CN1020729C - 制备2-氧代1,3-二氧戊环的工艺方法 - Google Patents
制备2-氧代1,3-二氧戊环的工艺方法 Download PDFInfo
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- CN1020729C CN1020729C CN86105205A CN86105205A CN1020729C CN 1020729 C CN1020729 C CN 1020729C CN 86105205 A CN86105205 A CN 86105205A CN 86105205 A CN86105205 A CN 86105205A CN 1020729 C CN1020729 C CN 1020729C
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 5
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- -1 nitrogenous compound Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000003672 processing method Methods 0.000 claims description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 17
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 17
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 16
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 13
- 230000008676 import Effects 0.000 claims description 9
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 8
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- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
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- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 4
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
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- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Secondary Cells (AREA)
- Catalysts (AREA)
Abstract
藉助环氧化物在某种催化剂存在下与二氧化碳进行反应制备2-氧代-1,3-二氧戊环的工艺方法,其中将至少一种催化剂在有或者没有某种惰性溶剂存在下掺入至少一种环氧化合物中并在40-180℃的温度下于常压或稍高的压力下导入二氧化碳使发生反应,生成相应的有机碳酸酯。所制得的2-氧代-1,3-二氧戊环可用来制备覆层形式及模制体形式的含尿烷基合成树脂。
Description
已知人们可以藉烯化氧在催化剂存在下与二氧化碳进行反应来制取2-氧代-1,3-二氧戊环(也称作碳酸亚烃酯)。在DE-OS2611087(联邦德国专利局公开说明书)中叙述了一种制备通式
所代表的诸碳酸亚烃酯的工艺方法,其中使烯化氧在一种由式ROH所代表的一种含质子(Prolic)物质和一种含氮碱组合而成的催化剂存在下,与CO2在0℃与200℃之间的温度及1至98巴压力下进行反应。含质子物质为水、醇及酚。作为含氮碱而列举的有三甲胺、三乙胺、吡啶或二甲基苯胺。关于取代基R至R′″仅作了一般性说明,即这些基团可以是氢或烷基、芳基、环烷基或者芳烷基。而没有更详细的说明。在实施例中,作为烯化氧被提及的只有环氧乙烷和环氧丙烷并且总是在加压下(至少为10巴)操作。
G.Rokicki及其苄同工作者在“Monal shefle fur Chnmie(化学月刊)”115(1984)第205~214页中叙述了在碱金属盐相转移催化剂存在下以CO2及环氧乙烷为原料制备环状碳酸酯的过程。用作相转移剂的有冠醚、1,4-二氮杂双环-[2.2.2]-辛烷(DABCO)、N,N,N,N-四甲基乙二胺(TMEDA)及三乙基苄基氯化铵(TEBA),还有聚乙二醇(但产率降低)。高产率,即几近理论值的产率仅当初始压力为40巴时才能达到。在6巴下操作时得到约低25%的产率,在1巴下产率甚至仅为8%。作为环氧组分被列举的有环氧乙烷与环氧丙烷、表卤代醇、缩水甘油、正丁基、烯丙基与苯基缩水甘油醚、氧化苯乙烯以及3,3-二取代环氧己烷。
G.Rokicki)的另一篇论文[Makromol.Chem.(高分子化学)186,第331~337页(1985)]叙述了在上述条件下使用2,2-双[4-(2,3-环氧丙氧基)苯基]丙烷或一种环氧树脂(Epikote 828)制
备环状碳酸氢酯的过程。
此外还已知(见PCT WO84/03,701),可以在一种醇如甲醇和一种取代或未取代[(un)substituted]膦化合物(作为催化剂)存在下用CO2处理烯化氧来制备碳酸亚烃酯。此时也在高压(21巴)下进行操作。由该出版物还知道,为了获得很好的产率,无论醇还是膦都非存在不可。
所以,由现有技术可知为了获得高产率,总是必须在高压下进行操作,必须使用一种含有助催化剂的催化剂混合物,并且(或者)为了获得满意的产率,必须有一种含质子物质存在。
本发明可以避免上述各种缺点。
因此,本发明的主题是一种在催化剂存在下藉环氧化物与二氧化碳反应制备2-氧代-1,3-二氧戊环的工艺方法,其中将至少一种环氧化合物在有或者没有惰性溶剂存在下与至少一种催化剂相混合并在40至180℃温度时于常压或稍高的压力下导入二氧化碳进行反应,生成相应的有机碳酸酯。按照此方法,原料化合物中的环氧基团可以部分地或者完全地进行反应。
该工艺方法的优点在于使用常压或稍高的压力,而且不需要花费高昂的设备投资。另外,应强调指出反应的高度选择性,也即实际上不发生现有技术中对这种反应机理所描述的、如均聚作用之类的环氧化物-副反应。再者,藉该工艺方法可以制取有具有多重功能并可在多种应用领域中使用的,具有贮存稳定性的环氧化物/碳酸酯混合物。
该工艺方法中所使用的压力一般为1~10巴,较好地是1~5巴,并以1~3巴为最佳。在大多数情况下使用常压,但在必要时也可以在加压下操作。该工艺方法的较佳湿度范围为50~160℃,60~145℃更佳。能与CO2反应并在一般情况下至少具有一个末端环氧基的环氧化物组分举例来说以下列化合物为宜:具有至少6个碳原子的脂族环氧化物,如1,2-环氧己烷、1,2-环氧辛烷和1,2-环氧十二烷(hexene、oclencanddodecene 1-oxides),缩水甘油及一般式
所代表的表代卤醇,其中Z代表氢原子、甲基或乙基,X代表卤原子或-OH基。这类表卤代醇的例子有表氯代醇、表溴代醇、1,2-环氧-2-甲基-3-氯丙烷及1,2-环氧-2-乙基-3-氯丙烷。
根据本发明,可以使用的其它环氧组分包括例如平均具有至少一个末端1,2-环氧基的那些不氧组分。优先选用的是平均至少含有一个取代或未取代缩水甘油醚基或者一个取代或末取代缩水甘油酯基的那些环氧化合物。还有环氧化的多重不饱和化合物及含酰胺基或尿烷基的环氧化物。
平均至少含有一个通式为
其中Z为氢、甲基或乙基)的环氧化合物举例来说有酚或具有一个或多个芳核的多元醇及酚醛清漆之缩水甘油醚或多缩水甘油醚、由含有一个或多个芳核的多元酚与具有2~4个碳原子的烯化氧之间的加成反应制得的醇类多羟基化合物之多缩水甘油醚以及具有一个或多个脂环的醇类多羟基化合物之多缩水甘油醚。所用的酚类举例来说有苯酚、各种甲酚、间苯二酚、对苯二酚、连苯二酚、间苯三酚、1,5-、2,7-、2,6-二羟基萘等、2,2-双对羟苯基丙烷及2,2-双对羟苯基甲烷(分别称为双酚A和双酚F)、2,4′-二羟基二苯基甲烷等。该反应形成缩水甘油醚的多元醇,举例来说有乙二醇、丙二醇、丁二醇、新戊二醇、己二醇、聚乙二醇、聚丙二醇等。属于此列的还有那些具有末端环氧基的增塑环氧树脂,它们是通过至少含有两个环氧基的环氧树脂与含有-OH或-COOH的物质如多无醇(例如上述的二元醇)、多元羧酸或者含有羧基或-OH的聚酯进行部分环氧基反应而制得。
其它的环氧化合物为至少具有一个由通式
所代表的取代或未取代缩水甘油酯基的饱和或烯不饱和羧酸的缩水甘油酯,式中Z代表氢原子、酸甲基或乙基。该类酸是脂族或芳族、饱和或不饱和的一元或多元羧酸,例如丙烯酸、甲基丙烯酸、丙酸、各种酞酸、四氢及六氢酞酸等。一种很常用
的缩水甘油酯可在市面上购得,这种缩水甘油酯是具有9至11个碳原子链长的饱和一元羧酸的混合物的缩水甘油酯[versalic acid(商品名,即一种有支链的烷烃羧酸)的缩水甘油酯],此混合物主要由叔酸组成(约94%)。在此,也包括那些经甲基丙烯酸缩水甘油酯与其它可共聚单体如苯乙烯及(甲基)丙烯酸酯共聚而制得的环氧树脂。此外,含有酰胺基或尿烷基的环氧化物也适用于该反应,例如三缩水甘油异氰尿酸酯或者缩水甘油掩蔽的六甲基二异氰酸酯。同样也可以使用上述诸环氧化合物的混合物。
对环氧化物与CO2的反应起催化作用的化合物是由通式
(R1,R2,R3,R4)
(6)所代表的季铵化合物,式中R1、R2、R3和R4相同或不相同,可以是具有1~4个碳原子的烷基或者苄基。X代表氯、溴、碘、OH及CO3。这类化合物的例子有三乙基溴化铵、三乙基碘化铵、胆碱、苄基三甲基氢氧化铵、苄基三甲基碳酸铵盐、苄基三丁基氯化铵、3-氯-2-羟丙基三甲基氯化铵、四乙基氢氧化铵及四乙基溴化铵等。别的催化剂是由通式(R1,R2,R3)P所代表的膦类化合物(phosphane,以前谓之phosphine),例如三苯基膦及三甲苯基膦。其它的催化剂是:胺,如1,4-二氮杂双环[2.2.2]辛烷(DABCO)、二甲氨基乙醇、哌嗪、4-二甲氨基吡啶(DMAP)、4-(1-吡咯烷基)吡啶等;胍,如N,N,N′,N′-四甲基胍;以及脒,如1,5-二氮杂双环[4.3.0]酮-5-烯(DBN)、1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)等,还有咪唑、其在1、2、4及5位上的烷基取代产物,其中烷基至多有4个碳原子,例如1-甲基咪唑、2-甲基咪唑、2-甲基-4-甲基咪唑等。芳基及芳烷基取代的咪唑如2-苯基咪唑、2-苯基-4-甲基咪唑等。
催化剂一般单独或以混合形式使用,用量为环氧化物组分重量的0.02~10%,以0.05~6%为佳,以0.05~3%更佳。
反应时间可在宽范围内变动。一般使反应进行到环氧基实际上完全转化。举例来说,反应藉助滴定环氧来控制,并在分析精度范围内达到“环氧基贫乏或无环氧基”的时候使反应终止。以此方法制得可藉已知方法进一步处理的、由任何环氧化合物生成的碳酸烷基酯。
此外,在使用聚环氧化物时也可经使反应在任何所需的时刻终止,从而使制得的化合物除了碳酸酯基团以外还具有末发生反应的环氧基。后者具有这样的优点,即视所需要进行的进一步处理及应用产物的情况而定,环氧基可以在碳酸酯基存在下进行选择性反应,反之碳酸酯基也可以在环氧基存在下进行选择性反应。一般说来,如果使用聚环氧化物(环氧基数n≥2),则在此情况下使反应进行到已反应的环氧基数为0.1n~0.9n为止。
添加作为助催化剂碱金属或碱土金属的卤化物或碳酸盐可以改善催化剂的效果,其用量为环氧化物组分重量的0.1~10%,以0.2~5%为佳,以0.4~2.5%更佳。这里可以使用金属锂、钠、钾、镁及钙的氯化物、溴化物、碘化物或碳酸盐,其中以KI及NaI为佳。但一般仅当需要提高反应性而且它们不损害可应用性并能藉简单操作予以分离时才使用助催化剂。
环氧化合物与CO2的反应可以在有或没有溶剂存在时进行。如果环氧化合物在50℃以上为液态,则一般不使用溶剂。但如果环氧化合物在反应温度下为粘稠状物,因而难以使二氧化碳在搅拌下均匀分散于其中,或者预定要在溶液中对反应产物作进一步处理,则一般要使用溶剂。
芳烃如甲苯、二甲苯以及在石油裂解时产生的混合烃,还有醚如二氧六环、四氢呋喃、乙二醇二甲醚及二甲醇二甲醚以及其它对环氧基惰性的溶剂均可作为溶剂使用。
在下列各实施例中,“份”均指重量份数,%均为重量百分比。
实施例
以双酚A的二环氧甘油醚为原料制备双碳酸盐的一般说明,实施例1至38
在一个装有搅拌器、温度计及一根导气管的装置(必要时为耐压装置)中,放入具有表中所列环氧化物含量的工业级双酚A的二环氧甘油醚,必要时将它们溶于所说明的溶剂中,并在加入催化剂及必要时的助催化剂之后,在搅拌并导入二氧化碳的条件下将其加热到所说明的反应温度。如果在加压下操作,反应装置要事先用二氧化碳洗涤。缩水甘油醚使用Hoechst股分公司生产的“BeckopoxEP140”(环氧化物含量为8.6%)及
“BeckopoxEP301”(环氧化物含量为3.3%)。
在不断通入二氧化碳的情况下,在所述反应温度及压力下继续搅拌,直到由滴定测得所希望的环氧化合物剩余量已达到为止。如果使用不溶性催化剂,则趁热过滤并在必要时减压蒸除所存在的溶剂。
实施例1~7叙述了由双酚A的二环氧甘油醚的部分反应制成的含碳酸酯基的环氧树脂的制备。对照实例37及38是根据现有技术进行的对比试验。
按实施例8至36制备的二碳酸酯可以用甲氧基丙醇重结晶;例如实施例16的产物经重结晶后具有下列性质:
红外吸收:1790cm-1
元素分析:C(实测)64.4C(计算)64.5
H(实测)5.8H(计算)5.6
已化合CO2
的碳酸酯含量:18.6%
表1中使用的缩写符号:
BTBA:苄基三丁基氯化铵
BTMA:苄基三甲基氯化铵
Choline:N-(2-羟乙基)-三甲基氢氧化铵(45%的甲醇溶液)
CHPTMA:3-氯-2-羟丙基三甲基氯化铵
DABCO:1,4-二氮杂二环[2.2.2]辛烷
DBN:二氮杂二环[4.3.0]壬烯-(5)
DGDME:二环氧甘油二甲醚
DMAP:4-二甲氨基吡啶
TEBA:四乙基溴化铵
TMG:1,1,3,3-四甲基胍
TPP:三苯膦
TritonB:苄基三甲基氢氧化铵(40%的甲醇溶液)
TTP:三甲苯膦(表见文后)
39)将254份美国道化学公司出品、商品为“环氧树脂DER 736”的市售聚丙二醇的二环氧甘油醚(环氧化物含量:8.3%)与2.2份碘化钾及3.5份苄基三丁基氯化铵一起在同时导入二氧化碳的条件下,在120℃加热20小时。反应时间结束后,将反应混合物过滤并冷却之。产量:280份(90.5%)的一种粘稠状嫩黄色树脂。红外吸收:1804cm,环氧化物含量:0.3%,化合物的CO2含量:17.1%。
40)将326份美国道化学公司生产的、商品名为“环氧树脂DER732”的聚丙二醇的二环氧甘油醚(环氧化物含量:4.9%)与1份氯化钾相混合并在同时导入二氧化碳的条件下与1.6份溶于甲醇成为40%溶液的苄基三甲基氢氧化铵相混合。接着在导入二氧化碳的条件下于120℃继续搅拌,直到环氧化物含量小于0.2%为止。
制得339份(91.9%)的一种粘稠、透明的树脂。红外吸收:1804cm-1,环氧化物含量:0.11%,化合的CO2含量:11.1%。
41)将142份缩水甘油甲基丙烯酸酯、1.3份三苯膦及0.6份碘化钾在有0.3份对苯二酚单甲醚存在下加热到80℃。
在导入二氧化碳的情况下继续搅拌17小时。经过滤及冷却后,得到181份(98.1%)的一种黄色透明粘稠液。环氧化物含量:0.3%
元素分析:
C(实测):51.3%C(计算):51.6%
H(实测):5.6%H(计算):5.4%
沸点:135~137℃/0.1~0.2乇。
42)将142份缩水甘油甲基丙烯酸酯、0.7份二氮杂二环辛烷以及0.5份碘化锂在80℃,在0.3份对苯二酚单甲醚存在下加热。
在导入CO2的情况下继续搅拌9小时,经过滤和冷却后得到179份、(96.8%)的一种黄色透明液体。环氧化物含量:0.2%,沸点:136°C/0.1-0.2乇。
43)在耐压反应装置中,将1420份缩水甘油甲基丙烯酸酯、13份三苯膦及5份碘化钾在3份对苯二酚单甲醚存在下,在80℃,在二氧化碳压力稳定在1.5巴的条件下搅拌10小时。过滤后,得到1780份(95.9%)的一捉嫩黄色粘稠液。红外吸收:1797、1723cm-1环氧化物含量:0.3%。
44)室温下将260份Versatic酸的缩水甘油酯(环氧化物含量:6.2%)在导入二氧化碳的情况下与2份40%苄基三甲基氢氧经铵的甲醇溶液及0.5份氯化钾相混合。接着在继续导入二氧化碳的情况下把混合物加热到120℃并继续搅拌12小时,直到环氧化物含量达0.3%时为止。产量:300份(99%),产品是一种嫩黄色粘稠液。红外吸收:1733、1801cm-1,环氧化物含量:0.25%,化合的
CO2含量:14.1%。
45)将260份Versatic酸的缩水甘油酯(环氧化物含量:6.2%)、4.7份三苯膦及3.3份碘化钾在导入二氧化碳的情况下,在120℃加热18小时。产量:299份(98.8%)产品是一种嫩黄色粘稠液。红外吸收:1733、1801cm,环氧化物含量:0.25%,化合的CO2含量14.1%。
46)将128份1,2-环氧辛烷、2.2份三苯膦及1.9份碘化钾在通入二氧化碳的情况下,在120℃加热,搅拌继续到环氧化物含量低于0.2%时为止。过滤后,得到125份(93.3%)的一种黄色透明液。红外吸收:1800cm-1,环氧化物含量:0.1%,化合的CO2含量:22.9%。
47)将565份1,2-环氧十二烷、5.7份四乙基溴化铵及1.9份碘化钠在通入二氧化碳的情况下,在120℃加热,搅拌继续到环氧化物含量低于0.5%时为止。过滤后,得到674份(97.1%)的一种黄色透明液。红外吸收:1800cm,环氧化物含量:0.3%,化合的CO2含量:18.7%。
48)将300份的一种工业纯1,3-新戊醇二环氧甘油醚(环氧化物含量:10.7%)在室温,在通入二氧化碳的情况下1.3份三通(Triton)B相混合并在120℃加热。在继续导入二氧化碳的情况下与继续搅拌直到环氧化物含量低于0.3%时为止(约17小时)。得到351份(94.7%)的一种嫩黄色液体。红外吸收:1794cm-1,环氧化物含量:0.1%,化合的CO2含量:21.9%。
49)使282份的一种工业纯1,4-丁二醇二环氧甘油醚(环氧化物含量:11.4%)如实施例48中所述在有1.3份三通(Triton)B存在下,在120℃与二氧化碳反应。得到341份(92.8%)的一种粘稠液,红外吸收:1793cm-1,环氧化物含量:0.25%,化合的CO2含量:20.4%。
50)使320份的一种工业纯1,6-己二醇二环氧甘油醚(环氧化物含量:1%)如实施例48所述在1.3份三通(Triton)B存在下与二氧化碳反应。得到379份(93.2%)的一种嫩黄色树脂。红外吸收:1794cm-1,环氧化物含量:<0.1%,化合物CO2含量:20.4%。
51)将330份的一种含缩水甘油基的市售酚醛清漆(道化学公司制造的DEN731)(环氧化物含量:9.1%)溶于141份二甘油醇二甲醚中并在通入二氧化碳的同时与1.2份4-二甲氨基吡啶混合。经加热到100℃之后,在不断以通入二氧化碳的情况下继续搅拌到环氧化物含量低于0.1%时为止(持续时间约为16小时)。经减压蒸馏出溶剂之后提到380份(92.4%)的一种含碳酸酯基的无色透明酚醛清漆。环氧化物含量:0.1%,化合物的CO2含量:19.0%。
52)将200份商品缩水甘油醚(Hoechst股份公司的“BeckopoxEP080”)(环氧化物含量:8%)在25℃时与0.5份2-乙基-4-甲基咪唑相混合,并在通入二氧化碳的情况下在110℃加热。接着继续搅拌到环氧化物含量低于0.3%时为止。产量:218份(90.1%)嫩黄色粘稠液。环氧化物含量:0.3%。化合的CO2含量:17.1%。
53)将260份商品三缩水甘油异氰脲酸酯(Ciha-Geigy公司的“Araldite PT810”)与260份二甘醇二甲醚及1份2-乙基-4-甲基咪唑混合,并在通入二氧化碳的情况下在120℃加热。在继续通入二氧化碳的条件下,继续搅拌到环氧化物含量低于0.5%为止,此时析出一种自色结晶状产物。在反应结束后,抽滤出沉淀物并在60℃干燥。产量:318份(86.7%)产物为一种白色结晶状化合物。溶点:204~210℃(分解),环氧化物含量:0.9%,化合的CO2含量:27.4%。
54)将300份聚己二酸亚乙基酯(用10摩尔乙二醇和11摩尔己二酸经检沸酯化作用而制得,OH值:56)溶于90份二乙二醇二甲醚中并在70℃加热。在添加0.1份4-二甲氨基吡啶之后,将44份酞酸酐分数小份加入其中。在酸值达到40之后,使反应混合物与118份双酚A型的一种工业纯二缩水甘油醚(BechopoxEP140,环氧化物含量为8.6%)混合,并与0.3份铬-Ⅲ-辛酸盐混合,然后在110℃加热。在酸值达到1后,添加0.5份4-二甲氨基吡啶,并在通入二氧化碳的情况下在120℃加热混合物,继续搅拌到环氧化物含量低于0.05%为止。产量:550份透明粘稠的树脂溶液,环氧化物含量0.04%,化合的CO2含量:2.0%。
55)用凝胶渗透色谱法分析了实施例24和37(对照例1)的反应产物的组成。柱的载体材料是Waters Millipore公司生产、定名为Ultrastyragel的聚苯乙烯(1000-100埃,1000磅/平方英
寸)。
实施例 含量(%)
二碳酸酯 单碳酸酯 双环氧 聚合物比
化物 例(%)
24 90.2 7.0 - 2.8
37(Ⅵ) 27.9 5.9 - 66.2
分析结果清楚地说明了本发明的环氧化合物与CO2的反应的选择性。在聚合物比例对应于在这些条件下所用的工业纯环氧化物比例基本上保持不变的同时,在使用三乙胺作催化剂的情况下聚合物含量提高到整个物料的66.2%。
如果提高三乙胺的添加量,例如象实施例38(对照例2)那样提高3%,则反应产物在反应1小时后胶凝。
表1
二环氧甘油醚 用量 用量
实施例 催化剂 助催化剂
环氧化物 用量(份) (份) % (份) %
含量(%)
1 8.6 30000 TPP 380 1.3 - - -
2 8.6 30000 Triton B 270 0.9 - - -
3 8.6 1000 Triton B 5 0.5 - - -
4 8.6 1000 TPP 2 1.2 KI 9 0.9
5 3.3 1000 Triton B 5 0.5 - - -
6 8.6 1716 DABCO 4 0.23 - - -
7 8.6 1488 TTP 9.8 0.66 - - -
8 8.6 186 BTBA 2.5 1.34 KI 2 1.1
9 8.6 186 BTMA 1.8 1.0 KI 2 1.1
10 8.6 186 CHPTMA 1.9 1.0 K2CO32 1.1
11 8.6 186 TPP 2.5 1.34 NaI 1.1 0.6
12 8.6 186 TPP 2.6 1.4 LiI 2.3 1.23
13 8.6 186 TPP 2.6 1.4 CaCl21.5 0.8
14 8.6 186 DABCO 1.0 0.5 KI 2.0 1.1
15 8.6 186 TPP 3 1.6 NaBr 2.0 1.1
16 8.6 186 TPP 2.6 1.4 KI 1.1 0.6
17 8.6 186 Triton B 4.5 2.4 KCl 1 0.5
18 8.6 30000 TPP 400 1.3 KCl 210 0.7
19 8.6 1860 TEBA 21 1.12 KI 20 1.1
20 8.6 1860 TTP 27 1.45 NaI 10 0.55
21 8.6 30000 Triton B 270 0.9 - -
22 8.6 1681 Cholin 9.4 0.6 -
23 8.6 1000 TPP 7 0.7 NaI 4 0.4
24 8.6 1000 Triton B 9 0.9 - -
25 8.6 1000 Triton B 9 0.9 - -
26 3.3 1286 Triton B 4.5 0.35 - -
27 3.3 1221 Triton B 4 0.33 - -
28 8.6 1412 DBN 3.76 0.27 - -
29 8.6 1407 TMG 3.5 0.25 - -
30 8.6 1110 TMG 2.8 0.25 - -
31 8.6 1180 DMAP 3.1 0.26 - -
32 8.6 1370 4-乙基-4-甲基-咪唑 3.2 0.23 - -
33 8.6 1277 4-乙基-4-甲基-咪唑 3.0 0.23 - -
34 8.6 1338 1-甲基咪唑 2.9 0.2 - -
35 8.6 1185 2-甲基咪唑 2.1 0.2 - -
36 8.6 1225 咪唑 1.8 0.15 - -
37(V1) 8.6 1315 三乙胺 9 0.7 - -
38(V2) 8.6 1286 三乙胺 39 3.0 - -
表1(续)
实施例 溶剂 用量 温度 压力 反应时间 收率(份)熔点 环氧化物 化合的
(份) (℃) (巴) (小时) % (Fp) 含量(%) CO2
量(%)
1 - - 130 2 16 33700 - 3.8 10.2
2 - - 120 2 5 33200 - 4.0 9.8
3 DGDME 200 120 1 4 1090 - 4.5 8.5
4 二甲苯 200 120 1 7 1080 - 4.2 9.4
5 - 300 120 1 8 1039 - 1.5 4.3
6 - - 120 1 16 1908 - 2.7 12.5
7 正丁醇 372 118 1 12 - 1585 - 3.5 11.1
8 - - 140 1 16 97.1 222 50-53 0.2 18.6
9 - - 120 1 20 97.8 223 49-52 0.3 18.4
10 - - 120 1 12 97.2 223 51-53 0.1 18.6
11 - - 120 1 17 97.9 224 52-53 0.2 18.5
12 - - 120 1 19 96.2 220 51-52 0.2 18.5
13 - - 140 1 29 96.5 219 48-50 0.5 18.0
14 - - 120 1 14 97.8 223 51-52 0.3 18.5
15 - - 130 1 24 96.9 221 50-52 0.3 18.1
16 - - 120 1 18 97.9 224 50-52 0.2 18.6
17 - - 130 1 13 96.5 220 51-53 0.3 18.0
18 - - 130 2 26 95.5 220 49-51 0.4 18.2
19 - - 140 2 17 98.5 35790 51-53 0.1 18.7
20 - - 130 1 27 95.8 2260 51-53 0.4 18.1
21 - - 120 2 17 97.5 2180 51-53 0.1 18.0
22 - - 120 1 19 92.3 36050 49-52 0.4 17.7
23 DGDME 300 120 1 12 97.8 1826 50-51 0.2 18.4
24 DGDME 200 120 1 15 96.9 1205 46-47 0.1 18.1
25 二甲苯 200 120 1 16 97.6 1195 47-50 0.2 17.9
26 二甲苯 322 130 1 24 92.9 1200 - 0.2 7.8
27 DGDME 398 130 1 20 95.0 1296 - 0.05 7.6
28 - - 120 1 16 96.8 1265 51-52 0.1 18.1
29 DGDME 352 120 1 11 95.3 1685 53-57 0.1 18.3
30 DGDME 10 100 1 19 95.4 1654 56-57 0.4 18.0
31 DGDME 10 100 1 15 92.8 1295 125-138 0.1 18.7
32 DGDME 15 100 1 15 92.0 1350 112-131 0.2 18.4
33 - - 100 1 16 91.2 1550 49-52 0.5 17.8
34 DGDME 10 100 1 18 90.2 1420 51-53 0.3 18.2
35 - 10 100 1 17 91.8 1480 49-51 0.7 17.2
36 - - 120 1 17 95.5 1320 53-55 0.2 18.3
37(V1) 正丁醇 329 120 1 16 -
38(V2) 正丁醇 322 120 1 1小时后
胶凝
Claims (12)
1、环氧化物在催化剂存在下与二氧化碳进行反应来制备2-氧代-1,3-二氧戊环类化合物的工艺方法,其特征在于,将至少一种环氧化合物在有或者没有一种惰性溶剂存在下与至少一种催化剂混合,并在40-180℃温度下,同时在常压或稍高压力下导入二氧化碳进行反应。
2、按照权利要求1的工艺方法,其特征在于,采用的压力为1-3巴。
3、按照权利要求1或2的工艺方法,其特征在于,所用催化剂的量为环氧化物组分重量的0.15-3%。
4、按照权利要求1的工艺方法,其特征在于,还使用一种助催化剂,其用量为环氧化物组分重量的0.4-2.5
5、按照权利要求1的工艺方法,其特征在于,环氧化合物与二氧化碳的反应仅只部分地进行。
6、按照权利要求1的工艺方法,其特征在于,单独或以混合形式使用下列化合物作为催化剂:通式(R1,R2,R3,R4)N+X-所代表的季铵化合物,胺类、胍类、及咪唑类这组的含氮化合物。
7、按照权利要求6的工艺方法,其特征在于,使用苄基三甲基氢氧化铵,苄基三甲基碳酸铵,苄基三甲基氯化铵,3-氯-2羟基丙基三甲基氯化铵,四乙基溴化铵、胆碱、1,4-二氮杂二环(2.3.2)辛烷,1,1,3,3-四甲基胍、4-二甲氨基吡啶、三苯基-及三甲苯基膦、咪唑、1-甲基和2-甲基咪唑以及2-乙基-4甲基咪唑。
8、按照权利要求4的工艺方法,基特征在于,使用碱金属或碱土金属的卤化物或碳酸盐作为助催化剂。
9、按照权利要求8的工艺方法,其特征在于,使用碘化钠或碘化钾作为助催化剂。
10、按照权利要求1的工艺方法,其特征在于,环氧化合物至少具有一个末端1,2-环氧基。
11、按照权利要求10的工艺方法,其特征在于,用作环氧化合物的是至少有6个碳原子的脂族环氧化物。
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DEP3529263.6 | 1985-08-16 | ||
DE19853529263 DE3529263A1 (de) | 1985-08-16 | 1985-08-16 | Verfahren zur herstellung von 2-oxo-1,3-dioxolanen |
DEP352926 | 1985-08-16 |
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CN1020729C true CN1020729C (zh) | 1993-05-19 |
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Families Citing this family (95)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3600602A1 (de) * | 1986-01-11 | 1987-07-16 | Hoechst Ag | Verfahren zur herstellung von 2-oxo-1,3-dioxolanen |
DE3809840C2 (de) * | 1988-03-21 | 1993-11-11 | Dainippon Ink & Chemicals | Lagerstabile wäßrige Emulsionen Cyclocarbonatgruppen enthaltender Polymere |
US7119202B1 (en) | 1989-02-08 | 2006-10-10 | Glaxo Wellcome Inc. | Substituted-1,3-oxathiolanes and substituted-1,3-dioxolanes with antiviral properties |
US6350753B1 (en) | 1988-04-11 | 2002-02-26 | Biochem Pharma Inc. | 2-Substituted-4-substituted-1,3-dioxolanes and use thereof |
US6903224B2 (en) | 1988-04-11 | 2005-06-07 | Biochem Pharma Inc. | Substituted 1,3-oxathiolanes |
US5270315A (en) * | 1988-04-11 | 1993-12-14 | Biochem Pharma Inc. | 4-(purinyl bases)-substituted-1,3-dioxlanes |
UA45942A (uk) * | 1989-02-08 | 2002-05-15 | Біокем Фарма, Інк. | 1,3-оксатіолан, його похідні, спосіб (варіанти) його одержання та фармацевтична композиція |
GB9009861D0 (en) | 1990-05-02 | 1990-06-27 | Glaxo Group Ltd | Chemical compounds |
US5095124A (en) * | 1990-09-10 | 1992-03-10 | Isp Investments Inc. | Process for the preparation of alk-1-enyl ether cyclocarbonate |
DE4030283A1 (de) * | 1990-09-25 | 1992-03-26 | Ruetgerswerke Ag | Verfahren zur herstellung cyclischer carbonate |
US5091543A (en) * | 1990-10-15 | 1992-02-25 | Arco Chemical Technology, Inc. | Preparation of cyclic carbonates using alkylammonium and tertiary amine catalysts |
US5587480A (en) * | 1990-11-13 | 1996-12-24 | Biochem Pharma, Inc. | Substituted 1,3-oxathiolanes and substituted 1,3-dithiolanes with antiviral properties |
US6228860B1 (en) | 1990-11-13 | 2001-05-08 | Biochem Pharma Inc. | Substituted 1,3-oxathiolanes with antiviral properties |
US6369066B1 (en) | 1990-11-13 | 2002-04-09 | Biochem Pharma, Inc. | Substituted 1,3-oxathiolanes with antiviral properties |
DE4129752C2 (de) * | 1991-09-04 | 1994-01-05 | Dainippon Ink & Chemicals | Verfahren zur Herstellung von 2-Oxo-1,3-dioxolanen |
DE4129753C2 (de) * | 1991-09-04 | 1995-05-04 | Dainippon Ink & Chemicals | Verfahren zur Herstellung von Cyclocarbonatverbindungen |
US5179214A (en) * | 1991-09-23 | 1993-01-12 | Texaco Chemical Company | Process for manufacturing alkylene carbonates |
US5283356A (en) * | 1992-08-03 | 1994-02-01 | Texaco Chemical Company | Process for manufacturing alkylene carbonates using metal phthalocyanine catalysts |
DK0678105T3 (da) * | 1993-01-06 | 1998-08-10 | Akzo Nobel Nv | Oligomere, sterisk hindrede polyamintværbindere ogovertræksammensætninger indeholdende disse |
US5340889A (en) * | 1993-07-19 | 1994-08-23 | Texaco Chemical Company | Liquification of bis-carbonates of bis-glycidyl ethers |
US5431791A (en) * | 1993-12-21 | 1995-07-11 | Basf Corporation | Cathodic electrodeposition method utilizing cyclic carbonate-curable coating composition |
ES2131623T5 (es) * | 1993-12-21 | 2006-08-01 | Basf Corporation | Composicion de revestimiento endurecible de carbonatos ciclicos. |
DE4344510A1 (de) * | 1993-12-24 | 1995-06-29 | Hoechst Ag | Flüssige Zweikomponenten-Überzugsmittel |
DE19505892C1 (de) * | 1995-02-21 | 1996-03-14 | Goldschmidt Ag Th | Verfahren zur Herstellung von Carbonatgruppen enthaltenden Organopolysiloxanen |
DE19512316A1 (de) * | 1995-04-01 | 1996-10-02 | Hoechst Ag | Härtungsmittel für elastische Epoxidharz-Systeme |
DE19625344A1 (de) * | 1996-06-25 | 1998-01-08 | Herberts Gmbh | Wäßriges Überzugsmittel und dessen Verwendung zur Herstellung von Füllerschichten |
ES2176751T3 (es) * | 1996-06-25 | 2002-12-01 | Du Pont | Aductos de epoxido-aminouretano y agentes de revestimiento a base de sistema epoxidos y su utilizacion. |
US6077929A (en) * | 1996-10-09 | 2000-06-20 | Akzo Nobel N.V. | Internally blocked polyamine crosslinkers and coating compositions containing the same |
RU2100355C1 (ru) * | 1996-10-31 | 1997-12-27 | Институт физиологически активных веществ РАН | Способ каталитического связывания двуокиси углерода |
US6184273B1 (en) | 1997-09-30 | 2001-02-06 | Basf Corporation | Coating composition containing a compound with latent functionality |
DE19819586A1 (de) | 1998-04-30 | 1999-11-04 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von 1,3-Dioxolan-2-onen |
US5998568A (en) * | 1999-01-14 | 1999-12-07 | Reichhold, Inc. | Polyesters prepared from alkoxylated intermediates |
US5969056A (en) * | 1999-01-14 | 1999-10-19 | Reichhold, Inc. | Process for preparing esterification products from cyclic organic carbonates using catalysts comprising quaternary ammonium salts |
US6924379B2 (en) * | 2003-05-30 | 2005-08-02 | Council Of Scientific And Industrial Research | Process for preparation of cyclic carbonate |
US20080214386A1 (en) * | 2004-03-01 | 2008-09-04 | Toshikazu Takahashi | Catalyst for Cyclic Carbonate Synthesis |
JP4930992B2 (ja) * | 2004-03-04 | 2012-05-16 | 独立行政法人産業技術総合研究所 | 環状カーボネート製造用触媒 |
DE102004035542A1 (de) | 2004-07-22 | 2006-02-09 | Henkel Kgaa | Zwei-Komponenten-Bindemittel |
US20070213545A1 (en) * | 2005-12-22 | 2007-09-13 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
ZA200610757B (en) * | 2005-12-22 | 2008-05-28 | Shell Int Research | A process for the preparation of a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
US7750170B2 (en) * | 2005-12-22 | 2010-07-06 | Shell Oil Company | Process for mixing an oxidant having explosive potential with a hydrocarbon |
US20070197801A1 (en) * | 2005-12-22 | 2007-08-23 | Bolk Jeroen W | Method of installing an epoxidation catalyst in a reactor, a method of preparing an epoxidation catalyst, an epoxidation catalyst, a process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitables for such a process |
US20070197808A1 (en) * | 2005-12-22 | 2007-08-23 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
US20070203352A1 (en) * | 2005-12-22 | 2007-08-30 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
US20070203349A1 (en) * | 2005-12-22 | 2007-08-30 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
US20070203350A1 (en) * | 2005-12-22 | 2007-08-30 | Bolk Jeroen W | Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process |
US7459589B2 (en) * | 2005-12-22 | 2008-12-02 | Shell Oil Company | Process for the preparation of an alkylene glycol |
US20080154051A1 (en) * | 2006-12-20 | 2008-06-26 | Jeroen Willem Bolk | Method of installing an epoxidation catalyst in a reactor, a method of preparing an epoxidation catalyst, an epoxidation catalyst, a process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitable for such a process |
ATE537159T1 (de) | 2008-06-18 | 2011-12-15 | Basf Se | Verfahren zur herstellung von glycidylestern |
JP2010100539A (ja) * | 2008-10-21 | 2010-05-06 | Jsr Corp | 環状カーボナート化合物の製造方法 |
WO2010089264A1 (de) | 2009-02-05 | 2010-08-12 | Basf Se | Verfahren zur herstellung von biscarbonaten |
FR2952933B1 (fr) * | 2009-11-20 | 2012-05-25 | Centre Nat Rech Scient | Precurseurs biscarbonates, leur procede de preparation et leurs utilisations |
CN102146071A (zh) * | 2010-02-08 | 2011-08-10 | 任旭 | 一种合成(2,3-环碳酸甘油酯)(甲基)丙烯酸酯的方法 |
CN102146070A (zh) * | 2010-02-08 | 2011-08-10 | 任旭 | 一种合成甘油碳酸酯丙烯基醚的方法 |
JP5496750B2 (ja) * | 2010-04-07 | 2014-05-21 | 株式会社クラレ | α,β−不飽和エステルの製造方法 |
KR101829939B1 (ko) * | 2010-06-10 | 2018-02-19 | 닛산 가가쿠 고교 가부시키 가이샤 | 액정 배향 처리제, 액정 배향막, 및 액정 표시 소자 |
TWI466864B (zh) * | 2011-02-18 | 2015-01-01 | Univ Ishou | 離子液體聚合物催化二氧化碳生成環碳酸酯之方法 |
KR101521072B1 (ko) | 2011-02-24 | 2015-05-15 | 다이니치 세이카 고교 가부시키가이샤 | 가스 배리어층을 형성하기 위한 도료 조성물, 가스 배리어성 필름, 및 가스 배리어성 필름의 제조방법 |
JP5604329B2 (ja) * | 2011-02-24 | 2014-10-08 | 大日精化工業株式会社 | ガスバリア性フィルムおよび該ガスバリア性フィルムの製造方法 |
JP5809847B2 (ja) | 2011-05-02 | 2015-11-11 | 大日精化工業株式会社 | ポリヒドロキシウレタン微粒子の製造方法 |
WO2013081157A1 (ja) * | 2011-12-02 | 2013-06-06 | 和光純薬工業株式会社 | 環状カーボネートの製造方法 |
JP2013136571A (ja) * | 2011-12-02 | 2013-07-11 | Daikin Industries Ltd | 含フッ素環状カーボネートの製造方法 |
DE102014206574A1 (de) | 2014-04-04 | 2015-10-08 | Henkel Ag & Co. Kgaa | Zwei-Komponenten-Bindemittel mit Cyclocarbonat- und Epoxidgruppen |
CN105294642B (zh) * | 2014-07-16 | 2018-01-16 | 中国科学院大连化学物理研究所 | 一种催化甘油制备化工产品的方法 |
DE102015113351A1 (de) | 2014-09-20 | 2016-03-24 | Fischerwerke Gmbh & Co. Kg | Härtbares Kunstharz mit erheblichen Anteilen an cyclischen Carbonatgruppen, sowie/und Cyclocarbonatharz-basierte Befestigungssysteme, deren Herstellung und Verwendung |
DE102015115942A1 (de) | 2014-11-20 | 2016-05-25 | Fischerwerke Gmbh & Co. Kg | Mannich-Basen, deren Herstellung und ihre Verwendung als Härter beispielsweise in Kunstharzzusammensetzungen |
JP6635668B2 (ja) * | 2015-03-24 | 2020-01-29 | 日鉄ケミカル&マテリアル株式会社 | カーボナート樹脂、その製造方法、カーボナート樹脂組成物及びその硬化物 |
CN105126912B (zh) * | 2015-06-11 | 2017-12-08 | 江苏师范大学 | 极温和条件下二氧化碳与环氧乙烷衍生物反应制备碳酸乙烯酯衍生物的催化体系及制备方法 |
RU2018141403A (ru) | 2016-04-29 | 2020-05-29 | Хенкель Аг Унд Ко. Кгаа | Амин-функциональные полимеры и способы получения таких полимеров |
EP3401348A1 (en) | 2017-05-11 | 2018-11-14 | Henkel AG & Co. KGaA | Method for producing functionalized polyesters |
EP3409707A1 (en) | 2017-05-30 | 2018-12-05 | Henkel AG & Co. KGaA | Method for producing functionalized polyesters |
EP3428216B1 (en) | 2017-07-11 | 2022-11-02 | Henkel AG & Co. KGaA | Method for producing functionalized polyesters |
CN111406048B (zh) * | 2017-12-15 | 2023-05-12 | 巴斯夫欧洲公司 | 制备甘油碳酸酯甲基丙烯酸酯的方法 |
MX2020012660A (es) | 2018-06-19 | 2021-02-02 | Henkel Ag & Co Kgaa | Compuestos de cianuro de doble metal altamente activos. |
EP3725820B1 (en) | 2019-04-16 | 2022-04-06 | Henkel AG & Co. KGaA | Use of functionalized alpha-angelica lactones |
CN110437200B (zh) * | 2019-07-09 | 2021-04-02 | 惠州凯美特气体有限公司 | 基于二氧化碳原料的碳酸丙烯酯制备方法 |
CA3146215A1 (en) | 2019-07-09 | 2021-01-14 | Henkel Ag & Co. Kgaa | Two component (2k) composition based on modified epoxy resins |
EP3798246B1 (en) | 2019-09-27 | 2024-01-31 | Henkel AG & Co. KGaA | One component (1k) composition based on modified epoxy resin |
EP3831863B1 (en) | 2019-12-04 | 2023-07-05 | Henkel AG & Co. KGaA | One component (1k) composition based on epoxy resin |
EP3831862B1 (en) | 2019-12-04 | 2023-06-28 | Henkel AG & Co. KGaA | One component (1k) composition based on epoxy resin |
EP3835381B1 (en) | 2019-12-13 | 2023-02-08 | Henkel AG & Co. KGaA | Two component (2k) curable adhesive composition |
EP3835378A1 (en) | 2019-12-13 | 2021-06-16 | Henkel AG & Co. KGaA | Two component (2k) curable adhesive composition |
EP3835383B1 (en) | 2019-12-13 | 2023-04-12 | Henkel AG & Co. KGaA | One component (1k) curable adhesive composition |
EP3835386B8 (en) | 2019-12-13 | 2024-01-10 | Henkel AG & Co. KGaA | Two component (2k) curable adhesive composition |
EP3916033A1 (en) | 2020-05-28 | 2021-12-01 | Henkel AG & Co. KGaA | One component (1k) composition based on epoxy resin |
EP3943564A1 (en) | 2020-07-21 | 2022-01-26 | Henkel AG & Co. KGaA | Room temperature stable, electrically conductive 1k epoxy formulation |
TW202219214A (zh) | 2020-08-27 | 2022-05-16 | 德商漢高股份有限及兩合公司 | 導電性單組分型(1k)環氧樹脂調配物 |
US20220111582A1 (en) | 2020-10-13 | 2022-04-14 | Cabot Corporation | Conductive photo-curable compositions for additive manufacturing |
EP4015557A1 (en) | 2020-12-21 | 2022-06-22 | Henkel AG & Co. KGaA | Two component (2k) epoxy formulation |
EP4050060A1 (en) | 2021-02-26 | 2022-08-31 | Henkel AG & Co. KGaA | A photocurable adhesive or sealant composition |
EP4050061A1 (en) | 2021-02-26 | 2022-08-31 | Henkel AG & Co. KGaA | Near-infrared (nir) sensitized adhesive and sealant compositions |
EP4159784A1 (en) | 2021-09-30 | 2023-04-05 | Henkel AG & Co. KGaA | Two component (2k) composition based on epoxy (meth)acrylate resin |
WO2023241875A1 (en) | 2022-06-17 | 2023-12-21 | Henkel Ag & Co. Kgaa | Two component (2k) curable adhesive composition |
CN115181087A (zh) * | 2022-08-25 | 2022-10-14 | 山东东岳高分子材料有限公司 | 一种离子液体复合催化剂制备碳酸乙烯酯的方法 |
EP4332144A1 (en) | 2022-09-05 | 2024-03-06 | Henkel AG & Co. KGaA | One component (1k) curable adhesive composition |
WO2024078879A1 (en) | 2022-10-12 | 2024-04-18 | Henkel Ag & Co. Kgaa | Two component (2k) epoxy formulation |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2873282A (en) * | 1952-04-05 | 1959-02-10 | Jefferson Chem Co Inc | Catalytic process for producing alkylene carbonates |
US2773070A (en) * | 1952-10-31 | 1956-12-04 | Jefferson Chem Co Inc | Catalytic process for producing alkylene carbonates |
US2994705A (en) * | 1958-12-08 | 1961-08-01 | Pure Oil Co | Preparation of cyclic alkylene carbonates in the presence of organic phosphonium compounds |
US2993908A (en) * | 1958-12-16 | 1961-07-25 | Pure Oil Co | Preparation of cyclic alkylene carbonates |
DE1543555C3 (de) * | 1966-11-11 | 1975-10-23 | Erdoelchemie Gmbh, 6000 Koeln | Verfahren zur kontinuierlichen Herstellung von cyclischen Glykolcarbonaten |
FR1538576A (fr) * | 1967-07-26 | 1968-09-06 | Ethylene Plastique Sa | Nouvelle méthode de préparation des carbonates d'alcène |
US3535342A (en) * | 1968-02-07 | 1970-10-20 | Dow Chemical Co | Process for making alkylene carbonates |
JPS4822702B1 (zh) * | 1969-01-27 | 1973-07-07 | ||
JPS4736738U (zh) * | 1971-05-08 | 1972-12-23 | ||
FR2149592A5 (zh) * | 1971-08-13 | 1973-03-30 | Mercier J | |
IT1034323B (it) * | 1975-03-17 | 1979-09-10 | Anic Spa | Procedimento per la preparazione di alchilencarbonati |
IT1034962B (it) * | 1975-04-09 | 1979-10-10 | Snam Progetti | Procedimento per la preparazione di glicoli alchilenici |
FR2328011A1 (fr) * | 1975-10-15 | 1977-05-13 | Ugine Kuhlmann | Nouveaux agents de durcissement des resines phenoliques utilisees dans l'industrie du bois, leurs procedes de fabrication et de mise en oeuvre |
US4314945A (en) * | 1977-12-22 | 1982-02-09 | Union Carbide Corporation | Alkylene carbonate process |
IT1095606B (it) * | 1978-04-14 | 1985-08-10 | Montedison Spa | Processo per la sintesi di alchilencarbonati |
JPS5531682A (en) * | 1978-08-29 | 1980-03-06 | Tatsuro Okamura | Light shielder for automobile |
JPS56128778A (en) * | 1980-03-14 | 1981-10-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of alkylene carbonate |
JPS5731682A (en) * | 1980-07-30 | 1982-02-20 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of alkylene carbonate |
JPS6059218B2 (ja) * | 1980-12-23 | 1985-12-24 | 株式会社日本触媒 | アルキレングリコ−ルの製造方法 |
JPS57183784A (en) * | 1981-05-01 | 1982-11-12 | Mitsubishi Petrochem Co Ltd | Preparation of organic carbonate |
JPS57202317A (en) * | 1981-06-09 | 1982-12-11 | Dainippon Ink & Chem Inc | Curable resin composition |
DE3237138C2 (de) * | 1981-10-16 | 1984-05-17 | Ppg Industries, Inc., Pittsburgh, Pa. | Verfahren zur Herstellung von Ethylencarbonat oder von Gemischen aus Ethylencarbonat und Ethylenglykol |
US4786741A (en) * | 1982-11-15 | 1988-11-22 | Scientific Design Company, Inc. | Preparation of alkylene carbonates |
JPS5913776A (ja) * | 1982-07-14 | 1984-01-24 | Mitsubishi Petrochem Co Ltd | アルキレンカ−ボネ−トの製造方法 |
GB8307613D0 (en) * | 1983-03-18 | 1983-04-27 | Bp Chem Int Ltd | Carbonates |
-
1985
- 1985-08-16 DE DE19853529263 patent/DE3529263A1/de not_active Withdrawn
-
1986
- 1986-08-04 EP EP86110736A patent/EP0212409B1/de not_active Expired - Lifetime
- 1986-08-04 DE DE8686110736T patent/DE3669717D1/de not_active Expired - Lifetime
- 1986-08-04 AT AT86110736T patent/ATE51225T1/de not_active IP Right Cessation
- 1986-08-14 DK DK387386A patent/DK164864C/da not_active IP Right Cessation
- 1986-08-14 ES ES8601130A patent/ES2000286A6/es not_active Expired
- 1986-08-14 PT PT83209A patent/PT83209B/pt not_active IP Right Cessation
- 1986-08-14 FI FI863298A patent/FI86719C/fi not_active IP Right Cessation
- 1986-08-14 AR AR86304909A patent/AR242201A1/es active
- 1986-08-15 ZA ZA866149A patent/ZA866149B/xx unknown
- 1986-08-15 CA CA000516014A patent/CA1334851C/en not_active Expired - Fee Related
- 1986-08-15 JP JP61190730A patent/JP2565875B2/ja not_active Expired - Lifetime
- 1986-08-15 MX MX003452A patent/MX170907B/es unknown
- 1986-08-15 AU AU61506/86A patent/AU585385B2/en not_active Ceased
- 1986-08-15 BR BR8603901A patent/BR8603901A/pt not_active IP Right Cessation
- 1986-08-15 NO NO863302A patent/NO863302L/no unknown
- 1986-08-16 CN CN86105205A patent/CN1020729C/zh not_active Expired - Fee Related
- 1986-08-16 KR KR1019860006754A patent/KR940008751B1/ko not_active IP Right Cessation
-
1987
- 1987-10-21 US US07/111,979 patent/US4892954A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPS6245584A (ja) | 1987-02-27 |
FI86719C (fi) | 1992-10-12 |
FI863298A (fi) | 1987-02-17 |
DK164864B (da) | 1992-08-31 |
CN86105205A (zh) | 1987-02-11 |
AR242201A1 (es) | 1993-03-31 |
JP2565875B2 (ja) | 1996-12-18 |
AU6150686A (en) | 1987-02-19 |
NO863302L (no) | 1987-02-17 |
ES2000286A6 (es) | 1988-02-01 |
NO863302D0 (no) | 1986-08-15 |
FI863298A0 (fi) | 1986-08-14 |
DK387386D0 (da) | 1986-08-14 |
CA1334851C (en) | 1995-03-21 |
PT83209B (pt) | 1989-03-30 |
DK387386A (da) | 1987-02-17 |
DK164864C (da) | 1993-01-18 |
EP0212409A3 (en) | 1987-10-21 |
KR870002117A (ko) | 1987-03-30 |
DE3669717D1 (de) | 1990-04-26 |
MX170907B (es) | 1993-09-22 |
PT83209A (en) | 1986-09-01 |
US4892954A (en) | 1990-01-09 |
KR940008751B1 (ko) | 1994-09-26 |
EP0212409B1 (de) | 1990-03-21 |
AU585385B2 (en) | 1989-06-15 |
FI86719B (fi) | 1992-06-30 |
ATE51225T1 (de) | 1990-04-15 |
EP0212409A2 (de) | 1987-03-04 |
ZA866149B (en) | 1987-04-29 |
BR8603901A (pt) | 1987-03-24 |
DE3529263A1 (de) | 1987-02-19 |
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