CN106750327A - A kind of modified polyether and its preparation method and application - Google Patents
A kind of modified polyether and its preparation method and application Download PDFInfo
- Publication number
- CN106750327A CN106750327A CN201611241727.4A CN201611241727A CN106750327A CN 106750327 A CN106750327 A CN 106750327A CN 201611241727 A CN201611241727 A CN 201611241727A CN 106750327 A CN106750327 A CN 106750327A
- Authority
- CN
- China
- Prior art keywords
- modified polyether
- preparation
- polymer
- molecular weight
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The present invention provides a kind of modified polyether and its preparation method and application.The modified polyether has structure shown in formula I, and wherein n is the integer selected from 10 75.The modified polyether that the present invention is provided is in CO2In there is dissolubility higher, and preparing raw material is with low cost, preparation process is simple, extends close CO2The species of polymer, as close CO2Polymer segments can develop into surfactant, chelating agent, dispersant, thickener or CO2Adsorbent is simultaneously applied to liquid or supercritical CO2In system, potentiality are had a wide range of applications.
Description
Technical field
The invention belongs to functional polymer technical field, it is related to a kind of modified polyether and its preparation method and application.
Background technology
Environmental problem is increasingly taken seriously in terms of development of chemical industry, and many traditional chemical engineerings and technique consumption are simultaneously
A large amount of VOCs are discharged, is badly in need of environment-friendly, safe, economic reagent and is replaced volatile organic solvent.Relatively
In big speak more conventional solvent, liquid or supercritical carbon dioxide (CO2) it is a kind of good replacement reagent.CO2With nontoxic, no
Fire and storage capacity is big, its super critical condition easily reaches, simple advantage is post-processed, so that CO2Superfluid extract,
Pharmaceuticals industry, polymer engineering, Polymer Synthesizing, Polymer Processing and intensified oil reduction technical field have very successful application.
But CO2It is a kind of Weak solvent, it is even more so for polarity and high molecular weight material, this severely limits CO2Application.It is a kind of
Effective solution is to introduce " close CO2Material ".Usual parent CO2Material refers to that can just be dissolved in liquid or super at low pressures
Critical CO2Polymer or oligomer, close CO2Material can turn into surfactant, chelating agent, dispersant and increasing with designs
Thick dose etc. is applied to liquid or supercritical CO2System.
The close CO for studying at present2Material in, molecular weight for 13000g/mol commercial Krytox polymer (poly- hexafluoro
Propylene oxide) concentration be 1wt% when, in CO2In solution presasure be 7.5MPa；Molecular weight gathers for the fluorination of 250000g/mol
When acrylate concentration is 5wt%, in CO2In solution presasure be less than 15MPa.Due to Krytox polymer and fluorinated polypropylene
Acid esters is in liquid or supercritical CO2Middle dissolubility is very high, these close CO2Material is used for synthesizing amphipathic block copolymer surface
Activating agent is used for CO2The emulsion polymerization of dicyandiamide solution or suspension polymerisation, such as lactic acid-hexafluoro oxypropylene block copolymer nonionic
Surfactant, fluorinated acrylic ester-ethylene glycol block copolymer nonionic surfactant.But fluoropolymer price ratio
Costly, it is limited in CO2The application in field.In order to extend liquid or supercritical CO2Application, identify and design and be new
Close CO2Polymer is one of the study hotspot in the field.
But up to the present, close CO2Type of polymer is still few, such as PPOX and polyvinyl acetate, its
Middle low-molecular-weight PPOX is in CO2In have good dissolubility (molecular weight for 725g/mol PPOX dissolve
Pressure is less than 10MPa), therefore have been based on the surfactant of PPOX and be widely studied, such as PPOX
Sodium sulfonate ionic surface active agent, PPOX-epoxyethane block copolymer nonionic surfactant etc..But due to
Polypropylene oxide polymer inter-chain action power causes by force very much PPOX in CO2In dissolubility be strongly depend on molecular weight,
Molecular weight increase causes its dissolubility to significantly reduce, and such as molecular weight is molten when the PPOX concentration of 2000g/mol is 1wt%
Decompression force is higher than 20MPa, and molecular weight is higher than 30MPa for the PPOX solution presasure of 3000g/mol.
The content of the invention
In view of above-mentioned close CO2Polymer is in liquid or supercritical CO2Present in problem, it is an object of the invention to provide
A kind of close CO2Modified polyether and its preparation method and application.The modified polyether is in CO2In have dissolubility higher, and prepare
Low raw-material cost, preparation process is simple, extend close CO2The species of polymer, has a wide range of applications potentiality.
The purpose of the present invention is achieved by the following technical programs：
The present invention provides a kind of modified polyether, with structure shown in formula I：
Wherein：N is the integer selected from 10-75.
The modified polyether is named as " dimethyl silicone polymer dipropylene glycol ether ".
In above-mentioned modified polyether, it is preferable that the molecular weight of the modified polyether is 2000-10000g/mol.
In above-mentioned modified polyether, it is preferable that the modified polyether is in CO2In solution presasure be less than 20MPa.
The present invention also provides the preparation method of above-mentioned modified polyether, and it is comprised the following steps：
Step one, adds two (diethylin) dimethylsilanes and dipropylene glycol in reaction vessel, first vacuumizes,
Nitrogen is then passed to, the step of vacuumizing and lead to nitrogen is repeated at least one times；
Step 2, under vacuum heating response；
Step 3, improves vacuum and continues heating response, obtains modified polyether.
In above-mentioned preparation method, the reaction equation for preparing of the modified polyether is shown below：
In above-mentioned preparation method, it is preferable that two (diethylin) dimethylsilane and the dipropylene glycol
Mol ratio is (0.9-1.05)：1.
In above-mentioned preparation method, it is preferable that in step 2 and step 3, the temperature of heating response is 65-70 DEG C；
In above-mentioned preparation method, it is preferable that in step one, the step of vacuumizing and lead to nitrogen is repeated three times.
In above-mentioned preparation method, it is preferable that in step 2, the vacuum pressure under vacuum condition is 30-50KPa, reaction
Time is 20-24h.
In above-mentioned preparation method, it is preferable that in step 3, the vacuum pressure under vacuum condition is 0-2KPa, during reaction
Between be 2-3h.
Two (diethylin) dimethylsilanes that the present invention is provided are according to bibliography (Synthesis and
Characterization of New Photosensitive Poly(oxyaryleneoxydisilane)s from 1,2-
Bis(diethylamino)tetramethyldisilane and Various Bisphenols.Journal of
polymer Science:Part A:Polymer Chemistry, Vol.28,2997-3005 (1990)) described in preparation
Method is prepared or is conventionally prepared acquisition using raw materials such as dichlorosilane, diethylamine；The present invention is provided
Dipropylene glycol be commercially available acquisition.
In the modified polyether that the present invention is provided, the main polymer chain of the modified polyether is made up of silicon unit and ether unit,
Equivalent to the introducing dimethyl-silicon construction unit on PPOX main chain.From thermodynamics analysis, to PPOX master
Chain introduces dimethyl-silicon construction unit, reduces the active force of polypropylene oxide polymer interchain, makes it in liquid or overcritical
CO2In have dissolubility higher.
The present invention also provides above-mentioned modified polyether as close CO2Polymer segments develop into surfactant, chelating agent,
Dispersant, thickener or CO2In liquid or supercritical CO after adsorbent2Application in system.
The modified polyether that the present invention is provided is in CO2In have dissolubility higher, and preparing raw material it is with low cost, prepare work
Skill is simple, extends close CO2The species of polymer, as close CO2Polymer segments can develop into surfactant,
Chelating agent, dispersant, thickener or CO2Adsorbent is simultaneously applied to liquid or supercritical CO2In system, have a wide range of applications latent
Power.
Brief description of the drawings
Fig. 1 is the nuclear magnetic spectrogram of modified polyether in the embodiment of the present invention 1；
Fig. 2 is the gel permeation chromatography figure of modified polyether in the embodiment of the present invention 1；
Fig. 3 be the embodiment of the present invention 1 in modified polyether in CO2Middle dissolubility test curve figure；
Fig. 4 is the modified polyether of different molecular weight in the embodiment of the present invention 2 and the PPOX of different molecular weight in CO2
In solution presasure comparison diagram.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to it is of the invention can practical range restriction.
Embodiment 1
The present embodiment provides a kind of modified polyether, and its structural formula is as follows：
This implementation also provides the preparation method of above-mentioned modified polyether, and it is comprised the following steps：
Step one, adds a contracting of two (diethylin) dimethylsilanes and 1.459g of 2.081g in the beaker of 25mL
DPG, first vacuumizes, and then passes to nitrogen, repeats 3 displaced airs of the step of vacuumizing and lead to nitrogen；
Step 2, is heated to 70 DEG C of reaction 20h under conditions of the vacuum of 35kPa；
Step 3, improves vacuum to vacuum pressure and is 2kPa and continues to react 2h in 70 DEG C, obtains modified polyether.
Nuclear magnetic resonance experiment is carried out to modified polyether manufactured in the present embodiment, experimental result is as shown in Figure 1.
The absorption vibration peak of all corresponding hydrogen atoms is can be seen that by the nuclear magnetic spectrogram of Fig. 1, the absorption to hydrogen atom is shaken
Dynamic peak carries out nuclear magnetic spectrum parsing, Si-CH3H atom chemical shift be 0.12ppm, C-CH3H atom chemical shift be
1.10ppm and 1.16ppm, C-CH and C-CH2H atom chemical shift be 3.29-4.04ppm.Analysis result is modified poly- with this
Ether structure composition is consistent, so as to prove to have obtained corresponding polymer.
Gel permeation chromatography experiment is carried out to modified polyether manufactured in the present embodiment, experimental result is as shown in Figure 2.
Fig. 2 gel permeation chromatographies figure is converted through treatment, so as to obtain the molecular weight data of the present embodiment modified polyether, such as
Shown in table 1.
Table 1
| Number-average molecular weight Mn | Weight average molecular weight Mw | PDI(Mw/Mn) |
| 2000 | 2900 | 1.5 |
To modified polyether manufactured in the present embodiment in CO2In carry out dissolubility test, experimental result is as shown in Figure 3.
As seen from Figure 3, the concentration of the present embodiment modified polyether is that cloud point pressure is less than in the range of 0.2-1wt%
16MPa。
Embodiment 2
This implementation provides the modified polyether of different molecular weight and the PPOX of different molecular weight in CO2Middle solution presasure
Contrast experiment.
The preparation method reference implementation example 1 of the modified polyether of this implementation different molecular weight, the modified polyether for preparing
Molecular weight ranges are 2000g/mol to 10000g/mol, and in the present embodiment, the molecular weight ranges of PPOX are 1500g/
Mol to 2600g/mol；In experiment, the modified polyether of use and the concentration of PPOX are 0.4wt%, and experimental result is such as
Shown in Fig. 4.
From Fig. 4 experimental results, when the molecular weight of modified polyether increases to 10000g/mol by 2000g/mol, in CO2
In solution presasure be only increased to 20MPa from 14MPa；And the molecular weight of PPOX increases to 2600g/ by 1500g/mol
During mol, in CO2In solution presasure be quickly raised to 22MPa from 12MPa.Compare with PPOX, modified polyether dissolubility
Apparently higher than PPOX, and increase with polymer molecular weight, less, molecular weight is up to its solution presasure elevated-levels
The solution presasure of the modified polyether of 9200g/mol is less than 20MPa.
In sum, the modified polyether that the present invention is provided is in CO2In there is dissolubility higher, and preparing raw material low cost
Honest and clean, preparation process is simple, extends close CO2The species of polymer, as close CO2Polymer segments can develop into table
Face activating agent, chelating agent, dispersant, thickener or CO2Adsorbent is simultaneously applied to liquid or supercritical CO2In system, with extensive
Application potential.
Claims (10)
1. a kind of modified polyether, the modified polyether has structure shown in formula I：
Wherein：N is the integer selected from 10-75.
2. modified polyether according to claim 1, it is characterised in that：The molecular weight of the modified polyether is 2000-
10000g/mol。
3. modified polyether according to claim 1, it is characterised in that：The modified polyether is in CO2In solution presasure be less than
20MPa。
4. the preparation method of modified polyether described in any one of claim 1-3, it is comprised the following steps：
Step one, adds two (diethylin) dimethylsilanes and dipropylene glycol in reaction vessel, first vacuumizes, then
Nitrogen is passed through, the step of vacuumizing and lead to nitrogen is repeated at least one times；
Step 2, under vacuum heating response；
Step 3, improves vacuum and continues heating response, obtains modified polyether.
5. preparation method according to claim 4, it is characterised in that：Two (diethylin) dimethylsilane with it is described
The mol ratio of dipropylene glycol is (0.9-1.05)：1.
6. preparation method according to claim 4, it is characterised in that：In step 2 and step 3, the temperature of heating response
Degree is 65-70 DEG C.
7. preparation method according to claim 4, it is characterised in that：In step one, repetition is vacuumized and leads to nitrogen
Step 3 time.
8. preparation method according to claim 4, it is characterised in that：In step 2, the vacuum pressure under vacuum condition
It is 30-50KPa, the reaction time is 20-24h.
9. preparation method according to claim 4, it is characterised in that：In step 3, the vacuum pressure under vacuum condition
It is 0-2KPa, the reaction time is 2-3h.
10. modified polyether described in any one of claim 1-3 is used as close CO2Polymer segments develop into surfactant, chelating
Agent, dispersant, thickener or CO2In liquid or supercritical CO after adsorbent2Application in system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611241727.4A CN106750327B (en) | 2016-12-29 | 2016-12-29 | A kind of modified polyether and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611241727.4A CN106750327B (en) | 2016-12-29 | 2016-12-29 | A kind of modified polyether and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106750327A true CN106750327A (en) | 2017-05-31 |
| CN106750327B CN106750327B (en) | 2019-10-11 |
Family
ID=58923508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611241727.4A Active CN106750327B (en) | 2016-12-29 | 2016-12-29 | A kind of modified polyether and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106750327B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283325A (en) * | 2019-07-01 | 2019-09-27 | 上海麦浦新材料科技有限公司 | A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106413A (en) * | 1993-06-24 | 1995-08-09 | 戈尔德施米特股份公司 | Silane with hydrophilic group and preparation and application of same |
| CN102884109A (en) * | 2010-04-06 | 2013-01-16 | 道康宁公司 | Reactive amine-functional silicone-polyether block copolymers |
| US20130345318A1 (en) * | 2012-06-22 | 2013-12-26 | Evonik Industries Ag | Silicone polyethers and preparation thereof from polyethers bearing methylidene groups |
| US20140031734A1 (en) * | 2012-01-04 | 2014-01-30 | Momentive Performance Materials Inc. | Silicone adhesive compositions |
-
2016
- 2016-12-29 CN CN201611241727.4A patent/CN106750327B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106413A (en) * | 1993-06-24 | 1995-08-09 | 戈尔德施米特股份公司 | Silane with hydrophilic group and preparation and application of same |
| CN102884109A (en) * | 2010-04-06 | 2013-01-16 | 道康宁公司 | Reactive amine-functional silicone-polyether block copolymers |
| US20140031734A1 (en) * | 2012-01-04 | 2014-01-30 | Momentive Performance Materials Inc. | Silicone adhesive compositions |
| US20130345318A1 (en) * | 2012-06-22 | 2013-12-26 | Evonik Industries Ag | Silicone polyethers and preparation thereof from polyethers bearing methylidene groups |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283325A (en) * | 2019-07-01 | 2019-09-27 | 上海麦浦新材料科技有限公司 | A kind of preparation method for the organic silicon surfactant being used to prepare hard polyurethane foam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106750327B (en) | 2019-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI317741B (en) | Nanoscale polymerized hydrocarbon particles and methods of making and using such particles | |
| CN116426024B (en) | Method for passivating end group of fluorine elastomer | |
| CN113072695B (en) | Preparation method of foam stabilizing surfactant with good low-temperature fluidity | |
| EP3318583B1 (en) | Improved method for producing hydroxy group-containing vinyl ether polymer | |
| CN105061750A (en) | High-double bond content allyl polyether production method | |
| CN106750327B (en) | A kind of modified polyether and its preparation method and application | |
| CN111393655A (en) | Organosilicon surfactant and application thereof in preparation of polyurethane rigid foam | |
| CN108047805A (en) | A kind of compound levelling agent and its preparation method and application | |
| CN114191854A (en) | Polyether modified organic siloxane emulsion type defoaming agent and preparation method thereof | |
| CN107964063B (en) | PFOA-free polymer and preparation method and application thereof | |
| CN104324655B (en) | A kind of low bubble polyether surfactant and synthetic method thereof | |
| EP3437630B1 (en) | Gel composition, cosmetic and manufacturing method for gel composition | |
| Lv et al. | Structure and properties of the graft copolymer of starch and p‐hydroxybenzoic acid using horseradish peroxidase | |
| JP6266287B2 (en) | Polymer composition and water / oil repellent | |
| CN110818890A (en) | Super-spreading wetting agent and preparation method thereof | |
| Jahan et al. | Volumetric and acoustic properties for binary mixtures of N, N-Dimethylformamide with 2-butanol and 2-pentanol at temperatures between 298.15 K and 318.15 K | |
| CN111437632A (en) | Method for preparing emulsion type defoaming agent by utilizing polyether modified silicone oil | |
| CN204073476U (en) | A kind of decompression distillation system produced for silicones | |
| CN113527655B (en) | Fluorine-containing nonionic macromolecular surfactant and preparation method thereof | |
| CN101628975A (en) | Method for compounding polytetrahydrofuran polypropylene glycol block polyether | |
| CN102898640A (en) | Preparation method of octafluoropentyl alcohol polyoxyethylene ether | |
| CN107602758A (en) | Child room interior wall special emulsion and preparation method thereof | |
| CN108129648A (en) | A kind of toluenediamine polyether polyol and preparation method thereof | |
| CN104874328A (en) | Environment-friendly anti-fog and anti-pollution fluorine-containing surfactant and preparing method thereof | |
| CN110819470B (en) | Online cleaning agent for olefin separation water washing tower, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |