KR101666171B1 - Polycarbonate polyol and method for preparing the same - Google Patents

Abstract

The present invention relates to polycarbonate polyols and processes for their preparation. According to the production method of the present invention, a polycarbonate polyol containing a bio-derived monomer is prepared by a method of obtaining a polymer having an appropriate molecular weight by introducing a cutting agent after the preparation of a polymer, instead of the conventional method through a condensation reaction. According to the production process of the present invention, problems such as low reactivity, deterioration due to long-time high-temperature reaction, molecular weight control, and carbonate-containing material in the terminal group can be solved.

Description

Polycarbonate polyol and method of preparing same [0002]

The present invention relates to a polycarbonate polyol and a process for producing the same, and more particularly, to an environmentally-friendly and amorphous polycarbonate polyol using a biomolecule monomer and a process for producing the same.

Polyurethane is a polymer compound containing a urethane (-NHCOO-) bond formed by the reaction between a polyol and an isocyanate in the middle part. Polyurethane is used in a wide range of applications ranging from elastomers to engineering plastics, since it can be designed as a material having various physical properties depending on the structure and kind of the soft phase and the hard phase, the content, the block length, and the degree of fine phase separation.

Polyols having various structures such as polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol are used as the polyol having two or more -OH groups in the terminal group, which is used in the production of polyurethane. Among them, polycarbonate polyol is superior to polyether and polyester polyol in hydrolysis resistance, heat resistance, light resistance and oxidation resistance, and is used for special purpose of high performance polyol.

On the other hand, as the demand for biomass-derived polymers is increased, the development of biopolyols is actively promoted and commercialized (J.of Korean Oil Chemists Soc., 2012, 531-542). Although eco-friendly polycarbonate polyols are mainly studied mainly on aliphatic polycarbonate polyols derived from CO ₂ , they are not derived from biomass.

The polyol to be used as a raw material for polyurethane should be in the form of a liquid, amorphous at room temperature, have a very high -OH ratio in the terminal group, and have a technology capable of controlling the molecular weight according to the application. In the case of a polycarbonate polyol containing a bio-derived diol such as isosorbide, it may be deteriorated to yellow or brown at a high temperature due to the characteristics of isosorbide.

In order to prepare a polycarbonate polyol containing isosorbide, Korean Laid-open Patent Publication No. 2013-0092383 discloses a polyol having 1 to 15 carbon atoms and at least one diol selected from isosorbide, isomannide, And then condensation polymerization with a carbonic acid diester. However, isosorbide is a secondary alcohol which is less reactive due to condensation polymerization, has a longer polymerization time, and has a high polymerization temperature of 180 캜, which is expected to deteriorate isosorbide. In addition, the polycarbonate polyol produced through polymerization has a very high possibility that a diphenyl carbonate-derived material is present in the terminal group. Also, it is based on expensive hexane diol (1,6-hexanediol), which causes a problem of low productivity in terms of price.

In order to solve the above-mentioned problems, the present invention provides an environmentally friendly and amorphous polycarbonate polyol using a bio-derived monomer.

The present invention also provides a process for producing the polycarbonate polyol having high productivity, a simple process, and easy physical properties of the final product.

In order to solve the above problems, according to one embodiment of the present invention,

The repeating units of the formulas (1) to (3) are connected to each other by a carbonyl group (-C═O-), or one of the terminals is bonded to hydrogen to form a -OH terminal , Polycarbonate polyol.

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

x, y and z are the numbers of moles of the respective repeating units, z / (x + y + z) satisfies 0.01 to 0.3,

n is an integer from 5 to 20,

R is a heterocycloalkylene having 4 to 30 carbon atoms.

According to another embodiment of the present invention,

A first step of preparing an aliphatic polycarbonate by reacting a diol represented by the following general formula (1a), a diol represented by the following general formula (2a) and dimethyl carbonate with a base catalyst to remove the generated methanol; And

And a second step of introducing a diol represented by the following general formula (3a) into the aliphatic polycarbonate as a cleaving agent to carry out transesterification reaction.

[Formula 1a]

(2a)

[Chemical Formula 3]

In the general formula (2a), n is an integer of 5 to 20,

In the above formula (3a), R is a heterocycloalkylene having 4 to 30 carbon atoms;

Z / (x + y + z) satisfies 0.01 to 0.3 when the mole number of the formula (1a) is x, the mole number of the formula (2a) is y and the mole number of the formula (3a) is z.

According to the production method of the present invention, a polycarbonate polyol containing a bio-derived monomer is prepared by a method of obtaining a polymer having an appropriate molecular weight by introducing a cutting agent after the preparation of a polymer, instead of the conventional method through a condensation reaction.

According to the production process of the present invention, problems such as low reactivity, deterioration due to long-time high-temperature reaction, molecular weight control, and carbonate-containing material in the terminal group can be solved. That is, a polycarbonate polyol having a desired molecular weight and containing most of the terminal groups thereof is -OH and is not deteriorated and is transparent and contains a bio-derived substance can be provided in an easier production method.

In addition, it is possible to provide a polycarbonate polyol having a price competitiveness based on 1,4-butanediol which is not widely used as an expensive 1,6-hexanediol base but has been widely commercialized.

Therefore, it is possible to increase the possibility of using the polycarbonate polyol containing a bio-derived monomer, which is not widely used at present, because of its high price and difficulties in the production method, and at the same time, it can be applied to the development of bio-polyurethane excellent in hydrolysis resistance and heat resistance.

1 is an NMR graph of a polycarbonate polyol prepared according to an embodiment of the present invention.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

Also in the present invention, when each element is referred to as being formed on or "on " each element, it is meant that each element is formed directly on top of each element, It may be additionally formed on the substrate, between the layers, on the object, and on the substrate.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the polycarbonate polyol of the present invention and its production method will be described in more detail.

The polycarbonate polyol according to one embodiment of the present invention may contain,

The repeating units of the formulas (1) to (3) are connected to each other by a carbonyl group (-C═O-), or one of the terminals is bonded to hydrogen to form a -OH terminal .

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

x, y and z are the numbers of moles of the respective repeating units, z / (x + y + z) satisfies 0.01 to 0.3,

n is an integer from 5 to 20,

R is a heterocycloalkylene having 4 to 30 carbon atoms.

In the general formula (2), n may preferably be an integer of 5 to 10.

According to one embodiment of the present invention, the formula 3 may be derived from the monomers of the following formulas 4 to 6.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The polycarbonate polyol of the present invention, which is prepared by using at least one of isosorbide, isomannide, isodide, and biodegradable monomer, It is a bio-polycarbonate polyol containing monomers and is eco-friendly. Preferably, isosorbide, which is a compound of formula (4), which is commercially available, can be used.

According to one embodiment of the present invention, the ratio of x: y may be 99: 1 to 51:49, or 90:10 to 51:49, or 80:20 to 51:49. If the molar ratio of x is too high to exceed the above range, the polycarbonate polyol may exhibit crystallinity, and if the molar ratio of x is too low, the price of the final product may relatively increase.

The polycarbonate polyol of the present invention contains 50 mol% or more of repeating units derived from 1,4-butanediol which is relatively inexpensive and different from 1,6-hexanediol-based polycarbonate polyol, thereby lowering the production cost . However, when 1,4-butanediol alone is used as a monomer, a solid crystalline polycarbonate polyol is produced. Therefore, by using the diol compound of the above formula (2) as a comonomer of a linear diol in polymer polymerization, a proper liquid amorphous polycarbonate polyol Can be obtained.

The polycarbonate polyol of the present invention comprises repeating units represented by the above formulas (1) to (3), wherein when the number of moles of the formula (1) is x, the number of moles of the formula (2) is y, z / (x + y + z) satisfies a range of from about 0.01 to about 0.3, preferably from about 0.05 to about 0.3, more preferably from about 0.1 to about 0.3. That is, the repeating unit of the above formula (3) is contained in an amount of about 1 to about 30 mol%, preferably about 5 to about 30 mol%, and more preferably about 10 to 30 mol% based on the total repeating units .

According to the process for producing a polycarbonate polyol of the present invention described later, the repeating unit of the above formula (3) is incorporated as a repeating unit of the polycarbonate polyol by introducing a compound of the following formula (3a) as a polymer scission agent.

[Chemical Formula 3]

In the above formula (3a), R is a heterocycloalkylene having 4 to 30 carbon atoms.

Therefore, the number average molecular weight of the polycarbonate polyol finally obtained decreases as the molar ratio of the compound of formula (3a) used as a cleaving agent increases. That is, the number of moles of the repeating unit of Formula 3 and the number average molecular weight of the polycarbonate polyol are in inverse proportion. Accordingly, the polycarbonate polyol having a desired molecular weight can be prepared by adjusting the amount of the compound of Formula 3a based on the above fact. In order to obtain an appropriate molecular weight range, about 1 to about 30 mol% .

According to one embodiment of the present invention, the number average molecular weight of the polycarbonate polyol typically represents a molecular weight suitable for use as a polyol, such as from about 200 to about 20,000 g / mol, or from about 500 to about 10,000 g / mol, or from about 1,000 to about 10,000 g / mol.

According to one embodiment of the present invention, the polycarbonate polyol has a glass transition temperature (Tg) of from about -80 to about -20 캜, or from about -70 to about -30 캜, or from about -60 to about -30 캜 Lt; / RTI >

According to an embodiment of the present invention, the polycarbonate polyol is amorphous, and a constant melting point (Tm) is not present or may be 40 DEG C or less.

The polycarbonate polyol of the present invention can be represented by the following general formula (7).

(7)

In Formula 7,

m is the number of repeating units, is an integer of 2 to 200,

B is - (CH ₂ ) ₄ -, - (CH ₂ ) n- or -R-,

n and R are as defined in formulas (2a) and (3a).

As shown in Formula 7, the polycarbonate polyol of the present invention is a polycarbonate polyol in which the repeating units of the above formulas 1 to 3 are bonded to each other by a carbonyl group (-C═O-) Terminal may be combined with hydrogen to form a -OH terminal.

The polycarbonate polyol produced through the condensation reaction contains a carbonate terminal group (- (C = O) OMe) in a high content, for example, 5 mol% or more of the total terminal number, The polycarbonate polyol has disadvantages such that the polymerization degree is not increased when the polyurethane reaction is carried out. However, in the polycarbonate polyol of the present invention, most of the terminal groups are -OH, and the ratio of the terminal groups derived from the carbonate is extremely low at 0.001 mol% or less, so that it can be usefully used as a raw material for the production of polyurethane.

A method for producing a polycarbonate polyol according to another embodiment of the present invention comprises:

A first step of preparing an aliphatic polycarbonate by reacting a diol represented by the following general formula (1a), a diol represented by the following general formula (2a) and dimethyl carbonate with a base catalyst to remove the generated methanol; And

And a second step in which the diol represented by the following formula (3a) is introduced into the aliphatic polycarbonate as a cleaving agent in the first step to carry out transesterification reaction.

 [Formula 1a]

(2a)

[Chemical Formula 3]

In the general formula (2a), n is an integer of 5 to 20,

In the above formula (3a), R is a heterocycloalkylene having 4 to 30 carbon atoms;

Z / (x + y + z) satisfies 0.01 to 0.3 when the mole number of the formula (1a) is x, the mole number of the formula (2a) is y and the mole number of the formula (3a) is z.

In the above formula (2a), n may preferably be an integer of 5 to 10.

The first step can be carried out according to the following reaction formula (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1,

l is the number of repeating units, is an integer of 10 to 10,000,

A is - (CH ₂ ) ₄ - or - (CH ₂ ) n- and n is an integer of 5 to 20.

The first step reaction represented by Reaction Scheme 1 is a step of producing an aliphatic polycarbonate by polymerizing 1,4-butanediol of Formula 1a and alkylene diol of Formula 2a with dimethyl carbonate.

According to an embodiment of the present invention, 1,4-butanediol of Formula 1a and diol of Formula 2a may be used in a ratio of 99: 1 to 51:49, or 90:10 to 51:49, or 80:20 to 51:49, : 49 molar ratio. If the molar ratio of 1,4-butanediol is in excess of the above range, the polycarbonate polyol may exhibit crystallinity, and if the molar ratio of 1,4-butanediol is too low, the production cost may increase.

The molar ratio of 1,4-butanediol of Formula 1 to the diol component including alkylene diol of Formula 2a and dimethyl carbonate may be about 1.0: 1.2 to about 1.0: 2.0. Theoretically, the first stage reaction is a reaction in which the diol component and dimethyl carbonate react at a molar ratio of 1: 1. However, when the diol component and the dimethyl carbonate have the same molar ratios as above, a more efficient esterification reaction can occur.

According to an embodiment of the present invention, the base catalyst used in the first step reaction may include a lithium cation (Li ⁺ ), a sodium cation (Na ⁺ ), or a potassium cation (K ⁺ ). The base catalyst may be used at a concentration of about 0.01 to about 0.1 mol% based on the total amount of the diols of Formula (Ia) and Formula (IIa) charged in the first step. If the concentration of the base catalyst is too low, the reaction may not occur. If the concentration of the base catalyst is too high, the molecular weight of the polymerized polymer may be low.

More specifically, the base catalyst, the diol represented by Formula 1a, the diol represented by Formula 2a, and dimethyl carbonate are mixed. Then, the reaction is carried out for about 1 hour to about 3 hours while gradually removing the generated methanol by gradually raising the temperature from about 80 ° C to about 130 ° C at normal pressure. After confirming that the rate of distillation of methanol is gradually decreased, the temperature of the reactor is raised to about 190 ° C, and the reactor is connected by a vacuum pump, and the pressure in the reactor is gradually reduced from about 570 mmHg to about 0.3 mmHg, Polymerization proceeds for a period of time. During the polymerization, the methanol is continuously removed under reduced pressure and the degree of polymerization is increased. When the polymerization is continuously carried out, it is confirmed that as the degree of polymerization of the reactant is increased, the melt viscosity of the resulting polymer is also continuously increased, and a polymer of a polymer is produced.

The aliphatic polycarbonate obtained after the first step reaction according to the above-mentioned method has a number average molecular weight of about 20,000 g / mol or more, for example, about 20,000 to about 300,000 g / mol.

Next, in the second step reaction, the diol represented by the following formula (3a) is introduced into the aliphatic polycarbonate obtained in the first step as a cleaving agent to carry out the transesterification reaction. This second stage reaction can be represented by the following reaction formula (2).

[Chemical Formula 3]

In the above formula (3a), R is a heterocycloalkylene having 4 to 30 carbon atoms.

[Reaction Scheme 2]

In the above Reaction Scheme 2,

1 and m are the number of each repeating unit, 1 is an integer of 10 to 10,000, m is an integer of 2 to 200,

A is - (CH ₂ ) ₄ - or - (CH ₂ ) n-,

B is - (CH ₂ ) ₄ -, - (CH ₂ ) n- or -R-,

n and R are as defined in formulas (2a) and (3a).

According to an embodiment of the present invention, the formula (3a) may be selected from the compounds represented by the following formulas (4) to (6).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The second stage reaction represented by the above-mentioned Reaction Scheme 2 can be carried out by introducing a diol of the above-mentioned formula (3a) into the polymer aliphatic polycarbonate of the first stage after completion of polymerization to carry out an esterification exchange reaction, To produce a substituted and lower molecular weight polycarbonate polyol.

More specifically, in the reaction of the second step, the polymer aliphatic polycarbonate of the first stage after completion of the polymerization is depressurized, and then the diol of Formula 3a is introduced in a nitrogen atmosphere.

In the second step reaction, the compound of formula (3a) is incorporated as a repeating unit of the polycarbonate polyol by introducing the compound of the formula (3a) as a cleavage agent of the polymer polycarbonate obtained in the first step reaction.

Therefore, the number average molecular weight of the polycarbonate polyol finally obtained decreases as the molar ratio of the compound of formula (3a) used as a cleaving agent increases. That is, the number of moles of the repeating unit of Formula 3 and the number average molecular weight of the polycarbonate polyol are in inverse proportion.

Accordingly, the polycarbonate polyol having a desired molecular weight can be prepared by adjusting the amount of the compound of formula (3a) based on this fact. To obtain an appropriate molecular weight range, the compound of formula (3a) is added in an amount of about 1 to about 30 mole%, preferably about 5 to about 30 mole%, more preferably about 5 to about 30 mole%, relative to the total amount of the diol Can be added in an amount of about 10 to 30 mol%.

The diol of formula (3a) is randomly distributed in the polymer chain of the polymer aliphatic polycarbonate of the first step by the transesterification reaction, and as a result, the polymer chain of the polymer aliphatic polycarbonate And the molecular weight is reduced.

More specifically, the diol of formula (3a) is added to the polymer aliphatic polycarbonate obtained by the first step reaction at a temperature of about 150 ° C or lower, and then about 1 To about 5 hours. It was confirmed visually that the aliphatic polycarbonate having a high viscosity was slowly released when about 10 to about 30 minutes had elapsed after the diol having the formula (3a) was added, and it was confirmed that a low molecular weight material having a low viscosity was produced as the reaction proceeded The reaction can be terminated.

According to an embodiment of the present invention, the temperature at which the diol of Formula 3a is introduced may be in a range of about 150 ° C or less. If the introduction temperature of the diol of Formula 3a is higher than 150 ° C, the diol of Formula 3a may be deteriorated.

The diol of formula (3a) is a low-reactivity secondary alcohol. When the diol of formula (3a) is used as a monomer for the condensation reaction, the polymer is not easily polymerized, .

However, according to the process for producing a polycarbonate polyol of the present invention as described above, a diol having the low reactivity is introduced as a cleaving agent for the polymer polycarbonate after the high-molecular polycarbonate is first prepared, The condition becomes unnecessary.

In addition, since the reaction can be carried out at a low temperature of 150 ° C or less, in which the diol of formula (3a) does not deteriorate, the transparent oil-type polycarbonate polyol can be easily produced. On the other hand, when the polycarbonate polyol is produced through the condensation polymerization using the diol of the above formula (3a), a polymerization temperature of up to 180 ° C is required. Therefore, careful temperature control is necessary. There is a problem that the diol of 3a is deteriorated.

In addition, by introducing the diol of formula (3a) as a cleavage agent, a polycarbonate polyol in which most of the terminal groups are substituted with -OH and has no terminal group derived from a carbonate can be produced. On the other hand, when a polycarbonate polyol is produced through a condensation reaction, it is unavoidable that a carbonate-derived end group is produced.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for illustrating the present invention more specifically, and the scope of the present invention is not limited by these embodiments.

< Example >

The content ratio, molecular weight, melting point, and glass transition temperature of each component in the reaction product obtained in the examples were measured according to the following methods. The following abbreviations were used for the materials used.

(1) Identification of the structure of the final product and the content ratio of each diol (mol%)

The polycarbonate polyol obtained in the examples was dissolved in chloroform (CDCl ₃ ) solvent for NMR (nuclear magnetic resonance), and a small amount was taken. The structure of the final product was confirmed by 500 MHz NMR. The integral value of each 1H- Respectively.

(2) Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (MWD)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured at 40 캜 by using a tetrahydrofuran (THF) solvent by gel permeation chromatography (GPC), and polystyrene was used as a standard substance.

The molecular weight distribution (MWD) was calculated by the method of Mw / Mn.

(3) Melting point (Tm) and glass transition temperature (Tg)

(DSC). The temperature was increased from -50 ° C to 200 ° C at a rate of 10 ° C / min, and then gradually decreased to 10 ° C / min.

(4) Abbreviation

BDO: 1,4-butanediol (butanediol)

HDO: 1,6-hexanediol (hexanediol)

DMC: Dimethyl carbonate (dimethyl carbonate)

ISB: Isosorbide (isosorbide)

NaOMe: Sodium methoxide (sodium methoxide)

Example  One

Step 1: Preparation of Polymer Polycarbonate

To the reactor was added 1,4-butanediol (63.0 g, 699 mmole), 1,6-hexanediol (9.2 g, 78 mmole), NaOMe (21 mg, total moles of 1,4-butanediol and 1,6- 0.05 mol% in total) and dimethyl carbonate (110 g, 1219 mmole) were added in this order, and the inside of the reactor was replaced with nitrogen while stirring for 30 minutes. After the stirrer and the cooling condenser were connected to the reactor, the temperature of the reactor was gradually increased from 80 ° C to 130 ° C for 2 hours to proceed the polymerization reaction. The reaction was carried out while distilling off the methanol generated in the reaction at normal pressure. After confirming that the distillation rate of the effluent gradually decreased, the cooling condenser connected to the reactor was changed to a vacuum system while raising the temperature of the reactor to 190 ° C.

When the temperature of the reactor reached 190 ° C, the condensation reaction was carried out while gradually reducing the pressure of the reactor from 570 mmHg to 0.3 mmHg over a period of 2 hours by operating a vacuum pump. The reaction was further continued for 2 hours under a reduced pressure of 0.3 mmHg . During the course of the reaction, the melt viscosity of the reactant gradually increased, confirming that the torque value of the stirrer was 40 or more, and the reaction was terminated.

¹ H-NMR graph of the polycarbonate polyol obtained in Example 1 is shown in Fig.

Step 2: Polycarbonate Of polyol  Produce

After the first step reaction was completed and the vacuum system of the reactor was removed, the temperature of the reactor was lowered to 150 DEG C under a nitrogen atmosphere. When the temperature of the reactor reached 150 ° C, isosorbide (17 g, 117 mmole) was added thereto, followed by cleavage reaction for 3 hours, and the reaction was terminated.

It was confirmed visually that when the isosorbide was introduced for about 30 minutes, the polymer having a high viscosity was slowly released. When the reaction was terminated, it was confirmed that a low molecular weight substance having a low viscosity was produced in the reactor.

Example  2 to 9

In Example 1, the reaction was carried out in the same manner as in Example 1, except that the amounts of raw materials used were different.

The amounts of the raw materials used in Examples 1 to 9 are shown in Table 1 below.

BDO HDO DMC ISB Example 1 63.0 g, 699 mmole 9.2 g, 78 mmole 110 g, 1219 mmole 17 g, 117 mmole Example 2 56.0 g, 621 mmole 18.4 g, 155 mmole 110 g, 1219 mmole 17 g, 117 mmole Example 3 49 g, 543.7 mmole 27.5 g, 233 mmole 110 g, 1219 mmole 17 g, 117 mmole Example 4 56.0 g, 621 mmole 18.4 g, 155 mmole 110 g, 1219 mmole 5.7 g, 39 mmole Example 5 56.0 g, 621 mmole 18.4 g, 155 mmole 110 g, 1219 mmole 11.4 g, 78 mmole Example 6 56.0 g, 621 mmole 18.4 g, 155 mmole 110 g, 1219 mmole 22.7 g, 155 mmole Example 7 56.0 g, 621 mmole 18.4 g, 155 mmole 110 g, 1219 mmole 34.1 g, 233 mmole Example 8 63g, 699mmole 9.2 g, 78 mmole 110 g, 1219 mmole 34.1 g, 233 mmole Example 9 49 g, 543.7 mmole 27.5 g, 233 mmole 110 g, 1219 mmole 11.4 g, 78 mmole

The results of measurement of the BDO: HDO molar ratio and the BDO: HDO: ISB molar ratio in the bio polycarbonate polyol obtained in Examples 1 to 9 are shown in Table 2 below.

HDO: BDO mole ratio BDO: HDO: ISB mole ratio Example 1 10:90 77: 8: 15 Example 2 20:80 68: 17: 15 Example 3 30:70 60: 25: 15 Example 4 20:80 76: 19: 5 Example 5 20:80 72: 18: 10 Example 6 20:80 64: 16: 20 Example 7 20:80 56: 14: 30 Example 8 10:90 63: 7: 30 Example 9 30:70 63: 27: 10

The physical properties of the first stage product and the second stage product (final product) in Examples 1 to 9 were evaluated and are shown in Table 3 below.

Example No. 2. Number average molecular weight
(Molecular weight distribution) Glass transition temperature (캜) The state of the final product The first stage product final
product The first stage product final
product After 1 day A month later Example 1 57,000
(1.9) 2,017
(1.9) -38 -48 Transparent oil Suspension oil Example 2 56,000
(2.0) 2,152
(1.8) -41 -45 Transparent oil Transparent oil Example 3 66,000
(2.1) 2,372
(1.8) -45 -38 Transparent oil Transparent oil Example 4 56,000
(2.0) 4,507
(1.9) -41 -44 Transparent oil Wax Example 5 56,000
(2.0) 3,420
(1.9) -41 -45 Transparent oil Suspension oil Example 6 56,000
(2.0) 1,925
(1.9) -41 -45 Transparent oil Transparent oil Example 7 56,000
(2.0) 1,124
(1.7) -41 -44 Transparent oil Transparent oil Example 8 65,000
(1.9) 1,235
(1.8) -38 -47 Transparent oil Transparent oil Example 9 59,000
(2.1) 3,250
(1.9) -45 -38 Transparent oil Transparent oil

The results of Tables 1 to 3 indicate that the polycarbonate polyol obtained according to the production method of the present invention has various number average molecular weight, molecular weight distribution and glass transition temperature depending on the ratio of BDO, HDO and ISB, A certain melting point (Tm) was not measured due to the amorphous nature of the oil form. In addition, it remained stable amorphous state after one month. Particularly, as the ratio of ISB in the polycarbonate polyol increased, it showed more stable amorphousness and a tendency to lower the number average molecular weight.

Comparative Example  One

Step 1: Preparation of Polymer Polycarbonate

To the reactor, 1,4-butanediol (70.0 g, 777 mmole), NaOMe (21 mg, 0.05 mol% based on the molar amount of 1,4-butanediol) and dimethyl carbonate (110 g, 1219 mmole) were sequentially added as a base catalyst, The inside of the reactor was replaced with nitrogen for 30 minutes.

After the stirrer and the cooling condenser were connected to the reactor, the temperature of the reactor was gradually increased from 80 ° C to 130 ° C for 2 hours to carry out the transesterification reaction. The reaction was carried out while distilling off the methanol generated in the reaction at normal pressure. After confirming that the distillation rate of the effluent gradually decreased, the cooling condenser connected to the reactor was changed to a vacuum system while raising the temperature of the reactor to 190 ° C.

When the temperature of the reactor reached 190 ° C, the condensation reaction was carried out while gradually reducing the pressure of the reactor from 570 mmHg to 0.3 mmHg over a period of 2 hours by operating a vacuum pump. The reaction was further continued for 2 hours under a reduced pressure of 0.3 mmHg . During the course of the reaction, the melt viscosity of the reactant gradually increased, confirming that the torque value of the stirrer was 40 or more, and the reaction was terminated.

Step 2: Polycarbonate Of polyol  Produce

After the first step reaction was completed and the vacuum system of the reactor was removed, isosorbide (17 g, 117 mmole) was added at 190 DEG C under a nitrogen atmosphere. After the cleavage reaction was carried out in a nitrogen atmosphere at 190 ° C for 1 hour, the temperature was lowered to 150 ° C and the cleavage reaction was further performed for 2 hours, and the reaction was terminated.

At this time, after about 10 minutes from the introduction of isosorbide at 190 ° C., the color of the material inside the reactor began to change to yellow, and the color of the transparent material of the reactor changed to dark brown within 30 minutes.

Comparative Example  2

In Comparative Example 1, the first stage reaction was the same except that in the second stage reaction, the first stage reaction was terminated and the vacuum system of the reactor was removed, and then the temperature of the reactor was lowered to 180 ° C under a nitrogen atmosphere. Isosorbide was added at 180 ° C. and cleavage reaction was performed at 180 ° C. for 1 hour. Then, the temperature was lowered to 150 ° C., and further cleavage reaction was carried out for 2 hours, after which the reaction was terminated.

At this time, after about 10 minutes after the injection of isosorbide at 180 ° C., the color of the material inside the reactor started to change to yellow, and the color of the transparent material of the reactor changed to dark yellow within 30 minutes.

Comparative Example  3

In Comparative Example 1, the first stage reaction was the same except that in the second stage reaction, the first stage reaction was terminated and the vacuum system of the reactor was removed, and then the temperature of the reactor was lowered to 170 ° C under a nitrogen atmosphere. Isosorbide was added at 170 占 폚, cleavage reaction was carried out at 170 占 폚 for 1 hour, the temperature was lowered to 150 占 폚, and further cleavage reaction was carried out for 2 hours, and the reaction was terminated.

At this time, it was confirmed that the color of the transparent material in the reactor turned yellow within 30 minutes after the isosorbide was injected at 170 ° C.

Comparative Example  4

In Comparative Example 1, the first stage reaction was the same except that in the second stage reaction, the first stage reaction was terminated and the vacuum system of the reactor was removed, and then the temperature of the reactor was lowered to 160 ° C under a nitrogen atmosphere. Isosorbide was added at 160 캜, cleavage reaction was carried out at 160 캜 for 1 hour, the temperature was lowered to 150 캜, and further cleavage reaction was carried out for 2 hours, after which the reaction was terminated.

At this time, it was confirmed that the color of the transparent material of the reactor slightly changed to yellow within 1 hour after the injection of isosorbide at 160 ° C.

Comparative Example  5

In Comparative Example 1, the first stage reaction was the same except that in the second stage reaction, the first stage reaction was terminated and the vacuum system of the reactor was removed, and then the temperature of the reactor was lowered to 150 ° C under a nitrogen atmosphere. Isosorbide was added at 150 캜 and cleavage reaction was carried out at 150 캜 for 3 hours, and the reaction was terminated.

After the isosorbide was added, the material of the reactor remained transparent.

The physical properties of the first stage product and the second stage product (final product) in the above Comparative Examples 1 to 5 were evaluated and are shown in Table 4 below.

Number average molecular weight
(Molecular weight distribution) Glass transition temperature (캜) The state of the final product The first stage product final
product The first stage product final
product Degree of deterioration After 1 day
condition Comparative Example 1 58,000
(2.1) 2,129
(1.9) -36 -55 Dark brown deterioration Wax Comparative Example 2 62,000
(2.0) 2,410
(1.8) -36 -54 Dark yellow deterioration Wax Comparative Example 3 68,000
(1.9) 2,623
(1.7) -36 -55 Deterioration in yellow Wax Comparative Example 4 74,000
(2.0) 2,721
(1.9) -36 -54 Slight deterioration Wax Comparative Example 5 63,000
(2.1) 2,564
(1.9) -36 -55 Not degraded Wax

Referring to the results of Comparative Examples 1 to 5 in Table 4, a wax, that is, a solid crystalline polycarbonate polyol was produced by not including a diol of Formula 2a such as HDO.

Also, referring to the results of Comparative Examples 1 to 4, when the starting temperature of the second-step reaction is set to 190 ° C, 180 ° C, 170 ° C, or 160 ° C, isosorbide deterioration occurs and amorphous polycarbonate polyol Is not formed.

Claims (11)

The repeating units of the formulas (1) to (3) are connected to each other by a carbonyl group (-C═O-), or one of the terminals is bonded to hydrogen to form a -OH terminal , Polycarbonate polyol:
[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,
x, y and z are the numbers of moles of the respective repeating units, z / (x + y + z) satisfies 0.01 to 0.3,
n is an integer from 5 to 20,
R is a heterocycloalkylene having 4 to 30 carbon atoms.
The method according to claim 1,
(3) is a polycarbonate polyol derived from at least one selected from the monomers of the following formulas (4) to (6)
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The method according to claim 1,
and x: y is from 99: 1 to 51:49.
The method according to claim 1,
A polycarbonate polyol having a number average molecular weight of 200 to 20,000 g / mol.
The method according to claim 1,
A polycarbonate polyol having a glass transition temperature (Tg) of -80 to -20 占 폚.
The method according to claim 1,
Amorphous, polycarbonate polyol.
A first step of preparing an aliphatic polycarbonate by reacting a diol represented by the following general formula (1a), a diol represented by the following general formula (2a) and dimethyl carbonate with a base catalyst to remove the generated methanol; And
And a second step of introducing a diol represented by the following formula (3a) into the aliphatic polycarbonate as a cleaving agent to carry out an ester exchange reaction:
[Formula 1a]

(2a)

[Chemical Formula 3]

In the general formula (2a), n is an integer of 5 to 20,
In the above formula (3a), R is a heterocycloalkylene having 4 to 30 carbon atoms;
Z / (x + y + z) satisfies 0.01 to 0.3 when the mole number of the formula (1a) is x, the mole number of the formula (2a) is y and the mole number of the formula (3a) is z.
8. The method of claim 7,
Wherein the formula (3a) is selected from compounds represented by the following formulas (4) to (6):
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

8. The method of claim 7,
and x: y is from 99: 1 to 51: 49.
8. The method of claim 7,
Wherein the base catalyst comprises lithium cations (Li ⁺ ), sodium cations (Na ⁺ ) or potassium cations (K ⁺ ), And 0.01 to 0.1 mol% based on the amount of the polycarbonate polyol.
8. The method of claim 7,
Wherein the step of performing the transesterification reaction is carried out at a temperature of 150 DEG C or less.

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