can be used. Suitable catalysts are those with a large surface area (e.g. ⑽6⑽ m2 / g) and a small average pore size (e.g. 20-500 angstroms). Other systems are catalysts with a small surface area (such as 1,000 cubic meters per gram) and a large average pore size. Their pore size distribution is characterized by 98% of the pore volume being defined by pore diameters greater than 4000 angstroms) (for example, 118_eight 5,654 253, still _ Α5? 6125422. ^ Α035076? 706) 〇 # Raney ^ ^ ^ oxygen cut or dioxy cut / oxidized name _, coated on nickel with carbon as a carrier And / or precious metal catalysts such as Pt, Ru, Rh, pd. : Should: Generally, it is carried out between 0 and 50 (rc 'preferably between 20 and 20, and Dou Cun between 60 and 200 ° C. ^ The solvent used in the reaction is described in, For example, the de_lake surface reaction is generally carried out at a pressure of 1 bar to 100 bar, θ ^ ^ bar is preferably 20 to 300 bar, especially 40 to 200 bar pressure. 499452 A7 B7 V. Description of the invention (9 ) Examples Examples 1 and j Flush a 1-liter high-pressure steam cooker with an inert gas. Add polymer solution and catalyst (table). After closing the high-pressure steam cooker, repeatedly apply protective gas, then hydrogen. After releasing the pressure, Set the nitrogen pressure and heat the batch to the relative reaction temperature. After the hydrogen absorption starts, the reaction pressure remains fixed. The reaction time is the time from heating the batch to the completion of the hydrogenation reaction of the polystyrene, or for If the hydrogenation reaction is incomplete, it is the time required until the hydrogen absorption reaches its saturation value. After the reaction is terminated, the polymer solution is filtered. The product is precipitated in methanol, and the dried isolated product has the physical properties listed in the table. (Please read the back first Please fill out this page again.) The printed paper size of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 499452 A7 B7 V. Description of the invention (10) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

< l Long. W neodymium & 〇Ό (N 315 460 off? AJ ^ — 98.4 oo T—H reaction time C minutes) 〇Τ—Η rH o Ό m _ aJ < N 875 (psig) oor—H reaction 'temperature (° C) ο un r—Η o Ό Wall S 冁 side inch in mr—Η 12.53 Solvent (ml) 2300 CYH 200MC P + 100MT BE Polystyrene weight (g) oo (N 100.22) Example number (N '^ < Inch ^ ^ ^ --Pill s Ge 2 According to the present invention β ^ / 众 ％ s-(N (N inch (NI9, v-sn (inch soil guest ^^ / ^^^ «sword ^ 019 £ 1 ^ 2 Two ^. UJ99S οα 6 psqpbDug (rn Mf SJEqsgiMpnq, ϋν Asvpq ”ir« / ^ 00 ° .08v $ lAf; 8SI manufacturing o mechanical age ((N ^ ¾ ^ ¾ ^ ¾ ^ ¾ ^ ¾ (I -12 -(Please read the notes on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 499452 A7 V. Description of the invention (11) The surface catalyst (table) hydrogenates polystyrene dissolved in cyclohexane at 140 (control) Example 1). The ignition temperature of cyclohexane is 260 ° C, which can cause problems when forming industrial-scale products because it is necessary to avoid contact of the solvent / air on hot metal surfaces at temperatures close to the ignition temperature. Compared with Comparative Example 1, the method according to the present invention (Example 2) caused complete hydrogenation, but the ignition temperature of all the solvents used was higher than 310 ° C. (Please read the phonetic on the back? Matters before filling out this page) Order, Printed on line · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 499452 A7 B7 V. Description of the Invention () [^ No Patent Application No. 88104276 ROC Patent Appln. No. 88104276 Supplementary Example + Text-Attached # (一)

Suppjemental Working Exampl in Chinese-Rnd n \ (submitted on December 28, 2001) ^ (Submitted on December 28, 2001), Example 3 will be 6.1 grams of styrene-isoprene-styrene copolymer ( 10% by weight of isoprene, Mw = 97.38 kg / mole, Mw / Mn = 1.607) was dissolved in 481 g of methylcyclopentane, and then placed in 1300 ml of a stirrer and slurry South pressure steamed Yangang Steel. The reactor was closed after adding 0.76 grams of handle / stone dioxide catalyst (0.9% handle / stone oxide, batch number 08078, Engelhard, De Meem, the Netherlands), and the pressure was purged with nitrogen, and finally with hydrogen Pressurize to 90 bar. The temperature of the reactor was then raised to 200 ° C and the pressure was adjusted to 100 bar. The reactor was kept in this condition for 9 hours. After the hydrogenation was completed, the palladium-catalyst was removed from the product solution by filtering with 0.2 µm of polyamine under nitrogen pressure, and white pellets were obtained by precipitation with acetone. The product was carefully dried in a vacuum oven at 80-90 ° C and identified by Ή-NMR and GPC analysis. The results are shown in Table 1. Chromatography was performed using a calibration curve obtained using polystyrene as a standard. 2) The degree of hydrogenation (D.O.H.) was measured from the Ή-NMR spectrum. This paper size applies to ^ _ house standards " 7CNS) A4 size (210 X 297 public Ή ---- see supplement 1 (please read the precautions on the back before filling this page) Order --------- Table 1 · GPC and NMR data of hydrogenated polymers: Examples [kg / mole] MWD [kg / mole] Mw / Mn1} doh2) [%] 3 52.07 79.60 1.529 .90 1) Mw, Mn is a relative molecular weight. It is printed due to gel penetration in THF

Claims (1)

499452 Six, apply for special A8 B8 C8 D8 Patent Application No. 88104276 ROC Patent Appln. No. 88104276 Application for Amendment to the Chinese Text of Mao Cun Fan Chi (Annex 2) Amended Clafe & ki Chiriese J- Enel · ⑴ (Republic of China 9 (Submitted m Chirxes ^-1½ Quartz I 丨 Day: nn flprembe ^ tr (presented), 2001) 1. A method for hydrogenating aromatic polymers, as appropriate, in the presence of a catalyst, where the solvent used is a branched hydrocarbon of formula (I) R1 R4-C-R2 (I) (Please read the notes on the back before filling out this page) 2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R1, R2, R3 and R4 groups represent straight chain or branched CrC10 alkyl and at least one of R1, R2, R3 and R4 may represent hydrogen, or R2 and R3 together with the two carbon atoms connected to form a C3-C1G carbocyclic ring, and its boiling temperature is 45 ° C to 400 ° C and ignition temperature (DIN51794) higher than 280 ° C, or use a mixture of this hydrocarbon with a solvent suitable for hydrogenation reaction. The method according to item 1 of the application, wherein the solvent is at least one selected from the group consisting of: 2,2,3-trimethylbutane; 2,2-dimethylbutane; 2,3-dimethyl Butane; fluorenylcyclopentane; 2-methylpentane; 3-methylpentane; 3,3-diethylpentane; 2,4-difluorenylpentane; 2,2-difluorenyl Pentane; 2,3-dimethylpentane; 2,4-difluorenyl-3-ethylpentane; 2,2,3-tri-methylpentane; 2,3,3-trifluorenyl Pentane; 2,2,4-trifluorenylpentane (isooctane); 2,2,3,3-tetrafluorenyl-14-88078-claim -------- order · --- -----. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4 ^ 452, printed by A8, B8, C8, D8, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, applying for patent coverage. 2,2,3,4-tetramethylpentane; 2,3,3,4-tetramethylpentane; 2-fluorenylhexane; 3-methylhexane; 2-methyl-4-ethyl Hexane; third butyl cyclohexane; 2-methylheptane; 2,5,5-trimethylheptane; 3,3-dimethyl-heptane; 2,2,5-trimethyl Heptane. 3. A method according to item 1 of the scope of patent application, wherein a solvent mixture comprising at least one branched saturated smoke and at least one solvent suitable for a hydrogenation reaction is used. 4. The method according to item 1 of the scope of patent application, wherein the volume concentration of the saturated branched hydrocarbon is 1 to 80%. 5. The method according to item 4 of the scope of patent application, wherein the volume concentration of the saturated branched hydrocarbons is 5 to 70% based on the total amount of the solvent. 6. The method according to item 1 of the scope of patent application, wherein the concentration of the polymer is 80 to 1% by weight based on the total weight of the solvent and the polymer. 7. The method according to item 6 of the application, wherein the concentration of the polymer is 50 to 10% by weight based on the total weight of the solvent and the polymer. 8. The method according to item 7 of the scope of patent application, wherein the concentration of the polymer is 40 to 15% by weight, based on the total weight of the solvent and the polymer. 9. The method according to item 1 of the scope of patent application, wherein the aromatic polymer is selected from the group consisting of the following polymers: Polystyrene, optionally substituted on the benzene ring and / or vinyl group, or a compound selected from ethylene , Propylene, isoprene, isobutylene and butadiene monomers. 10. The method according to item 1 of the scope of patent application, wherein the (weight average) molecular weight of the aromatic polymer is 1,000 to 10,000 () ⑻. -15-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) ^ J -----— Order --------- line · (Please read the precautions on the back first (Fill in this page again) 499452 A8 B8 C8 D8 6. Scope of patent application 11. According to the method in the scope of patent application No. 10, the (weight average) molecular weight of the aromatic polymer is 60,000 to 1,000,000. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -16 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)