CN106133008B - 催化剂树脂 - Google Patents
催化剂树脂 Download PDFInfo
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- CN106133008B CN106133008B CN201580017511.7A CN201580017511A CN106133008B CN 106133008 B CN106133008 B CN 106133008B CN 201580017511 A CN201580017511 A CN 201580017511A CN 106133008 B CN106133008 B CN 106133008B
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- weight
- resin
- vinyl aromatic
- resin beads
- mono
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- 125000003118 aryl group Chemical group 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J3/12—Powdering or granulating
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08J7/12—Chemical modification
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
一种制造多个树脂珠粒的方法,其包含(a)提供反应混合物,其包含单乙烯基芳香族单体、多乙烯基芳香族单体以及致孔剂,(b)对所述反应混合物执行水性悬浮聚合以形成树脂珠粒,以及(c)磺化所述树脂珠粒。还提供多个树脂珠粒,其中所述树脂珠粒包含单乙烯基芳香族单体的聚合单元和多乙烯基芳香族单体的聚合单元,其中所述树脂珠粒具有15到38m2/g的BET表面积和0.7或更高的体积容量。还提供一种制造一种或多种反应物的化学反应的产物的方法,所述方法包含使所述一种或多种反应物在所述多个此类树脂珠粒存在下彼此反应。
Description
一种制备(甲基)丙烯酸的烷基酯的方法为使(甲基)丙烯酸与烷基醇在催化剂存在下反应。一些适用的催化剂为强酸性阳离子交换树脂(“SAC树脂”)。历史上,SAC树脂已可以两种类型中的一种形式获得:凝胶树脂或大孔树脂。历史上,典型凝胶树脂在不使用致孔剂的情况下制得且以相对较低交联水平制得;虽然其在用作催化剂时倾向于有效,但其倾向于具有较差物理韧性。历史上,典型大孔树脂使用致孔剂且以相对较高交联水平制得;虽然其在用作催化剂时倾向于较不有效,但其倾向于具有良好物理韧性。因此,在过去,当需要催化剂时,必需在凝胶树脂与大孔树脂之间进行选择;即,必需牺牲催化有效性或物理韧性。
美国专利5,866,713公开一种制备(甲基)丙烯酸酯的方法。美国专利5,866,713的方法涉及使(甲基)丙烯酸与C1-3醇在强酸性离子交换树脂存在下反应。美国专利5,866,713公开的树脂中无一者具有高催化有效性水平和高物理强度水平两者。需要提供一种具有高催化有效性水平和高物理强度水平两者的树脂。
以下为本发明的陈述。
本发明的第一方面为一种制造多个树脂珠粒的方法,其包含
(a)提供反应混合物,其包含单乙烯基芳香族单体、多乙烯基芳香族单体和致孔剂,其中
(i)所述单乙烯基芳香族单体的量以所述单乙烯基芳香族单体的重量加所述多乙烯基芳香族单体的重量计为93重量%到96重量%,
(ii)所述多乙烯基芳香族单体的量以所述单乙烯基芳香族单体的重量加所述多乙烯基芳香族单体的重量计为4重量%到6.5重量%,
(iii)致孔剂的量以所述单乙烯基芳香族单体的重量加所述多乙烯基芳香族单体的重量计为34.5重量%到39重量%,
(b)对所述反应混合物执行水性悬浮聚合以形成树脂珠粒,以及
(c)磺化所述树脂珠粒。
本发明的第二方面为利用第一方面的方法制得的多个树脂珠粒。
本发明的第三方面为多个树脂珠粒,其中所述树脂珠粒包含
(i)以所述树脂珠粒的重量计,93重量%到96重量%单乙烯基芳香族单体的聚合单元,
(ii)以所述树脂珠粒的重量计,4重量%到7重量%多乙烯基芳香族单体的聚合单元,
其中所述树脂珠粒具有15到38m2/g的BET表面积和0.7或更高的体积容量。
本发明的第四方面为一种制造一种或多种反应物的化学反应的产物的方法,所述方法包含使所述一种或多种反应物在第二方面或第三方面的多个树脂珠粒存在下彼此反应。
以下为本发明的详细描述。
如本文所用,除非上下文另外明确指示,否则以下术语具有所指定的定义。
如本文所用的“树脂”为“聚合物”的同义词。如本文所用,“聚合物”是由较小化学重复单元的反应产物组成的相对大的分子。聚合物可具有线性、分支链、星形、环形、超支化、交联或其组合的结构;聚合物可具有单一类型的重复单元(“均聚物”)或其可具有多于一种类型的重复单元(“共聚物”)。共聚物可具有随机配置、依序配置、嵌段配置、其它配置或其任何混合或组合的各种类型的重复单元。
可以彼此反应形成聚合物的重复单元的分子在本文中称为“单体”。因此形成的重复单元在本文中称为单体的“聚合单元”。
乙烯基单体具有结构其中R1、R2、R3以及R4各自独立地为氢、卤素、脂肪族基团(如烷基)、经取代脂肪族基团、芳基、经取代芳基、另一经取代或未经取代的有机基团或其任何组合。如本文中所用,“(甲基)丙烯酸”意指丙烯酸或甲基丙烯酸;“(甲基)丙烯酸酯”意指丙烯酸酯或甲基丙烯酸酯。如本文中所用,乙烯基芳香族单体为其中R1、R2、R3以及R4中的一个或多个含有一个或多个芳香族环的单体。单乙烯基芳香族单体为每分子恰好具有一个非芳香族碳-碳双键的乙烯基芳香族单体。多乙烯基芳香族单体为每分子具有两个或更多个非芳香族碳-碳双键的乙烯基芳香族单体。
珠粒为材料的粒子。珠粒为球形或大致球形的。珠粒大小通过以珠粒集合的体积计的平均直径表征。珠粒的平均直径为0.1到2mm。树脂珠粒为其中珠粒的组合物含有以珠粒的重量计80重量%或更多量的聚合物的珠粒。
珠粒集合的一些特征如下评估。表面积利用BET(Brunauer、Emmett和Teller)方法测量,报导为每单位重量样品的特征面积。孔隙体积单点吸附方法用氮作为吸附分子来测量,报导为每单位重量样品的特征体积。孔径评估为平均孔隙宽度(4V/A,利用BET方法)。优选地利用以下程序制备用于测量表面积的样品:将湿树脂进料到柱中且用连续溶剂步骤交换溶剂:甲醇,接着甲苯,以及利用异辛烷;在35℃到80℃下真空干燥所得树脂。
水分保持能力(MHC)通过润湿特定体积的树脂且用布氏漏斗(Buchner funnel)移除过量水来测量。在移除过量水之后,记录湿润树脂的重量。树脂接着在105℃下烘箱干燥12小时,且记录干重。MHC从以下方程式计算:
其中
MHC=水分保持能力,报导为百分比
WD=干燥树脂的重量(克)
WM=在干燥期间所移除的水的重量
珠粒集合的其它特征如下评估。体积容量(Vol.Cap.)通过测量呈酸形式的树脂的体积来测量。酸形式树脂的质子用Na洗脱,且质子的量通过用NaOH滴定来测定。用以下方程式计算体积容量:
且重量容量(W.Cap.)如以下方程式中利用树脂的干基测量:
其中
VC=体积容量(Vol.Cap.)(每升当量(eq/L))
VNaOH=中和所用的NaOH溶液体积(毫升)
V空白,NaOH=中和空白样品所用的NaOH溶液体积(毫升)
NNaOH=用于滴定的NaOH浓度(eq/L)
W湿润=Wm=湿润树脂中存在的水的重量
VM=湿润树脂的体积(毫升)
上述方程式中的10用于100ml样品用于从树脂上用于阳离子交换的1,000ml洗脱剂的滴定的情况。
珠粒集合的其它特征如下评估。调和平均粒径(HMPS)利用贝克曼库尔特(BeckmanCoulter)Rapid vue粒子形状和大小分析仪测量并报导;以mm单位报导。损耗倾向(MeOH损耗)通过比较水中树脂的体积变化与其中水已交换甲醇的树脂体积来测量。水中树脂填充床树脂的已知体积通过传递通过数个床体积的甲醇来交换,且因此从树脂中移除水。总共需要最少5个床体积的甲醇来从树脂结构中移除水。树脂的最终体积在溶剂交换结束时记录,且与水中初始体积相比;以百分比(%)单位报导。表观密度通过以下方式测量:根据水分保持能力(MHC)脱水树脂,称重树脂,填充在柱中,且接着根据使用水的上向流方法,使树脂床膨胀至少40%,且在暂停水流后,使树脂填充在柱中。记录最终体积,且重量与最终体积比率用于计算在25℃下的表观密度(g/ml)。
如果将在25℃下溶解在100g溶剂中的化合物的量为1克或更少,那么所述化合物被视为不可溶于所述溶剂中。
本发明的方法涉及一种反应混合物,其含有(i)单乙烯基芳香族单体、(ii)多乙烯基芳香族单体以及(iii)致孔剂。
优选地,单乙烯基芳香族单体含有不溶于水的一种或单体。优选的单乙烯基芳香族单体苯乙烯和经烷基取代的苯乙烯;更优选的为苯乙烯、α-甲基苯乙烯、乙基苯乙烯以及其混合物;更优选的为苯乙烯。单乙烯基芳香族单体的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计93.5重量%或更多;更优选地94重量%或更多。单乙烯基芳香族单体的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计96重量%或更少;优选地95.5重量%或更少;更优选地95重量%或更少。
优选地,多乙烯基芳香族单体含有不溶于水的一种或单体。优选的多乙烯基芳香族单体为二乙烯基苯。多乙烯基芳香族单体的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计4重量%或更多;优选地4.5重量%或更多;更优选地5重量%或更多。多乙烯基芳香族单体的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计6.5重量%或更少;更优选地6重量%或更少。
致孔剂为在25℃下为液体且不溶于水的化合物。致孔剂在25℃下在存在于反应混合物中的单乙烯基芳香族单体和多乙烯基芳香族单体的混合物中为可溶的(呈存在于反应混合物中的量)。通过单乙烯基芳香族单体和多乙烯基芳香族单体的聚合形成的聚合物不可溶于致孔剂中。优选的致孔剂为C4-C8烷烃、每分子经一个或多个羟基取代的C4-C10烷烃、烷基脂肪酸以及其混合物;更优选的为每分子经一个或多个羟基取代的C4-C10烷烃;更优选的为每分子恰好经一个羟基取代的支链C4-C8烷烃;最优选的为4-甲基-2-戊醇(也称为甲基异丁基甲醇或MIBC)。
致孔剂的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计34.5重量%或更多;更优选地35重量%或更多;更优选地35.5重量%或更多。致孔剂的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计39重量%或更少;优选地38重量%或更少;更优选地37重量%或更少;更优选地36.5重量%或更少。
优选地,反应混合物不含除一种或多种单乙烯基芳香族单体和一种或多种多乙烯基芳香族单体以外的单体。
在本发明的方法中,对反应混合物执行水性悬浮聚合。水性悬浮聚合为其中产生树脂珠粒的方法。在水性悬浮聚合的方法中,优选地,反应混合物的液滴分散于水中,优选地在搅拌下。一种或多种悬浮液稳定剂优选地用于使液滴稳定。优选地,液滴还含有一种或多种不可溶于水中且可溶于液滴中的单体中的引发剂。液滴任选地另外含有种粒粒子。种粒粒子为在悬浮聚合方法之前形成的聚合物粒子。优选地,引发剂分解以形成一个或多个自由基,其引发自由基乙烯基聚合,将液滴中的大部分或所有单体转化成聚合物,形成聚合物珠粒。优选地,水性悬浮聚合的方法将各液滴转化成树脂珠粒。优选地,转化成聚合物的聚合单元的单体的量为以单乙烯基芳香族单体和多乙烯基芳香族单体的重量总和计80重量%或更多;更优选地90重量%或更多;更优选地95重量%或更多;更优选地99重量%或更多。优选地,所形成的聚合物不溶于水的。
优选地,树脂珠粒的组合物具有以树脂珠粒的重量计93.3重量%或更多、更优选地94重量%或更多量的单乙烯基芳香族单体的聚合单元。优选地,树脂珠粒的组合物具有以树脂珠粒的重量计96重量%或更少、更优选地95重量%或更少量的单乙烯基芳香族单体的聚合单元。
优选地,树脂珠粒的组合物具有以树脂珠粒的重量计4重量%或更多、更优选地5重量%或更多量的多乙烯基芳香族单体的聚合单元。优选地,树脂珠粒的组合物具有以树脂珠粒的重量计7重量%或更少、优选地6重量%或更少量的多乙烯基芳香族单体的聚合单元。
优选地,在树脂珠粒形成之后,其与水性悬浮聚合中使用的水分离。优选地,树脂珠粒通过加热或通过用接着会通过蒸发移除的水溶性溶剂洗涤来干燥。优选地,致孔剂也从树脂珠粒中移除。优选地,在干燥方法期间移除致孔剂。必要时,致孔剂可通过以下方式移除:用适当溶剂洗涤树脂珠粒,随后通过蒸发移除所述树脂珠粒。
将通过水性悬浮聚合形成的树脂珠粒磺化。磺化为其中将磺酸酯基团(其具有结构-SO3H)连接到聚合物的方法。磺酸酯基团优选地呈酸形式。优选地,磺化的方法包括使树脂珠粒与硫酸反应。优选地,在从水性悬浮聚合方法中使用的水中分离树脂珠粒之后,执行磺化。优选地,磺化在除水以外的溶剂中执行。优选地,在本发明的树脂珠粒中,由磺酸酯基团的摩尔数除以树脂珠粒的聚合单元中的芳香族环的摩尔数所形成的商数为0.8或更高;更优选地0.9或更高。优选地,在本发明的树脂珠粒中,由磺酸酯基团的摩尔数除以树脂珠粒的聚合单元中的芳香族环的摩尔数所形成的商数为1.2或更低;更优选地1.1或更低。
优选地,本发明的树脂珠粒的BET表面积为15m2/g或更高;更优选地20m2/g或更高;更优选地25m2/g或更高;更优选地30m2/g或更高。优选地,本发明的树脂珠粒的BET表面积为38m2/g或更低;更优选地35m2/g或更低。
优选地,本发明的树脂珠粒的体积容量(VC)为0.7或更高;更优选地0.8或更高;更优选地0.9或更高;更优选地0.95或更高。优选地,本发明的树脂珠粒的体积容量(VC)为2.0或更低;更优选地1.7或更低;更优选地1.3或更低。
优选地,本发明的树脂珠粒的孔隙体积为0.1cm3/g或更高;更优选地0.15cm3/g或更高;更优选地0.18cm3/g或更高。优选地,本发明的树脂珠粒的孔隙体积为0.29cm3/g或更低;更优选地0.25cm3/g或更低;更优选地0.22cm3/g或更低。
优选地,本发明的树脂珠粒的平均孔径为10nm或更多;更优选地20nm或更多。优选地,本发明的树脂珠粒的平均孔径为70nm或更少;更优选地50nm或更少;更优选地30nm或更少;更优选地28nm或更少。
优选地,本发明的树脂珠粒的水分保持能力(MHC)为64%或更高;更优选地69.5%或更高。优选地,本发明的树脂珠粒的MHC为78%或更低。
优选地,本发明的树脂珠粒的重量容量(Wt.Cap.)为5.13%或更高;更优选地5.17%或更高。优选地,本发明的树脂珠粒的重量容量为5.3%或更低;更优选地5.2%或更低。
评估树脂珠粒集合的孔隙率特征的另一方法在本文中已知为分配测试。此测试由S.J.Kuga,《色谱杂志(Journal of Chromatography)》,第206卷,第449-461页,1981教示。必要时,树脂被中和成Na+形式,且接着用20mM磷酸钠缓冲水溶液洗涤。树脂接着使用潮湿真空过滤脱水以移除珠粒之间的水,在潮湿真空过滤中在树脂珠粒上方通过真空抽取100%相对湿度的空气。使含有各种大小溶质的测试溶液与珠粒接触,且允许混合物达到平衡。通常,极小溶质将相对易于扩散到树脂珠粒集合中,且上清液溶液将耗乏溶质。类似地,通常,极大溶质将极不易于扩散到树脂珠粒集合中,且上清液中所述溶质的浓度将保持几乎不变。上清液使用20mM磷酸钠缓冲水溶液作为流动相(与用于洗涤树脂的溶液一致)通过凝胶渗透色谱分析,且测定扩散到树脂珠粒集合中的各种大小的溶质的量。由此,测定各种个别大小溶质的孔隙体积(毫升/克树脂)。典型地,对于0.5nm或更小的溶质,树脂珠粒集合的孔隙体积将为0.5ml/g或更大。许多树脂将展现截止值,其为大小,高于其所述大小的任何溶质将具有0.1ml/g或低于0.1ml/g的孔隙体积。
本发明的树脂珠粒的优选用途是作为化学反应的催化剂。优选地,一种或多种反应物在本发明的多个树脂珠粒存在下彼此反应以形成一种或多种产物。优选的化学反应为醇醛缩合、脱水、芳香族物的烷基化、缩合、二聚、酯化、醚化、水合以及其组合。更优选的为脱水、酯化以及其组合。更优选的为具有如下反应物和产物的酯化反应:
其中R5和R6为有机基团。优选地,R5为连接到羧基的烃基或烃基,也就是说,能够与结构I中展示的羧基形成酸酐基团。更优选地,R5为具有1到20个碳原子的烃基;更优选地,R5为具有8到20个碳原子的烃基或为结构IV的烃基
其中R7为氢或烷基;更优选地,R7为氢或甲基。更优选地,R5为结构IV的烃基。更优选地,R7为甲基。优选地,R6为烷基。更优选地,R6为具有1到20个碳原子的烷基。更优选地,R6为具有8到20个碳原子的烷基或具有1到4个碳原子的烷基。更优选地,R6为具有1到4个碳原子的烷基;更优选地,R6为甲基。优选地,在其中R5或R6为具有8个或更多碳原子的基团的实施例中,优选的是,R5或R6中的恰好一个(而非两个)为具有8个或更多碳原子的基团。
一些优选的酯化反应如下:
<u>酸(结构I)</u> | <u>醇(结构II)</u> | <u>酯(结构III)</u> |
马来酸酐 | 甲醇 | 马来酸二甲酯 |
月桂酸 | 甲醇 | 月桂酸甲酯 |
硬脂酸 | 甲醇 | 硬脂酸甲酯 |
丙烯酸 | 甲醇 | 丙烯酸甲酯 |
丙烯酸 | 乙醇 | 丙烯酸乙酯 |
丙烯酸 | 丙烯酸丁酯 | 丙烯酸丁酯 |
丙烯酸 | C<sub>8</sub>-C<sub>20</sub>烷基醇 | 丙烯酸,C<sub>8</sub>-C<sub>20</sub>烷基酯 |
甲基丙烯酸 | 甲醇 | 甲基丙烯酸甲酯 |
甲基丙烯酸 | 乙醇 | 甲基丙烯酸乙酯 |
甲基丙烯酸 | 丙烯酸丁酯 | 甲基丙烯酸丁酯 |
甲基丙烯酸 | C<sub>8</sub>-C<sub>20</sub>烷基醇 | 甲基丙烯酸,C<sub>8</sub>-C<sub>20</sub>烷基酯 |
还涵盖本发明的树脂的用途,其中树脂用并非碱金属或碱土金属的金属浸渍。当使用此类金属时,优选的为Ru、Th、Pt、Pd、Ni、Au、Ag、Cu以及其混合物;更优选的为Pd、Rh和Cu。当其中树脂用并非碱金属或碱土金属的金属浸渍的本发明的树脂时,在树脂存在下进行的优选的化学反应为氢解、硝酸盐还原、碳-碳偶合(例如赫克(Heck)和铃木(Suzuki)反应)、氧化、氢甲酰化以及烯烃、酮、醇、炔烃或酸的选择性还原。
优选地,当树脂用作催化剂时,树脂不用并非碱金属或碱土金属的金属浸渍。优选地,并非碱金属或碱土金属的金属的量以树脂的重量计为0.1重量%或更少;更优选地0.01重量%或更少。
优选地,使反应物和树脂珠粒彼此接触。举例而言,反应物和树脂珠粒可置放到容器中且搅拌。对于另一实例,树脂珠粒和酸可进料到反应器中,且醇以半连续添加形式添加,直到在用于副产物(如水或二甲醚)的蒸馏条件下在压力或大气条件、在30℃到200℃范围内的温度下实现高转化率。对于另一实例,所述方法也可为连续流经方法,其中原料含有反应物,其与树脂珠粒在填充床反应器配置中接触。此类连续方法可在30℃到200℃的温度范围(与催化剂热稳定性界限值相容)和0.1到10MPa的压力中运作,其中原料线性每小时空间速度(LHSV)为0.1到15(h-1)。优选地,在反应物与树脂珠粒接触时,反应物彼此反应以形成产物。优选地,反应在35℃或高于35℃、更优选地50℃或高于50℃下进行。优选地,反应在130℃或更低下进行。
以下是本发明的实例。
实例1:水性悬浮聚合和磺化以形成树脂珠粒的方法
水性悬浮聚合使用标准技术,使用300g水相(水和悬浮剂)、270g有机相(单体(苯乙烯(STY)和二乙烯基苯(DVB)、引发剂和致孔剂)进行。所使用的致孔剂为以总有机相计34-40%的甲基异丁基甲醇(MIBC)。典型的混合、时间和温度用于合成步骤。在聚合之后,所得聚合物珠粒用过量水洗涤且烘箱干燥。此树脂的磺化利用标准磺化方法执行。结果为交联聚(STY-共-DVB)磺化树脂。
实例2:转化成酸形式
一些商业树脂以钠形式获得。在用作催化剂之前,这些树脂如下转化成酸形式。将70mL树脂与去离子水一起进料到柱中。1升HCl 4%(以重量计)溶液以250mL/h往下流,接着2升去离子水以250mL/h往下流。流出物的最终pH经证实在2-3内。
实例3:甲醇与甲基丙烯酸反应
呈酸形式的60mL催化剂用600mL去离子水在柱中用下向流方法以120毫升/小时洗涤。催化剂在布氏漏斗(Buchner funnel)中干燥以移除过量水,且与MeOH一起再进料到柱中。2000mL甲醇在下向流方法中以120毫升/小时经由柱流动。在方法结束时,催化剂以在甲醇中的浆料形式转移到量筒中,且记录体积。催化剂接着在布氏漏斗中干燥以移除过量甲醇。将150.0g甲醇称重且用于将催化剂和甲醇进料到500mL反应器中。将40mg抑制剂MEHQ称重且进料到反应器中,且在300rpm下搅拌以用于所有运作。将反应器在30分钟内加热到60℃。将40g甲基丙烯酸(GMAA)进料到反应器中,且将反应物在60℃下保持6小时。在以下反应时间获取1mL样品用于气相色谱:10秒、1小时、2小时、3小时和4小时。开始原位红外测量,随后进料GMAA,且在4小时运作期间每30秒测量样品。原位红外测量用于追踪运作的动力学且估计反应速率观察到的常数。
实例4:利用BET方法测量孔隙率.
树脂实例11如在实例1中制得。树脂实例11为具有6%DVB,用35%MIBC制得的苯乙烯/二乙烯基苯共聚物。比较实例C12如在实例1中用7%DVB和35%MIBC制得。还测试的为DiaionTM PK-208树脂和DiaionTM PK-212树脂,来自三菱化学(Mitsubishi Chemical);和DowexTM CM-4树脂,来自陶氏化学公司(Dow Chemical Company)。
如下制备样品。用水湿润的60ml树脂在垂直柱中制备。500ml甲醇经由柱以2BV/hr向下流动,接着500ml甲苯以2BV/hr向下流动,接着500ml异辛烷以2BV/hr向下流动。树脂接着在45℃下在真空下干燥24小时。
孔隙率包括孔的表面积(SA)、总孔隙体积(PV)和平均直径(diam)。结果如下:
注释1:二乙烯基苯的聚合单元,以聚合物的干重计,以重量计
注释(2):甲基异丁基甲醇,在制造树脂时用作致孔剂,以聚合物的干重计,以重量计。
注释3:体积容量(meq/L)
注释4:用于制造DowexTM CM-4的致孔剂的量以单乙烯基芳香族单体的重量加多乙烯基芳香族单体的重量计大于39重量%。
实例5:物理韧性
树脂的物理韧性利用渗透冲击磨损(OSA)评估,其利用渗透冲击磨损(OSA)执行,其利用催化剂的体积扩增作用执行,制得树脂的填充床的柱,且接着使以下溶液经由柱流动:去离子水,接着稀酸(4重量%水性HCl),接着去离子水,接着4重量%水性NaOH,且使用去离子水洗涤进行精整。进行40个循环,且在方法结束时测量树脂损坏率。树脂损坏率通过显微镜观察测量,其中计数总共100个珠粒,且损坏的一个记录为一个百分比。树脂的物理韧性越低,损坏%越高。
以下苯乙烯/二乙烯基苯共聚物树脂如在实例1中制得:比较树脂C1-C2和实例树脂3-5。还测试的为DiaionTM PK-212树脂,来自三菱化学。比较树脂C1和C2为比较的,因为MIBC的水平过低。DiaionTM PK-212树脂为比较的,因为其BET表面积低于15m2/g。
测试这些树脂,且OSA结果如下:
<u>样品</u> | <u>DVB%<sup>(1)</sup></u> | <u>MIBC%<sup>(2)</sup></u> | <u>损坏%</u> |
比较树脂C1 | 6 | 0 | 47 |
比较树脂C2 | 6 | 34 | 15 |
实例树脂3<sup>(3)</sup> | 6 | 35 | 2 |
实例树脂4 | 6 | 36 | 1 |
比较树脂5 | 7 | 35 | 1 |
PK-212 | 6% | 未知 | 5 |
注释(1):二乙烯基苯的聚合单元,以聚合物的干重计,以重量计
注释(2):甲基异丁基甲醇,在制造树脂时用作致孔剂,以聚合物的干重计,以重量计。
注释(3):实例树脂3为实例树脂11的复制制备物
比较树脂C1具有0%MIBC;因为不存在致孔剂,其具有极低孔隙率且具有极高损坏%。比较树脂C2仅具有34%MIBC;其孔隙率仍不足够高,且其具有不可接受高的损坏%。PK-212的孔隙率为6.38m2/g(表面积),0.0304cm3/g(孔隙体积),0.0010cm3/g微孔隙率和19.01nm(孔隙直径4V/A),且具有不可接受高的损坏%。
实例6:甲基丙烯酸转化成甲基丙烯酸甲酯
上文所述的红外测量得到转化率%,其为所产生的甲基丙烯酸甲酯的摩尔除以在反应开始时存在的甲基丙烯酸的摩尔。转化率%(“Conv%”)被视为催化剂有效性的量度。
样品如在实例1中制得且如实例3中所述测试。结果如下(“nt”意指不经测试)。比较C21具有过少DVB。比较C26具有过多MIBC。
<u>样品</u> | <u>DVB%</u><sup>(1)</sup> | <u>MIBC%</u><sup>(2)</sup> | <u>2小时下转化率%</u> | <u>3小时下转化率%</u> | <u>4小时下转化率%</u> |
比较C21 | 3 | 36 | 60 | nt | 77 |
树脂22 | 4 | 36 | 60 | nt | 78 |
树脂23 | 5 | 36 | 61 | nt | 76 |
树脂24 | 6 | 36 | 57 | 67 | 76 |
比较25 | 7 | 36 | 49 | nt | 71 |
比较C26 | 6 | 40 | 40 | 50 | 57 |
注释(1):二乙烯基苯的聚合单元,以聚合物的干重计,以重量计
注释(2):甲基异丁基甲醇,在制造树脂时用作致孔剂,以聚合物的干重计,以重量计。
实例树脂22-24展示出优于比较C25和C26的催化有效性。实例树脂22-24展示以下趋势,在相等的MIBC下,递增的DVB引起递减的转化率%;由此趋势,推断,具有更高DVB含量的样品将具有甚至更低的转化率%。因此,推断具有7%或高于7%的DVB的样品将具有不可接受低的转化率%。比较C21展示可接受的催化有效性,但还预期展示出不可接受低的物理韧性。如下制得且测试几乎与C21一致的样品:
<u>样品</u> | <u>DVB%<sup>(1)</sup></u> | <u>MIBC%<sup>(2)</sup></u> | <u>损坏%</u> |
比较C27 | 3 | 35 | 33.09 |
注释(1)和(2)如上
实例7:特征
各种树脂被制成具有以下特征。“unk”意指未知;“nt”意指不经测试。
<u>实例</u> | <u>DVB%</u> | <u>MIBC%</u> | <u>MHC%</u> | <u>重量容量</u> | <u>体积容量</u> | <u>HMPS</u> | <u>密度</u> | <u>MeOH损耗</u> |
31 | 5.0 | 34.8 | 70.6 | 5.18 | 1.11 | 0.661 | 1.12 | 0.854 |
32 | 4.0 | 34.8 | 73.6 | 5.20 | 0.99 | 0.668 | 1.10 | 0.771 |
C33<sup>(1)</sup> | 3.0 | 34.8 | 77.8 | 5.24 | 0.83 | 0.779 | 1.08 | 0.735 |
C34<sup>(1)</sup> | 7.0 | 34.8 | 67.6 | 5.13 | 1.20 | 0.809 | 1.13 | 0.900 |
C35<sup>(1)</sup> | 7.0 | 34.8 | 68.2 | 5.19 | 1.24 | 0.584 | 1.13 | 0.871 |
PK-208<sup>(1)</sup> | 4.0 | unk | 69.0 | 5.14 | 1.19 | 0.650 | nt | 0.841 |
PK-212<sup>(1)</sup> | 6.0 | unk | 60.4 | 5.12 | 1.57 | 0.734 | nt | 0.860 |
PK-216<sup>(1)</sup> | 8.0 | unk | 55.0 | 5.16 | 1.85 | 0.683 | nt | 0.916 |
PK-218<sup>(1)</sup> | 9.0 | unk | 53.5 | 5.04 | 1.88 | 0.679 | nt | 0.909 |
注释(1):比较
实例8:分配测试
各种样品使用分配测试测量。下文展示高于其孔隙体积下降低于0.1ml/g的“截止值”大小:
<u>实例</u> | <u>DVB%</u> | <u>MIBC%</u> | <u>截止值大小</u> |
31 | 5.0 | 34.8 | 大于10nm |
32 | 4.0 | 34.8 | 大于10nm |
PK-208<sup>(1)</sup> | 4.0 | unk | 小于2nm |
PK-212<sup>(1)</sup> | 6.0 | unk | 小于2nm |
PK-216<sup>(1)</sup> | 8.0 | unk | 小于2nm |
PK-218<sup>(1)</sup> | 9.0 | unk | 小于2nm |
注释(1):比较
Claims (4)
1.一种制造多个树脂珠粒的方法,其包含
(a)提供反应混合物,其包含单乙烯基芳香族单体、多乙烯基芳香族单体和甲基异丁基甲醇,其中
(i)所述单乙烯基芳香族单体的量以所述单乙烯基芳香族单体的重量加所述多乙烯基芳香族单体的重量计为93.5重量%到96重量%,
(ii)所述多乙烯基芳香族单体的量以所述单乙烯基芳香族单体的重量加所述多乙烯基芳香族单体的重量计为4重量%到6.5重量%,
(iii)所述甲基异丁基甲醇的量以所述单乙烯基芳香族单体的重量加所述多乙烯基芳香族单体的重量计为34.5重量%到39重量%,
(b)对所述反应混合物执行水性悬浮聚合以形成树脂珠粒,以及
(c)磺化所述树脂珠粒。
2.根据权利要求1所述的方法,其中所述单乙烯基芳香族单体为苯乙烯。
3.根据权利要求1所述的方法,其中所述多乙烯基芳香族单体为二乙烯基苯。
4.多个树脂珠粒,其利用根据权利要求1所述的方法制得。
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US5866713A (en) | 1996-08-20 | 1999-02-02 | Mitsubishi Chemical Corporation | Method for preparing (meth)acrylic acid ester |
US5804606A (en) * | 1997-04-21 | 1998-09-08 | Rohm & Haas Company | Chelating resins |
DE10050680A1 (de) * | 2000-10-13 | 2002-04-18 | Bayer Ag | Verfahren zur Herstellung stabiler gelförmiger Kationenaustauscher |
US7098252B2 (en) * | 2002-04-01 | 2006-08-29 | Rohm And Haas Company | Preparation of macroreticular polymers |
KR102039575B1 (ko) * | 2011-12-28 | 2019-11-01 | 다우 글로벌 테크놀로지스 엘엘씨 | 강산 촉매 조성물 |
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2015
- 2015-03-26 TW TW104109704A patent/TWI544021B/zh active
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- 2015-04-09 JP JP2016560542A patent/JP6592001B2/ja active Active
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CN1073458A (zh) * | 1991-12-19 | 1993-06-23 | 陶氏化学公司 | 接种多孔共聚物及由其制备的离子交换树脂 |
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EP3129431A1 (en) | 2017-02-15 |
TWI544021B (zh) | 2016-08-01 |
JP6592001B2 (ja) | 2019-10-16 |
JP2017518390A (ja) | 2017-07-06 |
WO2015157550A1 (en) | 2015-10-15 |
CN106133008A (zh) | 2016-11-16 |
TW201602201A (zh) | 2016-01-16 |
EP3129431B1 (en) | 2019-12-11 |
KR102413851B1 (ko) | 2022-06-27 |
KR20160143699A (ko) | 2016-12-14 |
US20170183474A1 (en) | 2017-06-29 |
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