CN115651149A - Highly branched polycarbonate polyol compositions - Google Patents

Abstract

The invention relates to a highly branched polycarbonate polyol composition. The present invention addresses the problem of providing a polycarbonate polyol which is easy to handle, has high tensile strength and elongation when used in the production of polyurethane, and has excellent durability. The solution of the present invention is a highly branched polycarbonate polyol composition having a structure derived from an aliphatic diol and a structure derived from a polyol, wherein the branching factor g' is 0.55 to 0.82.

Description

Highly branched polycarbonate polyol composition

This application is a divisional application, the original application number is 201910026690.0, the application date is January 11, 2019, and the invention name is "highly branched polycarbonate polyol composition".

technical field

The present invention relates to polyurethane compounds useful as coatings, coating agents, leveling agents, or their raw materials; compositions containing the above polyurethane compounds; and novel hyperbranched polycarbonate polyol compositions providing their cured products.

Background technique

Polyurethane compounds are widely used as raw materials for coatings, coating agents, and adhesives, for example, for the interior and exterior of aircrafts and automobiles, exterior walls and flooring materials of houses, components of home appliances and electronic materials, and the like. The coating film of the above-mentioned paint, coating agent, etc. not only needs to show a beautiful appearance, but also protects the base material, so it needs to have durability, etc. in addition to hardness and strength. As a raw material of polyurethane used for this purpose, it is known that polycarbonate polyol reacts with an isocyanate compound to provide, for example, polycarbonate polyols that can be used in rigid foams, flexible foams, paints, adhesives, artificial leather, ink adhesives, etc. Polyurethane resin. Polyurethane resin using polycarbonate diol provides a material excellent in water resistance, heat resistance, oil resistance, stress relaxation performance, abrasion resistance, weather resistance, etc. due to the high cohesive force derived from the carbonate group (see non-patent literature 1 and non-patent literature 2). In order to impart physical properties such as high hardness and high modulus of elasticity, for example, polycarbonate polyols having a branched chain structure using polyols are used (Patent Document 1).

On the other hand, hyperbranched polymers having a highly branched three-dimensional structure are attracting attention as novel materials. Unlike polymers with a simple branched chain structure, hyperbranched polymers can be easily prepared by one-pot synthesis where molar mass and branched chain structure cannot be controlled. Regarding hyperbranched polymers, it is considered that thermal properties, mechanical properties, solubility, rheological properties, etc. are brought about by the high degree of branching (see Non-Patent Documents 3 and 4 and Patent Document 2).

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2012-184380

Patent Document 2: US Publication No. 20090093589

non-patent literature

Non-Patent Document 1: Latest polyurethane material and applied techniques, CMC Publishing Company, Chapter 2, page 43

Non-Patent Document 2: Costa, V. and Nohales, A, Enhanced polyurethane based on different polycarbonatediols, SAGE Publications, Journal of Elastomer & Plastics, 2012, 45(3), 217-238. )

Non-Patent Document 3: Voit, B.I. and Lederer, A., ACS, Chemical Reviews, 109, 5924-5973, Hyperbranched and highly branched polymer architectures-synthetic strategies and major characterization aspects

Non-Patent Document 4: Wang, Z.Fu, Y.Guo, P.Ren, L.Wang, H. and Qiang, T., Synthesis, characterization, and properties of PCDL aliphatic hyperbranched polyurethanecoatings John Wiley&Sons, Inc., Journal of Applied Polymer Science, 2013, 2671-2679

Contents of the invention

The problem to be solved by the invention

As mentioned above, physical properties such as good durability, excellent elongation, and high tensile strength are required for polyurethane resins, but polycarbonate diols having a linear structure are mostly solid at room temperature, and from polyurethane production The handling aspect of departure is sometimes inconvenient. In addition, in polyurethane resins using conventionally known polycarbonate polyols, physical properties such as hardness and modulus of elasticity are insufficient in durability, and improvement is required.

Accordingly, an object of the present invention is to provide a polycarbonate polyol that is easy to handle, has high tensile strength and elongation when made into polyurethane, and is excellent in durability.

means to solve the problem

As a result of repeated studies, the present inventors found that a hyperbranched polycarbonate polyol composition having a structure derived from aliphatic diol and a structure derived from polyol and having a branching factor g' of 0.55 to 0.82 can solve the above-mentioned problems , thus completing the present invention.

Specific means for solving the above-mentioned problems are as follows.

[1] A highly branched polycarbonate polyol composition having a structure derived from an aliphatic diol and a structure derived from a polyol, and having a branching factor g' of 0.55 to 0.82.

[2] The hyperbranched polycarbonate polyol composition according to the above [1], wherein the hyperbranched polycarbonate polyol composition has a number average molecular weight (Mn) of 200 to 10,000.

[3] The hyperbranched polycarbonate polyol composition according to any one of the above [1] to [2], which has a hydroxyl value of 50 mgKOH/g to 500 mgKOH/g.

[4] The hyperbranched polycarbonate polyol composition as described in any one of the above [1] to [3], wherein the amount (molar ratio) of the aliphatic diol and the polyol is expressed as "the total amount of the polyol The number of moles of hydroxyl groups/the total number of moles of hydroxyl groups of the aliphatic diol" is 0.3 to 4.0 in conversion.

[5] The hyperbranched polycarbonate polyol composition as described in any one of the above [1] to [4], wherein the hyperbranched polycarbonate polyol composition is made of aliphatic diol, polyhydric A substance obtained by reacting an alcohol with a carbonate.

[6] The hyperbranched polycarbonate polyol composition according to any one of the above [1] to [5], which is liquid at room temperature.

[7] A polyurethane composition obtained by using the hyperbranched polycarbonate polyol composition described in any one of [1] to [6] above.

[8] A synthetic leather obtained by using the hyperbranched polycarbonate polyol composition described in any one of the above-mentioned [1] to [6].

[9] An aqueous polyurethane resin dispersion obtained by using the hyperbranched polycarbonate polyol composition described in any one of the above-mentioned [1] to [6].

The effect of the invention

According to the present invention, it is possible to obtain a polycarbonate polyol which is easy to handle, has high tensile strength and elongation when made into polyurethane, and is excellent in durability. In addition, the physical properties of the polymer may change depending on the preparation method, but in the present invention, the use of a hyperbranched polymer whose terminal functional groups are concentrated on the particle-like molecular surface, especially the state of the reaction point, which is a problem in terms of durability, is balanced. Physical properties with less offset can be obtained.

Detailed ways

Embodiments of the present invention will be described in detail below. It should be noted that the polymer compound of the present invention can obtain products having various structures through the reaction of various raw material compounds. Therefore, even if a polymer compound can describe various structures included in the general formula, it cannot be unambiguously shown by the structure. In addition, it is difficult to directly measure and identify its physical properties and distinguish them from existing compounds by equipment analysis and the like. Therefore, in the present invention, the "aqueous polyurethane resin dispersion" is specified by the production method as necessary.

[Highly branched polycarbonate polyol composition]

The highly branched polycarbonate polyol composition of the present invention is a polycarbonate polyol composition with a branching factor g' of 0.55-0.82. In the present invention, "highly branched" refers to a state in which the branching factor g' calculated by gel permeation chromatography (GPC) is 0.55 to 0.82.

The branching factor g' is 0.55 to 0.82, preferably 0.58 to 0.80, more preferably 0.60 to 0.78, even more preferably 0.60 to 0.75. Hereinafter, unless otherwise stated, the part where the branching factor g' is described as 0.55 to 0.82 also applies to the description of the above-mentioned preferred range.

(OH Value)

The hydroxyl value of the hyperbranched polycarbonate polyol composition can be calculated by the following steps.

0.9 g of the hyperbranched polycarbonate polyol composition and a phthaloylating agent (a mixture of 160 g of phthalic anhydride and 1000 mL of pyridine) were reacted at around 100° C. for 30 minutes. Next, a mixed solution of water and pyridine was added to the reaction solution, followed by titration with a 0.5 mol/L potassium hydroxide aqueous solution.

The phthalylating agent was titrated with a 0.5 mol/L potassium hydroxide aqueous solution (this is a blank test for obtaining a blank value).

Hydroxyl value (mgKOH/g) = [B (mL) - A (mL)] × f × 28.05/S (g) + acid value (mgKOH/g)...Formula (2)

A: The amount of 0.5 mol/L potassium hydroxide aqueous solution required for titrating the sample (mL)

B: The amount of 0.5 mol/L potassium hydroxide aqueous solution required for titrating the blank (mL)

f: Titration rate of 0.5 mol/L potassium hydroxide aqueous solution

S: weight of sample (g)

In addition, the acid value can be calculated by the following method.

A 10-g sample was prepared by dissolving a 50/50 (weight ratio) solution of toluene/ethanol, and titrated with a 0.1N KOH ethanol solution. The acid value was calculated|required by the following formula.

5.61×(C－B ¹ )×f/s

Here, ^B is the amount (mL) of the 0.1N KOH ethanol standard solution required for neutralizing the blank, C is the amount (mL) of the 0.1N KOH ethanol standard solution required for neutralizing the sample, and f is 0.1 The factor of the KOH ethanol standard solution of N, s is the weight (g) of the sample.

(branching factor (g'))

The branching factor (g') of the hyperbranched polycarbonate polyol composition can be calculated by gel permeation chromatography (GPC).

Regarding GPC, as a column, one Shodex KF-G, two KF-805L, and one KF-800D were installed, and as a detector, HLC-8220GPC manufactured by Tosoh Corporation with TriSEC302TDA manufactured by Viscotek was used, and the elution The liquid is tetrahydrofuran, the flow rate is 1.0mL/min, the concentration is 0.1w/v%, the injection volume is 300μL, and the temperature is 40°C. The analysis software OmniSec4.0 is used to perform Mark-Houwink drawing, and the intrinsic viscosity is calculated. Branching degree g'.

(number average molecular weight (Mn))

The number average molecular weight (Mn) of the hyperbranched polycarbonate polyol composition is 200-10000, preferably 350-10000, more preferably 400-8000, more preferably 450-6000, particularly preferably 500-5000.

The number average molecular weight (Mn) was calculated|required with the viscosity detector using the GPC similar to the above.

(Properties at room temperature)

Regarding the properties of the hyperbranched polycarbonate polyol at room temperature, the sample heated at 80° C. for 3 hours was left at 25° C. for 24 hours, and the state thereafter was visually confirmed.

The branching factor g' of the highly branched polycarbonate polyol composition of the present invention is 0.55-0.82. By setting the branching factor g' within this range, it is easy to handle as a liquid at room temperature.

The hyperbranched polycarbonate polyol composition only needs to have a branching factor g' of 0.55 to 0.82 substantially, and a part of the terminal hydroxyl group may also become an unsaturated bond (such as a terminal ethylene), an ether bond (such as a terminal methoxy group) , Terminal phenoxy).

Here, the ratio of terminal hydroxyl groups in the terminal structure of the hyperbranched polycarbonate polyol composition can be measured by 1H-NMR, and is preferably 90% or more, more preferably 95% or more. By setting it as this range, for example, the increase of the molecular weight of the urethanization reaction using the hyperbranched polycarbonate polyol composition of this invention can be aimed at.

In addition, the proportion of primary terminal hydroxyl groups in the terminal hydroxyl groups is preferably 95% or more. By being within this range, for example, the urethanization reaction using the hyperbranched polycarbonate polyol composition of the present invention proceeds smoothly.

(Manufacture of hyperbranched polycarbonate polyol composition)

The production method of the hyperbranched polycarbonate polyol composition is not particularly limited, for example, by mixing polyol, aliphatic diol, carbonate and catalyst, while distilling off low boiling point components (for example, by-produced alcohol, etc.) Side reaction and other methods to carry out.

It should be noted that the reaction of the present invention can also temporarily obtain the prepolymer of hyperbranched polycarbonate polyol (molecular weight is lower than target hyperbranched polycarbonate polyol), in order to further increase the molecular weight and make the prepolymer reaction, etc., the reaction is divided into two or more times to carry out. Hereinafter, each component constituting the hyperbranched polycarbonate polyol composition and conditions for preparation will be described.

(aliphatic diol)

As aliphatic diols, for example: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol , 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. have 2 carbon atoms ～12 linear aliphatic diols;

2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol or 3-methyl-1,5-pentanediol, 2,2,4-trimethylhexanediol or 2,4,4-trimethylhexanediol, 1,5-hexanediol and other branched aliphatic diols with 3 to 18 carbon atoms;

Cyclic aliphatic diols having 6 to 18 carbon atoms, such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

In addition, these can be used individually or in combination of 2 or more types.

(Polyol)

Examples of the polyhydric alcohol include compounds having three or more hydroxyl groups in one molecule, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

In addition, these can be used individually or in combination of 2 or more types.

(molar ratio of aliphatic diol to polyol)

The amount (molar ratio) of the aliphatic diol and polyhydric alcohol is not particularly limited as long as the branching factor g' of the highly branched polycarbonate polyol composition is in the range of 0.55 to 0.82 (molar ratio). It is preferably 0.3 to 4.0 in terms of the total number of moles of hydroxyl groups of alcohols/the total number of moles of hydroxyl groups of aliphatic diols.

(Carbonate)

Carbonic esters, for example, include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, propylene carbonate ( 4-methyl-1,3-dioxolan-2-one), trimethylene carbonate), butylene carbonate (4-ethyl-1,3-dioxolan-2-one), tetracarbonate As cyclic carbonates such as methylene ester and 5-methyl-1,3-dioxan-2-one, dimethyl carbonate, diethyl carbonate, and ethylene carbonate are preferably used.

In addition, these can be used individually or in combination of 2 or more types.

The amount of the carbonate used is preferably 0.25 mol to 0.65 mol, more preferably 0.30 mol to 0.60 mol, based on 1 mol of "the total hydroxyl group of the polyhydric alcohol and the aliphatic diol" used.

By setting it as this range, the target hyperbranched polycarbonate polyol composition can be efficiently obtained with sufficient reaction rate.

(catalyst)

As the catalyst used in the reaction to obtain the hyperbranched polycarbonate polyol composition of the present invention, known transesterification catalysts can be used, for example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, Strontium, barium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, cerium and other metals and their hydroxides, alkoxides, carboxylates, carbonates, bicarbonates, sulfates, phosphates, nitric acid Salts, organic metals, etc., sodium hydride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltindimethoxide, Dibutyltin oxide.

In addition, these catalysts can be used individually or in mixture of 2 or more types.

The amount of the above-mentioned catalyst used is preferably 0.001 to 0.1 mmol, more preferably 0.005 to 0.05 mmol, more preferably 0.01 to 0.03 mmol, relative to 1 mole of the "total hydroxyl group of polyol and aliphatic diol". Millimoles.

By being within this range, the target hyperbranched polycarbonate polyol composition can be efficiently obtained without complicating post-processing.

It should be noted that the catalyst may be used once at the start of the reaction, or may be used (addition) divided into two or more times at the start of the reaction and after the start of the reaction.

(reaction temperature and reaction pressure)

The reaction temperature in the reaction to obtain the hyperbranched polycarbonate polyol composition of the present invention can be appropriately adjusted according to the type of carbonate, and is preferably 50°C to 250°C, more preferably 70°C to 230°C.

In addition, the reaction pressure in the reaction to obtain the hyperbranched polycarbonate polyol composition of the present invention is not particularly limited as long as the reaction is carried out while removing low-boiling components, but it is preferably under normal pressure or reduced pressure. conduct.

By being within this range, the target hyperbranched polycarbonate polyol composition can be efficiently obtained without causing successive reactions and side reactions.

Preferably, hyperbranched polycarbonate polyol composition of the present invention is by following formula (I):

-(OC(=O)-OR) _n -OH(I)

(In the formula, R is a group derived from an aliphatic diol, n is the number of repeating units, and is an integer of 1 or more) means that a group derived from a polyol having a branching factor g' of 0.55 to 0.82 combined structure. In the structure represented by the above formula (I) having a branching factor g' of 0.55 to 0.82, each R and n may be different or the same. In addition, the structures represented by the above-mentioned formula (I) having a branching factor g' of 0.55 to 0.82 may independently bond to groups derived from the same or different polyols.

(Highly branched polyurethane composition)

A polyurethane composition can be obtained by reacting the hyperbranched polycarbonate polyol composition of the present invention obtained as described above with a polyisocyanate (hereinafter sometimes referred to as "urethane reaction"). The present invention also relates to the polyurethane obtained by using the above hyperbranched polycarbonate polyol composition.

(polyisocyanate)

As the above-mentioned polyisocyanate, it can be appropriately selected according to the purpose and application, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5- Diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenylene isocyanate, xylylene diisocyanate (XDI), phenylene diisocyanate, etc. Araliphatic diisocyanate; 4,4'-methylenebiscyclohexyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diylbis(methylene) diisocyanate Aliphatic diisocyanates such as isocyanate and trimethylhexamethylene diisocyanate.

In addition, these polyisocyanates can be used individually or in mixture of 2 or more types, and a part or all of the structure can be derivatized by isocyanurate, carbodiimidization, or biuretization, etc.

The consumption of polyisocyanate can be designed by the mol ratio (isocyanate group/hydroxyl (mol)) of the isocyanate group of polyisocyanate and the hydroxyl group of hyperbranched polycarbonate polyol composition, preferably this molar ratio reaches 0.8～1.5, more preferably Reach the amount of 0.9 ~ 1.3.

(chain extender)

In the urethane reaction, in order to increase the molecular weight, a chain extender can be used. As the chain extender used, it can be appropriately selected according to the purpose and use, for example, use:

water;

Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1 -Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, benzenemethanol, bis(p-hydroxy)biphenyl, bis(p-hydroxyphenyl)propane, 2,2- Bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy) Low molecular polyols such as phenyl]cyclohexane;

Polyester polyol, polyester amide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol and other polymer polyols;

Ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, penta Polyamines such as ethylene hexamine.

It should be noted that for the chain extender, for example, refer to "Latest Polyurethane Application Technology" (CMC Corporation, 1985 issue), and for the above-mentioned polymer polyol, for example, refer to "Polyurethane Foam" (Polymer Publication ,year 1987).

(urethane catalyst)

In the urethane reaction, in order to increase the reaction rate, a known polymerization catalyst can be used, for example, a tertiary amine or an organometallic salt of tin or titanium or the like can be used.

In addition, regarding a polymerization catalyst, you may refer to pages 23-32 of Keiharu Yoshida's "Urethane Resin" (Nihon Kogyo Shimbun, 1969).

(solvent)

Urethane reaction can be carried out in the presence of a solvent, for example, use: ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, δ-valerolactone, ε-caprolactone and other esters; Amides such as amides, diethylformamide, and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; methyl isobutyl ketone , cyclohexanone and other ketones; benzene, toluene and other aromatic hydrocarbons.

The urethane reaction may be performed by adding a terminal terminator in order to adjust the molecular weight.

In addition, according to the purpose, heat stabilizers, light stabilizers, plasticizers, inorganic fillers, lubricants, colorants, silicone oils, foaming agents, flame retardants, etc. may be present in polyurethane.

The obtained polyurethane can be made into flexible polyurethane foam, rigid polyurethane foam, thermoplastic polyurethane, solvent-based polyurethane solution, water-based polyurethane resin dispersion, and the like. In addition, they can be processed into molded articles such as artificial leather or synthetic leather, heat insulating materials, cushioning materials, adhesives, paints, coating agents, films, and the like.

[Waterborne hyperbranched polyurethane resin dispersion]

In addition, the present invention also relates to the aqueous hyperbranched polyurethane resin dispersion obtained by using the above hyperbranched polycarbonate polyol composition. The aqueous hyperbranched polyurethane resin dispersion specifically for example can be manufactured by carrying out the following steps in sequence: making the hyperbranched polycarbonate polyol composition of the present invention, polyisocyanate and the polyol containing acidic group in the solvent A step of reacting in the presence or absence of a urethane prepolymer; a step of neutralizing the acidic groups in the prepolymer with a neutralizing agent; dispersing the neutralized prepolymer in A step in an aqueous medium; a step of reacting the prepolymer dispersed in the aqueous medium and the chain extender.

In addition, in each process, a catalyst is used as needed, thereby promoting reaction and controlling the amount of by-products.

The aqueous hyperbranched polyurethane resin dispersion derived from the hyperbranched polycarbonate polyol composition of the present invention can provide a film with excellent adhesion, flexibility and touch, so it can be especially suitable for artificial leather or synthetic leather.

As the hyperbranched polycarbonate polyol composition, polyisocyanate, solvent, and chain extender, those described above can be used.

(Polyols with acidic groups)

When producing an aqueous polyurethane resin dispersion, in order to disperse in an aqueous medium, an acidic group-containing polyol can be used. Therefore, the amount of the above-mentioned polyisocyanate can be determined by the molar ratio of the isocyanate group of the polyisocyanate to the total hydroxyl group of the polyol (polycarbonate polyol, polyol containing acidic groups described later, and all polyols such as low-molecular polyol described below). (isocyanate group/hydroxyl group (mol)), it is preferably an amount to achieve the molar ratio of 0.8 to 2.0, more preferably 0.9 to 1.8.

Examples of the acidic group-containing polyhydric alcohol include dimethylol alkanoic acids such as 2,2-dimethylol propionic acid and 2,2-dimethylol butyric acid; Glycine, N,N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, etc., preferably dimethylol alkanoic acid, more It is preferable to use an alkane acid having 4 to 12 carbon atoms containing two methylol groups.

It should be noted that these acidic group-containing polyols can be used alone or in combination of two or more, and the amount used is not particularly limited as long as the polyurethane resin can be dispersed in an aqueous medium.

(neutralizer)

Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, Organic amines such as methylethanolamine, diethylethanolamine, N-methylmorpholine, and pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide, and ammonia, organic amines are preferably used, and tertiary amines are more preferably used.

In addition, these neutralizing agents can be used individually or in mixture of 2 or more types, and the usage-amount is not specifically limited as long as it can neutralize the acidic group in a polyurethane resin.

(aqueous medium)

Examples of the aqueous medium include water such as tap water, ion-exchanged water, distilled water, and ultrapure water; or a mixed medium of water and a hydrophilic organic solvent.

Examples of the hydrophilic organic solvent include: ketones such as acetone and methyl ethyl ketone; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether ; Methanol, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol and other alcohols; amides such as β-alkoxypropionamide represented by Idemitsu Kosan's "Equa Amid"; 2 -(Dimethylamino)-2-methyl-1-propanol (DMAP) and other hydroxyl-containing tertiary amines.

As the quantity of the said hydrophilic organic solvent in the said aqueous medium, 0-20 mass % is preferable.

(Low Molecular Polyol)

In the urethanization reaction of the present invention, a low-molecular polyhydric alcohol may be present in order to adjust the molecular weight. Examples of usable low-molecular polyhydric alcohols include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, etc.

In addition, these low-molecular-weight polyols can be used individually or in mixture of 2 or more types.

Example

Next, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited to this.

In addition, the measurement of the hydroxyl value, the branching factor g', the number average molecular weight, and the property at room temperature was performed by the method demonstrated above. In addition, the measurement of acid value, viscosity, APHA, glass transition temperature, tensile strength and elongation at break was performed as follows.

[acid value]

A sample obtained by dissolving 10 g of a sample in a 50/50 (weight ratio) solution of toluene/ethanol was prepared, and titrated with a 0.1 N KOH ethanol solution. The acid value is obtained by the following formula: 5.61×(CB ¹ )×f/s. Here, ^B is the amount (mL) of the 0.1N KOH ethanol standard solution required for neutralizing the blank, C is the amount (mL) of the 0.1N KOH ethanol standard solution required for neutralizing the sample, and f is 0.1 The factor of the KOH ethanol standard solution of N, s is the weight (g) of the sample.

[viscosity]

Regarding the viscosity, LVDV II+Pro cone and a plate viscometer manufactured by Brookfield were used together with a spindle cone model CPE-41, and the viscosity was measured under the condition of melting at 80°C.

[APHA]

Measurement was performed in accordance with JIS K 1557. The degree of yellowing is expressed in units of APHA.

[Glass transition temperature]

Measurement was performed using a differential scanning calorimeter (DSC). A sample of 8 mg to 10 mg was used, and the temperature increase program was set from 80°C to 250°C at a heating rate of 20°C/min. The glass transition temperature was specified from the inflection point of the second scan.

[Tensile Strength and Elongation at Break]

According to ISO 527, it was carried out in an environment with a temperature of 23°C and a humidity of 50%. Specifically, the tensile strength and elongation at break were measured at a test piece of a polyurethane resin film having a thickness of 0.05 mm to 0.10 mm at a width of 5 mm, a test length of 20 mm, and a test speed of 100 mm/min.

Embodiment 1 (synthesis of highly branched polycarbonate polyol composition (1))

Mix 60.00 g (0.45 moles) of trimethylolpropane, 126.97 g (1.07 moles) of 1,6-hexanediol, and Methyl ester 172.18g (1.91mol) and lithium hydroxide 0.0013g (0.054mmol) (total hydroxyl moles of trimethylolpropane/total hydroxyl moles of 1,6-hexanediol=0.45*3/1.07* 2=0.63), and reacted at 100° C. to 200° C. for 7 hours while distilling off low boiling point components under normal pressure.

Furthermore, the pressure was reduced to 13.3 kPa over 10 hours, and then cooled to room temperature to obtain a hyperbranched polycarbonate polyol composition (1) as a viscous liquid.

The physical property values of the obtained hyperbranched polycarbonate polyol composition (1) are as follows.

Hydroxyl value: 197mgKOH/g

Acid value: 0.30mgKOH/g

Viscosity (80°C): 460cP

APHA: 75

Number average molecular weight (Mn): 710

Branching factor g': 0.7648

Properties at room temperature: liquid

Embodiment 2 (synthesis of highly branched polycarbonate polyol composition (2))

Mix 60.00 g (0.45 moles) of trimethylolpropane, 218.62 g (1.85 moles) of 1,6-hexanediol, and 266.89g (2.96 mol) of methyl ester and 0.0020g (0.083 mmol) of lithium hydroxide (total hydroxyl moles of trimethylolpropane/total hydroxyl moles of 1,6-hexanediol=0.45*3/1.85* 2=0.36), and reacted at 100° C. to 200° C. for 7 hours while distilling off low boiling point components under normal pressure.

Furthermore, the pressure was reduced to 13.3 kPa over 10 hours, and then cooled to room temperature to obtain a hyperbranched polycarbonate polyol composition (2) as a viscous liquid.

The physical property values of the obtained hyperbranched polycarbonate polyol composition (2) are as follows.

Hydroxyl value: 121mgKOH/g

Acid value: 0.21mgKOH/g

Viscosity (80°C): 3800cP

APHA: 65

Number average molecular weight (Mn): 1640

Branching factor g': 0.7298

Properties at room temperature: liquid

Comparative example 1

As Comparative Example 1, polycarbonate diol (manufactured by Ube Industries, Ltd., brand name: ETERNACOLL (registered trademark) UH-200) produced using 1,6-hexanediol and carbonate as raw materials was used.

The physical property values of Comparative Example 1 are as follows.

Hydroxyl value: 56mgKOH/g

Acid value: 0.01mgKOH/g

Viscosity (80°C): 2000cP

APHA: 15

Branching factor g': 1

Appearance at room temperature: waxy

Comparative example 2

33.5 g (0.25 mol) of trimethylolpropane, 177.0 g (1.50 mol) of 1,6-hexanediol, and dicarbonate 186.57g (2.07 moles) of methyl ester and 0.0020g (0.083 mmol) of lithium hydroxide (total hydroxyl moles of trimethylolpropane/total hydroxyl moles of 1,6-hexanediol=0.25*3/1.50* 2=0.25), and reacted at 100° C. to 200° C. for 7 hours while distilling off low boiling point components under normal pressure.

Furthermore, the pressure was reduced to 13.3 kPa over 10 hours, and then cooled to room temperature to obtain a polycarbonate polyol.

The physical property values of the obtained polycarbonate polyol are as follows.

Hydroxyl value: 167mgKOH/g

Acid value: 0.15mgKOH/g

Viscosity (80°C): 440cP

APHA: 15

Number average molecular weight (Mn): 926

Branching degree g': 0.8417

Appearance at room temperature: waxy

It can be seen that: hyperbranched polycarbonate polyol compositions (1)～(2) are liquid at room temperature, in contrast, comparative examples 1～2 are waxy, hyperbranched polycarbonate polyol composition of the present invention Alcoholic compositions are compositions that are easy to handle.

Embodiment 3 (synthesis of highly branched polyurethane resin (A))

Mix the polycarbonate diol 28.50g of hyperbranched polycarbonate polyol composition (1) 1.50g, the polycarbonate diol 28.50g of comparative example 1, 1, 2.97 g of 4-butanediol, 0.05 g of dibutyltin dilaurate, and 92 g of dimethylformamide were stirred at 70°C. Next, 11.74 g of isophorone diisocyanate was added, and it was made to react at 80 degreeC with stirring for 5 hours, and the hyperbranched polyurethane resin (A) was obtained.

Embodiment 4 (synthesis of highly branched polyurethane resin (B))

Mix hyperbranched polycarbonate polyol composition (2) 1.50g, the polycarbonate diol (28.50g, 1 , 2.89g of 4-butanediol, 0.05g of dibutyltin dilaurate, and 92g of dimethylformamide were stirred at 70°C. Next, 11.78g of isophorone diisocyanate was added and reacted at 80°C while stirring After 5 hours, a highly branched polyurethane resin (B) was obtained.

Comparative Example 3 (synthesis of polyurethane resin (C))

Mix polycarbonate diol 30.00g, 1,4-butanediol 3.06g, dibutyltin dilaurate 0.05g and 92 g of dimethylformamide was stirred at 70°C. Next, 11.62 g of isophorone diisocyanate was added, and it was made to react at 80 degreeC with stirring for 5 hours, and the polyurethane resin (C) was obtained.

Comparative Example 4 (synthesis of polyurethane resin (D))

1.50 g of the polycarbonate polyol of Comparative Example 2, 28.50 g of the polycarbonate diol of Comparative Example 1, and 1,4-butanediol were mixed in a 500 mL five-port reactor equipped with a nitrogen injection port, a thermometer, a cooling pipe, and a stirrer. 2.91 g of alcohol, 0.05 g of dibutyltin dilaurate, and 92 g of dimethylformamide were stirred at 70°C. Next, 11.84 g of isophorone diisocyanate was added, and it was made to react at 80 degreeC with stirring for 5 hours, and the polyurethane resin (D) was obtained.

Manufacture of polyurethane resin film

Polyurethane resins (A) to (D) were applied on a glass substrate. It should be noted that the mold size of the substrate is 20 cm×10 cm×3 mm. This was dried at 70°C for 1 hour and at 120°C for 2 hours to form a polyurethane resin film on the glass substrate.

The tensile strength and elongation at break of the polyurethane resin film were measured. The measurement results are shown in Table 1 below.

[Table 1]

Example 3 Example 4 Comparative example 3 Comparative example 4 Polyurethane resin (A) (B) (C) (D) Tensile strength (MPa) 64 85 50 65 Elongation at break (%) 840 820 820 640

As can be seen from the results of table 1: compared with the polyurethane resin film of comparative example 3 manufactured by the polycarbonate diol of comparative example 1, by the hyperbranched polycarbonate polyol of the present invention of embodiment 1 and embodiment 2 The polyurethane resin films of Example 3 and Example 4 produced by the compositions (1) and (2) had high tensile strength and high stress at 300% elongation while maintaining elongation at break.

In addition, compared with the polyurethane resin film of Comparative Example 4 manufactured from the polycarbonate polyol of Comparative Example 2, the polyurethane resin films of Example 3 and Example 4 had the same or higher tensile strength and high elongation at break. rate, a film with excellent mechanical properties can be obtained.

[Durability Test]

Durability tests were carried out using films produced from the hyperbranched polycarbonate polyol composition of the present invention. With regard to weather resistance and hydrolysis resistance, the presence or absence of deformation was visually observed after a lapse of time under specific conditions, and the tensile strength and elongation at break were measured, and evaluated from their retention rates. Heat resistance was evaluated by the degree of yellowing.

The weather resistance was evaluated by exposing the polyurethane sample to a QUV accelerated weather resistance tester in accordance with ASTM G154. The samples were alternately and automatically switched to the following procedures for a total of 26 hours of exposure: 1) exposure to 313nm UV-B at 60°C for 4 hours at 0.49W/m ² /nm; and 2) exposure at 50°C A condensation reaction with water was performed for 4 hours. Regarding the retention of tensile strength and elongation at break, the tensile strength and elongation at break were measured for the sample after the exposure test, and evaluated as a percentage of the film before exposure as 100. In addition, the presence or absence of deformation was judged visually.

Heat resistance was evaluated by measuring the degree of yellowing by the yellowness index (YI) according to ASTM E313-05(C). Heat was applied to the sample in an oven at 120° C. for 240 hours, and the heat resistance was evaluated by the amount of change in YI (ΔYI).

The hydrolysis resistance was evaluated by immersing the sample in a water bath at 40° C. for 72 hours, and calculating the retention rate of tensile strength and elongation at break. In addition, the presence or absence of deformation was judged visually.

The results are shown in Table 2 below.

[Table 2]

The polyurethane resin film obtained by using the highly branched polycarbonate polyol composition of the present invention has a high retention ratio of tensile strength and elongation at break, and no deformation is observed in the appearance. Furthermore, the yellowing was also small, indicating that a polyurethane resin film excellent in durability was obtained as a whole.

Claims (8)

1. A highly branched polycarbonate polyol composition having a structure derived from an aliphatic diol and a structure derived from a polyol, the polyol having a branching factor g' of 0.55 to 0.82, the polyol being a compound having 3 or more hydroxyl groups in one molecule,

the hydroxyl value of the highly branched polycarbonate polyol composition is 50 mgKOH/g-197 mgKOH/g.

2. The hyperbranched polycarbonate polyol composition as defined in claim 1 wherein the number average molecular weight Mn of the hyperbranched polycarbonate polyol composition is from 200 to 10000.

3. The highly branched polycarbonate polyol composition according to any one of claims 1 to 2, wherein the molar ratio of the aliphatic diol to the polyol is 0.3 to 0.63 in terms of "the total hydroxyl groups of the polyol/the total hydroxyl groups of the aliphatic diol".

4. The highly branched polycarbonate polyol composition according to any one of claims 1 to 2, wherein the proportion of terminal hydroxyl groups in the terminal structure of the highly branched polycarbonate polyol composition is 90% or more.

5. The highly branched polycarbonate polyol composition of any of claims 1-2, which is liquid at room temperature.

6. A polyurethane composition obtained using the highly branched polycarbonate polyol composition described in any one of claims 1 to 5.

7. A synthetic leather obtained using the highly branched polycarbonate polyol composition according to any one of claims 1 to 5.

8. An aqueous polyurethane resin dispersion obtained using the highly branched polycarbonate polyol composition described in any one of claims 1 to 5.