CN115785431A - Polyether polyol containing carbamate structure and synthesis method and application thereof - Google Patents
Polyether polyol containing carbamate structure and synthesis method and application thereof Download PDFInfo
- Publication number
- CN115785431A CN115785431A CN202211472416.4A CN202211472416A CN115785431A CN 115785431 A CN115785431 A CN 115785431A CN 202211472416 A CN202211472416 A CN 202211472416A CN 115785431 A CN115785431 A CN 115785431A
- Authority
- CN
- China
- Prior art keywords
- polyether
- polyether polyol
- amine
- propylene carbonate
- reaction
- 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.)
- Pending
Links
Images
Abstract
The invention relates to the technical field of polyurethane synthesis, and discloses polyether polyol containing a carbamate structure, a synthesis method and application thereof, wherein the method comprises the following steps: adding propylene carbonate, multi-element polyether amine and a combined catalyst into a reactor, mechanically stirring and condensing and refluxing in an inert gas atmosphere for reaction, and removing the propylene carbonate by reduced pressure distillation after the reaction is finished to obtain the polyether polyol. The method selects propylene carbonate and macromolecular polyether amine as raw materials, and is matched with an autonomously designed catalyst to catalyze and realize the improvement of the proportion of primary hydroxyl of the product and the improvement of the amino conversion efficiency of the polyether amine.
Description
Technical Field
The invention relates to the technical field of polyurethane synthesis, in particular to polyether polyol containing a carbamate structure and a synthesis method and application thereof.
Background
Polyurethane, also called polyurethane, includes a soft segment and a hard segment in its molecular structure, wherein the hard segment mainly affects the softening temperature, melting temperature and high temperature performance of polyurethane, and the soft segment affects the oil resistance, hydrolysis resistance, low temperature performance and other performances. The polyurethane hard segment is generally composed of a carbamate structure and a polyisocyanate molecular chain; the soft segment part is composed of oligomer polyols such as polyether, polyester and the like, and the performances of different types of polyols are different.
The polyester polyol contains more ester bonds with strong polarity, and the polyether polyol contains more rotatable ether bonds. Therefore, the polyurethane synthesized by using the polyester polyol as a soft segment has high strength, oil resistance and thermal oxidation stability and poor hydrolysis resistance; the polyurethane synthesized by polyether polyol as a soft segment has good flexibility, low-temperature performance and hydrolysis resistance, but has poor strength. Generally, when the molecular weight of the polyurethane is the same, if the soft segment is polyester, the strength of the polyurethane is improved along with the increase of the molecular weight of the polyester polyol; if the soft segment is a polyether, the strength of the polyurethane decreases as the molecular weight of the polyether polyol increases, but the elongation increases. The molecular chain of polyether polyol synthesized by the traditional method contains ether bond, the ether bond is easy to rotate, the molecular chain flexibility is good, the flexibility and hydrolysis resistance of polyurethane prepared by the polyether polyol are good, but the thermal stability and the mechanical strength of the polyurethane are inferior to those of polyurethane prepared by taking the polyester polyol as a raw material, the cost of the polyester polyol is high, and the hydrolysis resistance of the prepared polyurethane is poor.
Therefore, it is necessary to develop a novel polyol which has the advantages of both polyols and eliminates the disadvantages of both polyols. Analysis of the polyester polyol reveals that: the polyester polyol contains a large amount of hydrogen bonds, so that the strength of the polyester polyol is greatly improved; the hard segment in the polyurethane is characterized by the performance of a urethane bond. It is therefore contemplated to incorporate urethane structures in polyether polyols. If a carbamate structure is introduced into polyether polyol with good flexibility, the added hydrogen bond improves the thermal stability and the mechanical strength, and meanwhile, the flexibility and the hydrolysis resistance are also reserved.
CN108779379A discloses a method for increasing the structure of urethane, polyether or polyester polyol is reacted with isocyanate monomer. However, the isocyanate monomer is expensive and extremely toxic, is not easy to be stored in a water-sensitive manner, is an environment-friendly and safe chemical raw material which is not advocated for use and actively seeks for an alternative scheme.
Non-isocyanate polyurethane reactions have also been developed, which are generally synthesized by reacting polyamines with polycyclic carbonates, without the need to use isocyanate raw materials during the preparation process, and without the influence of moisture. At present, the research is still immature, and the direct reaction preparation is mostly aimed at the direct reaction of the two-membered cyclic carbonate and the primary diamine, but the product has small molecular weight and lacks of a network structure, so that the mechanical property, the solvent resistance and the hydrolysis resistance of the product are poor, and the application is limited. The failure to develop more polyamines to react with the polycyclic carbonates is also limited mainly by the research on catalyst systems, and the search for efficient catalysts is the focus of the current research project.
Propylene carbonate (abbreviated as PC) is a five-membered ring in which one hydrogen is substituted by a methyl group, has high reactivity, and is widely used as a solvent, an electrolyte, and the like. The propylene carbonate can be prepared by cycloaddition reaction of carbon dioxide and propylene oxide, and the reaction atom has high utilization rate and high carbon fixation rate, namely one propylene oxide can fix one carbon dioxide. However, the production capacity of propylene carbonate is nearly surplus, the application field is limited, and other purposes are urgently needed to be developed to improve the added value and the digestion production capacity. Such as non-isocyanate polyurethanes, but the synthesis of non-isocyanate polyurethanes is difficult.
CN112898576A discloses a method for synthesizing polyether polyol containing a carbamate structure by using tetrabutyl titanate, anhydrous zinc acetate and sodium ethoxide as catalysts and micromolecular saturated carbonate, an asymmetric carbonate monomer, a silane coupling agent with primary amino, phenyl sulfonyl chloride and polyether amine as reactants. Although the method synthesizes non-isocyanate polyurethane, the raw materials are excessive in the reaction process, the catalyst is complex, the primary amino silane coupling agent is easy to self-crosslink in the reaction process, and the post-treatment is troublesome.
Disclosure of Invention
Aiming at the problems of complex synthesis method, low catalytic efficiency, low raw material conversion rate and the like of non-isocyanate polyurethane in the prior art, the invention provides the synthesis method of polyether polyol containing a carbamate structure, wherein propylene carbonate and macromolecular polyether amine are selected as raw materials, and an autonomously designed catalyst is matched to catalyze and realize the improvement of the proportion of primary hydroxyl in a product and the improvement of the amine conversion efficiency of the polyether amine.
In order to achieve the purpose, the invention adopts the technical scheme that:
a synthesis method of polyether polyol containing a carbamate structure comprises the following steps:
adding propylene carbonate, multi-element polyether amine and a combined catalyst into a reactor, mechanically stirring and condensing and refluxing in an inert gas atmosphere for reaction, and removing the propylene carbonate by reduced pressure distillation after the reaction is finished to obtain the polyether polyol.
In order to obtain the ideal polyether polyol containing the urethane bond, the polyether polyol containing the urethane structure is obtained by ring-opening polymerization by taking the polyether amine and the propylene carbonate as raw materials in consideration of the reactivity of the raw materials, the simplicity of the synthesis process and the economy. The reaction system comprises the following advantages:
the propylene carbonate has high activity, the ring opening is easy, a single ring is replaced by only one hydrogen, the singleness of space selection is easily caused due to reasons such as steric hindrance and the like in the synthetic process, the generated structure is single, the reaction is easy to carry out, the by-product is low, and the conversion rate of raw materials is high. The poly-ether amine provides an amino structure, and a plurality of amino nonlinear types are easy to synthesize a net structure, so that the mechanical strength of the product is enhanced, and the mechanical strength of the polyurethane prepared from the polyether polyol is improved.
In addition, because the propylene carbonate capacity in the current market is close to surplus, the application field is relatively limited, the method of the invention can also widen the application range of the propylene carbonate and improve the utilization value of the propylene carbonate.
The multi-element polyether amine is multi-element amine containing ether bond, including any one of ternary polyether amine, quaternary polyether amine and pentabasic polyether amine; the molecular weight of the multi-polyether amine is 200-500;
preferably, the multi-polyether amine is a ternary polyether amine; the product synthesized by the ternary polyether amine can be effectively crosslinked by selecting the product synthesized by the ternary polyether amine in consideration of the application of synthesizing polyurethane by using the polyalcohol and the controllability of the structure of the synthesized product.
Further preferably, the polyetheramine comprises ZT-143, ZT-1500, ZD-1200, ZED-601, ZED-901.
The combined catalyst is a composition of a zinc-cobalt double metal cyanide complex and an organic base, wherein the mass ratio of the zinc-cobalt double metal cyanide complex to the organic base is 1. Namely the mass ratio of the zinc-cobalt double metal cyanide complex is 45.45-76.92 percent, and the mass ratio of the organic base is 23.08-54.55 percent. With the increase of the organic base ratio, the catalyst activity shows a tendency of increasing and then decreasing, and therefore, the ratio of the two needs to be reasonably controlled.
At present, the zinc-cobalt double metal cyanide complex is generally used as a catalyst for ring-opening polymerization of epoxy compounds, and is rarely used in a reaction system of amine and epoxy compounds.
The concrete is embodied in the following two aspects: (1) generally, the basic substance-initiated polymerization mechanism is usually the initiation of proton transfer and thus chain extension, and is not related to the zinc-cobalt double metal cyanide complex catalyst, however, the invention discovers that after part of specific organic base participates in the reaction, the active center of the double metal complex is subjected to the synergistic action of the organic base, and the efficiency of the anion-cation coordination polymerization is accelerated. After the propylene carbonate is subjected to ring-opening polymerization under the catalytic action of the zinc-cobalt double metal cyanide complex, the replacement reaction of the multi-polyether amine and the active structure of the zinc-cobalt double metal cyanide complex catalyst is accelerated in the presence of organic alkali, and the coordination efficiency is not influenced.
(2) As the cyclic carbonate in the propylene carbonate is an asymmetric special structure and has selectivity in the ring opening process, and the traditional catalyst does not have high selectivity of catalyzing a ring opening position, the inventor surprisingly finds that the zinc-cobalt double metal cyanide complex catalyst selected by the invention has high selectivity on the ring opening position of an asymmetric carbonate monomer, the proportion of primary hydroxyl of the obtained polyether polyol can reach 98.12-99.34%, and the method is very favorable for the subsequent synthesis of polyurethane.
The zinc-cobalt double metal cyanide complex comprises one of zinc-cobalt (Zn-Co) double metal cyanide complex, nickel-cobalt (Ni-Co) double metal cyanide complex, and nickel-copper (Ni-Cu) double metal cyanide complex;
the organic base comprises any one or more of 1, 8-diazabicyclo-bicyclo (5, 4, 0) -7-undecene (DBU), triethylenediamine (DABCO), 2-dimethylolpropionic acid (DMPA), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN).
The structural formulas of the organic bases are respectively as follows:
DBU：
DBN：
DABCO：
DMPA：
the mol ratio of the propylene carbonate to the amino in the multi-element polyether amine is 1-8: 1; considering that the molecular weight and viscosity of poly-ether amine are higher than those of propylene carbonate, and the propylene carbonate is a small molecular raw material and is convenient to remove after the reaction is finished, the synthesis method adopts a method of properly excessive propylene carbonate to obtain higher amino conversion rate. Preferably, the molar ratio of the propylene carbonate to the amine group in the polyether polyamine is 1-5, more preferably 1-4.83: 1.
therefore, the combined catalyst is 0.2-2wt% of the total mass of the propylene carbonate and the multi-element polyether amine, and preferably accounts for 0.31-1.85 wt%.
The reaction is carried out for 14 to 30 hours at the temperature of between 90 and 150 ℃ in the atmosphere of normal pressure inert gas, and the flow rate of the inert gas is 3 to 5L/h; the reaction stirring speed is 100 r/min-300 r/min;
the temperature for removing the propylene carbonate by reduced pressure distillation is 120-150 ℃, the time is 1-3 h, and the absolute vacuum degree is 0 Pa-10 kPa.
In the synthesis method, the amino conversion rate of the multi-element polyether amine is more than 95%, the reaction efficiency is high, and the optimal conversion rate is 95.05-99.51%; the conversion rate of the propylene carbonate is more than 95 percent, preferably 95.35 to 96.37 percent; the proportion of primary hydroxyl in the obtained polyether polyol is more than 95 percent, and preferably 96.16 to 99.34 percent;
the combined catalyst in the synthesis method has the catalytic efficiency of more than 100g/g, preferably more than 110g/g or more than 120 g/g, and further preferably has the catalytic efficiency of 119-196 g/g.
The structure of the polyether polyol prepared by the synthesis method is shown as the following formula:
wherein n is a natural number of 3 to 5, and R represents an oxygen-containing saturated alkyl group having not less than 6 carbon atoms, preferably an oxygen-containing saturated alkane having 6 to 20 carbon atoms.
The polyether polyol has the molecular weight of 800-1200 and the molecular weight distribution below 1.5, is small molecular polyether polyol and can be mainly used in the hard foaming field of polyurethane.
The viscosity of the polyether polyol is 9000-13000 mPa.s, preferably 9194-12839 mPa.s, and the amine value of the polymer is 0.030-0.040 mmol/g, preferably 0.030-0.037 mmol/g; the low molecular weight and high viscosity indicate that the hydrogen bonding effect in the molecules is strong, and the polyurethane prepared by taking the molecular weight as the raw material has higher mechanical strength.
The proportion of primary hydroxyl in the polyether polyol can reach more than 95 percent, such as more than 98 percent, and preferably 96.16 to 99.34 percent; the obtained polyether polyol has high primary hydroxyl ratio, good molecular regularity and high reaction activity, and can keep relatively high activity when used for preparing high molecular weight polyurethane and increase the structure controllability of a polyurethane finished product due to the high primary hydroxyl ratio.
The invention also provides the application of the polyether polyol in preparing polyurethane, the invention obtains the polyol containing urethane bonds under the condition of not using isocyanate monomers, the molecular weight range is 800-1200, the primary hydroxyl content is high, the polyether polyol can replace the soft segment polyol in the polyurethane, and the polyether polyol can also be used in the aspects of pesticides, medicines, resin modification and the like.
The polyether polyol containing the urethane structure, which is synthesized by using the polyamine, has the following advantages in the aspect of preparing polyurethane: (1) due to the effect of the polyamine, the functionality is more than 2, which is beneficial to the crosslinking of polyurethane, and no micromolecule crosslinking agent is needed to be added in the synthesis process of the crosslinking polyurethane. (2) The polyether polyol has the molecular weight range of 800-1200, can also be used as a chain extender or a cross-linking agent in polyurethane synthesis, and has a wide application range.
The invention also provides polyurethane which comprises the polyether polyol, a foaming agent, polyisocyanate, a catalyst and a foaming stabilizer.
The polyurethane is prepared by adding the polyether polyol, the foaming agent, the polyisocyanate, the catalyst and the foaming stabilizer into a container, mixing, and mixing and foaming under high-speed stirring.
Preferably, the polyurethane comprises 12 to 75 parts of the polyether polyol, 1 to 3 parts of a foaming agent, 3.6 to 45 parts of polyisocyanate, 0.002 to 0.15 part of a catalyst and 1 to 9 parts of a foaming stabilizer by weight.
Further preferably, the polyurethane comprises polyether polyol Toluene Diisocyanate (TDI), a catalyst dibutyltin dilaurate, a foam stabilizer polysiloxane-polyoxyalkylene copolymer and foaming agent ultrapure water.
The polyurethane has a tensile strength of 150kPa or more, an elongation at break of 90% or more, and a dimensional change of 1% or less.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method selects propylene carbonate and macromolecular polyether amine as raw materials, and is matched with an autonomously designed catalyst to catalyze and realize the improvement of the proportion of primary hydroxyl of a product and the improvement of the amine conversion efficiency of the polyether amine.
(2) The polyether polyol prepared by the invention has the molecular weight of 800-1200, the molecular weight distribution is below 1.5, the polyether polyol is a product with small molecule high viscosity, the hydrogen bond function in the molecule is strong, the primary hydroxyl occupation ratio is high, the reaction activity is high, the polyurethane prepared by using the polyether polyol as a raw material has high mechanical strength, the functionality is more than 2 due to the effect of polyamine, the crosslinking of the polyurethane is facilitated, the mechanical strength of polyurethane resin is further improved, and no small molecule crosslinking agent needs to be added in the synthesis process of the crosslinked polyurethane.
(3) The invention adopts the propylene carbonate with excessive market productivity as the raw material, widens the application range of the propylene carbonate, improves the utilization value of the propylene carbonate, avoids using isocyanate monomer with higher toxicity, is economic and environment-friendly, is beneficial to the environment and meets the aim of sustainable development.
Drawings
FIG. 1 is a graph comparing primary hydroxyl content, viscosity, and amine group conversion for example 23 and comparative examples 16-22.
Fig. 2 is a stress-strain graph of an application example and a comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all purchased from the market, and the polyether polyamine is prepared according to the method described in CN 111286014B by taking ternary polyether amine ZT-143,Zn-Co double metal cyanide as self-made by the applicant, specifically the preparation method of example 2 in Chinese patent CN 111286014B.
The method for measuring the amino conversion rate comprises the following steps: after the reaction, in order to accurately measure the amine value of the system after the reaction, the product before vacuum distillation was selected, and the amine value of the product was measured by hydrochloric acid titration, and ethanol was used as a solvent dissolution product. The solution concentration is 0.01 g/mL-0.03 g/mL,0.08 mol/L-0.1 mol/L hydrochloric acid aqueous solution is titrated, 0.1wt% -0.5 wt% bromophenol blue ethanol solution is used as an indicator, the titration end point is changed from blue to green, and the hydrochloric acid titration method can only measure the amine group value of primary amine, so the method is used for measuring the amine group conversion rate of the polyurethane polyol.
Calculation formula of amine value:
wherein am represents an amine number (m mol/g), V Acid(s) Represents the volume (L), C) of hydrochloric acid consumed for titration Acid(s) Represents the hydrochloric acid concentration (mol/L) used for titration, m Sample (II) Represents the mass of sample used for titration.
The relationship between amine number and amine group conversion is:
wherein, C Polyether amine % represents the conversion of the polyetheramine polyol, m Polyether amine Represents the charge of the polyetheramine, am represents the measured amine number, m Sample (A) Representing the sample mass used for titration, 6.38 represents the amine value of ZT-143, and 93.8% represents the proportion of primary amines in ZT-143 in the total amine groups (including primary and secondary amine groups).
Conversion rate of propylene carbonate: after the reaction is finished, the product is distilled under reduced pressure to remove excessive propylene carbonate, and the conversion rate of the propylene carbonate is calculated according to the mass difference. C% conversion of propylene carbonate is calculated by the formula:
wherein m is 1 Represents the total mass of propylene carbonate added, m 2 The mass of propylene carbonate obtained by distillation under reduced pressure is shown.
The molecular weight of the polyether polyol was measured by Gel Permeation Chromatography (GPC), the viscosity was measured by a rotational viscometer, and the measurement temperature was 45 ℃.
The proportion of primary hydroxyl in the product polyether polyol is measured by referring to the method recorded in CN 111307888B, specifically in example 1, and the structure of the product is correspondingly adjusted according to the invention, specifically: PEG4000 in example 1 was replaced with the polyether polyol of the present invention.
In addition, since the polyether polyols of the present invention contain residual primary amino groups, the calculation formula needs to be modified, and the modified formula is:
wherein x represents a hydroxyl value (mg KOH/g), m represents a mass (g) of a test sample, C 0 Represents the concentration (mol/L) of the sodium hydroxide solution, V 0 Represents the consumption (mL) of the sodium hydroxide solution at the time of the potential jump recorded when the sample is measured, V 1 Represents the consumption (mL) of the sodium hydroxide solution at the time of the potential jump recorded when the blank sample was measured, and am represents the measured amine value (m mol/g).
The performance test standards of the polyurethane material prepared in the following specific embodiment are respectively as follows: surface strength: measured according to GB/T20219-2015; tensile strength: measured according to GB 9641-1988; elongation at break: measured according to GB 9641-1988; rate of change in size: determined according to GBT 8811-2008.
EXAMPLES 1-8 compounding of catalyst
Before the reaction, mixing was carried out according to the ratio of table 1: and (2) lowering the Zn-Co double metal cyanide and the organic base catalyst into a reaction kettle with magnetic stirring, stirring for half an hour at 350r/min, and carrying out vacuum drying for one hour at room temperature to obtain the combined catalyst.
TABLE 1 compounding ratio of combination catalysts
| Serial number | Organic base | Zn-Co double metal cyanide: mass ratio of organic base |
| Example 1 | DBU | 1:0.3 |
| Example 2 | DBN | 1:0.24 |
| Example 3 | DABCO | 1:0.17 |
| Example 4 | DMPA | 1:0.26 |
| Example 5 | DBU | 1:1.2 |
| Example 6 | DBN | 1:0.96 |
| Example 7 | DABCO | 1:0.68 |
| Example 8 | DMPA | 1:1.04 |
Examples 9 to 33
The preparation of polyether polyol was carried out according to the reaction raw materials and process conditions of table 2, the reaction steps are generally as follows: adding propylene carbonate, multi-polyether amine and a combined catalyst into a reactor, and reacting in the presence of N 2 And mechanically stirring under the atmosphere, condensing, refluxing and reacting, and removing propylene carbonate by reduced pressure distillation after the reaction is finished to obtain the polyether polyol.
The combined catalyst adopts the catalyst prepared in the embodiment 1-8, the reaction is carried out in the nitrogen atmosphere at normal pressure, the nitrogen flow is 4L/h, and the reaction stirring speed is 200r/min; the temperature for removing the propylene carbonate by reduced pressure distillation is 130 ℃, the time is 2 hours, and the absolute vacuum degree is 4kPa.
After the reaction, the conversion rate of the reaction amine group, the conversion rate of the propylene carbonate, the molecular weight, the viscosity and the primary hydroxyl ratio of the product were measured, and the results are summarized in tables 2 and 3.
TABLE 2 examples 9-33 polyether polyol preparation Process and conversion etc
TABLE 3 examples 9-33 product molecular weights, molecular weight distributions, viscosities, etc
From the results of the above examples, it can be seen that the reaction has high conversion rate of amine group and high proportion of primary hydroxyl group in the product under proper conditions, wherein the ratio of propylene carbonate: amine group (mass ratio) =1:1, example 2 is used as a catalyst, the amount of the catalyst is 0.86wt%, the temperature is 125 ℃, the reaction time is 24 hours, and the reaction effect is best.
Comparative examples 1 to 8
The preparation of polyether polyol containing a carbamate structure comprises a catalyst, polyether amine and propylene carbonate. In the case that the DMC catalyst is Zn-Co double metal cyanide, the amount of the catalyst is 0.86wt%, the temperature is 125 ℃, and the catalytic effect is adjusted under the condition that the reaction time is 24 hours, wherein the amount of the organic base and the amount of the organic base are excessive or insufficient, and the specific conditions are shown in Table 4.
TABLE 4 comparative examples 1-8 preparation conditions and amine group conversion
From the results of the above comparative examples, it can be seen that the composition of the catalyst has a large influence on the catalytic efficiency under appropriate conditions, and the catalytic efficiency shows a tendency of increasing first and then decreasing as the organic base content increases. The reasons for this may be: when the content of the organic alkali is too high, the proton transfer efficiency initiated by the alkaline substance is improved, and the content of the active center of the bimetallic catalyst is relatively reduced, so that the coordination efficiency is influenced, and the catalytic efficiency of the catalyst is reduced; when the organic base content is too low, the synergistic effect of the organic base is not achieved, and therefore, the ratio of the organic base to the Zn-Co double metal cyanide catalyst needs to be reasonably controlled.
Comparative examples 9 to 15
The preparation of polyether polyol containing urethane structure includes catalyst, polyether amine and propylene carbonate. The influence of the catalyst amount on the catalytic efficiency was understood by adjusting the catalyst amount in the catalyst selection example 2 at 125 ℃ for 24 hours, as shown in table 5.
TABLE 5 comparative examples 9-15 preparation conditions and amine group conversion
It can be seen from the above comparative example results that under appropriate conditions, the catalytic efficiency of the catalyst increases with the increase of the catalyst dosage, and the best effect is achieved when the dosage is about 0.9wt%, and further increase of the dosage does not bring about further increase of the amine group conversion rate, but rather decreases.
From the results of the above comparative examples, it can be seen that, when other reaction conditions are the same, the catalytic efficiency is greatly reduced when the organic base proportion in the mixed catalyst is too high or too low; when the amount of the catalyst used is too low, the catalytic efficiency is also low.
Comparative examples 16 to 22
Comparative examples 16 to 22 were conducted in the same manner as in the case of the reaction in the absence of a catalyst, and the results are shown in Table 6 and FIG. 1, respectively, using a Zn-Co double metal cyanide catalyst, a small molecule triethylamine, tetrabutylammonium bromide, sodium hydroxide, DBU, DBN, etc. alone as a catalyst.
TABLE 6 comparative examples 16-22 preparation conditions and product conditions
As can be seen from Table 6 and the comparative example results in FIG. 1, the effect of using other conventional catalysts is not ideal and the primary hydroxyl ratio is not high. From the results of the above examples, it can be seen that, when the reaction conditions are the same, the product selectivity of the traditional organic base catalyst alone is lower than the selectivity of the organic base used together with the zinc-cobalt bimetallic catalyst, which indicates that the zinc-cobalt bimetallic catalyst and the organic base have synergistic effect and can improve the product selectivity. The reactivity of the single zinc-cobalt bimetallic catalyst is lower than that of the zinc-cobalt bimetallic catalyst used together with organic base. It is also shown that the synergistic effect not only improves the product selectivity but also promotes the activity of the reaction.
Application example
Using the polyether polyols prepared in examples 9-11 as starting materials, polyurethanes were prepared according to the formulations of Table 7, specifically: adding polyether polyol into a reaction kettle, starting stirring Toluene Diisocyanate (TDI) at the rotating speed of 200r/min for 1min, adding a catalyst, a foam stabilizer and a foaming agent in sequence, and setting the rotating speed to 2000r/min to obtain polyurethane foam.
The raw materials adopted in the reaction are specifically as follows: the polyether polyol HSH-206 used in the comparative examples had a molecular weight of 854 to 945 and a functionality of 3, from Nantong Deng chemical Co.
Isocyanate: toluene Diisocyanate (TDI), chemical reagents of the national drug group, inc.
Catalyst: dibutyl tin dilaurate, national chemical group chemical reagents ltd.
Foam stabilizer: polysiloxane-polyoxyalkylene copolymers, dow chemical company.
Foaming agent: ultrapure water.
TABLE 7 formulation for the preparation of polyurethanes
The properties of the prepared polyurethane material, such as surface hardness, tensile strength, elongation at break, dimensional change rate, were tested, and the results are shown in table 8.
TABLE 8 mechanical Properties and dimensional stability of the polyurethanes
Where ε L, ε W, and ε T represent the dimensional change in length, width, and thickness, respectively, of the test specimen.
The stress-strain curves of comparative examples and application examples 1 to 3 are shown in FIG. 2, and from the data of application examples 1 to 3 and comparative examples, it can be seen that the polyurethane foam prepared using the polyol of the present invention has greatly improved mechanical properties in terms of surface hardness, strength, etc., and can effectively improve the dimensional stability of the foam, as compared with the conventional polyether polyol existing in the market.
Claims (10)
1. A method for synthesizing polyether polyol containing a carbamate structure is characterized by comprising the following steps: adding propylene carbonate, multi-element polyether amine and a combined catalyst into a reactor, mechanically stirring and condensing and refluxing in an inert gas atmosphere for reaction, and removing the propylene carbonate by reduced pressure distillation after the reaction is finished to obtain the polyether polyol.
2. The method for synthesizing polyether polyol containing a urethane structure according to claim 1, wherein the polyether amine is polyether amine containing ether bond, and comprises any one of ternary polyether amine, quaternary polyether amine and pentabasic polyether amine; the molecular weight of the multi-polyether amine is 200-500.
3. The method of synthesizing polyether polyols containing urethane structures as claimed in claim 1, wherein said polyetheramines include ZT-143, ZT-1500, ZD-1200, ZED-601, ZED-901;
and/or the combined catalyst is a composition of a zinc-cobalt double metal cyanide complex and an organic base, wherein the mass ratio of the zinc-cobalt double metal cyanide complex to the organic base is 1:0.3 to 1.2.
4. The method of synthesizing a polyether polyol having a urethane structure according to claim 3, wherein the zinc-cobalt double metal cyanide complex comprises one of a zinc-cobalt double metal cyanide complex, a nickel-cobalt double metal cyanide complex, and a nickel-copper double metal cyanide complex;
and/or the organic base comprises any one or more of 1, 8-diazabicyclo-bicyclo (5, 4, 0) -7-undecene, triethylene diamine, 2-dimethylolpropionic acid, 1, 5-diazabicyclo [4.3.0] non-5-ene.
5. The method for synthesizing polyether polyol containing a urethane structure according to claim 1, wherein the molar ratio of the propylene carbonate to the amine groups in the polyether polyamine is 1 to 8:1; the combined catalyst is 0.2-2wt% of the total mass of the propylene carbonate and the multi-element polyether amine.
6. The method for synthesizing polyether polyol containing a urethane structure according to claim 1, wherein the reaction is carried out for 14 to 30 hours at 90 to 150 ℃ in an atmosphere of atmospheric inert gas, and the flow rate of the inert gas is 3 to 5L/h; the reaction stirring speed is 100 r/min-300 r/min;
the temperature for removing the propylene carbonate by reduced pressure distillation is 120-150 ℃, the time is 1-3 h, and the absolute vacuum degree is 0 Pa-10 kPa.
7. The method for synthesizing polyether polyol containing a urethane structure according to claim 1, wherein in the synthesis method, the conversion rate of amine groups of the polyether amine is more than 95%, and the conversion rate of propylene carbonate is more than 95%; the proportion of primary hydroxyl in the obtained polyether polyol is more than 95 percent;
and/or the catalytic efficiency of the combined catalyst in the synthesis method is more than 100 g/g.
8. Polyether polyol obtained by the synthesis process according to any of claims 1 to 7, characterized in that it has the structure represented by the following formula:
wherein n is a natural number of 3-5, and R represents an oxygen-containing saturated alkyl group with a carbon atom number of more than or equal to 6.
9. The polyether polyol according to claim 8, wherein the polyether polyol has a molecular weight of 800 to 1200, a molecular weight distribution of 1.5 or less, a viscosity of 9000 to 13000 mPas, a polymer amine value of 0.030 to 0.040mmol/g, and a primary hydroxyl group content of the polyether polyol of 95% or more.
10. A polyurethane comprising the polyether polyol of claim 8 or 9, a blowing agent, a polyisocyanate, a catalyst and a foam stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211472416.4A CN115785431A (en) | 2022-11-23 | 2022-11-23 | Polyether polyol containing carbamate structure and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211472416.4A CN115785431A (en) | 2022-11-23 | 2022-11-23 | Polyether polyol containing carbamate structure and synthesis method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115785431A true CN115785431A (en) | 2023-03-14 |
Family
ID=85440433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211472416.4A Pending CN115785431A (en) | 2022-11-23 | 2022-11-23 | Polyether polyol containing carbamate structure and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115785431A (en) |
-
2022
- 2022-11-23 CN CN202211472416.4A patent/CN115785431A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2258745B1 (en) | Hydroxy compound, process for production thereof, and prepolymer and polyurethane each comprising the hydroxy compound | |
| CN104769008B (en) | The method for preparing polyether carbonate polyol | |
| CN104837885B (en) | The manufacture of New Thermoplastic Elastic Urethane body based on polyether carbonate polyol and purposes | |
| Sardon et al. | Homogeneous isocyanate-and catalyst-free synthesis of polyurethanes in aqueous media | |
| US7728175B1 (en) | Linear amine functionalized poly(trimethylene ether) compositions | |
| CN104130390B (en) | Polyether-type polyaspartate and preparation method thereof | |
| JP2012527508A (en) | Polyurea made from two polyetheramines and one prepolymer | |
| CN102432793A (en) | Environment-friendly polyurethane prepolymer and synthetic method thereof | |
| US20090192283A1 (en) | Process for preparing high performance waterborne aliphatic-aromatic mixed polyurethanes | |
| CN103764715B (en) | Process for making polyether alcohols having oxyethylene units by polymerization of ethylene carbonate in the presence of double metal cyanide catalysts | |
| EP2215144B1 (en) | Copolymers comprising a trimethylene carbonate and poly(trimethylene ether) glycols | |
| CN115785431A (en) | Polyether polyol containing carbamate structure and synthesis method and application thereof | |
| CN107636074B (en) | Novel formulations for polyurethane applications | |
| JP7276997B2 (en) | Polycarbonate diol composition | |
| KR101156599B1 (en) | Silane modified polyurethane prepolymer and preparation method thereof | |
| TW202000727A (en) | Polycarbonate diol and polyurethane formed therefrom | |
| CN110072913A (en) | Polyether thiourea is prepared for the method for carbonate polyol | |
| WO1997037762A1 (en) | Reactive amine catalysts for use in polyurethane polymers | |
| JP5521213B2 (en) | Chlorinated polyether copolymer and process for producing the same | |
| EP2914643A1 (en) | Polymers of [4-(methylether)-1,3-dioxolane-2-one of polyether polyol] | |
| KR20140107464A (en) | Hydroxylamino polymer and method for the production thereof | |
| CN109400861B (en) | Branched polycarbonate polyol, preparation method and application thereof | |
| CN116903854B (en) | Bio-based non-isocyanate polyurethane and preparation method thereof | |
| CN114736366B (en) | Hindered amine-terminated polyether, preparation method of hindered amine-terminated polyether and preparation method of slow-reaction polyurea | |
| KR101166720B1 (en) | Hydroxy-substituted aminosilane and preparation method 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 |