KR20220105815A - Thioether-containing polydimethylsiloxane-based polyurethane elastic polymer and manufacturing method thereof - Google Patents

Abstract

The present disclosure relates to a polydimethylsiloxane-based polyurethane polymer elastomer comprising thioether and a preparation method thereof. Specifically, in the preparation method of a PDMS-based polyurethane polymer elastomer according to one embodiment of the present invention, a PDMS-based polyol comprising thioether is used in a PDMS backbone unlike a conventional PDMS-based polyurethane so that the hydrophobicity of PDMS can be maximized and a polyurethane polymer with higher strength can be prepared. In addition, the elastic modulus of the polyurethane polymer can be controlled by comprising a thioether group as a side chain of the PDMS backbone.

Description

Polyurethane polymer elastomer based on thioether-containing polydimethylsiloxane and manufacturing method thereof

The present disclosure relates to a thioether-containing polydimethylsiloxane-based polyurethane polymer elastomer and a method for preparing the same.

[Description of state-funded R&D]

This research was conducted under the supervision of the Korea Institute of Science and Technology, the Ministry of Trade, Industry and Energy's industrial material core technology development project (Isphobic coating material technology development for response to extreme environments, task identification number: 1415167203), the construction technology research project of the Ministry of Land, Infrastructure and Transport ( Development of EMP shielding building materials and accessories, project identification number: 1615011504) and personal basic research project of the Ministry of Science and ICT (transition metal carbide maxine 2D nanomaterial synthesis and electromagnetic wave shielding/absorption/control technology development using the same, project identification number: 1711111882) was supported.

In various fields such as kitchenware fields including glass containers, plumbing fields including water pipes, semiconductor fields, construction fields, display screen fields, aviation fields and metal wiring related fields, hydrophobic and water repellency materials Demand is increasing. To this end, attempts are being made to modify the surface of a hydrophilic substrate to be hydrophobic. For example, products in which the hydrophilic surface is hydrophobized using an inorganic modifier and an organic polymer modifier have been marketed. .

A typical example of modifying urethane-based hydrophilic properties into hydrophobicity is the reaction with polydimethylsiloxane (PDMS). It is a silicone polymer suitable for surface modification of hydrophilic substrates such as hydrophobicity.

However, in the prior art, polyurethane has been synthesized using commercially designed polydimethylsiloxane as a starting material. The types of polyurethane composites to be synthesized are limited due to the limitations of the present invention, and there is a limit in that it is difficult to expect new properties of the composites.

Republic of Korea Patent Publication No. 10-2017-0075708

In one aspect, in order to solve the above problems, the present invention uses a PDMS-based polyol containing thioether in a polydimethylsiloxane (PDMS) backbone, further maximizing hydrophobicity, which is a unique characteristic of existing PDMS itself. At the same time, an object of the present invention is to provide a method for producing a PDMS-based polyurethane polymer elastomer capable of controlling the physical properties of the polyurethane polymer, specifically, elasticity and strength.

In order to achieve the above object, an embodiment of the present invention provides a polydimethylsiloxane (PDMS) PDMS-based polyol including a thioether group at both ends and at least one of side chains; and polyisocyanate; it provides a method for producing a PDMS-based polyurethane polymer elastomer, including the step of mixing and reacting.

In addition, another embodiment of the present invention provides a PDMS-based polyurethane polymer elastomer including a thioether group in at least one of both ends and side chains of the polydimethylsiloxane (PDMS) backbone.

The method for producing a PDMS-based polyurethane polymer elastomer according to an embodiment of the present invention maximizes the hydrophobicity of PDMS by using a PDMS-based polyol containing thioether in the PDMS backbone, unlike the existing PDMS-based polyurethane. In addition, it is possible to provide a polyurethane polymer having higher strength, and also to control the elastic modulus of the polyurethane polymer by including a thioether group as a side chain of the PDMS backbone.

1 is a view showing a synthesis route of a PDMS-based polyurethane polymer elastomer according to an embodiment of the present invention.
2 is a view showing the tensile test results of the polyurethane polymer elastomer according to Test Example 1.

Hereinafter, the present invention will be described in detail.

In one aspect, the present invention relates to a polydimethylsiloxane (PDMS) PDMS-based polyol including a thioether group at both ends and at least one of side chains; And polyisocyanate; may relate to a method for producing a PDMS-based polyurethane polymer elastomer, including the step of reacting by mixing.

As an embodiment, the PDMS-based polyol including the thioether group may be represented by the following Chemical Formula 1:

[Formula 1]

Here, R ₁ and R ₂ may each independently be selected from C ₁ -C ₂₅ aliphatic hydrocarbons, and more specifically, from C _1-25 alkyl, C _2-25 alkenyl and C _2-25 alkynyl. It may be a selected saturated or unsaturated chain hydrocarbon, and n is each independently an integer of 3 to 15.

In addition, at least one of the methyl groups (-CH ₃ ) bonded as a side chain is each independently a saturated or unsaturated chain hydrocarbon selected from C _1-25 alkyl, C _2-25 alkenyl and C _2-25 alkynyl, and - It may be substituted by any one selected from R ₃ -SR ₄ .

In one embodiment, R ₃ and R ₄ may each independently be selected from C ₁ -C ₂₅ aliphatic hydrocarbons, and more specifically, C _1-25 alkyl, C _2-25 alkenyl and C _2-25 It may be a saturated or unsaturated chain hydrocarbon selected from alkynyl.

In one embodiment, the saturated or unsaturated chain hydrocarbon may contain at least one of a hetero element including nitrogen, oxygen, and sulfur and a halogen element including fluorine, chlorine, bromine, and iodine in the middle or side chain of the chain. can

In one embodiment, at least one hydrogen atom of the saturated or unsaturated chain hydrocarbon may be substituted with at least one of fluorine, chlorine, bromine and iodine.

As an embodiment, the PDMS-based polyol including thioether groups at both ends may be synthesized through the following steps:

(1) -(Si(CH ₃ ) ₂ O) a hydroxyl group of a silanol derivative containing a hydroxyl group (-OH) at both ends of a PDMS backbone having a repeating unit in the form of _n - and vinylsilane ( synthesizing a PDMS derivative in which the end of the PDMS backbone is substituted with a vinyl group by a nucleophilic substitution reaction of the vinylsilane) derivative; and

(2) synthesizing a PDMS-based polyol containing thioether groups at both ends through a hydroxilylation reaction between the thiol derivative and the PDMS derivative in which both ends are substituted with vinyl groups synthesized in step (1), The thiol derivative is at least one selected from C1-C25 alkylthiol, C2-C25 alkenylthiol, C2-C25 alkynylthiol, C6-C25 arylthiol and (C6-C25 aryl)-(C1-C5 alkyl)thiol; step.

In one embodiment, the PDMS-based polyol containing a thioether group as the side chain may be synthesized through a hydrosilylation reaction between a PDMS derivative containing a vinyl group as a pendant group and a hydroxy group at both ends and a thiol derivative. can

The method for producing a PDMS-based polyurethane polymer elastomer according to an aspect of the present invention includes thioether in the PDMS backbone as described above, thereby further enhancing hydrophobicity, a unique characteristic of PDMS itself, and including oxygen in the PDMS backbone. Alternatively, it is possible to provide a polyurethane polymer having higher strength than the existing PDMS-based polyurethane composed only of carbon.

In addition, the method for producing a PDMS-based polyurethane polymer elastomer according to an aspect of the present invention includes thioether as a side chain of the PDMS backbone as described above, that is, by including sulfur in the side chain of the PDMS backbone. It is possible to control the modulus of elasticity of the polyurethane polymer.

In one embodiment, the polyisocyanate is diisocyanate, 4,4'-diisocyanate-methylenedicyclohexane (4,4'-isocyanato-3,3,5-trimethyl-5- Isocyanatomethyl-cyclohexane (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane), 1,4-tetramethylene diisocyanate (1,4-tetramethylene diisocyanate), 1,6-hexa Methylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- Diisocyanate (cyclohexane-1,3-diisocyanate), cyclohexane-1,4-diisocyanate (cyclohexane-1,4-diisocyanate), 2,4-hexahydrotoluene diisocyanate (2,4-hexahydrotoluene diisocyanate), 2 ,6-hexahydrotoluene diisocyanate (2,6-hexahydrotoluene diisocyanate), hexahydro-1,3-phenylene diisocyanate (hexahydro-1,3-phenylene diisocyanate), hexahydro-1,4-phenylene diisocyanate (hexahydro-1,4-phenylene diisocyanate), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolyrene-2, 4-diisocyanate (tolylene-2,4-diisocyanate), 4,4'-methylenediphenyl diisocyanate, isophorone diisocyanate, 1,4-diisocyanate Ito cyclohexane (1,4-diisocyanato cyclohexane), 1,4-diisocyane Ito benzene (1,4-diisocyanatobenzene), 2,4-diisocyanato toluene (2,4-diisocyanato toluene), 2,6-diisocyanato toluene (2,6-diisocyanato toluene), tetramethylxylene It may be any one or more selected from the group consisting of diisocyanate (tetramethylxylene diisocyanate) and p-xylene diisocyanate (p-xylene diisocyanate), but is not limited thereto, and both ends end in an isocyanate group (-NCO) If it is a compound, it is possible.

As an embodiment, the manufacturing method is a reaction by adding a chain extender to a prepolymer obtained by mixing and reacting the PDMS-based polyol and polyisocyanate to increase the molecular weight of the polyurethane polymer elastomer. It may further include the step of increasing.

In one embodiment, the chain extender is 1,4-butanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol , 1,8-octanediol, 1,9-nonanediol, ethylene glycol, diethyl bis hydroxymethyl malonate (diethyl bis hydroxymethyl malonate) and may be any one or more selected from the group consisting of propylene glycol, but limited thereto not, and any compound containing a hydroxyl group (-OH) at both ends is possible.

As an embodiment, the mixing ratio of the PDMS-based polyol and polyisocyanate may be 1:0.5 to 5 based on molar mass (g/mol). More specifically, the mixing ratio of the PDMS-based polyol and polyisocyanate is 1: 0.5, 1: 1, 1: 1.5, 1: 2, 1: 2.5, 1: 3, 1: based on molar mass (g/mol): 3.5, 1:4, 1:4.5 or 1:5.

In another aspect, the present invention may relate to a PDMS-based polyurethane polymer elastomer including a thioether group in at least one of both ends and side chains of the polydimethylsiloxane (PDMS) backbone.

In one embodiment, the PDMS skeleton including the thioether group may be represented by the following Chemical Formula 2:

[Formula 2]

Here, the descriptions of R ₁ , R ₂ , n and the side chain methyl group (—CH ₃ ) are the same as those described in detail with respect to Formula 1 above.

Hereinafter, the content of the present invention will be described in more detail through preparation examples and test examples. However, these preparations and test examples are only presented to understand the content of the present invention, the scope of the present invention is not limited to these preparations and test examples, and modifications and substitutions commonly known in the art and insertion may be performed, and this is also included in the scope of the present invention.

<Preparation Example 1> Preparation of PDMS-based polyurethane polymer containing thioether in polydimethylsiloxane (PDMS) backbone

In an embodiment of the present invention, a PDMS-based polyurethane polymer was prepared through the following Preparation Examples 1-1 to 1-4. The overall synthesis route and the structure of the finally synthesized PDMS-based polyurethane polymer are as shown in FIG. 1 .

Preparation Example 1-1. Preparation of PDMS-based polyols containing thioethers at both ends of the PDMS backbone

A PDMS-based polyol including thioether groups at both ends of a polydimethylsiloxane (PDMS) backbone according to an embodiment of the present invention was synthesized through the following reaction scheme.

First, polydimethylsiloxane (PDMS) (1 compound; SILANOL TERMINATED POLYDIMETHYLSILOXANE, Gelest) (1.0 equivalent) and chloro (dimethyl) vinylsilane (2 compounds) (2 compounds) substituted with hydroxyl groups at both ends (2.6 equivalent) reacted with a catalyst (triethylamine; trimethylamine, Net ₃ ) (2.6 equivalents) and a solvent (toluene; toluene) for 5 hours at room temperature through a coupling reaction to 3 compounds having vinyl groups at both ends was synthesized.

Then, the synthesized compound 3 (1.0 equiv.) was reacted with 2-mercaptoethanol (2.6 equiv.), a catalyst (AIBN) (0.2 equiv), and a solvent (THF) at 60° C. for 12 hours for hydrosilylation. ), a PDMS-based polyol (4 compounds) containing thioether groups at both ends of the PDMS backbone was synthesized through the reaction.

Preparation 1-2. Preparation of PDMS-based polyol containing thioether in the side chain of the PDMS backbone

A PDMS-based polyol including a thioether group in the side chain of the polydimethylsiloxane (PDMS) backbone according to an embodiment of the present invention, that is, sulfur in the pendant group, was synthesized through the following reaction scheme. .

Specifically, 1' compound (10-15% VINYLMETHYLSILOXANE) - DIMETHYLSILOXANE COPOLYMER, SILANOL TERMINATED, 25-40 cSt, Gelest) (1.0 equivalent) and 1-octanethiol ( 1-octanethiol) (1.3 equivalents) was reacted with a catalyst (AIBN) (0.2 equivalents) and solvent (THF) at 60° C. for 12 hours to form a thioether group on the side chain of the PDMS backbone through hydrosilylation reaction. A PDMS-based polyol (3' compound) containing

Preparation Example 1-3. Preparation of a prepolymer through urethane reaction of a PDMS-based polyol containing thioether on a polydimethylsiloxane (PDMS) backbone and diisocyanate

A prepolymer of a PDMS-based polyurethane including thioether in a polydimethylsiloxane (PDMS) backbone according to an embodiment of the present invention was synthesized through the following reaction scheme.

Specifically, the prepolymer (5) through the urethane reaction of 4 compounds (1.0 equivalents) and two diisocyanates (compounds A and B) (0.84 equivalents and 1.26 equivalents, respectively) prepared in Preparation Example 1-1 through the reaction scheme compound) was synthesized.

Preparation Example 1-4. Preparation of PDMS-based polyurethane polymer containing thioether in polydimethylsiloxane (PDMS) backbone

Through the following reaction formula, 1,4-butanediol (1.0 equivalent) as a chain extender was added to the 5 compound (1.0 equivalent), which is the prepolymer synthesized in Preparation Example 1-3, and finally the poly according to an embodiment of the present invention. 6 compounds, which are PDMS-based polyurethane polymers including thioether in a dimethylsiloxane (PDMS) backbone, were prepared.

<Test Example 1> Tensile test of PDMS-based polyurethane polymer elastomer

A tensile test was performed on the PDMS-based polyurethane polymer elastomer according to an embodiment of the present invention. Specifically, using a universal material tester (H5KT, Tinius Olsen), the gage length and test speed were set to 50 mm and 150 mm/min, respectively, and a tensile test was performed. The results are shown in FIG. 2 .

From the results of FIG. 2, O-PDMS ( CARBINOL (HYDROXYL) TERMINATED POLYDIMETHYLSILOXANE, 30-50 cSt , Gelest) (tensile strength: 12.0 MPa, modulus of elasticity: 17.4) MPa), S-PDMS (tensile strength: 16.6 MPa, elastic modulus: 16.6 MPa, modulus of elasticity: 53.3 MPa) using the PDMS-based polyurethane polymer, it can be seen that the strength is the best, except that the 3' compound prepared in Preparation Example 1-2 was used as a starting material in Preparation Example 1-1. PS-PDMS (tensile strength: 11.7 MPa, elastic modulus: 7.83 MPa) containing a thioether group as a pendant group to the PDMS backbone in S-PDMS, prepared through the same process as Examples 1-1, 1-3 and 1-4, was prepared. In the case of the used PDMS-based polyurethane polymer, it was confirmed that it exhibited the lowest elastic modulus.

That is, the PDMS-based polyurethane polymer elastomer according to an embodiment of the present invention has superior strength by including thioether in the PDMS backbone, and improves elasticity by including thioether in the pendant group of the PDMS backbone. You can see that it can be adjusted.

Claims (12)

a PDMS-based polyol including a thioether group in at least one of both ends and a side chain of a polydimethylsiloxane (PDMS) backbone; And polyisocyanate; A method for producing a PDMS-based polyurethane polymer elastomer, including the step of mixing and reacting. According to claim 1, wherein the PDMS-based polyol containing a thioether group is characterized in that represented by the following formula (1), PDMS-based polyurethane polymer elastomer production method:
[Formula 1]

Here, R ₁ and R ₂ are each independently a C ₁ -C ₂₅ aliphatic hydrocarbon,
At least one of the branched methyl groups (—CH ₃ ) is each independently a saturated or unsaturated chain hydrocarbon selected from C _1-25 alkyl, C _2-25 alkenyl and C _2-25 alkynyl, and —R ₃ —SR ₄ is substituted by any one selected from,
R ₃ and R ₄ are each independently a C ₁ -C ₂₅ aliphatic hydrocarbon,
n is each independently an integer from 3 to 15; The method of claim 2, wherein the C ₁ -C ₂₅ aliphatic hydrocarbon is at least one of a hetero element including nitrogen, oxygen, and sulfur in the middle or side chain of a chain, and a halogen element including fluorine, chlorine, bromine, and iodine. Containing, C _1-25 alkyl, C _2-25 alkenyl and C _2-25 A method of producing a PDMS-based polyurethane polymer elastomer, characterized in that it is a saturated or unsaturated chain hydrocarbon selected from alkynyl. The method of claim 3, wherein at least one hydrogen atom of the saturated or unsaturated chain hydrocarbon is substituted with at least one of fluorine, chlorine, bromine and iodine. According to claim 1, wherein the polyisocyanate is diisocyanate (diisocyanate), 4,4'-diisocyanato-methylenedicyclohexane (4,4'-isocyanato-3,3,5-trimethyl-5 -isocyanatomethyl-cyclohexane (1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane), 1,4-tetramethylene diisocyanate (1,4-tetramethylene diisocyanate), 1,6- Hexamethylene diisocyanate (HDI), 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3 - Diisocyanate (cyclohexane-1,3-diisocyanate), cyclohexane-1,4-diisocyanate (cyclohexane-1,4-diisocyanate), 2,4-hexahydrotoluene diisocyanate (2,4-hexahydrotoluene diisocyanate), 2,6-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate Isocyanate (hexahydro-1,4-phenylene diisocyanate), 1,3-phenylene diisocyanate (1,3-phenylene diisocyanate), 1,4-phenylene diisocyanate (1,3-phenylene diisocyanate), tolylene-2 ,4-diisocyanate (tolylene-2,4-diisocyanate), 4,4'-methylenediphenyl diisocyanate (4,4'-methylenediphenyl diisocyanate), isophorone diisocyanate, 1,4-diisocyanate Anato cyclohexane (1,4-diisocyanato cyclohexane), 1,4-diisocyane Ito benzene (1,4-diisocyanatobenzene), 2,4-diisocyanato toluene (2,4-diisocyanato toluene), 2,6-diisocyanato toluene (2,6-diisocyanato toluene), tetramethylxylene A method of producing a PDMS-based polyurethane polymer elastomer, characterized in that at least one selected from the group consisting of diisocyanate (tetramethylxylene diisocyanate) and p-xylene diisocyanate (p-xylene diisocyanate). According to claim 1, wherein the reaction by adding a chain extender (chain extender) to the prepolymer (prepolymer) obtained by mixing and reacting the PDMS-based polyol and polyisocyanate to increase the molecular weight of the polyurethane polymer elastomer Further comprising, a method for producing a PDMS-based polyurethane polymer elastomer. 7. The method of claim 6, wherein the chain extender is 1,4-butanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptane characterized in that at least one selected from the group consisting of diol, 1,8-octanediol, 1,9-nonanediol, ethylene glycol, diethyl bis hydroxymethyl malonate and propylene glycol, A method for producing a PDMS-based polyurethane polymer elastomer. The method according to claim 1, wherein the mixing ratio of the PDMS-based polyol and polyisocyanate is 1:0.5 to 5 based on molar mass (g/mol). A PDMS-based polyurethane polymer elastomer comprising a thioether group in at least one of both ends and side chains of a polydimethylsiloxane (PDMS) backbone. According to claim 9, wherein the PDMS skeleton comprising a thioether group is represented by the following formula (2), PDMS-based polyurethane polymer elastomer:
[Formula 2]

Here, R ₁ and R ₂ are each independently a C ₁ -C ₂₅ aliphatic hydrocarbon,
At least one of the branched methyl groups (—CH ₃ ) is each independently a saturated or unsaturated chain hydrocarbon selected from C _1-25 alkyl, C _2-25 alkenyl and C _2-25 alkynyl, and —R ₃ —SR ₄ is substituted by any one selected from,
R ₃ and R ₄ are each independently a C ₁ -C ₂₅ aliphatic hydrocarbon,
n is each independently an integer from 3 to 15; The method of claim 10, wherein the C ₁ -C ₂₅ aliphatic hydrocarbon is at least one of a hetero element including nitrogen, oxygen, and sulfur in the middle or side chain of a chain, and a halogen element including fluorine, chlorine, bromine, and iodine. Containing, C _1-25 alkyl, C _2-25 alkenyl and C _2-25 A method of producing a PDMS-based polyurethane polymer elastomer, characterized in that it is a saturated or unsaturated chain hydrocarbon selected from alkynyl. The method of claim 11, wherein at least one hydrogen atom of the saturated or unsaturated chain hydrocarbon is substituted with at least one of fluorine, chlorine, bromine and iodine.

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