TW201930396A - Method for manufacturing polycarbonate polyols and composition comprising the polycarbonate polyols - Google Patents

Abstract

A method for manufacturing polycarbonate polyols and a composition comprising the polycarbonate polyols are provided. The composition comprises: a polycarbonate polyol; and nanoscale silicate platelets having 10000 to 20000 (unit/per platelet) metal cations on its surface, wherein the composition has a viscosity from 265 to 1520 cps.

Description

Process for preparing polycarbonate polyol and polycarbonate polyol composition

The invention relates to a method for preparing a polycarbonate polyol, in particular to a method for preparing a polycarbonate polyol for reacting a carbonate compound with a diol compound by a nanosheet, and a polycarbonate polyol composition.

Polycarbonate polyols are excellent in transparency, heat resistance, and mechanical strength, and are widely used in industries such as electrical and electronic parts, automotive parts, optical recording media, and lenses.

However, the conventional polycarbonate polyol process is carried out by transesterification of an organic carbonate with a polyol at a specific pressure (1.5 to 100 bar) and temperature (100 ° C to 300 ° C), and an alcohol such as methanol is present during the reaction. Classes (depending on the type of organic carbonate) and unreacted carbonates are distilled off, and the reaction adds a catalyst containing an alkaline earth metal or a transition metal. The residues of these catalysts affect the product properties of the polycarbonate polyol. The selection and use of the media must be carefully evaluated. Therefore, it is necessary to develop a catalyst that can be easily removed in the process, or to develop a catalyst that remains in the product without affecting its properties.

The present disclosure provides a polycarbonate polyol composition comprising a polycarbonate polyol and a nanosheet having a surface/per platelet metal cation on the surface, wherein the polycarbonate polyol has a viscosity of 265 to 1520 cps.

The present disclosure provides a method for preparing a polycarbonate polyol, comprising: having a surface of 0.5 to 1.5 wt% having a surface of about 10,000 to 20,000 (unit/per platelet) based on the total weight of the carbonate compound and the diol compound. a metal cation nano bismuth tablet is added as a catalyst to a reaction system containing the carbonate compound and the diol compound, and the carbonate compound and the diol compound are subjected to a temperature increase reaction, and then a pressure reduction reaction is performed. A polycarbonate polyol is obtained.

The following specific embodiments are used to explain the disclosure of the disclosure. After reading the disclosure of the specification, those skilled in the art can easily understand the advantages and functions thereof.

It is to be understood that the structure, the proportions, the dimensions and the like of the drawings are merely for the purpose of the disclosure, and are intended to be understood and read by those of ordinary skill in the art, and are not intended to limit the disclosure Among the specific conditions, it does not have technical significance. Any changes in the structure, changes in the proportional relationship, or adjustments in the dimensions are intended to be included in the scope of the present disclosure without affecting the effects and the achievable objectives of the present specification. In the absence of substantial changes to the technical content, changes or adjustments in their relative relationship are considered to be within the scope of this disclosure.

In the present disclosure, a nano-ruthenium sheet having a specific metal cation on the surface is used as a catalyst, and a transesterification reaction system is added, and a cationic cation-catalyzed transesterification reaction on the surface is used, and after the reaction is terminated, a polyester polyol is obtained, and the nano-sized tablets are dispersed. In it. On the one hand, the nano-ruthenium tablets remain in the polycarbonate polyol and do not adversely affect the polyester polyol. On the other hand, the process of additionally adding inorganic filler particles to improve the physical properties of the material is simplified.

Specifically, the nano tablet according to the present disclosure is used as a catalyst for transesterification of an ester compound (or specifically a carbonate compound) with a diol compound to synthesize a polycarbonate containing a nano tablet. The ester polyol forms a polycarbonate polyol composition. By the special high specific surface area characteristics of the nanosheet and the cations on the surface, the efficiency of the catalytic reaction can be greatly increased, including the increase of the yield and the viscosity of the product, and a product with a larger molecular weight can be obtained. On the one hand, it can be avoided that the residual of the general metal catalyst affects the product properties of the polycarbonate polyol, and on the other hand, since the polycarbonate polyol synthesized by this method has been introduced into the inorganic nano crepe sheet material, further synthesis or When modifying polyurethanes (PUs) and polyesters, polyurethanes and polyesters containing nano-barium sheets can be obtained without additional addition, and the physical properties can be improved.

The carbonate compound may be ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, glycerin 1,2-carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and unterminated. Butyl phenyl carbonate, diphenyl carbonate, dibenzyl carbonate, benzyl phenyl carbonate, guaiacol carbonate, di-2-pyridyl carbonate, 1,3-dioxin Alkan-2-one, (R)-(+)-4-(methoxymethyl)-1,3-dioxolan-2-one, (S)-(-)-4-(methoxy Methyl)-1,3-dioxolan-2-one or a combination thereof.

The aforementioned diol compound may be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, poly Propylene glycol, polytetrahydrofuran, bisphenol-A or a combination thereof.

The nano-ply film has a thickness of about 1 to 5 nm and is geometrically formed as a thin silicate platelet having a high specific surface area (about 100 × 100 × 1 nm ³ ) and a surface area of about 700 to 800 m ^{2 .} /g, about 4 × 10 ¹⁶ pieces per gram. Each of the cymbals is independently present and does not stack and adsorb, and can be stably dispersed in an aqueous solution and an organic solution. Because of the special high specific surface area and the cations on the surface of the nanosheet, this nanosheet can be used as a catalyst to catalyze the transesterification of ester- or carbonate-based compounds with polyol compounds. Polymer or oligomer. In addition, about 100,000 to 300,000 Si-OH per surface of the nano-ruthenium sheet can further increase the mechanical, heat-resistant and the like properties of the polymer or oligomer-derived end material.

The method for preparing a nano silicate plate (NSP) comprises: delaminating with a natural clay by reacting Amine-terminated Mannich Oligomers (AMO) with a natural clay, and performing a chemical extraction step. Each piece of clay (ie, nano-butter) is independently dispersed in water and each piece of clay is independently present and does not stack and adsorb on each other, and is stably dispersed in an aqueous solution.

Next, an appropriate amount of a metal salt (for example, MgCl ₂ and LiCl) may be further added to a nano tablet (NSP-Na ⁺ -based) to carry out cation exchange with Na ⁺ on the nano tablet to synthesize A nano-ruthenium sheet having a specific metal cation on the surface (for example, NSP-Mg ²⁺ , NSP-Li ⁺ type nano-barium).

The specific experimental procedure is as follows: Take NSP-Na ⁺ (100 g, 0.1 wt%, 1 mmol) aqueous phase dispersion in the reaction flask, set up mechanical stirring and heating condensing device, and heat to 80 °C, then quickly pour into different valences. The metal halide ion salt (1.2 mmol) powder was stirred vigorously at 80 ° C for one hour to complete the ion exchange of NSP-M (M metal). The NSP-M dispersion is filtered in a suction funnel and washed with deionized water to a halogen-free ion residue to prepare a nano-ruthenium sheet having a specific metal cation on the surface, and the content of the metal cation is 10,000 to 20,000 (unit/per). Platelet).

The aforementioned nano-ruthenium sheet has at least one metal cation on the surface, wherein the metal cation may include Na ⁺ , Mg ²⁺ , Li ⁺ , K ⁺ , Sn ²⁺ , Ca ²⁺ , Yb ³⁺ , Cs ⁺ , Sc At least one of the groups consisting of ³⁺ , Y3 ⁺ , La3 ^+, and Ce4 ⁺ ; and the content of the metal cation on the surface of the nanosheet may be 10,000 to 20,000 (unit/per platelet).

In the reaction system, the content of the nano ruthenium catalyst is in the range of 0.5 to 1.5 wt% based on the total weight of the carbonate compound and the diol compound.

Among them, the content of metal cations is measured by an atomic absorption spectrometry method. Method: Take 5 g of soil sample, place it in a 250 mL Erlenmeyer flask, add 100 mL NH ₄ OAc (1 M NH ₄ OAc, pH=7.0) and shake for 20 minutes, then filter with filter paper and then use NH ₄ OAc solution. The soil sample was washed, and finally the filtrate was fixed to 200 mL, and the content of the exchangeable metal cation was measured by an atomic absorption spectrophotometry (AA).

The present disclosure can catalyze the transesterification reaction by using a cation-containing nano ruthenium catalyst to obtain a high viscosity and yield. After the reaction is completed, the polycarbonate polyol in which the nano crepe sheet is dispersed can be obtained to form a polycarbonate polyol composition, which simplifies the process and shortens the time required for the process, wherein the viscosity is measured by a Fungilab SMART instrument. Method measurement.

The present disclosure also provides a method for preparing a polycarbonate polyol, specifically, comprising: 0.5 to 1.5 wt% of the surface having a surface of about 10,000 to 20,000 based on the total weight of the carbonate compound and the diol compound ( Unit/per platelet) as a catalyst, a reaction system containing the carbonate compound and the diol compound is added as a catalyst, and the carbonate compound and the diol compound are subjected to a temperature rising reaction and then further The pressure reduction reaction is carried out to obtain a polycarbonate polyol. The temperature rising reaction may adopt a stage temperature rising reaction, and the pressure reducing reaction may adopt a stage type pressure reducing reaction.

In the method for preparing a polycarbonate polyol disclosed in the present disclosure, a polycarbonate polyol having a nano-barium sheet can be obtained, so that a nano-composite material can be prepared without adding an inorganic material in a subsequent application. On the other hand, the nanosheet can be further removed by centrifugation to obtain a high-purity polycarbonate polyol.

Taking the transesterification reaction of ethylene carbonate and 1,6-hexanediol as an example, the reaction formula is as follows:

More specifically, the present disclosure provides a method for preparing a polycarbonate polyol, wherein the temperature rising reaction comprises a phase one to a third phase, and the temperature is raised to about 90 to 110 ° C at a pressure of the reaction system. The temperature is about 0.5 to 1 hour; in this stage, the reaction system is heated to about 140 to 160 ° C under atmospheric pressure for about 1 to 2 hours; at this stage, the system is heated at atmospheric pressure. Up to about 170 to 190 ° C, holding temperature for about 4 to 6 hours; the aforementioned depressurization reaction comprises stage four to stage five, and the stage four steps down the reaction system to about 90 to 110 torr, the temperature is 170 to 190 ° C Holding the by-product for 1 to 2 hours, and depressurizing the reaction system to less than 50 torr at a temperature of 170 to 190 ° C for 1 to 2 hours to separate the by-product and unreacted The carbonate compound and the diol compound.

The disclosure illustrates the details by way of examples. However, the interpretation of the disclosure should not be limited to the following examples.

Embodiment 1

In a reactor with a mechanical stirrer, heating jacket, Dean-Stark Trap, water-cooled condenser and vacuum pump, 1,6-hexanediol (58.66 g; 0.50 mole) was sequentially packed. ), ethylene carbonate (41.04 g; 0.47 mole) and 1 gram of sodium ion nanosheet as a catalyst, the addition amount is 1 wt%, and then enters stage one, under nitrogen filling conditions and absolute pressure is maintained at 760 Torr, heated to 100 ° C, stirred by mechanical stirring (500 rmp) for 0.5 hour, entered stage two, heated to 150 ° C for 1 hour, then entered stage three, and then heated to 180 ° C for 4 hours. Then, in the fourth stage, the reactor is evacuated by a pump at a constant temperature of 180 ° C, and the vacuum value is reduced from 760 torr (ie, 1 atm; 760 mm-Hg) to 100 torr for 1 hour. Ethylene glycol (EG) with a lower boiling point (196 ° C) was observed to be removed through a Dean-Stark separator. Finally, enter stage 5, and then reduce the vacuum value to 50 torr for one hour to ensure that the by-product ethylene glycol and unreacted ethylene carbonate and 1,6-hexanediol are distilled off, and 70.8 g can be prepared. Polycarbonate polyol (PCPO), which is brown in color and semi-solid at room temperature. The nanopellet tablets were removed by centrifugation to obtain a polycarbonate polyol having a viscosity of 1520 cps.

Embodiment 2

The preparation conditions of the second embodiment are as described in the first embodiment, except that the amount of the sodium ion nanosheet is changed to 0.5% by weight, and the polycarbonate polyol having the nanosheet is centrifuged to remove the nanometer. The tablet gave 72.82 g of polycarbonate polyol in a brown color and was semi-solid at room temperature with a yield of 72%. The viscosity is 630 cps.

Embodiment 3

The preparation conditions of the third embodiment are as described in the first embodiment, except that the amount of the sodium ion nanosheet is changed to 1.5 wt%, and the polycarbonate polyol having the nanosheet is centrifuged to remove the nanometer. The sheet gave 69.89 g of a polycarbonate polyol, which was brown in color and semi-solid at room temperature, yield 69%. The viscosity is 540 cps.

Embodiment 4

The preparation conditions of the fourth embodiment are as described in the first embodiment, except that the catalyst is changed to a magnesium ion nanosheet, and the polycarbonate polyol having the nano-slice tablet is centrifuged to remove the nano-ruthenium sheet to obtain a polymer of 64.8 g. Carbonate polyol, the color is transparent yellowish, viscous liquid at room temperature, the yield is 65%. The viscosity is 265 cps.

Comparative example one

The preparation method and conditions of Comparative Example 1 are as described in Example 1, except that no catalyst is added. Comparative Example 1 gave 55.8 g of a polycarbonate polyol having a yellow color and a viscous liquid at room temperature in a yield of 56%. The viscosity is 225 cps.

Comparative example two

The preparation method and conditions of Comparative Example 2 are as described in Example 1, except that the amount of catalyst added is 3 wt%. Comparative Example 2 gave 40.9 g of a polycarbonate polyol having a yellow color and a viscous liquid at room temperature in a yield of 41%. The viscosity is 160 cps.

Comparative example three

The preparation method and conditions of Comparative Example 3 are as described in Example 1, except that the amount of catalyst added is 5 wt%. Comparative Example 3 gave 14 grams of polycarbonate polyol in a yellow color and a viscous liquid at room temperature with a yield of 14%. The viscosity is 130 cps.

Comparative example four

The preparation method and conditions of Comparative Example 4 were as described in Example 1, except that the catalyst was changed to magnesium ion nanosheet, and the addition amount was 3 wt%. The polycarbonate polyol obtained in Comparative Example 4 was yellow in color and was a viscous liquid at room temperature in a yield of 43%. The viscosity is 135 cps.

Comparative example five

The preparation method and conditions of Comparative Example 5 were as described in Example 1, except that the catalyst was changed to magnesium ion nanosheet, and the addition amount was 5 wt%. The polycarbonate polyol obtained in Comparative Example 5 was yellow in color and was a viscous liquid at room temperature in a yield of 32%. The viscosity is 190 cps.

The results of the above examples and comparative examples are shown in Table 1.

Table 1

It can be seen from Table 1 that the use of a specific amount of the metal cation-containing nano samarium sheet can greatly increase the viscosity and yield of the product, which is in line with industrial requirements.

As can be seen from Table 1, the present disclosure can provide a polycarbonate polyol comprising a nano-ruthenium sheet having a surface/per platelet metal cation on the surface, wherein the polycarbonate polyol has a viscosity of 265 to 1520 cps. . Therefore, when further synthesizing or modifying polyurethane (PU) and polyester (polyester), it is possible to enhance the physical properties without adding it.

The above embodiments are intended to illustrate the principles of the disclosure and its functions, and are not intended to limit the disclosure. Any person skilled in the art can modify the above embodiments without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of the present disclosure should be as set forth in the scope of the patent application described later.

no

no

Claims (7)

A polycarbonate polyol composition comprising: a polycarbonate polyol; and a nano-ruthenium sheet having a surface/per platelet metal cation on the surface, wherein the polycarbonate polyol has a viscosity of 265 to 1520 cps. The polycarbonate polyol composition according to claim 1, wherein the metal cation is selected from the group consisting of Na ⁺ , Mg ²⁺ , Li ⁺ , K ⁺ , Sn ²⁺ , Ca ²⁺ , Yb ³⁺ , At least one of the groups consisting of Cs ⁺ , Sc ³⁺ , Y ³⁺ , La ^{3+ ,} and Ce ⁴⁺ . A method for preparing a polycarbonate polyol, comprising: having a surface of from 0.5 to 1.5 wt% of a surface of 0.5 to 1.5 wt% of a metal cation of 10,000 to 20,000 (by weight) based on the total weight of the carbonate compound and the diol compound The rice bran sheet is added as a catalyst to a reaction system containing the carbonate compound and the diol compound, and the carbonate compound and the diol compound are subjected to a temperature rising reaction, followed by a pressure reduction reaction to obtain a polycarbonate. Polyol. The method for preparing a polycarbonate polyol according to claim 3, wherein the temperature increasing reaction comprises the first stage to the third stage, and the stage is heated to 90 to 110 ° C under atmospheric pressure. Holding the temperature for 0.5 to 1 hour; in this stage, the reaction system is heated to 140 to 160 ° C under atmospheric pressure for 1 to 2 hours; at this stage, the reaction system is heated to 170 at atmospheric pressure. Up to 190 ° C, holding temperature for 4 to 6 hours; the pressure reduction reaction comprises stage 4 to stage 5, and the stage is to reduce the reaction system to 90 to 110 torr, the temperature is 170 to 190 ° C, heating for 1 to 2 hours Separating by-products; and in this stage, the system is depressurized to less than 50 torr, at a temperature of 170 to 190 ° C, and heated for 1 to 2 hours to separate the by-product and the unreacted carbonate compound and the A diol compound. The method for producing a polycarbonate polyol according to claim 3, wherein the metal cation is selected from the group consisting of Na ⁺ , Mg ²⁺ , Li ⁺ , K ⁺ , Sn ²⁺ , Ca ²⁺ , Yb ³⁺ , At least one of the groups consisting of Cs ⁺ , Sc ³⁺ , Y ³⁺ , La ^{3+ ,} and Ce ⁴⁺ . The method for producing a polycarbonate polyol according to claim 3, wherein the carbonate compound is ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, glycerol 1,2-carbonate. , dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tert-butyl phenyl carbonate, diphenyl carbonate, dibenzyl carbonate, benzyl phenyl carbonate, guaiacol phenol carbonate ( Guaiacol carbonate), di-2-pyridyl carbonate, 1,3-dioxan-2-one, (R)-(+)-4-(methoxymethyl)-1,3-dioxolan Cyclo-2-one, (S)-(-)-4-(methoxymethyl)-1,3-dioxolan-2-one or a combination thereof. The method for preparing a polycarbonate polyol according to claim 3, wherein the diol compound is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol. 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, bisphenol-A or a combination thereof.