TW201402802A - A method is provided for preparing hydrogenated C5 aliphatic petroleum resins by adopting C5 aliphatic petroleum resins as feed and was prepared by - Google Patents
A method is provided for preparing hydrogenated C5 aliphatic petroleum resins by adopting C5 aliphatic petroleum resins as feed and was prepared by Download PDFInfo
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本發明提供一種加氫之脂肪族五碳系列石油樹脂及其加氫方法，尤指一種製程簡單且用於脂肪族五碳系列石油樹脂之脂肪族五碳系列石油樹脂之加氫方法。 The invention provides a hydrogenated aliphatic five-carbon series petroleum resin and a hydrogenation method thereof, in particular to a hydrogenation method of an aliphatic five-carbon series petroleum resin which is simple in process and is used for an aliphatic five-carbon series petroleum resin.
石油樹脂產品依其特殊的耐水性，耐酸和良好的黏合性，可用於添加於中或低級油漆、油墨或橡膠製品。而高級的石油樹脂產品主要是石油樹脂加氫飽和之產品，因其具有耐候性佳、熱穩定佳和顏色淺的優點，可添加於高級產品的膠黏劑、路標塗料、高級油漆、油墨或橡膠製品等，藉以用於表面塗覆。 Petroleum resin products can be used for medium or low grade paints, inks or rubber products due to their special water resistance, acid resistance and good adhesion. The advanced petroleum resin products are mainly petroleum resin hydrogenated products, which have the advantages of good weather resistance, good heat stability and light color. They can be added to advanced products of adhesives, road marking paints, advanced paints, inks or Rubber products, etc., for surface coating.
一般石油樹脂依原料和特性可分成不同種類，其中有五碳系列石油樹脂、九碳系列石油樹脂以及五碳系列和九碳系列共聚樹脂、雙環戊二烯樹脂和氫化石油樹脂等。五碳系列石油樹脂是以石油裂解的C5餾分，如異戊二烯、環戊二烯、1-戊烯等聚合而得，而九碳系列石油樹脂是以石油裂解的C9餾分，如茚、甲基苯乙烯、二乙烯苯等聚合而得。 Generally, petroleum resins can be classified into different types according to raw materials and characteristics, among which are five-carbon series petroleum resins, nine-carbon series petroleum resins, five-carbon series and nine-carbon series copolymer resins, dicyclopentadiene resins and hydrogenated petroleum resins. The five-carbon series petroleum resin is obtained by polymerizing a C 5 fraction of petroleum cracking, such as isoprene, cyclopentadiene, 1-pentene, etc., and the nine-carbon series petroleum resin is a C 9 fraction of petroleum cracking, such as It is obtained by polymerization of hydrazine, methyl styrene, divinylbenzene and the like.
近年來九碳系列石油樹脂以及五碳系列(尤指環戊二烯系化合物)及九碳系列共聚樹脂的加氫研究甚多，例如：TW第I237033號發明專利案揭示一種以茚和乙烯基甲苯形成的九碳系列石油樹脂之加氫方法，而TW第200406428號發明公開案亦揭示一種以環戊二烯系化合物和乙烯芳香族系化合物為主的五碳系列及九碳系列共聚樹脂之加氫方法，其係使用鈀和鉑為特定比例之雙金屬觸媒，進而維持 觸媒之壽命。而TW第I237033號發明專利案揭示一種由共軛二烯和乙烯基芳香族單體合成的改質氫化共聚物，該共聚物的重量平均分子量為10萬到100萬，該共聚物係用於建築材料、防震以及隔音材料或電線被覆材料等，因該共聚物的重量平均分子量遠大於一般石油樹脂之重量平均分子量，無法用於摻混於油漆或熱熔膠中。 In recent years, there have been many studies on hydrogenation of nine-carbon series petroleum resins and five-carbon series (especially cyclopentadiene-based compounds) and nine-carbon series copolymer resins. For example, TW No. I237033 discloses a kind of ruthenium and vinyl toluene. The hydrogenation method of the nine-carbon series petroleum resin formed, and the invention of TW No. 200406428 discloses a five-carbon series and a nine-carbon series copolymer resin mainly composed of a cyclopentadiene compound and a vinyl aromatic compound. Hydrogen method, which uses palladium and platinum as a specific ratio of bimetallic catalyst to maintain The life of the catalyst. And TW No. I237033 discloses a modified hydrogenated copolymer synthesized from a conjugated diene and a vinyl aromatic monomer, the copolymer having a weight average molecular weight of 100,000 to 1,000,000, and the copolymer is used for Building materials, shock-proof and sound-insulating materials or wire coating materials, etc., because the weight average molecular weight of the copolymer is much larger than the weight average molecular weight of the general petroleum resin, and cannot be used for blending in paint or hot melt adhesive.
復又TW第200404822號發明公開案係揭示一種石油樹脂之加氫方法，其目的係為了防止係為觸媒的金屬因中毒而失去活性，故使用了兩段式的氫化程序將石油樹脂氫化，並於兩段式之氫化程序中各使用不同的觸媒，前段之氫化程序係使用鈀系觸媒，後段之氫化程序係使用鎳系觸媒，藉以進行加氫和脫硫的反應，惟其兩段式之氫化程序以及於各氫化程序中需使用不同之觸媒，實為一繁雜之程序，進而降低其產業利用性。 The invention of the TW200404822 discloses a method for hydrogenating a petroleum resin, which aims to prevent the metal which is a catalyst from being inactivated due to poisoning, so a two-stage hydrogenation procedure is used to hydrogenate the petroleum resin. In the two-stage hydrogenation process, different catalysts are used. The hydrogenation process in the previous stage uses a palladium catalyst, and the hydrogenation process in the latter stage uses a nickel-based catalyst to carry out hydrogenation and desulfurization reactions. The hydrogenation process of the segment type and the use of different catalysts in each hydrogenation process are a complicated procedure, thereby reducing the industrial applicability.
惟上述之現有技術多為對九碳系列石油樹脂以及五碳系列(尤指環戊二烯系化合物)及九碳系列共聚樹脂之加氫方法之研究，甚少有對五碳系列石油樹脂之加氫方法之研究。此外，所述之現有技術提供之加氫方式係為兩段式之氫化程序以及需使用不同之觸媒或是使用雙金屬觸媒，在程序上實為一繁雜之過程，且無法降低成本，進而降低其產業利用性。 However, the above-mentioned prior art is mostly a study on the hydrogenation method of a nine-carbon series petroleum resin and a five-carbon series (especially a cyclopentadiene-based compound) and a nine-carbon series copolymer resin, and few of the five-carbon series petroleum resins are added. Research on hydrogen methods. In addition, the hydrogenation method provided by the prior art is a two-stage hydrogenation process and requires the use of different catalysts or the use of a bimetallic catalyst, which is a complicated process in the process and cannot reduce the cost. Thereby reducing its industrial utilization.
為了提供一種製程簡單且成本大幅降低之五碳系列石油樹脂之加氫方法，本發明提供脂肪族五碳系列石油樹脂之加氫方法，其中係將一脂肪族五碳系列石油樹脂作為進 料並以一段式之加氫流程氫化之，獲得加氫之脂肪族五碳系列石油樹脂，且該一段式之加氫流程係使用單一觸媒，該一段式之加氫流程係指該脂肪族五碳系列石油樹脂以及該單一觸媒以氫氣於一反應器內進行反應，其中該脂肪族五碳系列石油樹脂係由兩個以上之烯類化合物聚合而成，該烯類化合物係選自下列所構成的群組：長鏈且碳數為4至8之間之脂肪族單烯烴以及長鏈且碳數為4至8之間之脂肪族雙烯烴。 In order to provide a hydrogenation method for a five-carbon series petroleum resin which is simple in process and greatly reduced in cost, the present invention provides a method for hydrogenating an aliphatic five-carbon series petroleum resin, wherein an aliphatic five-carbon series petroleum resin is used as a And hydrogenating in a one-stage hydrogenation process to obtain a hydrogenated aliphatic five-carbon series petroleum resin, and the one-stage hydrogenation process uses a single catalyst, and the one-stage hydrogenation process refers to the aliphatic The five-carbon series petroleum resin and the single catalyst are reacted by hydrogen in a reactor, wherein the aliphatic five-carbon series petroleum resin is formed by polymerizing two or more kinds of the olefinic compounds, and the olefinic compound is selected from the following The group formed is an aliphatic monoolefin having a long chain and a carbon number of 4 to 8 and an aliphatic diolefin having a long chain and a carbon number of 4 to 8.
依據本發明，本發明所述之脂肪族五碳系列石油樹脂之數目平均分子量係介於，但不限於：800至1500之間。 According to the present invention, the number average molecular weight of the aliphatic five-carbon series petroleum resin of the present invention is, but not limited to, between 800 and 1,500.
依據本發明，本發明所述之聚合，其方式係例如，但不限於：使用的原料主要是來自石油腦經高溫裂解後的副產品，該副產品中含有不飽和化合物，該不飽和化合物係為長鏈且碳數為4至8之間之脂肪族單烯烴以及長鏈且碳數為4至8之間之脂肪族雙烯烴。這些不飽和化合物藉由弗里德爾-克拉夫茨(Friedel-Crafts)觸媒例如氯化鋁或三氟化硼等反應聚合，或以加熱方式聚合，取得脂肪族石油樹脂或脂肪族與芳香族共聚合之石油樹脂。聚合過程中所使用的溶劑係包括但不限於：苯、甲苯、二甲苯、環己烷、二甲基環己烷或乙基環己烷，更佳的，該溶劑係為二甲苯；聚合過程中，溶劑以原料單體(即，前述之不飽和化合物)為基礎，較佳的，係介於10至60 wt%之間，更佳的，係介於20至50 wt%之間；聚合的溫度係介於100至350℃之間，更佳的，係介於220至300℃之間；聚合壓力係介於0兆帕(Mpa)至3 Mpa之間，更佳的，係介於0 Mpa至2 Mpa之 間，由前述聚合條件聚合之石油樹脂係含有不飽和鍵。 According to the present invention, the polymerization according to the present invention is, for example, but not limited to, the raw material used is mainly a by-product from the pyrolysis of petroleum brain, and the by-product contains an unsaturated compound, and the unsaturated compound is long. An aliphatic monoolefin having a carbon number of 4 to 8 and an aliphatic diolefin having a long chain and a carbon number of 4 to 8. These unsaturated compounds are polymerized by Friedel-Crafts catalyst such as aluminum chloride or boron trifluoride, or polymerized by heating to obtain aliphatic petroleum resins or aliphatic and aromatic Copolymerized petroleum resin. The solvent used in the polymerization process includes, but is not limited to, benzene, toluene, xylene, cyclohexane, dimethylcyclohexane or ethylcyclohexane, and more preferably, the solvent is xylene; polymerization process Wherein the solvent is based on the starting monomer (i.e., the aforementioned unsaturated compound), preferably between 10 and 60 wt%, more preferably between 20 and 50 wt%; The temperature is between 100 and 350 ° C, more preferably between 220 and 300 ° C; the polymerization pressure is between 0 MPa (Mpa) and 3 Mpa, more preferably, the system is between 0 Mpa to 2 Mpa The petroleum resin polymerized by the aforementioned polymerization conditions contains an unsaturated bond.
依據本發明，本發明所述之長鏈且碳數為4至8之間之脂肪族單烯烴係包括直鏈且碳數為4至8之間之脂肪族單烯烴以及支鏈且碳數為4至8之間之脂肪族單烯烴。 According to the present invention, the aliphatic monoolefin having a long chain and having a carbon number of 4 to 8 according to the present invention comprises an aliphatic monoolefin having a linear chain and a carbon number of 4 to 8 and a branched chain and having a carbon number of An aliphatic monoolefin of between 4 and 8.
依據本發明，本發明所述之長鏈且碳數為4至8之間之脂肪族單烯烴係包括，但不限於：丁烯、戊烯、異戊烯、己烯或庚烯。 According to the present invention, the aliphatic monoolefins having a long chain and having a carbon number of 4 to 8 according to the present invention include, but are not limited to, butene, pentene, isopentene, hexene or heptene.
依據本發明，本發明所述之長鏈且碳數為4至8之間之脂肪族雙烯烴係包括直鏈且碳數為4至8之間之脂肪族雙烯烴以及支鏈且碳數為4至8之間之脂肪族雙烯烴。 According to the present invention, the aliphatic diolefin having a long chain and having a carbon number of 4 to 8 according to the present invention comprises an aliphatic diolefin having a linear chain and a carbon number of 4 to 8 and a branched chain having a carbon number of An aliphatic diolefin between 4 and 8.
依據本發明，本發明所述之長鏈且碳數為4至8之間之脂肪族雙烯烴係包括，但不限於：丁二烯、戊二烯、異戊二烯或甲基戊二烯。 According to the present invention, the aliphatic diolefins having a long chain and having a carbon number of 4 to 8 according to the present invention include, but are not limited to, butadiene, pentadiene, isoprene or methylpentadiene. .
較佳的，其中該單一觸媒係為貴金屬觸媒。 Preferably, the single catalyst is a precious metal catalyst.
依據本發明，本發明所述之貴金屬觸媒係包括，但不限於：鈀觸媒或鉑觸媒。 According to the present invention, the noble metal catalyst of the present invention includes, but is not limited to, a palladium catalyst or a platinum catalyst.
較佳的，其中該單一觸媒係為鎳觸媒。 Preferably, the single catalyst is a nickel catalyst.
較佳的，其中該一段式之加氫流程係為連續式。 Preferably, the one-stage hydrogenation process is continuous.
依據本發明，本發明所述之連續式加氫係指該進料以及該氫氣持續進入反應器進行反應並持續獲得加氫之脂肪族五碳系列石油樹脂。 According to the present invention, the continuous hydrogenation according to the present invention refers to the feed and the aliphatic five-carbon series petroleum resin which continuously enters the reactor for reaction and continuously obtains hydrogenation.
較佳的，其中該一段式之加氫流程係為批次式。 Preferably, the one-stage hydrogenation process is batch type.
依據本發明，本發明所述之批次式係指該進料以及該氫氣一起加入反應器進行反應，此時不再加入進料，但可補充氫氣，待反應完成後，一次獲得加氫之脂肪族五碳系 列石油樹脂。 According to the present invention, the batch type according to the present invention means that the feed and the hydrogen are fed into the reactor for reaction. At this time, the feed is not added, but the hydrogen can be supplemented. After the reaction is completed, the hydrogenation is obtained once. Aliphatic five carbon system Column petroleum resin.
較佳的，其中該將一脂肪族五碳系列石油樹脂以一段式之加氫流程氫化之更包括先使用飽和烴之碳氫溶劑溶解該脂肪族五碳系列石油樹脂，得到一脂肪族五碳系列石油樹脂溶液藉以作為進料，再以一段式之加氫流程氫化之。 Preferably, the hydrogenation of an aliphatic five-carbon series petroleum resin in a one-stage hydrogenation process further comprises first dissolving the aliphatic five-carbon series petroleum resin by using a hydrocarbon solvent of a saturated hydrocarbon to obtain an aliphatic five carbon. The series of petroleum resin solutions are used as feeds and then hydrogenated in a one-stage hydrogenation process.
依據本發明，本發明所述之飽和烴之碳氫溶劑係包括，但不限於：正庚烷溶劑或環己烷系溶劑。 According to the present invention, the hydrocarbon solvent of the saturated hydrocarbon according to the present invention includes, but is not limited to, an n-heptane solvent or a cyclohexane solvent.
較佳的，其中該脂肪族五碳系列石油樹脂係為該脂肪族五碳系列石油樹脂溶液的10重量百分比(wt%)至50wt%。 Preferably, the aliphatic five-carbon series petroleum resin is 10% by weight (wt%) to 50% by weight of the aliphatic five-carbon series petroleum resin solution.
較佳的，其中該一段式之加氫流程中的加氫壓力係介於4 MPa至10.0 MPa。 Preferably, the hydrogenation pressure in the one-stage hydrogenation process is between 4 MPa and 10.0 MPa.
較佳的，其中該一段式之加氫流程中的反應溫度為150℃至320℃。 Preferably, the reaction temperature in the one-stage hydrogenation process is from 150 ° C to 320 ° C.
較佳的，其中該一段式之加氫流程中的氫氣和進料的體積比為200至1600。 Preferably, the volume ratio of hydrogen to feed in the one-stage hydrogenation process is from 200 to 1600.
較佳的，其中該一段式之加氫流程中的反應液體空間流速為0.1至10每小時(hr-1)。 Preferably, the flow rate of the reaction liquid in the one-stage hydrogenation process is from 0.1 to 10 hours per hour (hr -1 ).
本發明亦提供一種加氫之脂肪族五碳系列石油樹脂，其係由前述之脂肪族五碳系列石油樹脂之加氫方法所製得，該加氫之脂肪族五碳系列石油樹脂由凝膠滲透色譜法(GPC)所測得之數目平均分子量係介於240至8000之間。 The invention also provides a hydrogenated aliphatic five-carbon series petroleum resin obtained by the hydrogenation method of the foregoing aliphatic five-carbon series petroleum resin, the hydrogenated aliphatic five-carbon series petroleum resin by gel The number average molecular weight measured by permeation chromatography (GPC) is between 240 and 8000.
本發明的優點在於，利用一段式之加氫流程以及僅使用單一觸媒之方式，氫化一脂肪族五碳系列石油樹脂，可得到良好的飽和率，且相較於兩段式之氫化程序以及於各氫化程 序中需使用不同之觸媒，本發明之製程簡單且成本大幅降低，進而增加其產業利用性。 The invention has the advantages that hydrogenation of an aliphatic five-carbon series petroleum resin by using a one-stage hydrogenation process and using only a single catalyst can obtain a good saturation rate compared to the two-stage hydrogenation process and For each hydrogenation process Different catalysts need to be used in the sequence, and the process of the invention is simple and the cost is greatly reduced, thereby increasing the industrial utilization.
此外，本發明利用該烯類化合物係限定於長鏈且碳數為4至8之間之脂肪族烯烴類的設計，由於並未使用任何芳香族系化合物，使本發明之加氫之脂肪族五碳系列石油樹脂，由於其含有的不飽和鍵比率低，故可增加石油樹脂的耐候性、熱穩定性以及降低色度，且由於其數目平均分子量係介於240至8000之間，故可用於摻混色度較低的油漆、熱熔膠或黏著劑中，藉以用於表面塗覆。 Further, the present invention utilizes a design in which the olefinic compound is limited to an aliphatic olefin having a long chain and a carbon number of 4 to 8, and the hydrogenated aliphatic group of the present invention is used since no aromatic compound is used. The five-carbon series petroleum resin can increase the weather resistance, thermal stability and chromaticity of the petroleum resin because of its low unsaturated bond ratio, and since the number average molecular weight is between 240 and 8000, it is available. It is used for surface coating in paints, hot melt adhesives or adhesives with low blending.
為能詳細了解本發明的技術特徵與實用功效，並可依照說明書的內容來實施，請參閱較佳實施例，以闡述本發明為達目的所使用的技術手段。 In order to understand the technical features and practical effects of the present invention in detail, and in accordance with the description of the present invention, reference should be made to the preferred embodiments.
本發明中之實驗備製流程中所述及各樣品之來源以及成分比例敘述如下： The source and composition ratios of the samples described in the experimental preparation process of the present invention are as follows:
一滴流式的固定床反應器：Xytel公司製，型號：316不銹鋼(美國)。 One-drop fixed bed reactor: manufactured by Xytel, model: 316 stainless steel (USA).
甲基環己烷：純度：99.9%，TEDIA公司產製(美國)。 Methylcyclohexane: Purity: 99.9%, manufactured by TEDIA (USA).
脂肪族五碳系列石油樹脂：購自中德石油樹脂有限公司市售產品，型號：FR(中國大陸濮陽市)，產品的原料是由四碳和五碳之脂肪族單烯烴以及四碳和五碳之脂肪族雙烯烴聚合而成，聚合後之數目平均分子量為1254。 Aliphatic five-carbon series petroleum resin: purchased from Sino-German Petroleum Resin Co., Ltd., the model: FR (Fuyang City, China), the raw materials of the product are four carbon and five carbon aliphatic monoolefins and four carbon and five The carbon aliphatic diolefin is polymerized, and the number average molecular weight after polymerization is 1,254.
矽藻土：表面積為256平方公尺/克(m2/g)，孔洞體積為0.31每毫升/克(mL/g)。 Diatomaceous earth: The surface area is 256 m ^ 2 /g (m 2 /g), and the pore volume is 0.31 per ml / g (mL / g).
脂肪族五碳系列石油樹脂與加氫之脂肪族五碳系列石 油樹脂的分析及檢測： Aliphatic five-carbon series petroleum resin and hydrogenated aliphatic five-carbon series stone Analysis and testing of oleoresin:
色澤辨識：脂肪族五碳系列石油樹脂之顏色目視為棕黃色，加氫之脂肪族五碳系列石油樹脂之顏色為水白透明。 Color identification: The color of the aliphatic five-carbon series petroleum resin is regarded as brownish yellow, and the color of the hydrogenated aliphatic five-carbon series petroleum resin is water white and transparent.
飽和程度：根據ASTM D5776滴定方法，溴指數表示樣品不飽和鍵含量，因此，溴指數的大小表示加氫石油樹脂的飽和程度。一般未加氫石油樹脂的溴指數為10,000毫克溴/100克(mgBr/100g)以上，加氫石油樹脂的溴指數為1,000 mgBr/100g以下。 Degree of saturation: According to the ASTM D5776 titration method, the bromine index indicates the content of the unsaturated bond of the sample, and therefore, the magnitude of the bromine index indicates the degree of saturation of the hydrogenated petroleum resin. The bromine index of the generally unhydrogenated petroleum resin is 10,000 mg bromine/100 g (mgBr/100 g) or more, and the hydrogenated petroleum resin has a bromine index of 1,000 mgBr/100 g or less.
飽和率(%)：100×(脂肪族五碳系列石油樹脂的溴指數一加氫之脂肪族五碳系列石油樹脂石油樹脂的溴指數)/脂肪族五碳系列石油樹脂的溴指數。 Saturation rate (%): 100 × (bromine index of aliphatic five-carbon series petroleum resin, bromine index of hydrogenated aliphatic five-carbon series petroleum resin petroleum resin) / bromine index of aliphatic five-carbon series petroleum resin.
分子量：由凝膠滲透色譜法(GPC)測得分子量。 Molecular weight: The molecular weight was determined by gel permeation chromatography (GPC).
本發明所述之一段式之加氫流程係如下：先準備一脂肪族五碳系列石油樹脂，其溴指數為13467 mgBr/100g且其顏色係為棕黃色，以甲基環己烷溶解該脂肪族五碳系列石油樹脂，得到一脂肪族五碳系列石油樹脂溶液以作為進料，其中該脂肪族五碳系列石油樹脂係為該脂肪族五碳系列石油樹脂溶液的10 wt%；該進料經由泵送入管線中，再將氫氣加入管線與該該進料混合，經由泵送入一滴流式的固定床反應器中以進行反應，其中該進料、氫氣混合以及反應係為連續式，其中加氫的條件係為：使用的催化劑之體積係為50 mL，該催化劑係包含鎳金屬以及作為鎳金屬載體的矽藻土，其中以矽藻土為 基礎，含有55 wt%之鎳金屬，且反應溫度為180℃，加氫壓力為5.5 MPa、氫氣和進料的體積比為600：1，液體空間流速(LHSV，liquid hourly space velocity)為0.5 hr-1，其中該一滴流式的固定床反應器的外圍係為電加熱的加熱罩，該加熱罩分成三段藉以分別對該一滴流式的固定床反應器進行上、中和下段進行加熱，各段皆可自由設定加熱的溫度；最後，獲得加氫之脂肪族五碳系列石油樹脂。 The hydrogenation process of one stage of the present invention is as follows: first prepare an aliphatic five-carbon series petroleum resin having a bromine index of 13467 mgBr/100g and a color of brownish yellow, and dissolving the fat with methylcyclohexane. a five-carbon series petroleum resin, which is obtained by feeding an aliphatic five-carbon series petroleum resin solution, wherein the aliphatic five-carbon series petroleum resin is 10 wt% of the aliphatic five-carbon series petroleum resin solution; By pumping into the pipeline, hydrogen is added to the pipeline and mixed with the feed, and pumped into a one-drop fixed bed reactor to carry out the reaction, wherein the feed, hydrogen mixing, and reaction are continuous. The condition for hydrogenation is: the volume of the catalyst used is 50 mL, and the catalyst comprises nickel metal and diatomaceous earth as a nickel metal carrier, wherein diatomaceous earth is used. Base, containing 55 wt% nickel metal, with a reaction temperature of 180 ° C, a hydrogenation pressure of 5.5 MPa, a hydrogen to feed volume ratio of 600:1, and a liquid hourly space velocity (LHSV) of 0.5 hr -1, wherein the periphery of the one-drop fixed bed reactor is an electrically heated heating hood, the heating hood being divided into three sections for respectively heating the upper, middle and lower sections of the one-drop fixed bed reactor, The heating temperature can be set freely in each section; finally, the hydrogenated aliphatic five-carbon series petroleum resin is obtained.
獲得加氫之脂肪族五碳系列石油樹脂之後，該加氫之脂肪族五碳系列石油樹脂流入氣液分離器藉以進行氣液分離，氣體流經濕式流量計以計算氣體的流量，而液體則由流量控制器以維持氣液分離器的液面以及進行該加氫之脂肪族五碳系列石油樹脂量的放流，最後進入液體產品槽中。該加氫之脂肪族五碳系列石油樹脂之溴指數為3194 mgBr/100g，其顏色變為淡黃色，飽和率為76.3%，其數目平均分子量係為900。 After obtaining the hydrogenated aliphatic five-carbon series petroleum resin, the hydrogenated aliphatic five-carbon series petroleum resin flows into the gas-liquid separator for gas-liquid separation, and the gas flows through the wet flow meter to calculate the gas flow rate, and the liquid Then, the flow controller maintains the liquid level of the gas-liquid separator and discharges the amount of the aliphatic five-carbon series petroleum resin which is subjected to the hydrogenation, and finally enters the liquid product tank. The hydrogenated aliphatic five-carbon series petroleum resin has a bromine index of 3194 mgBr/100 g, a color of pale yellow, a saturation ratio of 76.3%, and a number average molecular weight of 900.
本實施例與實施例1不同之處在於，其中反應溫度為190℃，氫氣和進料的體積比為360：1。本實施例所製得之加氫之脂肪族五碳系列石油樹脂之溴指數為1917 mgBr/100g，飽和率85.8%，其數目平均分子量係為826。 This example differs from Example 1 in that the reaction temperature is 190 ° C and the volume ratio of hydrogen to feed is 360:1. The hydrogenated aliphatic five-carbon series petroleum resin prepared in this example has a bromine index of 1917 mgBr/100 g, a saturation ratio of 85.8%, and a number average molecular weight of 826.
實施例3至8中，與實施例1不同之處在於，其中所使用之催化劑的體積系為30 mL，LHSV為1.0 hr-1，且實施例 3至8之反應溫度以及各製得之加氫之脂肪族五碳系列石油樹脂之飽和率以及數目平均分子量如下表1所示。 In Examples 3 to 8, the difference from Example 1 is that the catalyst used has a volume of 30 mL, an LHSV of 1.0 hr -1 , and the reaction temperatures of Examples 3 to 8 and the respective additions. The saturation ratio and number average molecular weight of the aliphatic five-carbon series petroleum resin of hydrogen are shown in Table 1 below.
由表1得知，反應溫度由200℃提高到280℃時，即，實施例3至實施例7，加氫之脂肪族五碳系列石油樹脂的飽和率由99.4%提高到100%，故得知升溫使得加氫效果提高，且石油樹脂裂解情形較少。然而，反應溫度再升到290℃時，即，實施例8，其加氫之脂肪族五碳系列石油樹脂的數目平均分子量也明顯降至243，且飽和率也下降至95%，故得知在高溫下，加氫之脂肪族五碳系列石油樹脂裂解情形嚴重，而且加氫過程無法補足裂解產生的烯類，故飽和率反而下降。 It can be seen from Table 1 that when the reaction temperature is increased from 200 ° C to 280 ° C, that is, in Examples 3 to 7, the saturation ratio of the hydrogenated aliphatic five-carbon series petroleum resin is increased from 99.4% to 100%, so It is known that the heating effect increases the hydrogenation effect, and the petroleum resin cracking situation is less. However, when the reaction temperature was further raised to 290 ° C, that is, in Example 8, the number average molecular weight of the hydrogenated aliphatic five-carbon series petroleum resin was also significantly lowered to 243, and the saturation rate was also lowered to 95%, so that it was known. At high temperature, the hydrogenation of the aliphatic five-carbon series petroleum resin is severely cracked, and the hydrogenation process cannot make up the olefins produced by the cracking, so the saturation rate decreases.
實施例9-11中，與實施例1不同之處在於，反應溫度為200℃，且實施例9至11之液體空間流速以及各製得之加氫之脂肪族五碳系列石油樹脂之飽和率以及數目平均分子量如下表2所示。 In Examples 9-11, the difference from Example 1 is that the reaction temperature is 200 ° C, and the liquid space flow rates of Examples 9 to 11 and the saturation ratio of each of the prepared hydrogenated aliphatic five-carbon series petroleum resins are obtained. And the number average molecular weight is shown in Table 2 below.
表2.實施例9至11之液體空間流速以及各製得之加氫之脂肪族五碳系列石油樹脂之飽和率以及數目平均分子
量
如表2所示，在LHSV由0.7 hr-1下降到0.2 hr-1時，即，實施例9至11，其飽和率由99.8%下降到99.2%，可得知LHSV的下降對的飽和率的影響不大。LHSV由0.7 hr-1下降到0.2 hr-1，數目平均分子量由1130降到955，可得知有少量裂解的情形發生。 As shown in Table 2, when the LHSV decreased from 0.7 hr -1 to 0.2 hr -1 , that is, in Examples 9 to 11, the saturation rate decreased from 99.8% to 99.2%, and the saturation rate of the falling pair of LHSV was known. The impact is small. The LHSV decreased from 0.7 hr -1 to 0.2 hr -1 , and the number average molecular weight decreased from 1130 to 955. It can be seen that a small amount of cleavage occurred.
實施例12中，與實施例1不同之處在於，反應溫度為200℃，氫氣和進料的體積比為360：1，本實施例所製得之加氫之脂肪族五碳系列石油樹脂的飽和率為99.2%，其數目平均分子量係為955。 In the embodiment 12, the difference from the first embodiment is that the reaction temperature is 200 ° C, the volume ratio of hydrogen to the feed is 360:1, and the hydrogenated aliphatic five-carbon series petroleum resin obtained in the present embodiment is The saturation ratio was 99.2%, and the number average molecular weight was 955.
實施例13中，與實施例1不同之處在於，反應溫度為200℃，氫氣和進料的體積比為860：1，LHSV為0.2 hr-1，本實施例所製得之加氫之脂肪族五碳系列石油樹脂的飽和率為99.0%，其數目平均分子量係為905。 In Example 13, the difference from Example 1 is that the reaction temperature is 200 ° C, the volume ratio of hydrogen to the feed is 860:1, and the LHSV is 0.2 hr-1. The hydrogenated fat obtained in the present example. The five-carbon series petroleum resin has a saturation ratio of 99.0% and a number average molecular weight of 905.
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| TWI733830B (en) * | 2016-06-07 | 2021-07-21 | 南韓商可隆股份有限公司 | Thermoplastic resin blend composition, master batch, and composition for forming biaxially stretched polyolefin-based film |
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| CN113087845A (en) * | 2021-03-26 | 2021-07-09 | 广东新华粤树脂科技有限公司 | Preparation method of long-chain olefin modified C9 petroleum resin |
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