CN108976406B - Chlorinated polyether diol and synthetic method thereof - Google Patents
Chlorinated polyether diol and synthetic method thereof Download PDFInfo
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- CN108976406B CN108976406B CN201810815916.0A CN201810815916A CN108976406B CN 108976406 B CN108976406 B CN 108976406B CN 201810815916 A CN201810815916 A CN 201810815916A CN 108976406 B CN108976406 B CN 108976406B
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- Prior art keywords
- chlorinated polyether
- butanediol
- polyether diol
- chloromethyl
- methyloxetane
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- 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
- C08G65/2603—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 the other compounds containing oxygen
- C08G65/2606—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 the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
- C08G18/5009—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms having chlorine atoms
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
Abstract
The invention discloses chlorinated polyether diol and a synthesis method thereof, wherein the chlorinated polyether diol has a structural formula As shown in (I), the synthesis process comprises the following steps: 1, 4-butanediol is taken as an initiator, 3-chloromethyl-3-methyl oxetane is taken as a monomer, and chlorinated polyether glycol is obtained through cationic ring-opening polymerization reaction. The synthesis method is simple, and the terminal hydroxyl groups of the chlorinated polyether glycol are primary hydroxyl groups with higher reaction activity, so that the polyurethane elastomer can have higher mechanical properties.
Description
Technical Field
The invention relates to chlorinated polyether diol and a synthesis method thereof, and the chlorinated polyether diol can be used as a raw material of a polyurethane elastomer, and belongs to the technical field of high polymer materials.
Background
The chlorinated polyether polyol is a common raw material in the polyurethane industry, the polyurethane elastomer prepared from the chlorinated polyether polyol has the characteristics of flame retardance, oil resistance, seawater resistance, high bonding strength and the like, and can be widely applied to special environments such as oil fields, oceans and the like, and in addition, the chlorinated polyether polyol can also be used for synthesizing other novel grafted polyether and functional group substituted polyether, for example, a chlorine atom is substituted by azide group to prepare azide polyether adhesive. Among them, the polyepichlorohydrin Polyol (PECH) is a typical representative, for example, guo feng chun et al "some property studies of hydroxyl terminated polyepichlorohydrin polyurethanes" science and engineering of high molecular materials, 1988, 5: 74-77 discloses the structure of polyepichlorohydrin Polyol (PECH) and the mechanical property of polyurethane thereof, wherein the structural formula of the PECH is as follows:
Most of hydroxyl groups at the tail end of a PECH molecular chain are secondary hydroxyl groups, and the activity is lower when the PECH molecular chain reacts with an isocyanate curing agent; and when the r value is 1.2, the prepared PECH polyurethane has the following mechanical properties: the tensile strength is 3.43MPa, the elongation is 375%, and the defects of low mechanical property exist.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide chlorinated polyether diol capable of endowing polyurethane elastomer with higher mechanical property and a synthesis method thereof.
The conception of the invention is as follows: the 3, 3-disubstituted oxetane monomer 3-chloromethyl-3-methyl oxetane is subjected to cationic ring-opening polymerization to obtain chlorinated polyether diol with a primary hydroxyl group as an end group, and a molecular chain of the chlorinated polyether diol has certain symmetry and can endow the polyurethane elastomer with higher mechanical property.
In order to solve the technical problems, the chlorinated polyether diol of the invention has the following structural formula:
Wherein x + y is 8-60 and is an integer.
The synthesis route of the chlorinated polyether diol is shown as follows:
Wherein x + y is 8-60 and is an integer.
The invention relates to a method for synthesizing chlorinated polyether diol, which comprises the following steps:
Sequentially adding 1, 2-dichloroethane, 1, 4-butanediol and boron trifluoride tetrahydrofuran complex into a four-neck round-bottom flask with a mechanical stirring device, a reflux condenser tube, a thermometer and a dropping funnel, stirring at the temperature of 20-30 ℃ for 30min, then beginning to dropwise add 3-chloromethyl-3-methyloxetane for 1-8 h, continuing to react for 24-48 h after dropwise adding, and reacting with Na 2CO3Neutralizing the aqueous solution, washing the organic phase to be neutral, and concentrating to obtain chlorinated polyether glycol (PCMMO for short); wherein the molar ratio of 3-chloromethyl-3-methyl oxetane to 1, 4-butanediol is 8-60: 1, and the molar ratio of boron trifluoride tetrahydrofuran complex to 1, 4-butanediol is 0.5~2:1。
The invention has the advantages that:
The PCMMO synthesis method is simple, the end group is a primary hydroxyl group with high reaction activity, the structure of a molecular chain has certain symmetry, and the polyurethane elastomer can be endowed with high mechanical properties. The tensile strength of the polyurethane elastomer prepared by using the PCMMO as the raw material is 5.65MPa, the elongation is 486 percent, and the tensile strength of the PECH polyurethane elastomer in the comparative document is 3.43MPa, and the elongation is 375 percent.
Detailed Description
The invention is further illustrated by the following examples.
Testing an instrument:
(1) The infrared spectrum is tested by a Nexus 870 Fourier transform infrared spectrometer of Nicolet company in the United states;
(2) Nuclear magnetism is tested by AVANCE AV500 type nuclear magnetic resonance instrument of Bruker company in Germany;
(3) the number average molecular weight was measured by GPC-50 gel permeation chromatography of the company, UK P L;
(4) The mechanical properties of the elastomer are tested by an Instron model 4505 universal material testing machine of the American Instron company;
(5) The hydroxyl value was measured by phthalic anhydride-pyridine acylation.
Example 1
30ml of 1, 2-dichloroethane, 1.8g (0.02mol) of 1, 4-butanediol and 2.8g (0.02mol) of boron trifluoride tetrahydrofuran complex are added in succession to a 100ml four-neck round-bottom flask equipped with mechanical stirring, reflux condenser, thermometer and dropping funnel, 24.1g (0.20mol) of 3-chloromethyl-3-methyloxetane are initially added after stirring at 20 ℃ for 30min, the reaction is continued for 24h after the addition is complete, Na is used 2CO3The reaction was terminated by neutralization with an aqueous solution, and the organic phase was washed with water to neutrality and concentrated to give 24.7g of a pale yellow viscous liquid with a yield of 95.4%.
Characterization data:
IR,νmax(cm-1):3387(O-H),2967、2934、2879(C-H),1109(C-O-C),724(C-Cl)。
1H NMR(CD3COCD3,500MHz):1.05,3.37,3.63。
13C NMR(CD3COCD3,500MHz):17.52,41.42,49.04,73.56。
The number average molecular weight of 1210 and the hydroxyl value of 88.1 mgKOH/g.
The above data indicate that the compound synthesized is a chlorinated polyether diol.
Example 2
60ml of 1, 2-dichloroethane, 1.8g (0.02mol) of 1, 4-butanediol and 2.8g (0.02mol) of boron trifluoride tetrahydrofuran complex are added in succession to a 150ml four-neck round-bottom flask equipped with mechanical stirring, reflux condenser, thermometer and dropping funnel, 38.6g (0.32mol) of 3-chloromethyl-3-methyloxetane are initially added after stirring at 25 ℃ for 30min, the reaction is continued for 30h after the addition is complete, Na is used 2CO3The reaction was terminated by neutralization with an aqueous solution, and the organic phase was washed with water to neutrality and concentrated to give 39.1g of a pale yellow viscous liquid with a yield of 96.8%.
The number average molecular weight of 2020, and the hydroxyl value of 52.2 mgKOH/g.
Example 3
90ml of 1, 2-dichloroethane, 1.8g (0.02mol) of 1, 4-butanediol and 4.2g (0.03mol) of boron trifluoride tetrahydrofuran complex are added in succession to a 250ml four-neck round-bottom flask equipped with mechanical stirring, reflux condenser, thermometer and dropping funnel, and after stirring at 25 ℃ for 30min, 60.3g (0.50mol) of 3-chloromethyl-3-methyloxetane are initially added dropwise over a period of 6h, and after the dropwise addition, the reaction is continued for 40h, followed by addition of Na 2CO3The reaction was terminated by neutralization with an aqueous solution, and the organic phase was washed with water to neutrality and concentrated to give 60.4g of a pale yellow viscous liquid with a yield of 97.3%.
The number average molecular weight is 3050 and the hydroxyl value is 34.5 mgKOH/g.
The chlorinated polyether diol has application performance
(1) Evaluation of miscibility with isocyanate curing agent
HDI tripolymer is selected as a curing agent, and the miscibility and reactivity of the PCMMO and the curing agent are examined.
The PCMMO and HDI tripolymer has good miscibility, the mixed solution is clear and transparent, and the formed mixed solution can be stably subjected to a curing reaction at the temperature of 60-80 ℃.
(2) Mechanical properties of elastomers
The PCMMO with the number average molecular weight of 1210 is used as a raw material, mixed with a curing agent HDI trimer, heated and cured, and when the r value is 1.2, the prepared polyurethane elastomer has the following mechanical properties: the tensile strength was 5.65MPa and the elongation was 486%.
Claims (2)
2. A method of synthesizing chlorinated polyether glycol according to claim 1, comprising the steps of:
Sequentially adding 1, 2-dichloroethane, 1, 4-butanediol and boron trifluoride tetrahydrofuran complex into a four-neck round-bottom flask with a mechanical stirring device, a reflux condenser tube, a thermometer and a dropping funnel, stirring at the temperature of 20-30 ℃ for 30min, then beginning to dropwise add 3-chloromethyl-3-methyloxetane for 1-8 h, continuing to react for 24-48 h after dropwise adding, and reacting with Na 2CO3Neutralizing the aqueous solution, washing the organic phase with water to be neutral, and concentrating to obtain chlorinated polyether glycol; wherein the molar ratio of 3-chloromethyl-3-methyloxetane to 1, 4-butanediol is 8-60: 1, and the molar ratio of boron trifluoride-tetrahydrofuran complex to 1, 4-butanediol is 0.5-2: 1.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2895921A (en) * | 1956-08-27 | 1959-07-21 | Hercules Powder Co Ltd | Preparation of oxetane polymers |
US4405762A (en) * | 1981-12-07 | 1983-09-20 | Hercules Incorporated | Preparation of hydroxy-terminated poly(3,3-bisazidomethyloxetanes) |
CN106750236A (en) * | 2016-12-18 | 2017-05-31 | 苏州大学 | A kind of copolyether containing fluoroalkyl and preparation method thereof |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2895921A (en) * | 1956-08-27 | 1959-07-21 | Hercules Powder Co Ltd | Preparation of oxetane polymers |
US4405762A (en) * | 1981-12-07 | 1983-09-20 | Hercules Incorporated | Preparation of hydroxy-terminated poly(3,3-bisazidomethyloxetanes) |
CN106750236A (en) * | 2016-12-18 | 2017-05-31 | 苏州大学 | A kind of copolyether containing fluoroalkyl and preparation method thereof |
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