CN108084426B - Poly (propylene carbonate) polyol with side chain containing carboxyl and preparation method thereof - Google Patents
Poly (propylene carbonate) polyol with side chain containing carboxyl and preparation method thereof Download PDFInfo
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- CN108084426B CN108084426B CN201711463134.7A CN201711463134A CN108084426B CN 108084426 B CN108084426 B CN 108084426B CN 201711463134 A CN201711463134 A CN 201711463134A CN 108084426 B CN108084426 B CN 108084426B
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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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
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a poly (propylene carbonate) polyol with a side chain containing carboxyl and a preparation method thereof, wherein the poly (propylene carbonate) polyol is prepared from the following components in parts by weight: 110-130 parts of polypropylene carbonate polyol, 5-26 parts of carboxyl-containing micromolecule diol and 0.24-4.8 parts of catalyst. The side chain carboxyl-containing polypropylene carbonate polyol is generated by dehydrating the polypropylene carbonate polyol and reacting the dehydrated polypropylene carbonate polyol with carboxyl-containing micromolecule diol and a catalyst. The invention provides the poly (propylene carbonate) polyol with the side chain containing the carboxyl and the preparation method thereof, the novel poly (propylene carbonate) polyol with the side chain containing the carboxyl is prepared, the used raw materials are environment-friendly and low in cost, the preparation process is simple, and the preparation method has practical application value.
Description
Technical Field
The invention relates to the technical field of organic polymer materials, in particular to poly (propylene carbonate) polyol with a side chain containing carboxyl and a preparation method thereof.
Background
The poly (propylene carbonate) polyol is a novel polycarbonate polyol, can be prepared by copolymerizing carbon dioxide and propylene oxide which are used as raw materials by using small molecular polyol as an initiator under the action of a catalyst, and has higher content of carbonate groups and ether groups in molecules. Because the high hydrolysis resistance of polyether and the high strength of aliphatic polycarbonate are achieved, the polyurethane has wide application in the field of polyurethane synthesis, and is especially used for synthesizing waterborne polyurethane materials with excellent performance.
At present, the research on polycarbonate polyol synthesized by taking carbon dioxide and propylene oxide as raw materials is carried out on a large scale at home and abroad. CN103865052 discloses a method for preparing polypropylene carbonate polyol by catalyzing copolymerization of carbon dioxide and propylene oxide using liquid double metal cyanide catalyst, and has entered into industrial application. And researches show that a series of waterborne polyurethane materials synthesized by taking the polypropylene carbonate polyol as a raw material have excellent performance. CN105482068, CN105504215, CN105885666 and the like disclose a series of aqueous polyurethane emulsions synthesized based on the polypropylene carbonate polyol and a hydrophilic chain extender containing small molecules in hard segments.
At present, the research on the waterborne polyurethane at home and abroad is mainly put on the polyurethane containing carboxyl at the hard segment and various applications thereof. However, it has been found that, in the production of an aqueous polyurethane having a carboxyl group in the hard segment, the dispersibility and the uniformity of the reaction block are not satisfactory, the appearance of the resultant aqueous polyurethane emulsion is poor, and the crystallinity of the hard segment is lowered. At present, the synthesis and application of the aqueous polyurethane emulsion containing soft segment ions are rarely researched at home and abroad, particularly the aqueous polyurethane containing the carboxylate radical ions at the soft segment, and related patents about the synthesis and application of the aqueous polyurethane containing the carboxyl at the soft segment are hardly available at home. Therefore, the industry is extremely short of a high-performance polymer polyol containing carboxyl groups in a soft segment and used for synthesizing waterborne polyurethane.
Aiming at the technical problems, the preparation method of the soft-segment carboxyl-containing polypropylene carbonate polyol and the preparation method thereof have the advantages of simple synthesis process and high production efficiency, and are the technical problems which are urgently needed to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problems that the dispersibility of a synthetic waterborne polyurethane emulsion and the uniformity of a reaction block are not ideal and the appearance is not good due to the fact that a hard segment of the poly (propylene carbonate) polyol prepared by the prior art contains carboxyl, and the crystallinity of the hard segment can be reduced.
In order to achieve the purpose, the invention adopts the following technical scheme: the poly (propylene carbonate) polyol with the side chain containing carboxyl is prepared from the following components in parts by weight: 110-130 parts of polypropylene carbonate polyol, 5-26 parts of carboxyl-containing micromolecule diol and 0.24-4.8 parts of catalyst. The poly (propylene carbonate) polyol is used as a main raw material, if the amount of the main raw material is less than 110 parts, the main raw material is too small to react with other added auxiliary reagents, if the amount of the main raw material is more than 130 parts, the reaction cannot be completed in the preparation process, and the purity of the generated propylene carbonate polyol with a side chain containing carboxyl is reduced; the carboxyl-containing micromolecule diol is combined to the polypropylene carbonate polyol as a soft segment to prepare the polypropylene carbonate polyol with the side chain containing carboxyl, the catalyst promotes the reaction speed of the polypropylene carbonate polyol and the carboxyl-containing micromolecule diol, the reaction time is shortened, if the adding amount is less than 0.24 part, the effect of catalytic reaction cannot be achieved, if the adding amount is more than 4.8 parts, the adding amount is too much, so that the generated polypropylene carbonate polyol with the side chain containing carboxyl contains more impurities, and the purity of the product is reduced.
Further, the composition is prepared from the following components in parts by weight: 115-125 parts of polypropylene carbonate polyol, 10-20 parts of carboxyl-containing micromolecule diol and 1-3 parts of catalyst. The catalyst promotes the reaction speed of the polypropylene carbonate polyol and the carboxyl-containing micromolecule diol and shortens the reaction time.
And further, the poly (propylene carbonate) polyol is synthesized by copolymerizing carbon dioxide and propylene oxide serving as initial raw materials under the action of an initiator and a catalyst, the molecular weight of the poly (propylene carbonate) polyol is 1000-100000, the hydroxyl functionality is 2-5, the mole fraction of carbonate groups in molecules is 0.25-0.45, and the number of double bonds in molecules is 1-5. When the molecular weight of the selected polypropylene carbonate polyol is less than 1000, the molecular weight of the synthesized polypropylene carbonate polyol with the side chain containing carboxyl is too small, and a stable cross-linking structure cannot be formed among molecules, so that the stability of the emulsion applied to preparation is poor, and when the molecular weight of the selected polypropylene carbonate polyol is more than 100000, the molecular weight of the synthesized polypropylene carbonate polyol with the side chain containing carboxyl is too large, the emulsion applied to preparation is easy to have uneven molecular distribution, and the color of the emulsion is not good; the mol fraction of the carbonate groups in the molecule is less than 0.3 or more than 0.4, which affects the structure and performance of the finally synthesized polypropylene carbonate polyol with carboxyl on the side chain, and causes uneven distribution of soft segments and hard segments.
And further, the molecular weight of the poly (propylene carbonate) polyol is 3000-50000, the hydroxyl functionality is 2-3, the mole fraction of carbonate groups in molecules is 0.3-0.4, and the number of double bonds in molecules is 2-4. The soft segment of the poly (propylene carbonate) polyol with the side chain containing carboxyl prepared by selecting the poly (propylene carbonate) polyol with the quality index has high bonding rate with the carboxyl.
Still further, the carboxyl-containing small molecular diol is one or two of dimethylolpropionic acid and dimethylolbutyric acid. The dimethylolpropionic acid and dimethylolbutyric acid have small molecular weight and are easy to combine with the polypropylene carbonate polyol to generate the polypropylene carbonate polyol with a side chain containing carboxyl.
Still further, the catalyst is one or more of tetrabutyl titanate, tetramethyl titanate, isobutyl titanate, triethylene diamine, tetrabutylammonium bromide and triethylamine. The catalyst can accelerate the reaction speed, shorten the reaction time and improve the preparation efficiency.
And further, the preparation method of the propylene carbonate polyol with the side chain containing carboxyl comprises the steps of weighing the components according to the formula, dehydrating the polypropylene carbonate polyol, adding carboxyl-containing micromolecule diol and a catalyst, heating to 130-180 ℃, and carrying out ester exchange reaction for 7-18 h to obtain the polypropylene carbonate polyol with the side chain containing carboxyl. The dehydration of the poly (propylene carbonate) polyol can avoid the hydrolysis of water and the poly (propylene carbonate) polyol which is generated by the reaction and has carboxyl on the side chain under the heating condition, the generation rate is reduced, the reaction speed is too slow when the reaction temperature is lower than 130 ℃, and the reaction is too violent when the reaction temperature is higher than 180 ℃, so that the reaction process cannot be controlled. If the ester exchange reaction time is less than 7 hours, the reaction time is too short, the reaction is insufficient, if the reaction time is more than 18 hours, side reaction may occur due to too long reaction time, the product performance is affected, and the polyol with large molecular weight can be alcoholyzed into the polyol with small molecular weight through the ester exchange reaction.
And further, dehydrating the polypropylene carbonate polyol to heat the polypropylene carbonate polyol to 115-125 ℃ under the vacuum degree of-0.08 MPa to-0.1 MPa, dehydrating for 2-3 hours, and cooling. The dehydration efficiency is improved by adopting vacuum heating dehydration, and the deterioration of the polypropylene carbonate caused by overhigh temperature is avoided.
Compared with the prior art, the invention has the beneficial technical effects that:
firstly, preparing a novel poly (propylene carbonate) polyol with a side chain containing carboxyl, and carrying out ester exchange reaction on carboxyl-containing micromolecule diol and the poly (propylene carbonate) under the action of a catalyst to synthesize the novel poly (propylene carbonate) polyol with the side chain containing carboxyl, wherein the carboxyl is combined in a soft segment, and the chemical property is better.
Secondly, the used raw materials are environment-friendly and low in cost. The practical poly (propylene carbonate) polyol is prepared by taking carbon dioxide and propylene oxide as raw materials, has the structures of carbonate and ether, has high strength, hydrolysis resistance and low cost, does not cause harm to the environment in large-scale production, and has great significance to environmental protection, energy conservation and emission reduction.
Thirdly, the preparation process is simple and has practical application value. The invention can alcoholyze the polymer polyol with large molecular weight into the polyol with small molecular weight by utilizing the ester exchange mechanism and is applied, and the preparation process is simple, easy to popularize and produce and has practical application value.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will now be further described with reference to the specific embodiments.
Example 1
Heating 120 parts by mass of polypropylene carbonate polyol with the molecular weight of 3000 and the hydroxyl functionality of 2 to 115 ℃ under the vacuum degree of-0.08 MPAa for dehydration, adding 12 parts of dimethylolpropionic acid and 0.24 part of triethylene diamine catalyst, heating to 130 ℃, and carrying out transesterification reaction for 7 hours to obtain the polypropylene carbonate dihydric alcohol with the side chain containing carboxyl.
Example 2
Heating 120 parts by mass of polypropylene carbonate polyol with the molecular weight of 10000 and the hydroxyl functionality of 2 to 120 ℃ under the vacuum degree of-0.09 MPAa for dehydration, adding 17 parts of dimethylolpropionic acid and 1.2 parts of triethylene diamine catalyst, heating to 150 ℃, and carrying out transesterification reaction for 9 hours to obtain the polypropylene carbonate dihydric alcohol with the side chain containing carboxyl.
Example 3
Heating 120 parts by mass of polypropylene carbonate polyol with the molecular weight of 30000 and the hydroxyl functionality of 2 to 125 ℃ under the vacuum degree of-0.095 MPAa for dehydration, adding 20 parts of dimethylolbutyric acid and 1.2 parts of triethylene diamine catalyst, heating to 150 ℃, and carrying out transesterification reaction for 9 hours to obtain the polypropylene carbonate diol with the side chain containing carboxyl.
Example 4
Heating 120 parts by mass of polypropylene carbonate polyol with the molecular weight of 30000 and the hydroxyl functionality of 2 to 120 ℃ under the vacuum degree of-0.08 MPAa for dehydration, adding 18 parts of dimethylolpropionic acid and 2 parts of tetrabutyl titanate catalyst, heating to 150 ℃, and carrying out transesterification reaction for 12 hours to obtain the polypropylene carbonate dihydric alcohol with the side chain containing carboxyl.
Example 5
Heating 120 parts by mass of propylene carbonate polyol with the molecular weight of 50000 and the hydroxyl functionality of 2 to 125 ℃ under the vacuum degree of-0.1 MPAa for dehydration, adding 19 parts of dimethylolpropionic acid and 3.6 parts of triethylamine catalyst, heating to 160 ℃, and carrying out transesterification reaction for 18h to obtain the polypropylene carbonate dihydric alcohol with the side chain containing carboxyl.
Example 6
Heating 120 parts by mass of propylene carbonate polyol with the molecular weight of 50000 and the hydroxyl functionality of 2 to 122 ℃ under the vacuum degree of-0.085 MPAa for dehydration, adding 5 parts of dimethylolpropionic acid and 2.4 parts of triethylene diamine catalyst, heating to 160 ℃, and carrying out transesterification reaction for 8 hours to obtain the polypropylene carbonate dihydric alcohol with the side chain containing carboxyl.
The poly (propylene carbonate) diol having carboxyl groups in the side chains obtained in examples 1 to 6 was sampled to prepare a 2% diol-tetrahydrofuran solution, and the molecular weight was measured.
The polypropylene carbonate diol having carboxyl groups on side chains prepared in examples 1 to 6 was reacted with a metered amount of isophorone diisocyanate, and ethylene diamine was used as a chain extender to synthesize a series of aqueous polyurethane emulsions having NCO/OH =1.7, and the appearance of the emulsions was observed. And 3000 molecular weight polypropylene carbonate dihydric alcohol which is not subjected to ester exchange, metered dimethylolpropionic acid and isophorone diisocyanate are taken to react, ethylenediamine is adopted as a chain extender, a waterborne polyurethane emulsion with NCO/OH =1.7 is synthesized, and the appearance of the emulsion is observed to be used as a comparative example 1.
The emulsions prepared in examples 1 to 6 and comparative example 1 were stored at 80 ℃ for 168 hours, and the emulsions were analyzed for stability. If the emulsion is stable, the storage period is considered to be greater than six months, otherwise, the storage period is considered to be less than six months. The results are given in table 1 below.
TABLE 1 comparison of the results of the quality of the products obtained in the different examples
| Name (R) | Molecular weight/g.mol-1 | Appearance of the emulsion | Storage stability |
| Example 1 | 1021 | Penetration of water | More than 6 months |
| Example 2 | 998 | Penetration of water | More than 6 months |
| Example 3 | 1019 | Penetration of water | More than 6 months |
| Example 4 | 991 | Penetration of water | More than 6 months |
| Example 5 | 1050 | Penetration of water | More than 6 months |
| Example 6 | 2998 | Clear and penetrate | More than 6 months |
| Comparative example 1 | 3000 | Blue light | More than 6 months |
In conclusion, the results of table 1 show that the propylene carbonate polyol having carboxyl groups in the side chains, which is prepared through transesterification, exhibits excellent appearance of the emulsion and excellent storage stability when used as a synthetic aqueous polyurethane emulsion. And through ester exchange reaction, carboxyl can not only be introduced on the soft segment in the polyurethane system, the dispersibility, the uniformity of the block and the appearance of the emulsion are improved, but also the polypropylene carbonate polyol with ultra-high molecular weight can be alcoholyzed into the polyol with small molecular weight and reused, and the method has great practical application value.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those of ordinary skill in the art can readily practice the present invention as described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (4)
1. A polypropylene carbonate polyol having a carboxyl group in a side chain, characterized in that: the composition is prepared from the following components in parts by weight: 110-130 parts of polypropylene carbonate polyol, 5-26 parts of carboxyl-containing micromolecule diol and 0.24-4.8 parts of catalyst, wherein the polypropylene carbonate polyol is synthesized by copolymerization of carbon dioxide and propylene oxide serving as starting raw materials under the action of an initiator and the catalyst, the molecular weight of the polypropylene carbonate polyol is 1000-100000, the hydroxyl functionality is 2-5, the mole fraction of carbonate groups in molecules is 0.25-0.45, and the number of double bonds in the molecules is 1-5; the carboxyl-containing micromolecule diol is one or two of dimethylolpropionic acid and dimethylolbutyric acid; the catalyst is one or more of tetrabutyl titanate, tetramethyl titanate, isobutyl titanate, triethylene diamine, tetrabutylammonium bromide and triethylamine; the preparation method of the carboxyl-containing polypropylene carbonate polyol comprises the following steps: weighing the components according to the formula, dehydrating the poly (propylene carbonate) polyol, adding carboxyl-containing micromolecule diol and a catalyst, heating to 130-180 ℃, and carrying out ester exchange reaction for 7-18 h to obtain the poly (propylene carbonate) polyol with side chains containing carboxyl.
2. The polypropylene carbonate polyol having carboxyl groups in the side chains according to claim 1, characterized in that: the composition is prepared from the following components in parts by weight: 115-125 parts of polypropylene carbonate polyol, 10-20 parts of carboxyl-containing micromolecule diol and 1-3 parts of catalyst.
3. The polypropylene carbonate polyol having carboxyl groups in the side chains according to claim 2, characterized in that: the molecular weight of the poly (propylene carbonate) polyol is 3000-50000, the hydroxyl functionality is 2-3, the mole fraction of carbonate groups in molecules is 0.3-0.4, and the number of double bonds in molecules is 2-4.
4. The polypropylene carbonate polyol having carboxyl groups in the side chains according to claim 1, characterized in that: the dehydration of the polypropylene carbonate polyol is to heat the polypropylene carbonate polyol to 115-125 ℃ under the vacuum degree of-0.08 MPa to-0.1 MPa, dehydrate for 2-3 hours and then cool.
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