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

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

A kind of 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 technique

Polyurethane adhesives have good low temperature resistance, excellent flexibility, abrasion resistance, oil resistance and chemical resistance, and are widely used in many fields. However, the strength of polyurethane itself is not high. If it is used in the field of sealants, some materials must be added to change its mechanical properties. Adding nanomaterials to polyurethane sealants is a convenient and effective way to improve the mechanical properties of polyurethane products.

In recent years, inorganic/organic nanocomposites have attracted extensive attention from researchers because they have the advantages of both inorganic nanomaterials and organic materials. Two-dimensional materials represented by graphene are commonly used inorganic materials. Due to their simple preparation, chemical inertness, and excellent thermal and mechanical properties, they are widely used in multi-field composite materials. Indium selenide (InSe) is a new type of two-dimensional nanomaterial with a unique nano-platform with a planar topology. Due to its unique morphology and physical and chemical properties, it can effectively improve the mechanical properties of polyurethane.

Technical issues resolved

In view of the challenges existing in the prior art, the purpose of the embodiments of the present invention is to provide a high-strength composite polyurethane sealant and a preparation method thereof. The method applies the addition of indium selenide two-dimensional nanomaterials, which can effectively improve the mechanical properties of polyurethane, and is of great significance to polyurethane composite materials.

Contents of the invention

In order to achieve the above object, the present invention mainly adopts the following technical solutions,

Step 1: preparing an InSe dispersion, including dispersing the indium selenide 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 Disperse in multiple isocyanates, separately or mixed. Preferably, the mass percentage of 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 for preparing polyurethane includes aromatic isocyanate and aliphatic and cycloaliphatic isocyanate. Further preferably, the aromatic isocyanate includes: diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) and the like. Further preferred, aliphatic and cycloaliphatic isocyanates include: 1,6-adipate diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl Cyclohexane (isovernon diisocyanate, IPDI) and 4,4'-diisocyanate dicyclohexylmethane, etc.

Further preferably, the isocyanate used to prepare polyurethane is diphenylmethane diisocyanate.

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

Further preferably, the polyol used for preparing polyurethane is polyether polyol.

Step 2: mixing the dispersion of step (1)(a) with an isocyanate or the dispersion of (1)(b) with a polyol and catalyst to produce a polymerization reaction; or mixing the dispersion of step (1)(c) and catalysts to produce polymerization reactions.

Preferably, the catalyst used for preparing polyurethane includes amine compounds or metal complexes.

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

Further preferably, examples of metal compound catalysts include compounds based on mercury, lead, tin, bismuth and zinc, including: mercury, bismuth and zinc carboxylates. Alkyl tin carboxylates, oxides and thiolate oxides, etc.

Further preferably, the catalyst used to prepare polyurethane is dibutyltin dilaurate.

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

In the method provided by the invention, the indium selenide two-dimensional nanometer material is added into the polyurethane sealant, and the tensile strength, shear strength and hardness of the product are obviously improved. Due to the large specific surface area of indium selenide two-dimensional nanomaterials, a small amount of indium selenide two-dimensional nanomaterials dispersed in the polyurethane matrix can be entangled with the polymer main chain through physical adsorption, forming a three-dimensional space network and making the strength of the composite material Increase.

Description of drawings

Figure 1. TEM image of two-dimensional indium selenide nanomaterials

Figure 2. Tensile strength diagram of polyurethane with InSe added to the polyether phase

Figure 3. Tensile strength graph of polyurethane with InSe added to the isocyanate phase

Figure 4. Tensile strength diagram of polyurethane added to polyether polyol and isocyanate mixtures with InSe

Detailed ways

Example 1

(1) Preparation of two-dimensional nanomaterials of indium selenide.

InSe crystals were stored in DMF solution, ground in a mortar, ultrasonicated with a 1200W probe for 10 hours, ultrasonicated in a water bath for 10 hours, centrifuged at 5000rpm for 10min to obtain InSe nanosheets with uniform particle size, centrifuged at 14000rpm for 10min, resuspended in absolute ethanol solution, centrifuged, Wash to obtain an InSe solution for later use. The morphology of the obtained sample was detected by TEM, and the result is shown in Figure 1, the InSe nanosheets are thin-layer sheet-like morphology with a size between 50-200nm.

(2) Preparation of InSe dispersion liquid.

To prepare an InSe dispersion, disperse 0.1-40% by mass of InSe two-dimensional nanomaterials in PPG-100 polyether polyol, and stir rapidly for 1 hour to obtain (a) dispersion.

(3) Mixing step.

40 parts of the dispersion in (a), 100 parts of liquefied MDI of Wanhua Chemical type 100LL and 0.02 parts of dibutyltin dilaurate were put into the reactor, and stirred and reacted under vacuum at 80° C. for 3 hours to initiate polymerization.

(4) Tensile strength test.

Colloidal tensile test standard: GB/T 1040.2-2006 Determination of tensile properties of plastics Part II: Test methods for molded and extruded plastics. The obtained polyurethane sealant was tested for tensile strength. The results are shown in Figure 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 polyurethane Tensile strength also increases, and in this case, the optimal addition amount is about 0.1% by mass.

Example 2

(1) Preparation of two-dimensional nanomaterials of indium selenide.

InSe crystals were stored in DMF solution, ground in a mortar, ultrasonicated with a 1200W probe for 10 hours, ultrasonicated in a water bath for 10 hours, centrifuged at 5000rpm for 10min to obtain InSe nanosheets with uniform particle size, centrifuged at 14000rpm for 10min, resuspended in absolute ethanol solution, centrifuged, Wash to obtain an InSe solution for later use.

(2) Preparation of InSe dispersion liquid.

To prepare the InSe dispersion liquid, disperse 0.1-40% InSe nanometer material in 100LL liquefied MDI of Wanhua Chemical, stir rapidly for 1 hour, and obtain (b) dispersion liquid.

(3) Mixing step.

100 parts of the dispersion of (b), 40 parts of PPG-100 polyether polyol and 0.02 parts of dibutyltin dilaurate were put into the reactor, and stirred and reacted under vacuum at 80° C. for 3 hours to cause polymerization.

(4) Tensile strength test.

Colloidal tensile test standard: GB/T 1040.2-2006 Determination of tensile properties of plastics Part II: Test methods for molded and extruded plastics. The obtained polyurethane sealant was tested for tensile strength. The results are shown in Fig. 3, when InSe is added to the isocyanate phase, the advantage can still be obtained at low InSe addition, in this case, the optimum addition is about 0.2% by mass.

Example 3

(1) Preparation of two-dimensional nanomaterials of indium selenide.

InSe crystals were stored in DMF solution, ground in a mortar, ultrasonicated with a 1200W probe for 10 hours, ultrasonicated in a water bath for 10 hours, centrifuged at 5000rpm for 10min to obtain InSe nanosheets with uniform particle size, centrifuged at 14000rpm for 10min, resuspended in absolute ethanol solution, centrifuged, Wash to obtain an InSe solution for later use.

(2) Preparation of InSe dispersion liquid.

To prepare an InSe dispersion, disperse 0.1-40% InSe nanomaterials in 100 parts of Wanhua Chemical 100LL liquefied MDI and 40 parts of PPG-100 polyether polyol, and stir rapidly for 1 hour to obtain (c) dispersion .

(3) Mixing step.

The dispersion liquid of (c) and 0.02 parts of dibutyltin dilaurate were put into a reaction kettle, and stirred and reacted under vacuum at 80° C. for 3 hours to generate a polymerization reaction.

(4) Tensile strength test.

Colloid tensile test standard: GB/T 1040.2-2006 Determination of tensile properties of plastics Part II: Test methods for molded and extruded plastics. The obtained polyurethane sealant was tested for tensile strength. The results are shown in Figure 4. In the polyether-isocyanate combination, the optimal InSe content is different. In this case, the optimal addition amount is about 0.5% by mass.

In summary, adding InSe nanosheets to isocyanate has a better effect per unit of InSe and a greater change in mechanical strength.

Claims (6)

1. A high-strength composite polyurethane sealant and a preparation method thereof. It is characterized in that it provides a new method for changing the properties of polyurethane by introducing indium selenide two-dimensional nanomaterial (InSe) into the polyurethane formula. Include the following steps: Step 1: preparing an indium selenide two-dimensional nanomaterial dispersion, including dispersing InSe in (a) one or more polyols, (b) one or more isocyanates, or (c) in one or more polyhydric Alcohol and one or more isocyanates dispersed, separately or mixed; Step 2: mixing the dispersion of step (1)(a) with an isocyanate or the dispersion of (1)(b) with a polyol and catalyst to produce a polymerization reaction; or mixing the dispersion of step (1)(c) and catalysts for polymerization reactions. 2. A high-strength composite polyurethane sealant and a preparation method thereof according to claim 1, characterized in that: the mass percentage of InSe in the InSe dispersion solution described in step 1 is 0.1-40%. Preferably, the mass percentage of InSe in the dispersion liquid is 0.1-1%. 3. a kind of high-strength composite polyurethane sealant and preparation method thereof according to claim 1, is characterized in that: the isocyanate that is used to prepare polyurethane described in step 1 comprises aromatic isocyanate and aliphatic and cycloaliphatic Isocyanate Preferably, the aromatic isocyanate includes: diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) and the like. Preferred aliphatic and cyclic aliphatic isocyanates include: 1,6-adipic diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclo Hexane (isovernon diisocyanate, IPDI) and 4,4'-diisocyanate dicyclohexylmethane, etc. 4. A kind of high-strength composite polyurethane sealant and preparation method thereof according to claim 1, characterized in that: the polyol used for preparing polyurethane described in step 1 includes polyether polyol and polyester polyol. 5. A high-strength composite polyurethane sealant and a preparation method thereof according to claim 1, characterized in that: the catalyst for preparing polyurethane described in step 2 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 Amines (DMEA). The catalyst may also contain a hydroxyl group or secondary amine, etc. Preferred examples of metal compound catalysts include compounds based on mercury, lead, tin, bismuth and zinc, including: mercury, bismuth and zinc carboxylates. Alkyl tin carboxylates, oxides and thiolate oxides, etc. 6. A kind of high-strength composite polyurethane sealant prepared according to claim 1.

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