CN101386674B - Dendritic poly (propyleneimine)-phosphazene catalyst and preparation and application thereof - Google Patents
Dendritic poly (propyleneimine)-phosphazene catalyst and preparation and application thereof Download PDFInfo
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- CN101386674B CN101386674B CN2008101549491A CN200810154949A CN101386674B CN 101386674 B CN101386674 B CN 101386674B CN 2008101549491 A CN2008101549491 A CN 2008101549491A CN 200810154949 A CN200810154949 A CN 200810154949A CN 101386674 B CN101386674 B CN 101386674B
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Abstract
A dendritical polyacrylic imide-phosphonitrile catalyst has the structure shown as follows, wherein R represents C1-C6 alkyl; and N is equal to between 1 and 4, and Q<-> is an anion representing C1-C8 alkoxy anion, aroxy anion or C1-C6 carboxylate anion. As the dendritical polyacrylic imide-phosphonitrile catalyst adopts a dendritical macromolecule which is highly branched and has a regular and controllable molecular structure as a carrier, the catalyst is surrounded by a plurality of phosphonitrile active groups which independently have catalytic actions during the reaction process so as to ensure the high activity of the catalyst. In addition, when the catalyst molecules reach certain size, the catalyst molecules can be separated and reclaimed through film separation means, thereby realizing the aim of repeated use. The catalyst has wide application prospect. The invention also discloses a method for preparing the catalyst.
Description
Technical field
The present invention relates to the phosphonitrile Catalysts and its preparation method, particularly dendrimer phosphonitrile Catalysts and its preparation method.The invention still further relates to the catalyzed polymerization of epoxide.
Background technology
Polyether glycol is the important source material of synthesis of polyurethane and nonionogenic tenside, in a plurality of fields extensive application.Polyethers is normally made by oxyethane, propylene oxide ring-opening polymerization in the presence of initiator and catalyzer.Industrial catalyzer commonly used mainly contains alkali metal hydroxide KOH and double metal cyanide (DMC) at present.Wherein the KOH low price is fit to various epoxide polymerization reactions, can remove from the product polyethers easily.The dmc catalyst catalytic activity is high, can prepare the polyethers of low-unsaturation-degree and higher molecular weight.Yet there is open defect separately in this two classes catalyzer, and the polyethers degree of unsaturation of making Catalyst Production as KOH is higher, and dmc catalyst is difficult to separate from product, and can not produce ethylene oxide-capped polyether product.
In recent years, multinomial patent report the employing phosphazene compound as the epoxide polymerization catalyst for reaction, as US5952457,5990352, EP0763555,0897940 and 0950679 etc.This class catalyzer has the advantage of KOH and dmc catalyst concurrently, has shown bright development prospect.Yet complicated preparation process causes their prices very expensive, and is difficult to separate from the product polyethers after the reaction, has limited its large-scale application.Therefore how to develop efficient, callable phosphonitrile catalyzer and become the focus that people pay close attention to.Patent EP1294794 has reported phosphazene compound has been loaded on the crosslinked organic polymer that after synthesis of epoxy compounds was finished, water or organic solvent washing went out catalyzer, reclaimed catalyzer then.But also there is the defective of self in it, becomes more inaccessibility as catalytic activity point after the load, and the polymer supported cognition of long-time in addition use produces swelling effect, influences catalytic performance.
Dendrimer has caused people's attention in recent years as support of the catalyst, the macromolecular controllable structure of this class, and molecular size is adjustable, and stable performance is a kind of good support of the catalyst.The more important thing is, active group loads on the catalyzer of making on the dendritic macromole and can be dissolved in the reaction medium, the character that has kept homogeneous catalyst, can not cause the decline of active site quantity, the molecular weight of the rear catalyst of load simultaneously reaches thousands of even up to ten thousand, can reclaim catalyzer by membrane separation technique, realize recycling.
Summary of the invention
The object of the present invention is to provide a kind of novel phosphonitrile catalyzer that is used for the epoxide polymerization reaction, this catalyst cupport is on dendrimer polypropylene imines molecule, molecular end has a plurality of phosphonitrile groups, is a kind of good epoxide polymerization catalysts.
Another object of the present invention is to provide the preparation method of this new catalyst.
Technical scheme of the present invention is as follows:
A kind of dendritic poly (propyleneimine)-phosphazene catalyst, it has following structure:
Wherein R represents C
1～C
6Alkyl; N=1～4, Q
-Be negatively charged ion, represent C
1～C
8Alkoxyl group negatively charged ion, aryloxy negatively charged ion or C
1～C
6Carboxylate anion.
A kind of preparation method of above-mentioned dendritic poly (propyleneimine)-phosphazene catalyst, it is made up of the following step:
Step 1. is dissolved in dendroid polypropylene imines in the organic solvent; be cooled to-20-0 ℃; add phosphorus pentachloride and 3 times of excessive triethylamines; under protection of inert gas; reacted 1～5 hour down at-40～0 ℃, phosphorus pentachloride is 4:1～32:1 with the ratio of the amount of substance of polypropylene imines, after reaction finishes; concentrated solution removes by filter precipitation.
Step 2. adds 3 times of excessive triethylamines in the filtrate of step 1, be cooled to-20-0 ℃, and excessive 3-5 phosphonitrile monomer doubly be dissolved in the organic solvent of appropriate amount; under protection of inert gas; be added dropwise in the above-mentioned solution, reacted 1～5 hour down, after reaction finishes at-40～0 ℃; decompression removes solvent; pour residue into a small amount of sherwood oil, filtering-depositing is after filtrate concentrates; vacuum-drying gets white chlorion type dendroid polypropylene imine phosphate nitrile compound
Step 3. is chlorion type dendroid polypropylene imine phosphate nitrile compound and alkali metal alcoholates, alkali metal phenolate or alkali metal carboxylate reaction, get final product behind the displacement negatively charged ion target product dendrimer phosphonitrile catalyzer.
The preparation method of above-mentioned dendritic poly (propyleneimine)-phosphazene catalyst, the described dendroid polypropylene of step 1 imines was 1～4 generation, structural formula is shown below:
Wherein, n=1～4.
The preparation method of above-mentioned dendritic poly (propyleneimine)-phosphazene catalyst, the monomeric structural formula of the described phosphonitrile of step 2 is shown below:
Wherein R represents C
1～C
6Alkyl.
The preparation method of above-mentioned dendritic poly (propyleneimine)-phosphazene catalyst, the described organic solvent of step 1 and step 2 can be methylene dichloride, chloroform, tetracol phenixin, lower alcohols or toluene.
The preparation method of above-mentioned dendritic poly (propyleneimine)-phosphazene catalyst, the described rare gas element of step 1 and step 2 is nitrogen, argon gas or helium, preferably nitrogen.
Dendrimer phosphonitrile catalyzer of the present invention is a kind of epoxide polymerization catalysts of excellent property, can be applicable to oxyethane, propylene oxide, 1,2-butylene oxide ring or Styryl oxide, the perhaps polymerization of their mixture.
Dendritic poly (propyleneimine)-phosphazene catalyst of the present invention, to have dendrimer highly branched and that molecular structure is regular, controlled be carrier owing to select for use, make the catalyzer periphery have a plurality of phosphonitrile active groups, and all active groups all independently play katalysis separately in reaction process, have guaranteed the high reactivity of catalyzer.In addition, catalyst molecule can carry out Separation and Recovery to it by the membrane sepn means again after reaching certain size, realizes the purpose of recycling, is with a wide range of applications.
Specific implementation method
The invention will be further described below by example, but do not limit protection scope of the present invention.
Embodiment 1
A. the preparation of methoxyl group dendritic poly (propyleneimine)-phosphazene catalyst
The first-generation polypropylene imines (n=1, Aldrich company buys) of 0.42g is dissolved in the 30ml methylene dichloride, is cooled to-20 ℃, nitrogen protection adds 0.66g phosphorus pentachloride and 3g triethylamine down, keeps temperature of reaction to be lower than 0 ℃ of reaction 5 hours.After reaction finished, concentrated solution filtered out precipitation.
In above-mentioned solution, add the 3g triethylamine, be cooled to-20 ℃, in solution, drip the 2.6g phosphonitrile monomer (NEt that is dissolved in the 50ml methylene dichloride under the nitrogen protection
2)
3P=NH after dripping, keeps 0 ℃ of reaction 5 hours.After reaction finished, decompression removed solvent, pours residue into sherwood oil, filters out precipitation, and after filtrate concentrated, vacuum-drying got white chlorion type phosphazene compound.This white mass is dissolved in anhydrous methanol, stirs adding 0.173g sodium methylate down, continue to stir 2 hours, and the concentrating under reduced pressure evaporate to dryness.30mlTHF is added in the resistates, after the elimination insoluble substance, filtrate is concentrated evaporate to dryness, promptly get methoxyl group dendritic poly (propyleneimine)-phosphazene catalyst 2.2g, productive rate is 65%.Nucleus magnetic resonance and Infrared spectroscopy, the result is as follows:
1H?NMR(CDCl
3，300MHz)：δ＝2.32～2.84(168H，-NH-CH
2，N-CH
2)，δ＝1.6～1.82(12H，-CH
2-)，δ＝0.9～1.2(216H，-CH
3)；IR(KBr)：3430cm
-1(N-H)，2925cm
-1(C-H)，1370、1210cm
-1(P＝N)，875cm
-1(P-N)
B. the polyreaction of propylene oxide
Be equipped with at 1000ml and add the 3g first-generation methoxyl group dendritic poly (propyleneimine)-phosphazene catalyst that is dissolved in the 20ml tetrahydrofuran (THF) in the stainless steel autoclave of thermometer, tensimeter, agitator and epoxide inlet tube, the 80g hydroxyl value is 168 polyoxytrimethylene triol.Be heated to 110 ℃ under stirring, nitrogen dehydration of decompression drum and small molecules solvent.Keep temperature of reaction, the feeding minor amount of propylene oxide makes reaction pressure rise to 0.2MPa earlier, observes to begin intermittently to feed propylene oxide after pressure descends, and pressure is maintained at about 0.3MPa in the reaction process, and reaction was carried out 3 hours.Decompression removes unreacted propylene oxide and small molecules, then reactive material is cooled to room temperature.Obtain colourless, the tasteless polyoxytrimethylene triol of 480g.By analysis, the hydroxyl value of polyethers is 28.
Embodiment 2
A. the preparation of acetoxyl dendritic poly (propyleneimine)-phosphazene catalyst
The 4th generation polypropylene imines (n=4, Aldrich company buys) of 0.68g is dissolved in the 30ml methylene dichloride, is cooled to 0 ℃, nitrogen protection adds 0.66g phosphorus pentachloride and 3g triethylamine down, keeps 0 ℃ of reaction 5 hours.After reaction finished, concentrated solution filtered out precipitation.
In above-mentioned solution, add the 3g triethylamine, be cooled to 0 ℃, in solution, drip the 3.4g phosphonitrile monomer (NEt that is dissolved in the 50ml methylene dichloride under the nitrogen protection
2)
3P=NH after dripping, keeps 0 ℃ of reaction 5 hours.After reaction finished, decompression removed solvent, pours residue into sherwood oil, filters out precipitation, and after filtrate concentrated, vacuum-drying got white chlorion type phosphazene compound.This white mass is dissolved in anhydrous methanol, stirs adding 0.343g sodium acetate down, continue to stir 2 hours, and the concentrating under reduced pressure evaporate to dryness.30mlTHF is added in the resistates, after the elimination insoluble substance, filtrate is concentrated evaporate to dryness, promptly get acetoxyl dendritic poly (propyleneimine)-phosphazene catalyst 3.9g, productive rate is 58%.
B. oxyethane, propylene oxide block polyreaction
To be dissolved in 3g the 4th generation acetoxyl dendritic poly (propyleneimine)-phosphazene catalyst of 20ml tetrahydrofuran (THF), 60g glycerine adds in the autoclave identical with embodiment 1.Be heated to 110 ℃ under stirring, nitrogen dehydration of decompression drum and small molecules solvent.Keep temperature of reaction, intermittently feed propylene oxide 600g, keep reaction pressure at about 0.3MPa in the reaction process, reaction has been carried out 4 hours.Decompression removes unreacted propylene oxide and small molecules, is cooled to room temperature.In order further to improve the molecular weight of the polyoxytrimethylene triol that generates, with reactant transfer to the 5L autoclave.The dried nitrogen purging of autoclave stirs down reactant is heated to 120 ℃, intermittently feeds the 3400g propylene oxide, keeps reaction pressure at about 0.3MPa in the reaction process, is reflected at and has carried out under 120 ℃ 16 hours.Decompression removes small molecules, and keeping temperature of reaction is 120 ℃, the about 0.3MPa of reaction pressure, and intermittent feeding 500g oxyethane, reaction has been carried out 8 hours.Reactant is cooled to room temperature, obtains the segmented copolymer of 4500g colorless and odorless.By analysis, the polyethers hydroxyl value is 24.
Claims (8)
1. dendritic poly (propyleneimine)-phosphazene catalyst is characterized in that it has following structure:
Wherein R represents C
1～C
6Alkyl; N=1～4, Q
-Be negatively charged ion, represent C
1～C
8Alkoxyl group negatively charged ion, aryloxy negatively charged ion or C
1～C
6Carboxylate anion.
2. method for preparing the described dendritic poly (propyleneimine)-phosphazene catalyst of claim 1 is characterized in that it is made up of the following step:
Step 1. is dissolved in dendroid polypropylene imines in the organic solvent; be cooled to-20-0 ℃; add phosphorus pentachloride and 3 times of excessive triethylamines; under protection of inert gas, reacted 1～5 hour down at-40～0 ℃, phosphorus pentachloride is 4:1～32:1 with the ratio of the amount of substance of polypropylene imines; after reaction finishes; concentrated solution removes by filter precipitation
Step 2. adds 3 times of excessive triethylamines in the filtrate of step 1, be cooled to-20-0 ℃, and excessive 3-5 phosphonitrile monomer doubly is dissolved in organic solvent; under protection of inert gas; be added dropwise in the above-mentioned solution, reacted 1～5 hour down, after reaction finishes at-40～0 ℃; decompression removes solvent; pour residue into sherwood oil, filtering-depositing is after filtrate concentrates; vacuum-drying gets white chlorion type dendroid polypropylene imine phosphate nitrile compound
Step 3. is chlorion type dendroid polypropylene imine phosphate nitrile compound and alkali metal alcoholates, alkali phenolate or the reaction of alkali-metal carboxylate salt, behind the displacement negatively charged ion, recrystallization get final product target product dendrimer phosphonitrile catalyzer.
3. the preparation method of dendritic poly (propyleneimine)-phosphazene catalyst according to claim 2, it is characterized in that: the described dendroid polypropylene of step 1 imines was 1～4 generation, and structural formula is shown below:
Wherein, n=1～4.
4. the preparation method of dendritic poly (propyleneimine)-phosphazene catalyst according to claim 2, it is characterized in that: the monomeric structural formula of the described phosphonitrile of step 2 is shown below:
Wherein R represents C
1～C
6Alkyl.
5. the preparation method of dendritic poly (propyleneimine)-phosphazene catalyst according to claim 2, it is characterized in that: the described organic solvent of step 1 and step 2 is methylene dichloride, chloroform or tetracol phenixin.
6. the preparation method of dendritic poly (propyleneimine)-phosphazene catalyst according to claim 2, it is characterized in that: the described rare gas element of step 1 and step 2 is nitrogen, argon gas or helium.
7. the preparation method of dendritic poly (propyleneimine)-phosphazene catalyst according to claim 6 is characterized in that:, described rare gas element is a nitrogen.
8. the application of the described dendritic poly (propyleneimine)-phosphazene catalyst of claim 1 in the epoxide polymerization reaction.
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Citations (3)
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|---|---|---|---|---|
| CN1151414A (en) * | 1995-09-12 | 1997-06-11 | 三井东压化学株式会社 | Polymerization catalyst for alkylene oxide compound and production process of poly (alkylene oxide) |
| CN1594369A (en) * | 2004-07-01 | 2005-03-16 | 上海交通大学 | Branch-shape macromolecular type thioxanthone photoinitiator and preparation method thereof |
| CN1976940A (en) * | 2004-07-01 | 2007-06-06 | 三井化学株式会社 | Novel supported phosphazene catalysts, novel compounds for the catalysts, and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151414A (en) * | 1995-09-12 | 1997-06-11 | 三井东压化学株式会社 | Polymerization catalyst for alkylene oxide compound and production process of poly (alkylene oxide) |
| CN1594369A (en) * | 2004-07-01 | 2005-03-16 | 上海交通大学 | Branch-shape macromolecular type thioxanthone photoinitiator and preparation method thereof |
| CN1976940A (en) * | 2004-07-01 | 2007-06-06 | 三井化学株式会社 | Novel supported phosphazene catalysts, novel compounds for the catalysts, and use thereof |
Non-Patent Citations (2)
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| 于剑昆.磷腈类催化剂及其在聚醚多元醇合成中的应用.聚氨酯工业.2004,19(5),10-14. * |
| 陈华,朱新宝,房连顺,王庆丽.磷腈类催化剂研究进展.江苏化工.2008,36(2),1-5. * |
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