TWI302909B - Method for producing a methacryloyl product - Google Patents

Description

Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Printed 1302909 A7 B7 V. INSTRUCTION DESCRIPTION (f) Field of the Invention The present invention relates to a process for producing a methacryioy1 product. BACKGROUND OF THE INVENTION Generally, the production of a methacryloy group-containing product (isobutyl storage group product or composition) is carried out via an initial isobutylene group compound and a functional compound. The reaction is carried out at a reaction temperature of 60 C to 150 ° C; and the reaction efficiency of the isobutylbutene-based product can be improved by setting the reaction temperature between 10 ° C and 18 ° C. However, if the reaction temperature is above 1.00 ° C, the isobutylene group in the compound is susceptible to polymerization; in order to reduce the polymerization of the isobutenyl group, a polymerization inhibitor which does not participate in the formation of the target product is used, such as Hydroquinone. Such a use has been disclosed in Japanese Unexamined Patent Publication No. Hei 2-110116, No. Hei. No. Hei. The polymerization inhibitor remains in the isobutylene based product. Therefore, the isobutylene based product produced by using the polymerization inhibitor has the following problems. For example, if you want to use light radiation or 4ONDA/0111TW, P1P2001129TW 1 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) "" (Please read the back first Note on this page)

Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1302909 A7 B7 V. INSTRUCTIONS (>) Heat, to polymerize or cure isobutylene based products, which takes a long time, and the resulting polymerization or curing is likely to be insufficient . In addition, the presence of a polymerization inhibitor stains the polymerized, cured isobutylene based product. However, if the amount of the polymerization inhibitor is reduced, the polymerization of the isobutenyl group cannot be prevented, and a by-product of polymerization is formed. Therefore, the conventional method does not efficiently produce an isobutylene based product. Disclosure of the Invention An object of the present invention is to provide a process for producing an isobutylene based product with high efficiency. In order to achieve the above object, the present invention provides a process for producing an isobutylene based product. The process comprises the step of reacting an initial isobutenyl compound with a starting functional group, the reaction being carried out at a sufficient elevated temperature which aids in the thermal depolymerization of any polymerized isobutenol group. (thermal depolymerization). The starting isobutylene based compound is preferably selected from the group consisting of methacrylic acid and methacrylate esters having an epoxy group or a hydroxyl group, and the methacrylate is preferably glycidyl. Glycidylmethacrylate, hydroxymethymethacrylate, or hydroxypropyl isobutyrate 4ONDA/0111TW, P1P2001129TW 2 This paper scale applies to China National Standard (CNS) A4 specification (210X297) ))) l·---------φ —------1τ^---^--- (Please read the notes on the back and fill out this page) 1302909 A7 B7 V. Invention Description ($) (hydroxypropylmethacrylate) ° (Please read the note on the back first to fill out this page) In a specific embodiment, the starting isobutylene based compound has an isobutylene group and a different isobutylene group. a first functional group, and the starting functional group has a first functional group; the first functional group and the second functional group are subjected to a reverse reaction step in the reaction step, based on the starting isobutylene And the starting compound based on the total weight of the functional compound, 0.1% by weight or less of the catalyst "and 0.2 wt% or less of the polymerization inhibitor is preferred, and this reaction step is preferably performed within 2 hours to complete. Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative In a specific embodiment, a first starting compound having an isobutylene group and a second starting compound reacted with the first starting compound are placed in a temperature controlled reactor. The reactor is then heated at a predetermined temperature which is sufficient to aid in the thermal depolymerization of any polymerized isobutenol groups which are maintained for a predetermined period of time. At the end, the reactant between the first starting compound and the second starting compound is rapidly cooled. The step of rapidly cooling the reactant preferably comprises the steps of extracting the solution containing the reactant from the reactor and coating the solution into a film shape; and the step may further comprise: extracting the solution containing the reactant from the reactor. 4ONDA/0111TW, which is coated on a cooled plate and then spread into a film shape, P1P2001129TW 3 This paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) 1302909 Δ7 Α7 Β7 V. BRIEF DESCRIPTION OF THE INVENTION (Step), or a step comprising directly dissolving the reactants in a liquid from the reactor. The preferred predetermined temperature is between 185 ° C and 300 ° C, preferably between 195 ° C and 300 ° C, particularly preferably between 205 ° and 300 ° C. The isobutylene based compound preferably comprises an unpolymerized isobutylene group. The first starting compound preferably comprises at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride, an isocyanate, an ester, a hydroxyl group and an amine group; The starting compound preferably contains at least one functional group corresponding to the functional group contained in the first starting compound, and is selected from the group consisting of a carboxyl group, an amine group, an epoxy group, a hydroxyl group, an acid anhydride, and an ester. BEST MODE FOR CARRYING OUT THE INVENTION A specific embodiment of the present invention will now be described in detail. A method for producing an isobutylene based product according to the present invention, characterized in that a compound having an isobutenyl group-containing compound is reacted with a compound having a starting functional group at a sufficiently high temperature, and the high temperature is helpful Thermal depolymerization of any polymerized isobutenol group, so that 4ONDA/0111TW, P1P2001129TW 4 paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ' ' ~~ (please read first Note on the back and fill out this page)

1T Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1302909 Δ7 Α7 Β7 V. Invention Description (5Ί The polymerization reaction of the sulfonium group did not occur. (Please read the back note first and then fill in this page) The isobutylene based compound, or the first starting compound, is a compound comprising at least one isobutylene group. Preferred starting isobutyl storage base compounds have functional groups other than the isobutylene group, and the functional group can start with The functional group compound is highly reacted. The starting methacrylic acid group compound preferably has a monofunctional group, the choice of which is dependent on the reactivity corresponding to the starting functional group compound, and the equivalent of the isobutylene based product. A functional group such as an epoxy group, a carboxyl group, an acid anhydride, an isocyanate, an ester, a trans group and an amine group, and among them, an epoxy group, a carboxyl group and a hydroxyl group are preferred. It is relatively reactive with the functional group of the starting functional group compound. The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, prints the starting functional group. a compound, or a second starting compound, is a compound having a functional group reactive with the starting isobutyl fluorenyl compound. The functional group in the starting functional group will follow the functional group of the starting isobutylene based compound. However, if the functional group contained in the starting isobutylene based compound is an epoxy group, the functional group in the starting functional group compound is preferably a carboxyl group or an amine group, if the starting isobutylene based compound is The functional group contained in the starting functional group is preferably an epoxy group, a hydroxyl group or an amine group. The functional group contained in the starting isobutylene based compound is isocyanate. The functional group in the starting functional group compound is preferably a hydroxyl group or an amine group. If the functional group contained in the starting isobutylene based compound is an ester, the functional group in the starting functional group compound is preferably a hydroxyl group. If 4ONDA/0111TW, P1P2001129TW 5 This paper size is applicable to China National Standard (CNS) Α4 specification (210Χ297 mm) 1302909 A7 A7 B7 V. Invention description (G) (Please read the note on the back first and then fill in The functional group contained in the starting isobutylene based compound is a hydroxyl group, and the functional group in the starting functional group compound is preferably an amine group, a carboxyl group or an ester. Among the above functional groups, an epoxy group is preferred. The base, hydroxyl group, carboxyl group and acid anhydride are relatively reactive with the functional group of the starting isobutylene based compound. The reaction between the starting isobutylene based compound and the starting functional group is carried out by the following reaction. Either one of: an addition reaction between an epoxy group and a thiol group, a dehydrating ester condensation between a thiol group and a thiol group, and an addition between an acid anhydride and a hydroxyl group. The reaction, the transesterification between the ester and the hydroxyl group, the isocyanate and the trans group, or the addition reaction between the isocyanate and the amine group. An isobutenyl group product different from the starting isobutylene group-based compound is obtained by a reaction between the starting isobutylene based compound and the starting functional group compound. In particular, the compounds stated below can be used as starting isobutylene based compounds: alkylmethacrylate esters, such as methyl isobutyl phthalate (methyl) Methacrylate) or butyl methacrylate; glycidyl isobutyrate; isobutyrate; methacryloxyethylisocyanate; methacrylate with cyclohexeneoxide structure; hydroxyethylmethacrylate; Hydroxypropylmethacrylate and the like. 4ONDA/0111TW, P1P2001129TW 6 This paper size is applicable to China National Standard (CNS) A4 specification (21〇Χ297 mm) 1302909 A7 B7 V. Inventive Note (Γ)) In the starting functional group compound, a relatively low molecular weight compound And a relatively high molecular weight polymer comprising at least one of the above functional groups. Specifically, a hydroxyl group-containing compound such as cyclohexanol, aliphatic alcohol, HALS (hindered amine light stabilizer) ethanol can be used, and examples thereof are disclosed in the following chemical formulas. 1 medium, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylol propane, ditrimethylol propane, isovaerythritol (ditrimethylol propane) Pentaerythritol), dipentaerythritol, bisphenol A, bisphenol F, hydrogenated biguanide A, alkylene oxide modified hydrogenated biguanide A, Novolak-type phenol Phenolic resin, hydroxyethyl methacrylate, trihydroxyethyl isocyanurate, fluoroethanol and hydrazine-containing ethanol; hydroxyl-containing compounds such as oleic acid, stearic acid, versatic Acid, benzoic acid, cinnamic acid, salicylic acid; anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride Itaconic anhydride, and these types of hydrolyzed dicarboxylic acids; phenyl glycidyl ether; epoxy-containing compounds, such as epoxy having a bisphenol A backbone a base resin, an epoxy resin having a phenolic Novolak skeleton, and triglycidyl isocyanurate; an isocyanate-containing compound such as Trilene diisocyanate or diisocyanate Isophorone diisocyanate and aliphatic isocyanate; function 4ONDA/0111TW, P1P2001129TW 7 This paper scale applies to Chinese National Standard (CNS) A4 specification (210'〆297 mm) (Please read the back Note: Please fill out this page again. τ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1302909 . A7 _____ B7 _ V. Invention Description (8) Functional Wnyi p〇iymers; Polyester; Polyamine Polyurethane; polyamine; polythioimide and polyether. It is to be noted that HALS ethanol is a generic term for a hindered amine structure and functions as a light stabilizer.

OH

(Please read the precautions on the back and fill out this page.) Functional vinyl polymers are prepared by polymerization of (a) functional vinyl groups or (b) functional vinyl groups. The copolymerization of the unit cell and other different vinyl units. In the case of carrying out (b), the mechanical properties, weather resistance and heat resistance of the cured product of the isobutylbutadiene-based product, the polymer, and the isocyanium-based product may vary depending on the type and proportion of the mixture. And adjust. The compounds described below can be used as starting units: Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printing acrylic acid, methacrylic acid, glycidylmethacrylate, hydroxyethyl acrylate , hydroxyethyl methacrylate, propylpropyl propyl; (hydroxypropyl acrylate, hydroxypropyl 4ONDA/0111TW, P1P2001129TW 8 paper size applicable to China Standard (CNS) A4 size (210X297 mm) 1302909 A7 B7 V. Illustrative (q) methacrylate), methacryloyl oxyethylisocyanate, maleic anhydride, Citric acid diacyl acid, alkyl acrylate ester and alkylmethacrylate ester can be used as functional vinyl units. Benzene storage, acrylonitrile And methacrylonitrile can be used as other vinyl units. · . . in the reaction state, alkyl Ethyl esters and methyl methacrylates, such as butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and Methyl propyl acrylate (11^11)^11^1^(^)^16) can be used as a functional vinyl polymer or as another unit. The functional vinyl unit is subjected to polymerization by a known method such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization, whether continuous or batch operation. When both the isobutylene based compound and the starting functional group compound are unpolymerized compounds, the unpolymerized reactive isobutenyl group product of the present invention is obtained, because the above starting compound has a relatively high reaction. Sexuality gives a good yield of isobutylene based products. 4ONDA/0111TW, P1P2001129TW 9 This paper size is applicable to China National Standard (CNS) A4 specification (21〇'〆297mm) (Please read the note on the back and fill out this page) System 1302909 7. A7 B7 V. INSTRUCTIONS (\0) (Please read the notes on the back and then fill out this page.) In the method of the present invention, the reaction temperature of the starting isobutyl storage sulfhydryl compound and the starting functional compound Within the range, polymerization of the isobutyl storage group may not occur because the reaction proceeds at a sufficiently high temperature, which contributes to the thermal depolymerization of the polymerized isobutenyl group. Although the temperature exceeds 10 ° C, thermal polymerization of the isobutylene group may occur, but the increase of the reaction temperature also promotes the thermal depolymerization of the polymerized isobutenyl group; that is, the heat of the isobutylene group The thermal depolymerization of the polymerization and the polymerized isobutenyl group exhibits an equilibrium state at a specific reaction temperature, and it is as if the thermal polymerization of the isobutylene group is not carried out. The preferred temperature range is between 185 ° C and 300 ° C, preferably between 195 ° C and 300 ° C, particularly preferably between 205 ° C and 300 ° C. In addition to the temperature and the type of the starting isobutylene compound, the most desirable temperature variation is within the above temperature range in accordance with the reaction state. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, according to the method of the present invention, an unpolymerized isobutylene fluorenyl product can be efficiently produced without using any polymerization inhibitor. This isobutenyl group product was hardly dyed because no polymerization inhibitor was used. Further, when used as a component of light irradiation or thermal polymerization, the isobutylene based product has good polymerizability because most of the isobutylene group in this product is not polymerized. When the reaction temperature is lower than 185 ° C, an undesired polymerization of an isobutylene group (side reaction) is apparent, thereby forming a by-product of polymerization. In this case 4ONDA/0111TW, P1P2001129TW 10 This paper scale applies to China National Standard (CNS) A4 specification (210'〆297 mm) 1302909 A7 B7 V. Inventive Note (丨I), because polymerization inhibition is required The agent reduces the purity and gelation of the target compound. If a large amount of polymerization inhibitor ' is used to prevent gelation of the target compound', a dyed target compound is obtained. Further, a large amount of polymerization inhibitor deteriorates the polymerizability and curability of the target compound. Further, a reaction temperature lower than 185 ° C is not recommended because it takes a long time to form a product; and a reaction temperature exceeding 300 ° C is also not recommended because the target compound is decomposed. According to the method of the present invention, the target compound or the isobutylene group-derived product can be efficiently produced without using a polymerization inhibitor because the starting isobutylene-based compound and the starting functional group compound are efficiently reacted. However, in order to prevent polymerization of the isobutenyl group as much as possible and the production of by-products, a certain amount of the polymerization inhibitor can be used without losing the properties (polymerizability and curability) of the target compound. In other words, in the reaction state in which the isobutylene group-forming product is produced, the isobutylene group only slightly undergoes polymerization. In this case, a deterioration of purity due to by-products is prevented by using a trace amount of a polymerization inhibitor, and a high-purity isobutylene group-based product is obtained. The amount of the polymerization inhibitor added is preferably 0.02% by weight or less, preferably 0.01% by weight or less, and particularly preferably 0.003% by weight or less based on the total weight of the starting isobutylene based compound and the starting functional group compound. The polymerization inhibitor at the above concentration will reduce the degree of dyeing of the reactants' and has good radical polymerizability. 4ONDA/011 ixw? P1P2001129TW 11 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill out this page). The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints 1302909 A7 B7 V. INSTRUCTIONS (\1) Hydroquinone, phenothiazine and hydroquinone monomethylether are inhibited by polymerization (please read the precautions on the back) This page is an example of the use of the agent. Further, according to the method of the present invention, the reaction between the starting isobutyl sulfonium-based compound and the starting functional group compound does not require a catalyst, however, it is still possible to use a catalyst at the time of the reaction to shorten the reaction time. The amount of the catalyst added is preferably 0.1% by weight or less, preferably 0.05% by weight or less, and particularly preferably 0.01% by weight or less, based on the total weight of the starting isobutylene based compound and the starting functional group compound; The catalyst will render the purity and properties of the target compound impure and toxic. Any known catalyst, such as an esterification catalyst and a transesterification catalyst, can be used as the catalyst herein. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. Further, when the reaction between the starting isobutylene based compound and the starting functional compound proceeds, the solvent demand is optional. A preferred solvent is a solvent which is difficult to react with the starting isobutylene based compound and the starting functional group compound. A reactive solvent can be used to meet the intended use of the target compound. For example, methylethylketone (MEK), ethoxyethyl propionate (EEP), and toluene can be used. In the process of the present invention, the reaction between the starting isobutylene based compound and the starting functional compound is preferably cooled rapidly, because the initial standard 4ONDA/0111TW, P1P2001129TW 12 paper scale applies to the Chinese national standard (CNS) A4 size (210X297 mm) 1302909 A7 B7 V. Description of invention (\3) (Please read the note on the back and fill out this page) The isobutylene group in the compound can reduce side reactions by rapid cooling. , to obtain a target compound of high purity. This rapid cooling can be carried out by extracting the reaction liquid from the reactor and coating the solution into a film shape; extracting the reaction liquid from the reactor and applying it to a cooling plate such as a conveyor. A method of forming a film shape; or a method of directly dissolving a reactant, such as a solvent or a monomer, in a liquid from a reactor. The cooling temperature is preferably below 120 ° C, l 〇 (TC below is preferred, 8 (TC below is best, below 60 ° C is particularly good. Although there is no lower limit on the cooling temperature, jingle low) At 〇 ° C, the cooling cost will increase. The film thickness is preferably below 30 mm, preferably below 20 legs, preferably below 10 mm, especially below 5 legs. When the film thickness is less than 0.5 mm, Productivity may be reduced. Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Further, in the method of the present invention, a third component can be added to the reaction between the starting isobutylene based compound and the starting functional group compound, Compliance with the intended use of the target reaction product. A second functional compound can be added as a third component, and the second functional group compound does not react with the starting isobutylbutenyl compound, but will start with Reaction of a functional group compound. A compound containing an acryloyl group, such as a propylene acid, a hydroxyethy acrylate, or an alkyl acrylate, can be regarded as a second functional group. In the method of the present invention, the reaction time between the starting isobutylene based compound and the starting functional group compound is about 2 hours. This is less than Xi 4ONDA/0111TW, P1P2001129TW 13 This paper scale is applicable to China. National Standard (CNS) A4 Specification (2丨〇><297 mm) 1302909 B7 V. Time taken by the method of the invention (\this). Specifically, the reaction time between the epoxy group and the carboxyl group And the reaction time between the hydroxyl group and the acid anhydride is about 30 minutes. In the conventional method, the reaction temperature is set as low as possible to lower the polymerization of the isobutylene group, and further use a catalyst in the reaction. Conventional techniques use polymerization inhibitors to enhance the efficiency of the reaction and to reduce the polymerization of the isobutenyl group. In contrast, in the process of the invention, the starting isobutylene based compound and the starting functional group are used. The reaction between the compounds can be carried out at a sufficiently high temperature which contributes to the thermal depolymerization of any polymerized isobutenyl group, making the isobutylene group The polymerization reaction does not substantially occur. Therefore, the isobutylene group-forming product can be produced without using a catalyst and a polymerization inhibitor. The isobutylene group in the isobutylene group is mostly unpolymerized, and The isobutenyl group-forming product has relatively high polymerizability and curability. Further, the time required for the reaction is short because the reaction temperature is higher than the conventional method. In other words, the isobutylene group-based product can be efficiently produced, and It is not necessary to use any catalyst or polymerization inhibitor (even if it is, it is very minute), and it is also possible to prevent the isobutenyl group-forming product from being dyed. Therefore, problems occurring in the prior art can be reduced in accordance with the present invention. 4ONDA/0111TW, P1P2001129TW 14 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) I-------Φ! (Please read the notes on the back and fill out this page), 11 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1302909 A7 A 7 B7 V. INSTRUCTIONS (\ ί) EXAMPLES The foregoing specific embodiments of the present invention will be further disclosed in detail in the following examples. Example 1: A stainless steel tubular reactor was charged with methacrylic acid i.osg' as a starting isobutylene based compound and cyclohexanol as a functional compound. 92 g. The solution was heated to 23 ° C by means of an oil bath (〇ul abth). The cyclohexylmethacrylate was obtained by dehydration esterification reaction between methacrylic acid and cyclohexanol for 37 minutes. According to gas chromatography (GC), the reaction rate of methyl cyclohexyl acrylate was 18.9%, and the yield was 0.38 g. Then, according to gel permeation chromatography (GPC), almost no undesired polymer component was found in the product containing methyl cyclohexyl acrylate. Further, it was visually inspected that the reaction product was not dyed. Example 2: The starting isobutylene based compound was changed to methyl methacrylate 1.00 g, and the starting functional group compound was changed to cyclohexanol 1.0 g. A titanate catalyst (0.012 g) was placed in the reactor. Except as mentioned above, in the same manner as in Example 1, and by transesterification, cyclohexylmethacrylate was obtained. 4ONDA/0111TW, P1P2001129TW 15 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back and fill out this page). The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints 1302909 A7 B7 5. Description of the invention (\G) (Please read the notes on the back and fill in the page.) According to gas chromatography (GC), the reaction rate of methyl cyclohexyl acrylate is 5%, and the yield is 〇. 〇 83g. Then, according to gel permeation chromatography (GPC), almost no undesired polymer component was found in the product. Further, it was visually inspected that the reaction product was not dyed. Example 3: The starting isobutylene based compound was changed to 60 g of methacrylate, and the starting functional compound was changed to 0.60 g of HALS ethanol. Further, 0.60 g of ethoxypropionic acid (EEP) was placed in the reactor as a solvent. The reaction temperature was 240 °C. In the same manner as in Example 1, except for the above. A methacrylate of HALS ethanol (hereinafter referred to as HALS methacrylate) is obtained by a dehydration esterification reaction. At the above reaction times of 15 and 30 minutes, the reaction solution was sampled for analysis of the content of HALS methacrylate.

According to gas chromatography (GC), it was confirmed that the HALS Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed methacrylate had a reaction rate of 13.4% (yield of 135 g) at a reaction time of 15 minutes, and the reaction time. The reaction rate for 30 minutes was 20.8% (yield was 〇.21 g). Next, according to gel permeation chromatography (GPC), there was almost no component of the polymer in the reactant solution at a reaction time of 15 minutes and 30 minutes. Further, it was visually inspected that the reactant solution and HALS methacrylate were dyed. 4ONDA/0111TW, P1P2001129TW 16 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1302909 A7 B7 V. Invention description (丨η) Example 4: (Please read the note on the back and fill out this page) The solvent in Example 3 was changed to methyl ethyl ketone (MEK) 0.60 g. The other components were the same as in Example 3, and the process was the same as in Example 1 except that the reaction temperature was changed to 240 °C. HALS methacrylate is obtained by dehydration esterification. At the reaction time of 15 and 30 minutes, the reaction solution was sampled and analyzed. According to gas chromatography (GC), it was confirmed that the reaction rate of HALS methacrylate at a reaction time of 15 minutes was 14.6% (yield was 148 g), and the reaction rate at the reaction time of 30 minutes was 24.8%. It is 0.25g). Next, according to gel permeation chromatography (GPC), there was almost no component of the polymer in the reaction solution at a reaction time of 15 minutes and 30 minutes. Further, it was visually inspected that the reaction liquid and HALS methacrylate were dyed. Example 5: Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed using glycidyl methacrylate as the starting isobutylene based compound, and by polymerization of 10% by weight of styrene, 80% by weight of butyl acrylate and 10 parts by weight of acrylic acid A mixed unit body of % is obtained, and the obtained carboxyl group-containing polymer is regarded as a starting functional group compound. The polymer had a weight average molecular weight (Mw) of 3,060, a number average molecular weight (?η) of 1,920, a Mw/Mn ratio of 1.6, and an acid value of 1.32 meq/g. 4ONDA/0111TW, P1P2001129TW 17 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1302909 Δ7 Α7 Β7 V. Invention description (\$) (Please read the note on the back and fill in this page) A 140 ml capacity pressure reactor of an electric heater, a stirrer and an extraction valve was charged with 10 g of a carboxyl group-containing polymer and heated to 230 °C. 33.8 g of a 50% toluene solution of glycidyl methacrylate was added, and a high pressure pump was supplied to a pressure-resistant reactor for liquid chromatography in 10 minutes. Once the temperature in the pressure-resistant reactor was as low as 210 ° C, it was then raised to 218 ° C. The reaction solution was extracted through an extraction valve within 10 minutes after the completion of the supply of glycidyl methacrylate, and the reaction solution was rapidly cooled. The pressure in the pressure-resistant reactor in the reaction was 0.8 Mpa. The acid value of the reaction liquid was measured, and the reaction liquid was also analyzed by using GPC and 1H-NMR. As a result, the acid value was 〇.57 meq/g (in terms of a polymer), and it was confirmed that the epoxy group in the glycidyl methacrylate reacted with the carboxyl group in the carboxyl group-containing polymer. The obtained reaction product had a weight average molecular weight (Mw) of 4,520, a number average molecular weight (??) of 2,200, and a Mw/Mn ratio of 2.05. The reaction product was visually inspected to be dyed. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives. The residual amount of glycidyl methacrylate in the reaction solution was quantitatively analyzed by GC. The residual amount was below the lower limit of detection. Quantitative analysis of the isobutylene sulfhydryl group by h-NMR confirmed that the amount of the isobutylene group introduced into the carboxyl group-containing polymer was equivalent to 98.4% of the glycidyl methacrylate. Example 6: Using methacrylic acid as the starting isobutylene based compound, and using glycidyl and epoxy groups as starting functional compounds, this polymerization 4ONDA/0111TW, P1P2001129TW 18 This paper scale applies to Chinese national standards ( CNS ) A4 specification (210X297 public Chu 1 1302909 A7 B7 V. Invention description ((Please read the back note first and then fill out this page) System from 2-ethylhexyl acrylate 80% by weight, and glycidyl methacrylate 20 The weight unit has a weight average molecular weight (Mw) of 3,670, a number average molecular weight of 2,130, a Mw/Mn ratio of 1.72, and an epoxy price of 1.41 meq/g. In a 140 ml capacity pressure reactor equipped with an electric heater, a stirrer and an extraction valve, 1 g of an epoxy group-containing polymer was charged and heated to 230 ° C. A 10% toluene solution of methacrylic acid was 18.4 g. The high-pressure pump was sent to the pressure-resistant reactor for liquid chromatography within 10 minutes. Once the temperature in the pressure-resistant reactor was as low as 217 ° C, it was then raised to 230 ° C. 10 minutes after the completion of the supply of methacrylic acid. Nei Jing The extraction valve extracts the reaction liquid and rapidly cools the reaction liquid. The pressure in the pressure-resistant reactor in the reaction is M5 Mpa. The epoch price of the reaction liquid is printed by the Ministry of Economic Intelligence's employee consumption cooperative. The reaction liquid was analyzed by GPC and 1H-NMR. The result showed that the epoxy value was 616.616 meq/g (in terms of polymer conversion). If all the carboxyl groups in the methacrylic acid were assumed to have reacted with the epoxy group of the epoxy group-containing polymer. The epoxy value of the reactant was 〇.646 meq/g. Therefore, it was confirmed that the functional group contained in the component disappeared by a nearly stoichiometric reaction. The weight average molecular weight (Mw) of the obtained reaction product was 4,760, the number average molecular weight (Μη) is 2,450, and the Mw/Mn ratio is 1.95, and the reaction product is not dyed by visual inspection. The residual amount of methacrylic acid in the reaction liquid is quantitatively analyzed by GC, and the residual amount is low. At the lower limit of detection. Use b-NMR to quantify isobutylene oxime. 4ONDA/0111TW, P1P2001129TW 19 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1302909 A7 B7 V. Invention Ming (丄0) analysis 'confirmed that the amount of isobutylene group introduced into the epoxy group-containing polymer is equivalent to 100% of the amount of methacrylic acid charged. (Please read the back note first and then fill out this page) Example 7: Using methacrylic acid As the starting isobutylene based compound, and the glycidyl group-containing and epoxy group-containing polymer are used as the starting functional group compound, this polymerization system is composed of cyclohexyl acrylate 90% by weight, and glycidyl isobutyric acid. A mixed unit body having a composition of 10% by weight of an ester is obtained by polymerization. The epoxy polymer had a weight average molecular weight (Mw) of 3,670, a number average molecular weight of 2,130, a Mw/Mn ratio of 1.72, and an epoxy value of 0.638 meq/g. In a 140 ml capacity pressure reactor having an electric heater, a stirrer, and an extraction valve, 100 g of an epoxy group-containing polymer and 50 g of toluene were charged, and heated to 190 °C. 35.4 g of a 50% toluene solution of methacrylic acid was sent to a pressure-resistant reactor for liquid chromatography in 12 minutes using a high pressure pump. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives. The reaction solution was extracted via an extraction valve at 0, 10, and 20 minutes after the completion of the supply of the acid. From the GC analysis of the reaction solution, the residual amount of methacrylic acid was measured, and the reaction rate was calculated. The results showed that the reaction rate of methacrylic acid after 78 minutes was 86%, 86% after 10 minutes, and 92% after 20 minutes. Further, it was visually inspected that the reaction product was not dyed. The Hazen unit color number of the reaction product was measured in accordance with JIS K0071 "Test Method for Color of Chemical Product", and its color number was 20. The Hazen unit of the reaction product is determined by the color of the sample solution and the standard 4ONDA/0111TW, P1P2001129TW. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297^PCT) 1302909 A7 B7 V. Description of the invention (>1 (Please read the notes on the back and fill out this page) Visually compare colorimetric solutions. This standard colorimetric solution was prepared by dissolving potassium hexachloro-platiate and cobalt(II) chloride hexahydrate in hydrochloric acid and diluting it. Example 8: The same procedure as in Example 7 except that the reaction temperature was changed to 210 °C. In Example 8, the reaction rate of methacrylic acid after 90 minutes was 90%, 97% after 10 minutes, and 100% after 20 minutes. The reaction product was not visually inspected and stained. The color number of the reaction product was 20. Example 9: The same procedure as in Example 7 except that the reaction temperature was changed to 230 °C. Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative Printed In Example 9, the reaction rate of methacrylic acid after 88 minutes was 88%, 93% after 10 minutes, and 94% after 20 minutes. The reaction product was not visually inspected and stained. The color number of the reaction product was 20. Example 10: In a 140ml capacity pressure stainless steel reactor with electric heater, mixer and extraction valve, 20g of MEK is installed and heated by electric heater to 235 4ONDA/0111TW, P1P2001129TW 21 The paper size is applicable to China National Standard ( CNS ) A4 size (210X297 mm) 1302909 A7 B7 V. Description of invention ((Please read the note on the back and fill out this page) °C. Then add 10% methacrylate containing i.51g, shrinking water for 10 minutes. A mixture of 24.9 g of glyceryl methacrylate and 20 g of MEK was introduced into the reactor. After the entire mixture was added, an additional reaction was carried out for 20 minutes to complete the reaction. During the reaction, the pressure in the reactor was 2 MPa. After the reaction was completed, the reaction was completed. The liquid was extracted from the extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction liquid were carried out. As a result of GCP analysis, almost no formation of a polymer component was observed. The reaction rates of methacrylic acid and glycidyl methacrylate were each 97.1% and 98.9%, and more than 90% of the loaded isobutylene group remained unreacted. Isobutyl fluorenyl group was carried out by using data from a GCP ultraviolet detector. Example 11: Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative printed in a 14〇ml capacity pressure stainless steel reactor with electric heater, mixer and extraction valve, containing dissolved MEK 20g and succinic anhydride 16.5g The electric heater was heated to 235 ° C. Then, for 10 minutes, a mixture containing 23.5 g of glycidyl methacrylate and 20 g of MEK was added to the reactor with a pump. After adding the entire mixture, an additional reaction was carried out for 2 minutes. The reaction was completed. During the reaction, the pressure in the reactor was 2 MPa. After the reaction was completed, the reaction solution was extracted through an extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction solution were carried out between glycidyl methacrylate and succinic anhydride. Get 24g of anti-4ONDA/0111TW, P1P2001129TW 22 This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 1302909 B7 V. Description of invention (Work 3) Reagents. Succinic anhydride and glycidyl methacrylate The reaction rates were 61.3% and 57.4%, respectively, and more than 90% of the loaded isobutylene groups remained unreacted (please read the back of the back sheet and fill out this page) Example 12: In a 140 ml capacity pressure stainless steel reactor equipped with an electric heater, a stirrer and an extraction valve, 20 g of MEK was charged and heated to 235 ° C with an electric heater. Then, for 1 minute, the Versatic was added with a pump. A glycidyl ester of acid (manufactured by Yuka Shell Epoxy Co., Ltd., product name: Cardura E10), a mixture of 29.7 g, 10.3 g of methacrylic acid and 20 g of MEK was introduced into the reactor. After the entire mixture was added, an additional reaction was carried out for 20 minutes, and the reaction was completed. During the reaction, the pressure inside the reactor was 2 MPa. After the reaction is completed, the reaction solution is extracted from the extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction solution were carried out. 39 g of the reactant was obtained between Cardura E10 and methacrylic acid. The reaction rates of Cardura E10 and methacrylic acid were 98.7% and 95.8%, respectively, and about 100% of the isobutylene group charged remained unreacted. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Staff Consumer Cooperatives Example 13: In a 140 ml capacity pressure stainless steel reactor equipped with an electric heater, a stirrer and an extraction valve, 20 g of MEK was charged and heated to 235 ° C with an electric heater. Then, for the next 10 minutes, 26.5 g of oleic acid (manufactured by Nippon Oil & Fats Co., Ltd.), 13.5 g of glycidyl isobutyl acrylate, and 4ONDA/0111 TW of MEK 20 g were added to the pump. P1P2001129TW 23 This paper scale applies to the Chinese National Standard (CNS) A4. Specifications (210X297 mm) 1302909 A7 B7 __ V. Description of the invention (> today) (Please read the notes on the back and fill out this page) Mix the mixture into the reactor. After the entire mixture was added, an additional reaction was carried out for 20 minutes, and the reaction was completed. During the reaction, the pressure inside the reactor was 2 MPa. After the reaction is completed, the reaction solution is extracted from the extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction solution were carried out. 36.8 g of a reactant was obtained between oleic acid and glycidyl methacrylate. The reaction rates of oleic acid and glycidyl methacrylate were 90% and 96%, respectively, and about 97% of the charged isobutylene group remained unreacted. Example 14: In a 140 ml capacity pressure stainless steel reactor equipped with an electric heater, a stirrer and an extraction valve, 20 g of dissolved MEK was charged and heated to 235 ° C with an electric heater. Then, for 10 minutes, a mixture of 24.1 g of hydroxyethyl acrylate, 15.9 g of methacrylic acid and 20 g of MEK was added to the reactor with a pump. After the entire mixture was added, an additional reaction was carried out for 20 minutes, and the reaction was completed. During the reaction, the pressure inside the reactor was 2 MPa. After the reaction is completed, the reaction solution is extracted from the extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction solution were carried out. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, 15.0 g of reactant was obtained between methyl hydroxyethyl methacrylate and methacrylic acid. The reaction rates of methyl hydroxyethyl methacrylate and methacrylic acid were 39.4% and 35.2%, respectively, and about 90% or more of the charged isobutylene group remained unreacted.

4ONDA/0111TW, P1P2001129TW This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1302909 B7 V. Invention Description (>5) Example 15: (Please read the back note and then fill out this page) A 140 ml capacity pressure stainless steel reactor equipped with an electric heater, a stirrer and an extraction valve was charged with MEK 2 〇g dissolved in an electric heater to 235 ° C. Then, a mixture of 33.2 g of PEG400 (polyethylene glycol (average molecular weight: 400)), 7.56 g of methacrylic acid and 20 g of MEK was added to the reactor through a pump for 1 minute. After the entire mixture was added, an additional reaction was carried out for 20 minutes, and the reaction was completed. During the reaction, the pressure inside the reactor was 2 MPa. After the reaction was completed, the reaction solution was extracted from the extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction solution were carried out. 6.0 g of reactant was obtained between PEG 400 and methacrylic acid. The reaction rates of PEG400 and methacrylic acid were 15.0% and 16.6%, respectively, and about 90% of the loaded isobutylene groups remained unreacted. Example 16: The Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs printed in a 140 ml capacity rust-resistant steel reactor equipped with an electric heater, a stirrer and an extraction valve, containing dissolved MEK 20 g and succinic anhydride 24.3 g, heated by an electric heater to 235t. Then, for 10 minutes, a mixture of 32.4 g of hydroxyethyl methacrylate and 3.3 g of MEK was added to the reactor with a pump. After the entire mixture was added, an additional reaction was carried out for 20 minutes, and the reaction was completed. During the reaction, the pressure in the reactor was 2 MPa. After the reaction was completed, the reaction liquid was extracted through an extraction valve and rapidly cooled. GC analysis and GPC analysis of the reaction solution were performed.

4ONDA/0111TW, P1P2001129TW This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 25 1302909 A7 A 7 B7 V. Description of invention (work u) 52g between hydroxyethyl methacrylate and succinic anhydride Reactant. The reaction rates of hydroxyethyl methacrylate and succinic anhydride were 95.8% and 89.0%, respectively, and about 90% or more of the charged isobutylene group remained unreacted. Comparative Example 1 The same operation as in Example 7 was carried out except that the reaction temperature was changed to 180 ° C, and the reaction time of the sampling was changed to 20 minutes, 60 minutes, and 390 minutes after the completion of the supply of the raw materials. The reaction rate of methacrylic acid was 69% in 20 minutes, 84% in 60 minutes, and 96% in 390 minutes. The reaction was dyed in pale yellow with a color number of 200. Comparative Example 2: The same operation as in Example 1 is carried out except that the reaction temperature is changed to 170 °C. Printed by the Ministry of Economic Affairs' Intellectual Property Bureau employee consumption cooperative (please read the note on the back and fill out this page). The reaction time for 20 minutes is methacrylate and glycidyl methacrylate, and the reaction rates are 85% and 87% respectively. According to the analysis of GCP, the reactant contains a polymer component. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to efficiently and efficiently produce an isobutylene-based compound 4ONDA/0111TW, P1P2001129TW 26 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1302909 B7 V. Description of the invention (: ι /]), this compound is colorless and highly polymerizable. By using an isobutylene based product, a colorless and easily curable component or polymer can be produced. (Please read the following notes on the back page and then fill out this page.) Although the present invention has been shown and described with respect to the specific embodiments thereof, it should be understood by those skilled in the art that any modifications or changes may be made without departing from the spirit of the invention. The scope of the present invention is defined by the scope of the appended claims. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. 4ONDA/0111TW, P1P2001129TW 27 The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Claims (1)

13 Six application patent scope 1. Bamboo year and month sub-cultivation (bundle) original ©i- Case No.: 90104410 Modified on August 14, 1997 - Replacement page A method for producing an isobutylene-based product, the method comprising an initial a reaction step between an isobutyl storage sulfhydryl compound and an initial functionalized group, the reaction being carried out at a predetermined high temperature between 185 t and 300 Torr, which contributes to any polymerized isobutylene group. The thermal depolymerization of the group makes the polymerization of isobutyl, - , . Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. 2 · Method for manufacturing isobutenyl-based products as described in the new scope _1: characterized by at least one enthalpy of iso-terenol-based compounds From the group consisting of epoxy group or methacrylic acid and methacrylate esters. ..... _, + .... . 3. The method for producing an isobutylene based product according to claim 2, characterized in that at least one methacrylate is selected from the group consisting of glycidylmethacrylate, a group consisting of hydroxymethymethacrylate and hydroxypropylmethacrylate. 4. The method for producing an isobutylene based product according to claim 1, wherein the starting isobutylene based compound has an isobutylene group and a first functional group different from the isobutylene group ( First functional group), and the starting functional group compound has a second functional group; the first functional group and the second functional group are in the reaction step. ί (Please read the back side of the precautions and then f page) The scale applies to China National Standard (CMS) A4 specification (210 X 297 public) 8888 ABCD 1302909 VI. Patent application case number: 90110410 The correction-replacement page will be reacted on August 14, 1997. , : (Please read the precautions on the back page again) 5. The method for producing isobutylene based products as described in the first paragraph of the patent application is based on starting isobutylene based compounds and Initial functionalization... The total amount of children used in the anti-eagle step, wherein the catalyst is 0.1 wt. · · · · · · % by volume, and the polymerization inhibitor is 0.2 wt. .%the following. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The oxime-based product of the method is unpolymerized - . ^ ^ (unpolymerized) compound. .... ·*-. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : · T. A first starting compound having an isobutylene group, 'and a second starting compound reacted with the first starting compound are placed in a temperature-controlled reactor; Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative The reactor is heated to a predetermined temperature between 185 t and 300 ° C which contributes to the thermal depolymerization of any polymerized isobutenyl groups such that the polymerization of the isobutenyl groups is substantially absent Occurs;: the predetermined temperature is maintained for a predetermined period of time; and the reactant between the first starting compound and the second starting compound is rapidly cooled. 8. For the method described in claim 7, wherein the rapid cooling of 29 paper scales applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A8 B8 C8 D8 1302909 VI. Application for patents No.: 90104410 Revision of August 14, 1997 - Replacement page - I (please read the back note on this page) The procedure of the reactants involves extracting the solution containing the reactant from the reactor and applying the solution. The method of coating the shape of the film. 9. The method of claim 7, wherein the rapid cooling.. . . . . . . . . . . The solution containing the reactants from the reactor is ... placed on a colled plate, and the solution is spread into a ::, · 'film shape step. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. The method of claim 7, wherein the step of rapidly cooling the reactants comprises dissolving the reactants directly in the liquid from the reactor. .. · .. Steps of the body. :: • · · · · · · · · 11. The method described in claim 7, wherein the predetermined temperature is between 195 ° C and 300 ° C. The method of claim 7, wherein the predetermined temperature is between 205 ° C and 300 ° C. The Ministry of Economic Affairs, the Intellectual Property Office, the employee consumption cooperative, and the method of claim 7, wherein the method of claim 7 A starting compound comprises at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride, an isocyanate, an ester, a trans group and an amine group. The method according to item 13, wherein the second initialization 30 paper scale is applicable to the Chinese national standard XCNS) A4 specification (210 X 297 mm) 88008 ABaD 1302909 VI. Application for patents: No. 90110410 August 1997 The 14th modification-replacement pager comprises at least one functional group corresponding to a functional group implicated by the first starting compound, selected from the group consisting of a carboxyl group, an amine group, an epoxy group, a hydroxyl group, an acid anhydride, and an ester. Construction • ' · · . . . ' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 ... a first having an isobutylene group and a first functional group, and also having a reaction with the first functional group: v.......... • The second initiation of the second energy base; the compounds are placed in a temperature controlled reactor; the reactor is heated to between 185 ° C and 300 ° C, . . . . . . . . . . . . . . . . . The sufficient high temperature contributes to the thermal depolymerization of any polymerized isobutenyl group, such that the polymerization of the isobutenyl group does not substantially occur; the predetermined temperature And maintaining for a predetermined period of time; and extracting from the reactor and rapidly cooling the reactant between the first starting compound and the second starting compound. 16. The method of claim 15, wherein the predetermined time is within 2 hours. 17. The method of claim 16, wherein the step of rapidly cooling comprises the step of coating the reaction solution into a film shape. 1 8. The method of claim 16, wherein the rapid cooling 31 paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) i IIII ! 1---- - I · m I (Society & MIS? Note on the back of this page). Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1302909 VI. Patent application scope A8 B8 C8 D8 Case number: 90110410 Amendment on August 14, 1997 The step of replacing the page, comprising the step of placing the reaction liquid on a cooling plate and coating the shape of a thin film. The method of claim 16, wherein the step of rapidly cooling, It contains the steps of directly dissolving the reactants in the liquid. Please read the precautions on this page and then t] m Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives print 32 This paper scale applies the Chinese National Standard (CMS) A4 specifications ( 210 X 297 mm)