CN116355576A

CN116355576A - High-strength composite polyurethane sealant and preparation method thereof

Info

Publication number: CN116355576A
Application number: CN202310388244.0A
Authority: CN
Inventors: 崔号东
Original assignee: Shenzhen Tenchy Silicone & Rubber Co ltd
Current assignee: Shenzhen Tenchy Silicone & Rubber Co ltd
Priority date: 2023-04-12
Filing date: 2023-04-12
Publication date: 2023-06-30

Abstract

The invention discloses a high-strength composite polyurethane sealant and a preparation method thereof. By introducing the selenized two-dimensional nano material into the polyurethane formula, a new method is provided for changing the mechanical property of polyurethane. Dispersing the two-dimensional nano-material of the selenide in one or more polyols, one or more isocyanates or one or more polyols and one or more isocyanates, and respectively mixing and reacting. Because the specific surface area of the Icelinium selenide two-dimensional nano material is large, a small amount of Icelinium selenide two-dimensional nano material is dispersed in the polyurethane matrix, and the Icelinium selenide two-dimensional nano material and the polymer main chain are wound together through physical adsorption, a three-dimensional space network is formed, so that the strength of the composite material is increased, and the high-strength composite polyurethane sealant is obtained and has a wide application prospect.

Description

High-strength composite polyurethane sealant and preparation method thereof

Technical Field

The invention relates to the field of sealants, in particular to a high-strength composite polyurethane sealant and a preparation method thereof

Background

Polyurethane adhesives have good low temperature resistance, excellent flexibility, wear resistance, oil resistance, chemical resistance and other properties, and are widely used in many fields. However, the strength of polyurethane is not high, if the polyurethane is used in the field of sealant, some materials are required to be added to change the mechanical properties of the polyurethane, and the addition of nano materials into the polyurethane sealant is a convenient and effective method for improving the mechanical properties of polyurethane products.

In recent years, inorganic/organic nanocomposite materials have been receiving attention from researchers because they have both the advantages of inorganic nanomaterial and organic material. The two-dimensional material represented by graphene is a common inorganic material, and is widely applied to composite materials in multiple fields due to simple preparation, chemical inertness, excellent thermal performance and mechanical performance. The selenizing-indium diselenide (InSe) is a novel two-dimensional nanomaterial, has a unique nano platform with a planar topological structure, and can effectively improve and change the mechanical properties of polyurethane due to the unique morphology and physical and chemical properties.

Technical problem to be solved

Aiming at the challenges in the prior art, the embodiment of the invention aims to provide a high-strength composite polyurethane sealant and a preparation method thereof. The method can effectively improve and change the mechanical properties of polyurethane by adding the selenized two-dimensional nano material, and has great significance on polyurethane composite materials.

Disclosure of Invention

In order to achieve the above purpose, the invention mainly adopts the following technical scheme,

step one: preparing an InSe dispersion comprising dispersing a selenized two-dimensional nanomaterial in one or more polyols, (b) in one or more isocyanates, or (c) in one or more polyols and one or more isocyanates, separately or in combination. Preferably, the mass percentage of the InSe in the InSe dispersion solution is 0.1-40%. Further preferably, the mass percentage of InSe in the dispersion is 0.1-1%

Preferably, the isocyanate used to prepare the polyurethane includes aromatic isocyanates and aliphatic and cycloaliphatic isocyanates. Further preferred, the aromatic isocyanate comprises: diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), and the like. Further preferred, the aliphatic and cyclic aliphatic isocyanates include: 1, 6-adipic acid diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3, 5-trimethylcyclohexane (isophorone diisocyanate, IPDI), 4' -diisocyanate dicyclohexylmethane, and the like.

Further preferred isocyanates for preparing polyurethanes are diphenylmethane diisocyanate.

Preferably, the polyol used for preparing polyurethane comprises polyether polyol and polyester polyol.

Further preferred polyols for preparing polyurethanes are polyether polyols.

Step two: mixing the dispersion of step (1) (a) with an isocyanate or the dispersion of (1) (b) with a polyol and a catalyst to produce a polymerization reaction; or mixing the dispersion of step (1) (c) with a catalyst to produce a polymerization reaction.

Preferably, the catalyst for preparing polyurethane comprises an amine compound or a metal complex.

Further preferred amine compound catalysts include tertiary amines such as triethylenediamine (TEDA, 1, 4-diazabicyclo [2.2.2] octane or DABCO), dimethylcyclohexylamine (DMEA), and dimethanol amine (DMEA). The catalyst may also contain a hydroxyl group, a secondary amine, or the like.

Further preferred examples of metal compound catalysts include mercury, lead, tin, bismuth and zinc based compounds, including: mercury, bismuth and zinc carboxylates. Alkyl tin carboxylates, oxides, and thiolate oxides, and the like.

Further preferred catalysts for the preparation of the polyurethane are dibutyltin dilaurate.

Compared with the prior art, the invention has the following advantages and beneficial technical effects:

according to the method provided by the invention, the selenized two-dimensional nanomaterial is added into the polyurethane sealant, so that the tensile strength, the shearing strength and the hardness of the product are obviously improved. Because the specific surface area of the two-dimensional nano material of the indium diselenide is large, a small amount of the two-dimensional nano material of the indium diselenide is dispersed in the polyurethane matrix, and the two-dimensional nano material of the indium diselenide and the polymer main chain are wound together through physical adsorption, so that a three-dimensional space network is formed, and the strength of the composite material is increased.

Drawings

FIG. 1 TEM topography of a two-dimensional nanomaterial of selenized

FIG. 2. Tensile Strength plot of InSe added to polyurethane in polyether phase

FIG. 3 tensile Strength diagram of polyurethane with InSe added to isocyanate phase

FIG. 4. Tensile Strength plot of polyurethane with InSe added to polyether polyol and isocyanate Mixed solution

Detailed Description

Example 1

(1) Preparing the two-dimensional nano material.

InSe crystal is stored in DMF solution, ground in a mortar, ultrasonically treated for 10 hours by a 1200W probe, ultrasonically treated in a water bath for 10 hours, centrifugated for 10 minutes at 5000rpm, inSe nanometer sheets with uniform particle size are obtained, the InSe nanometer sheets are separated for 10 minutes at 14000rpm, resuspended in absolute ethanol solution, centrifugated and washed to obtain InSe solution for standby. The morphology of the obtained sample was examined by TEM, and the result is shown in FIG. 1, wherein the InSe nano sheet has a lamellar morphology with a size of 50-200 nm.

(2) And (3) preparing an InSe dispersion liquid.

Preparing an InSe dispersion liquid, dispersing 0.1-40% of InSe two-dimensional nano material in PPG-100 polyether polyol by mass percent, and rapidly stirring for 1 hour to obtain a dispersion liquid (a).

(3) And (3) a mixing step.

40 parts of the dispersion of (a) was charged into a reaction vessel with 100 parts of liquefied MDI of the Wanhua chemical model 100LL and 0.02 part of dibutyltin dilaurate, and reacted at 80℃for 3 hours with stirring under vacuum to effect polymerization.

(4) And (5) detecting tensile strength.

Colloid tensile test standard was used: GB/T1040.2-2006 determination of Plastic tensile Properties second part: test methods for molded and extruded plastics. And (5) detecting the tensile strength of the obtained polyurethane sealant. As a result, as shown in fig. 2, when InSe was added to the polyether phase, the tensile strength of the resulting polyurethane was higher than that of the control sample without InSe, and when more InSe was added to the polyether phase, the tensile strength of the polyurethane was also increased, in which case the optimum addition amount mass% was about 0.1%.

Example 2

(1) Preparing the two-dimensional nano material.

InSe crystal is stored in DMF solution, ground in a mortar, ultrasonically treated for 10 hours by a 1200W probe, ultrasonically treated in a water bath for 10 hours, centrifugated for 10 minutes at 5000rpm, inSe nanometer sheets with uniform particle size are obtained, the InSe nanometer sheets are separated for 10 minutes at 14000rpm, resuspended in absolute ethanol solution, centrifugated and washed to obtain InSe solution for standby.

(2) And (3) preparing an InSe dispersion liquid.

Preparing InSe dispersion liquid, dispersing 0.1-40% InSe nano material in 100LL of the Van der Waals chemical model, and rapidly stirring for 1 hour to obtain (b) dispersion liquid.

(3) And (3) a mixing step.

100 parts of the dispersion of (b) was charged into a reaction vessel with 40 parts of PPG-100 polyether polyol and 0.02 part of dibutyltin dilaurate, and reacted at 80℃for 3 hours with stirring under vacuum to effect polymerization.

(4) And (5) detecting tensile strength.

Colloid tensile test standard was used: GB/T1040.2-2006 determination of Plastic tensile Properties second part: test methods for molded and extruded plastics. And (5) detecting the tensile strength of the obtained polyurethane sealant. As a result, as shown in fig. 3, when InSe is added to the isocyanate phase, advantages can still be obtained at low InSe addition amounts, in which case the optimum addition amount is about 0.2% by mass.

Example 3

(1) Preparing the two-dimensional nano material.

(2) And (3) preparing an InSe dispersion liquid.

Preparing InSe dispersion liquid, dispersing 0.1-40% InSe nano material in 100 parts of liquefied MDI with the chemical model number of 100LL and 40 parts of PPG-100 polyether polyol, and rapidly stirring for 1 hour to obtain (c) dispersion liquid.

(3) And (3) a mixing step.

(c) The dispersion of (2) and 0.02 part of dibutyltin dilaurate were charged into a reaction vessel, and the reaction was carried out under vacuum stirring at 80℃for 3 hours to effect polymerization.

(4) And (5) detecting tensile strength.

Colloid tensile test standard was used: GB/T1040.2-2006 determination of Plastic tensile Properties second part: test methods for molded and extruded plastics. And (5) detecting the tensile strength of the obtained polyurethane sealant. As a result, as shown in FIG. 4, the optimum amount of InSe in the polyether-isocyanate combination was different, and in this case, the optimum amount was about 0.5% by mass.

In conclusion, the effect per unit InSe is better and the change of mechanical strength is large by adding the InSe nano sheet into isocyanate.

Claims

1. A high-strength composite polyurethane sealant and a preparation method thereof. The method is characterized in that a new method for changing the property of polyurethane is provided by introducing selenizing-two-dimensional nanomaterial (InSe) into the polyurethane formula. The method comprises the following steps:

step one: preparing an ito selenide two-dimensional nanomaterial dispersion comprising dispersing InSe in (a) one or more polyols, (b) one or more isocyanates, or (c) one or more polyols and one or more isocyanates, separately or in admixture;

step two: mixing the dispersion of step (1) (a) with an isocyanate or the dispersion of (1) (b) with a polyol and a catalyst to produce a polymerization reaction; or mixing the dispersion of step (1) (c) with a catalyst to effect polymerization.

2. The high-strength composite polyurethane sealant and the preparation method thereof according to claim 1, wherein the high-strength composite polyurethane sealant is characterized in that: the mass percentage of the InSe in the InSe dispersion solution in the first step is 0.1-40%.

Preferably, the mass percentage of InSe in the dispersion liquid is 0.1-1%.

3. The high-strength composite polyurethane sealant and the preparation method thereof according to claim 1, wherein the high-strength composite polyurethane sealant is characterized in that: the isocyanate used for preparing the polyurethane in the step one comprises aromatic isocyanate and aliphatic and cyclic aliphatic isocyanate

Preferably, the aromatic isocyanate comprises: diphenylmethane diisocyanate (MDI) or Toluene Diisocyanate (TDI), and the like.

Preferably, the aliphatic and cyclic aliphatic isocyanates include: 1, 6-adipic acid diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3, 5-trimethylcyclohexane (isophorone diisocyanate, IPDI), 4' -diisocyanate dicyclohexylmethane, and the like.

4. The high-strength composite polyurethane sealant and the preparation method thereof according to claim 1, wherein the high-strength composite polyurethane sealant is characterized in that: the polyols described in step one for preparing polyurethanes include polyether polyols and polyester polyols.

5. The high-strength composite polyurethane sealant and the preparation method thereof according to claim 1, wherein the high-strength composite polyurethane sealant is characterized in that: the catalyst for preparing polyurethane in the second step includes an amine compound or a metal complex.

Preferably, the amine compound catalyst includes tertiary amines such as triethylenediamine (TEDA, 1, 4-diazabicyclo [2.2.2] octane or DABCO), dimethylcyclohexylamine (DMCHA), and dimethanol amine (DMEA). The catalyst may also contain a hydroxyl group, a secondary amine, or the like.

Preferably, examples of the metal compound catalyst include mercury, lead, tin, bismuth and zinc-based compounds including: mercury, bismuth and zinc carboxylates. Alkyl tin carboxylates, oxides, and thiolate oxides, and the like.

6. A high strength composite polyurethane sealant prepared according to claim 1.