CN104177226A - 一种聚醚用催化剂的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 32
- 229920000570 polyether Polymers 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims abstract description 13
- 150000008046 alkali metal hydrides Chemical class 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000007046 ethoxylation reaction Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth metal borates Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyethers (AREA)
Abstract
本发明涉及一种聚醚用催化剂的制备方法，其特征在于，包括如下步骤：将聚醚起始剂一次性加入到容器中，再将碱金属氢化物加入到容器中，加入速度小于5kg/h，边加边搅拌，搅拌过程中搅拌器不能触及容器壁，搅拌速度小于30r/min，使得两者充分反应，制得所述聚醚用催化剂。本发明制备的聚醚用催化剂可促使聚醚转化率提高，纯度提高，分子量分布范围较窄。
Description
技术领域
本发明涉及一种聚醚用催化剂的制备方法。
背景技术
聚醚单体主要用于生成混凝土减水剂，是由环氧乙烷开环聚合，烯醇封端的一种聚合物。该反应是一种乙氧基化反应，通常乙氧基化反应的催化剂由碱性催化剂和酸性催化剂。
在碱性催化剂方面，采用金属氧化物、氢氧化物或其复合物作为乙氧基化反应催化剂，可以使产品的相对分子质量分布变窄、副产物减少以及起始原料的转化刘提高。用碱土金属或IIIB族元素的氢氧化物、烷氧化物等催化乙氧基化反应时，采用多元酸，如磷酸、草酸、柠檬酸或酒石酸等作催化剂，可使反应诱导期明显变短、反应速度大大提高、具有较好的催化效果，产物选择性好，色泽浅，相对分子质量分布较窄。此外，碱土金属的碱性盐，如硫酸钙、硫酸钡、钙镁复合金属盐以及稀土金属硼酸盐等作为乙氧基化催化剂也均表现出明显的产物分布窄的效果。
在酸性催化剂的研究中，近年来研究较多的是采用以天然的蒙脱石结构为基础的固体酸催化剂，但由于其结构较为复杂，孔径大小等因素直接关系到乙氧基化的程度，这方面的工作还有待于进一步深化。
发明内容
本发明所要解决的技术问题是提供一种可促使聚醚转化率提高，纯度提高，分子量分布范围较窄的聚醚用催化剂的制备方法。
本发明解决上述技术问题的技术方案如下：一种聚醚用催化剂的制备方法，以聚醚起始剂(ROH)与碱金属氢化物(XH)反应制得，通式为：
R-OH+XH＝ROX+H2
包括如下步骤：
将聚醚起始剂一次性加入到容器中，再将碱金属氢化物加入到容器中，加入速度小于5kg/h，边加边搅拌，搅拌过程中搅拌器不能触及容器壁，搅拌速度小于30r/min，使得两者充分反应，制得所述聚醚用催化剂；其中，
所述聚醚起始剂为3-甲基-3-丁烯-1-醇和/或2-甲基-2-丙烯-1-醇其中的一种或两种混合物；
所述碱金属氢化物为氢化钠和/或氢化钾；
所述聚醚起始剂与所述碱金属氢化物的摩尔比为1∶1。
本发明的有益效果是：
本发明制备的催化剂在生产聚醚单体时，直接和起始剂一起投入到反应器中，达到投料温度后，投入环氧乙烷，即可开始反应。其优点在于发明制备的催化剂可以有效避免起始剂中含有水对成品的影响，催化剂遇到水后分解生成起始剂和碱金属的氢氧化物，亦可作为乙氧基化反应的催化剂，提高了产品转化率，纯度。
本发明制备的催化剂应及时使用，防止分解和受潮，一般应在7日内用完。
搅拌过程中物料温度不易超过90℃，否则容易引起自燃或起始剂自聚。应采用循环水降温。
搅拌过程中搅拌器不能触及容器壁，产生静电和火花，引起燃烧或爆炸。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步，所用容器为敞口不锈钢双层容器，且其体积为所述聚醚用催化剂体积的3倍以上。
进一步，搅拌过程中的温度小于90℃。超过90℃容易引起自燃或起始剂自聚。应采用循环水降温。
附图说明
图1为本发明聚醚用催化剂的制备方法的所需设备的结构图；
附图中，各标号所代表的部件列表如下：1、第一储罐，2、第二储罐，3、阀门，4、泵，5、成品出料口6、循环水入口，7、循环水出口，8、起始剂入口，9、碱金属氢化物入口，10、减速机，11、釜式反应器。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
如图1所示：反应在一容积为2L的釜式反应器11中进行。第一储罐1为304不锈钢，容积为1000L，用于装起始剂；第二储罐2为塑料吨桶，容积为1000L，用于装循环水；阀门3由304不锈钢材料制成，用于控制物料；泵4用于循环物料；釜式反应器11底部设有成品出料口5，循环水从循环水入口6进入釜式反应器11，然后再从循环水出口7进入到第二储罐2中；起始剂从起始剂入口8中进入到釜式反应器11内进行反应；碱金属氢化物通过碱金属氢化物入口9进入到釜式反应器11内进行反应；釜式反应器11内设有减速机10用于搅拌。先用氮气转换釜式反应器11的空气，加入72克甲基烯丙醇，按附表(见下表)加入催化剂。再于室温下用氮气置换釜式反应器11中的空气，开启减速机10开始搅拌，加热升温至80℃，再按附表通入一定量的环氧乙烷气体，同时将系统压力控制为0.25±0.05MPa。维持设定的反应温度熟化反应，反应7h后结束聚合反应。
附表：
从附表中可看出：按固定摩尔比(0.003∶1)的催化剂与起始剂，按设计分子量2420，需要通往入环氧乙烷2330g，所制得的聚醚的分子量如上表所示，采用ROX催化剂制得的样品分子量2420，最接近设计值。按设计分子量3000，需要加入环氧乙烷2950g，采用ROX作为催化剂，制得的产品分子量3000，和理论值一致。上表同样可以看出，本方法制的催化剂较传统催化剂有更好的产品收率；同时测得的分子量更接近理论计算值，表明分子量分布更集中。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (3)
1.一种聚醚用催化剂的制备方法，其特征在于，包括如下步骤：
将聚醚起始剂一次性加入到容器中，再将碱金属氢化物加入到容器中，加入速度小于5kg/h，边加边搅拌，搅拌过程中搅拌器不能触及容器壁，搅拌速度小于30r/min，使得两者充分反应，制得所述聚醚用催化剂；其中，
所述聚醚起始剂为3-甲基-3-丁烯-1-醇和/或2-甲基-2-丙烯-1-醇其中的一种或两种混合物；
所述碱金属氢化物为氢化钠和/或氢化钾；
所述聚醚起始剂与所述碱金属氢化物的摩尔比为1∶1。
2.根据权利要求1所述的聚醚用催化剂的制备方法，其特征在于，所用容器为敞口不锈钢双层容器，且其体积为所述聚醚用催化剂体积的3倍以上。
3.根据权利要求1所述的聚醚用催化剂的制备方法，其特征在于，搅拌过程中的温度小于90℃。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905524A (zh) * | 2015-12-23 | 2017-06-30 | 大连理工常熟研究院有限公司 | 一种双端烯基聚环氧丙烷的制备方法 |
| CN111013523A (zh) * | 2019-12-26 | 2020-04-17 | 江苏奥克化学有限公司 | 乙氧基化催化剂配制装置和方法 |
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| CN103068823A (zh) * | 2010-08-05 | 2013-04-24 | 日产化学工业株式会社 | 具有氰脲酸骨架的环氧化合物的制造方法 |
| WO2013093615A1 (en) * | 2011-12-22 | 2013-06-27 | Micurx Pharmaceuticals, Inc. | Tricyclic boron compounds for antimicrobial therapy |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103068823A (zh) * | 2010-08-05 | 2013-04-24 | 日产化学工业株式会社 | 具有氰脲酸骨架的环氧化合物的制造方法 |
| WO2013093615A1 (en) * | 2011-12-22 | 2013-06-27 | Micurx Pharmaceuticals, Inc. | Tricyclic boron compounds for antimicrobial therapy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905524A (zh) * | 2015-12-23 | 2017-06-30 | 大连理工常熟研究院有限公司 | 一种双端烯基聚环氧丙烷的制备方法 |
| CN106905524B (zh) * | 2015-12-23 | 2019-10-29 | 大连理工常熟研究院有限公司 | 一种双端烯基聚环氧丙烷的制备方法 |
| CN111013523A (zh) * | 2019-12-26 | 2020-04-17 | 江苏奥克化学有限公司 | 乙氧基化催化剂配制装置和方法 |
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