Amphiphilic polycarbonate polyol as well as preparation method and application thereof

Abstract

The invention provides amphiphilic polycarbonate polyol as well as a preparation method and application thereof. The amphiphilic polycarbonate polyol is prepared from 100 parts by mole of carbonic acid diester, 3-50 parts by mole of alkyl sulfonic acid sodium succinate and 110-400 parts by mole of polyol raw materials through ester exchange and condensation polymerization. According to the invention, the special monomer alkyl sulfonic sodium succinate is used, the prepared polycarbonate polyol contains a sulfonate structure, waterborne polyurethane can be prepared without waterborne chain extension, and the polycarbonate polyol is free of a benzene ring structure and low in product viscosity; meanwhile, the prepared polycarbonate polyol is subjected to devolatilization treatment, the content of small molecular impurities is low, side reactions in the polyurethane preparation process are few, and the prepared polyurethane material has the characteristics of low odor and low VOC (volatile organic compound) and can be applied to the industries of leather, coatings, adhesives and the like.

Description

Technical Field

[0001] This invention belongs to the field of polycarbonate polyol preparation, and relates to an amphiphilic polyester polyol, its preparation method and its uses. Background Technology

[0002] Polycarbonate-based polyurethane materials have excellent solvent resistance, abrasion resistance, weather resistance and heat resistance as leather and leather finishing agents, and are therefore widely used in industries such as automotive leather, furniture leather and clothing leather.

[0003] Waterborne polyurethane is more environmentally friendly than solvent-based polyurethane and is often used in the preparation of leather and leather finishing agents. Currently, waterborne polyurethane of the polycarbonate type is mainly prepared by reacting polycarbonate polyols with isocyanates, followed by waterborne chain extension and neutralization processes. However, the polyurethane emulsions prepared by this method have poor stability and low solid content. Furthermore, the presence of small molecule compounds in polycarbonate polyols causes unpleasant odors in leather products, affecting health. Chinese patent CN 115850676 A uses organic carbonates, aliphatic diols, and sodium dimethyl isophthalate-5-sulfonate as raw materials to prepare polycarbonate ionomers using a two-step melt polycondensation method, improving the product's hydrophilicity, transparency, and gas barrier properties. However, the sulfonate monomer sodium dimethyl isophthalate-5-sulfonate used in this method has a high melting point (>300℃), is insoluble in the reaction system, has a long reaction cycle, and produces high-viscosity polycarbonate products, increasing the difficulty of handling the products. Additionally, this method does not solve the odor problem of polycarbonate materials.

[0004] Therefore, it is of great significance to develop a new low-odor polycarbonate polyol and its application in the polyurethane field. Summary of the Invention

[0005] To address the aforementioned issues, this invention provides a low-odor amphiphilic polycarbonate polyol. By introducing an alkyl sulfonate structure into the polycarbonate polyol, the production process of waterborne polyurethane is simplified without increasing product viscosity. Simultaneously, the content of small molecule compounds in the product is reduced, thus resolving the odor problem in the final product.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] On one hand, the present invention provides an amphiphilic polycarbonate polyol, which is prepared from raw materials comprising the following components:

[0008] Component A: Dicarbonate, 100 moles;

[0009] Component B: Sodium alkyl sulfonate succinate, 3-50 moles, preferably 5-30 moles;

[0010] Component C: Polyol, 110-400 moles, preferably 150-300 moles.

[0011] In component A of the amphiphilic polycarbonate polyol of the present invention, the diester is selected from dialkyl carbonate, alkylene carbonate, and diaryl carbonate, etc. The dialkyl carbonate may be selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc.; the alkylene carbonate may be selected from ethylene carbonate, propylene carbonate, butyl carbonate, amyl carbonate, etc.; and the diaryl carbonate may be selected from diphenyl carbonate, etc. Preferably, the diester is selected from one or more of dimethyl carbonate, ethylene carbonate, and diphenyl carbonate; more preferably, the diester is dimethyl carbonate.

[0012] The structural formula of component B of the amphiphilic polycarbonate polyol described in this invention is as follows:

[0013]

[0014] Wherein, R is a C1-C20 alkyl chain, which can be straight or branched.

[0015] Preferably, component B is one or more of sodium 1,4-diethylsulfonate succinate, sodium sulfosuccinate-1,4-di(3-methylbutyl) ester, and sodium 1,4-di(octadecyl)sulfonate succinate; more preferably, component B is sodium 1,4-diethylsulfonate succinate.

[0016] In component C of the amphiphilic polycarbonate polyol of the present invention, the polyol is selected from polyols with 2-20 carbon atoms; preferably, the polyol is a diol with 2-12 carbon atoms; preferably, the polyol is selected from one or more of ethylene glycol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, butylethylpropanediol, diethylpentanediol, trimethylpentanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanediol, trimethylolpropane, glycerol, and pentaerythritol; more preferably, the polyol is selected from one or more of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol.

[0017] The raw materials of the amphiphilic polycarbonate polyol of the present invention further include a first catalyst. The amount of the first catalyst added is 0-500 ppm, preferably 50-300 ppm, based on the total mass of components A, B and C.

[0018] In some specific embodiments, the first catalyst is selected from one or more of titanium catalysts, tin catalysts, or antimony catalysts; preferably, the titanium catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate, or titanium dioxide; the tin catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, or stannous chloride; the antimony catalyst is selected from one or more of antimony acetate, antimony trioxide, or antimony glycolate; in some preferred embodiments, the first catalyst is a titanium catalyst, more preferably tetrabutyl titanate or tetraisopropyl titanate.

[0019] In this invention, the hydroxyl value of the amphiphilic polycarbonate polyol is 10-250 mg KOH / g; in some preferred embodiments, the hydroxyl value of the polycarbonate polyol is 30-150 mg KOH / g; in some more preferred embodiments, the hydroxyl value of the polycarbonate polyol is 50-120 mg KOH / g.

[0020] On the other hand, the present invention also provides a method for preparing the amphiphilic polycarbonate polyol, comprising the following steps:

[0021] Under an inert atmosphere, components A, B, and C are mixed and heated to 60-230℃ for 5-20 hours; then the pressure is further reduced to 0.01-10 kPa for vacuum polycondensation for 10-50 hours.

[0022] Preferably, a first catalyst may also be added to the reaction.

[0023] Preferably, the reaction temperature is 70-200℃.

[0024] Preferably, the pressure is reduced to 0.01-10 kPa to carry out the vacuum polycondensation reaction.

[0025] Preferably, after the reaction is complete, the product is subjected to a devolatilization process to remove some small molecules and reduce the product's taste.

[0026] In a specific embodiment, the devolatilization step specifically involves lowering the temperature of the reactor to 120-170°C and the vacuum degree to -0.09 to -0.1 MPa after the reaction is completed, and performing a devolatilization treatment for 0.5-5 hours to obtain the amphiphilic polycarbonate polyol.

[0027] The present invention also provides an aqueous polyurethane, which is obtained by reacting a component comprising the following raw materials:

[0028] Amphiphilic polycarbonate polyols: 70-89 wt%.

[0029] Diisocyanate monomer: 9-29 wt%,

[0030] Chain extender: 0.5-3wt%,

[0031] Second catalyst: 0.02-0.05 wt%.

[0032] The amphiphilic polycarbonate polyol is the polycarbonate polyol of this invention.

[0033] In one embodiment, the diisocyanate monomer is one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hexanedimethyl diisocyanate (HMDI), naphthalene diisocyanate (NDI), terephthalic diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), phenylmethylene diisocyanate (XDI), and cyclohexanedimethyl diisocyanate (HXDI), preferably, the diisocyanate monomer is isophorone diisocyanate (IPDI).

[0034] In one embodiment, the chain extender is one or more of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-cyclohexanediol, neopentanediol, and 1,6-hexanediol, preferably one or more of 1,4-butanediol, neopentanediol, and 1,6-hexanediol.

[0035] In some specific embodiments, the second catalyst is selected from tertiary amines and / or organometallic compounds, preferably from one or more of triethylenediamine, N,N-dimethylcyclohexylamine, dibutyltin dilaurate, stannous octoate, and bismuth carboxylate, and more preferably from stannous octoate and / or dibutyltin dilaurate.

[0036] The preparation method of waterborne polyurethane can refer to conventional methods in the field, for example: 1) Add the amphiphilic polycarbonate polyol, diisocyanate monomer, chain extender and second catalyst described in this invention to a reaction vessel, react under an inert atmosphere (such as nitrogen) until the NCO content reaches the theoretical value, add organic solvent, adjust the viscosity of the system, cool down and discharge to obtain polyurethane resin; 2) Add the polyurethane resin to an emulsification vessel, slowly add water according to a solid content of 30-60%, stir to emulsify, and remove the organic solvent by vacuum distillation to obtain waterborne polyurethane emulsion for leather.

[0037] Specifically, in step 1), the reaction temperature can be 70-80℃ and the reaction time can be 2-3 hours, which can be adjusted by those skilled in the art according to the actual production situation.

[0038] The positive effects of this invention are as follows:

[0039] (1) The amphiphilic polycarbonate polyol of the present invention contains a sulfonate structure, which can endow the polycarbonate polyol with amphiphilic properties and simplify the subsequent production process of waterborne polyurethane materials.

[0040] (2) The amphiphilic polycarbonate polyol of the present invention does not contain a benzene ring structure, and will not increase the interaction between molecular chains, thus maintaining low viscosity characteristics;

[0041] (3) The polycarbonate polyol and downstream polyurethane materials of the present invention have low content of small molecule impurities and low odor, and can be applied to industries such as automotive leather, clothing leather and home furnishing leather. Detailed Implementation

[0042] To better understand the technical solution of the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0043] The main raw materials used in the following examples and comparative examples are all commercially available chemicals. Dimethyl carbonate was purchased from Shandong Hualu Hengsheng; ethylene carbonate was purchased from Huasheng Lithium Battery; sodium 1,4-diethylsulfonate succinate and sodium sulfosuccinate-1,4-di(3-methylbutyl) ester were purchased from Shaanxi Didu New Materials Co., Ltd.; 1,4-butanediol, neopentyl glycol, ethylene glycol, 1,3-propanediol, adipic acid, terephthalic acid, and stannous octoate catalyst were all commercially available raw materials; IPDI was from Wanhua Chemical.

[0044] The product performance was measured in the embodiments and comparative examples of this invention using the following methods:

[0045] Determination of hydroxyl value: Refer to chemical industry standard HG / T 2709-1995;

[0046] Viscosity determination: Tested using a DV-2T rotational viscometer;

[0047] Odor determination: Refer to standard QB / T 2725-2005;

[0048] Small molecule content testing: Gas chromatography-mass spectrometry;

[0049] Emulsion stability: The prepared waterborne polyurethane was stored at room temperature and its condition was observed.

[0050] Molecular weight is calculated based on hydroxyl value. For example, the molecular weight of difunctional polyester polyols is calculated as follows: molecular weight = 112200 / hydroxyl value.

[0051] Example 1

[0052] Under inert gas protection, 9.01 kg of dimethyl carbonate, 8.34 kg of sodium 1,4-diethylsulfonic acid succinate, and 23.63 kg of 1,6-hexanediol were mixed and heated to 180 °C. 4.10 g of tetraisopropyl titanate was added, and the mixture was reacted for 12 h. The pressure was further reduced to 0.1 kPa for polycondensation reaction, and the reaction time was 25 h until the hydroxyl value reached 112 mg KOH / g. The reactor was then cooled to 150 °C, and the vacuum degree was -0.095 MPa. A devolatilization treatment was performed for 2.5 h to obtain amphiphilic polycarbonate polyol A, with a hydroxyl value of 112 mg KOH / g and an average molecular weight of 1000 g / mol.

[0053] Example 2

[0054] Under inert gas protection, 8.81 kg of ethylene carbonate, 1.39 kg of sodium 1,4-diethylsulfonic acid succinate, and 14.18 kg of 1,6-hexanediol were mixed and heated to 150 °C. 1.22 g of tetraisopropyl titanate was added, and the mixture was reacted for 20 h. The pressure was further reduced to 10 kPa for polycondensation reaction, and the reaction time was 46 h, until the hydroxyl value reached 56.1 mg KOH / g. The reactor was then cooled to 120 °C, and a vacuum of -0.09 MPa was applied for devolatilization treatment for 4 h to obtain amphiphilic polycarbonate polyol B with a hydroxyl value of 56.1 mg KOH / g and an average molecular weight of 2000 g / mol.

[0055] Example 3

[0056] Under inert gas protection, 9.01 kg of dimethyl carbonate, 18.02 kg of sodium sulfosuccinate-1,4-di(3-methylbutyl) ester, and 41.66 g of 1,5-pentanediol were mixed and heated to 230 °C. 20.61 g of tetrabutyl titanate was added, and the mixture was reacted for 5 h. The pressure was further reduced to 0.01 kPa for polycondensation reaction, which lasted for 19 h until the hydroxyl value reached 37.4 mg KOH / g. The reactor was then cooled to 170 °C, subjected to a vacuum of -0.100 MPa, and subjected to devolatilization for 0.5 h to obtain amphiphilic polycarbonate polyol C with a hydroxyl value of 37.4 mg KOH / g and an average molecular weight of 3000 g / mol.

[0057] Comparative Example 1

[0058] Under inert gas protection, 9.01 kg of dimethyl carbonate and 23.63 kg of 1,6-hexanediol were mixed and heated to 180 °C. 3.26 g of tetraisopropyl titanate was added, and the reaction was allowed to proceed for 12 h. The pressure was further reduced to 0.100 kPa for polycondensation for 25 h, until the hydroxyl value reached 112 mg KOH / g. The reactor was then cooled to 150 °C, subjected to a vacuum of -0.095 MPa, and subjected to devolatilization for 2.5 h to obtain amphiphilic polycarbonate polyol D with a hydroxyl value of 112 mg KOH / g and an average molecular weight of 1000 g / mol.

[0059] Comparative Example 2

[0060] Under inert gas protection, 9.01 kg of dimethyl carbonate, 8.95 kg of sodium dimethyl isophthalate-5-sulfonate, and 23.63 kg of 1,6-hexanediol were mixed and heated to 180 °C. 4.16 g of tetraisopropyl titanate was added, and the mixture was reacted for 12 h. The pressure was further reduced to 0.100 kPa for polycondensation reaction for 25 h until the hydroxyl value reached 112 mg KOH / g. The reactor was then cooled to 150 °C, subjected to a vacuum of -0.095 MPa, and subjected to devolatilization for 2.5 h to obtain amphiphilic polycarbonate polyol E with a hydroxyl value of 112 mg KOH / g and an average molecular weight of 1000 g / mol.

[0061] Application Examples 1-5

[0062] Application Examples 1-5 illustrate the preparation of waterborne polyurethane PUD-A to PUD-E.

[0063] According to the following formulation table, waterborne polyurethane can be prepared by following these steps: 1) Add the amphiphilic polycarbonate polyol, diisocyanate monomer (IPDI), chain extender and catalyst (stannous octoate T9) of the present invention to the reaction vessel according to the theoretical calculation amount, under nitrogen protection, react at 80°C for 2.5h until the NCO content reaches the theoretical value, add organic solvent, adjust the viscosity of the system, cool down and discharge; 2) Add polyurethane resin to the emulsification vessel, slowly add deionized water, emulsify at 2000r / min, and remove the organic solvent by vacuum distillation to obtain waterborne polyurethane emulsion for leather.

[0064] Table 1. Synthesis Formulation Table for Polyurethane Elastomers in Application Examples 1-5 (by Mass Fraction)

[0065]

[0066] Performance testing

[0067] The properties of waterborne polyurethane emulsions and membrane materials prepared from polycarbonate polyols were determined according to the aforementioned method, and the results are shown in the table below.

[0068] As shown in Table 2, the polycarbonate polyol prepared by this invention has a lower viscosity, while the product prepared using a sulfonate monomer containing a benzene ring has a higher viscosity. Furthermore, the polycarbonate polyol AC prepared by this invention is essentially odorless, indicating that the devolatilization process of this invention can effectively reduce the content of small molecules (small molecules with retention times between 5-8.5) and odor in the polycarbonate polyol (gas chromatography-mass spectrometry). Table 3 shows that without an aqueous chain extender, polycarbonate polyol D cannot be used to prepare aqueous polyurethane, while the amphiphilic polycarbonate polyol AC of this invention can be used to prepare a polyurethane emulsion with good stability without aqueous chain extension. This indicates that the polycarbonate polyol of this invention is amphiphilic, allowing for the preparation of aqueous polyurethane without aqueous chain extension, and the resulting polyurethane emulsion exhibits excellent stability.

[0069] Table 2 Comparison of small molecule compound content and odor in polycarbonate polyols of the examples and comparative examples.

[0070]

[0071] Table 3. Performance Comparison of Waterborne Polyurethanes Prepared from Polycarbonate Polyols in Examples and Comparative Examples

Claims

1. An amphiphilic polycarbonate polyol, characterized in that, It is prepared by raw materials comprising the following components: Component A: carbonic acid diester, 100 mole parts; Component B: sodium alkyl sulfosuccinate, 3-50 mole parts, preferably 5-30 mole parts; Component C: polyol, 110-400 mole parts, preferably 150-300 mole parts.

2. The polycarbonate polyol of claim 1, wherein, In the component A, the carbonic acid diester is selected from dialkyl carbonate, alkylene carbonate and diaryl carbonate, preferably, the dialkyl carbonate is selected from dimethyl carbonate, diethyl carbonate and dibutyl carbonate, the alkylene carbonate is selected from ethylene carbonate, propylene carbonate, butylene carbonate and pentylene carbonate, and the diaryl carbonate is selected from diphenyl carbonate; More preferably, the carbonic acid diester is selected from one or more of dimethyl carbonate, ethylene carbonate and diphenyl carbonate; more preferably, the carbonic acid diester is dimethyl carbonate.

3. The polycarbonate polyol according to claim 1 or 2, characterized in that, The component B has the following structure: In which R is a C1-C20 alkyl chain; Preferably, the component B is one or more of sodium 1,4-diethyl sulfosuccinate, sulfobutane-1,4-di(3-methylbutyl) ester sodium salt and sodium 1,4-di(octadecyl) sulfosuccinate; more preferably, the component B is sodium 1,4-diethyl sulfosuccinate.

4. The polycarbonate polyol according to any one of claims 1 to 3, characterized in that, In the component C, the polyol is selected from polyols with carbon atom number of 2-20; preferably, the polyol is dihydric alcohol with carbon atom number of 2-12; more preferably, the polyol is selected from one or more of ethylene glycol, 1,4-butanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, butyl ethyl propylene glycol, diethyl pentanediol, trimethyl pentanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexanediol, trimethylolpropane, glycerol and pentaerythritol; more preferably, the polyol is selected from one or more of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.

5. The polycarbonate polyol according to any one of claims 1 to 4, characterized in that, The raw materials of the amphiphilic polycarbonate polyol further comprise a first catalyst, the amount of the first catalyst is 0-500 ppm, preferably 50-300 ppm, based on the total mass of the component A, the component B and the component C; Preferably, the first catalyst is selected from one or more of titanium catalyst, tin catalyst or antimony catalyst; preferably, the titanium catalyst is selected from one or more of n-butyl titanate, tetraisopropyl titanate or titanium dioxide; the tin catalyst is selected from one or more of dibutyl tin dilaurate, stannous octoate or stannous chloride; the antimony catalyst is selected from one or more of antimony acetate, antimony trioxide or ethylene glycol antimony; in some preferred modes, the first catalyst is a titanium catalyst, more preferably n-butyl titanate or tetraisopropyl titanate.

6. The polycarbonate polyol according to any one of claims 1 to 5, characterized in that, The hydroxyl value of the polycarbonate polyol is 10-250 mg KOH / g; preferably, the hydroxyl value of the polycarbonate polyol is 30-150 mg KOH / g; more preferably, the hydroxyl value of the polycarbonate polyol is 50-120 mg KOH / g.

7. The method of making a polycarbonate polyol according to any one of claims 1-6, wherein, comprising the following steps: After mixing component A, component B and component C under the protection of inert atmosphere, the temperature is raised to 60-230℃, and the reaction is carried out for 5-20 h; further vacuum polycondensation reaction is carried out under reduced pressure of 0.01-10 kPa, and the reaction time is 10-50 h; Preferably, a first catalyst is added in the reaction; Preferably, the reaction temperature is 70-200℃; Preferably, the vacuum polycondensation reaction is carried out under reduced pressure of 0.01-10 kPa.

8. The preparation method according to claim 7, characterized in that, After the reaction is completed, the product is subjected to devolatilization treatment; Preferably, the devolatilization step specifically comprises the following steps: after the reaction is completed, the temperature of the reaction kettle is reduced to 120-170℃, the vacuum degree is -0.09 to -0.1 MPa, and the devolatilization treatment is carried out for 0.5-5 h, thereby obtaining the amphiphilic polycarbonate polyol.

9. An aqueous polyurethane, which is obtained by component reaction of the following raw materials: amphiphilic polycarbonate polyol: 70-89 wt%, diisocyanate monomer: 9-29 wt%, chain extender: 0.5-3 wt%, second catalyst: 0.02-0.05 wt%; the amphiphilic polycarbonate polyol is the polycarbonate polyol according to any one of claims 1-6; Preferably, the diisocyanate monomer is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hexa-cyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, xylylene diisocyanate, and cyclohexane dimethylene diisocyanate, and preferably the diisocyanate monomer is isophorone diisocyanate; Preferably, the chain extender is one or more of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, and 1,6-hexanediol, and preferably the chain extender is one or more of 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; Preferably, the second catalyst is selected from one or more of tertiary amines and / or organometallics, and preferably is one or more of triethylenediamine, N,N-dimethylcyclohexylamine, dibutyltin dilaurate, stannous octoate, and bismuth carboxylate, and more preferably is stannous octoate and / or dibutyltin dilaurate.

10. The method for preparing the waterborne polyurethane according to claim 9, comprising the following steps: 1) adding the amphiphilic polycarbonate polyol, diisocyanate monomer, chain extender and second catalyst into a reaction kettle, and reacting under the protection of inert atmosphere until the NCO content reaches the theoretical value, then adding an organic solvent to adjust the viscosity of the system, cooling and discharging to obtain a polyurethane resin; 2) adding the polyurethane resin into an emulsifying kettle, slowly adding water according to the solid content of 30-60%, stirring to emulsify, and removing the organic solvent to obtain a waterborne polyurethane emulsion. Preferably, the reaction temperature in step 1) is 70-80℃, and the reaction time is 2-3h.

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