An anti-aging and low-temperature resistant glue, its preparation method and application

Abstract

The present invention belongs to the field of adhesive technology, and specifically relates to an anti-aging and low-temperature resistant glue, its preparation method and application. The composition comprises the following components by weight: 60-80 parts of isocyanate; 70-90 parts of polyether polyol; TDI-modified Ti3C2T x The present invention improves the low temperature resistance of the glue by adding castor oil and 2-hydroxyethyl ricinoleate to the glue, and improves the low temperature resistance of the glue by compounding the two, and combines the TDI-modified Ti3C2T x The MoS2 composite material improves the mechanical properties of the glue. The anti-aging and low-temperature resistant glue prepared by the present invention has excellent performance and is widely used.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives, and more specifically relates to an anti-aging and low-temperature resistant glue, a preparation method thereof, and an application thereof. Background Art

[0002] Polyurethane adhesives offer excellent shear resistance, peel resistance, and low-temperature resistance, making them suitable for bonding most structural components. Polyurethane adhesives develop their adhesive properties through the reaction of excess -NCO reactive groups in the polymer with free active hydrogen in the air or on the substrate. Because temperature influences the adhesive properties of polyurethane adhesives, the low-temperature resistance of polyurethane adhesives is improved by adding modifying components.

[0003] CN113897166A discloses a two-component polyurethane glue comprising a component A and a component B. Component A comprises the following raw materials: isophorone diisocyanate; polyester polyol; ethylenediamine; a catalyst; and component B comprises the following raw materials: butyl rubber; N-(4-pyridinyl-methylene)methylamine; 4'-methoxyphenyl butanone; dextrin palmitate; and a bridging agent. A method for preparing the two-component polyurethane glue comprises preparing components A and B separately and then blending them to obtain the glue. The invention has the following advantages: the polyurethane resin has a high molecular weight, a complex graft structure, and high strength after curing; the butyl rubber can improve bonding strength and cold resistance; the steric hindrance of N-(4-pyridinyl-methylene)methylamine can restrict the diffusion movement of chain segments, thereby increasing the viscosity of the system; and the mixing of 4'-methoxyphenyl butanone and dextrin palmitate produces a cross-linking reaction in the presence of a bridging agent to form a macromolecular cross-linked structure, effectively improving the cold resistance and solvent resistance of the glue.

[0004] CN108165226A discloses a polymer for electronic potting glue and its preparation method. The polymer is made from the following raw materials in the following weight percentages: 10-35% isocyanate, 0-20% polyester polyol, 10-40% polyether polyol, 40-50% solvent, and 0.1-0.3% catalyst. The electronic potting glue prepared by the present invention has a long shelf life, excellent yellowing resistance after curing, high strength, and strong adhesion to electronic devices. It exhibits good fluidity and ease of handling during production. When applied to electronic devices, it reacts gently without generating bubbles, and the cured product exhibits excellent transparency.

[0005] CN115820195A discloses a polyurethane glue for high-gloss reflective materials. The raw materials, calculated by weight, include: 20-50 parts polyester polyol, 1-10 parts carboxylic acid compound, 5-15 parts isocyanate, 0.01-0.2 parts catalyst, 50-70 parts solvent, and 0-0.05 parts terminator. This invention utilizes a low-crystallinity polyester polyol, formed by the polymerization of succinic acid and 3-methyl-1,5-pentanediol, as the polyurethane glue base, improving the polyurethane glue's resistance to water washing, dry cleaning, grease, and perspiration. Furthermore, the reaction of dihydroxypropyl butyric acid with the low-crystallinity polyester polyol enhances the creep resistance of the polyurethane adhesive layer, preventing reflective particles from sinking in the reflective product. Furthermore, the reflective product exhibits good abrasion resistance and can withstand multiple flexing cycles in low-temperature environments without cracking.

[0006] By adding modifying components to the glue or modifying the raw materials themselves, the glue can be improved to still have excellent mechanical properties at low temperatures. The present invention provides an anti-aging and low-temperature resistant glue with excellent low-temperature resistance and mechanical properties. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the existing technology and provide an anti-aging and low-temperature resistant glue and its preparation method and application. The following components are included by weight: 60-80 parts of isocyanate; 70-90 parts of polyether polyol; TDI-modified Ti3C2T x The present invention improves the low temperature resistance of the glue by adding castor oil and 2-hydroxyethyl ricinoleate to the glue, and further improves the low temperature resistance of the glue by combining the two. x The MoS2 composite material improves the mechanical properties of the glue. The anti-aging and low-temperature resistant glue prepared by the present invention has excellent performance and is widely used.

[0008] The purpose of the invention is to provide an anti-aging and low-temperature resistant glue.

[0009] Another object of the present invention is to provide a method for preparing the anti-aging and low-temperature resistant glue.

[0010] Another object of the present invention is to provide an application of anti-aging and low-temperature resistant glue.

[0011] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0012] An anti-aging and low-temperature resistant glue, comprising the following components in parts by weight:

[0013] 60-80 parts of isocyanate;

[0014] 70-90 parts of polyether polyol;

[0015] TDI modified Ti3C2T x / MoS2 composite material 3 to 7 parts;

[0016] 3-5 parts castor oil;

[0017] 1-3 parts of 2-hydroxyethyl ricinoleate;

[0018] 30-40 parts of plasticizer;

[0019] 3-5 parts of dibutyltin dilaurate;

[0020] 4-8 parts of silane coupling agent;

[0021] 1 to 3 parts of anti-aging agent.

[0022] Preferably, the isocyanate is diphenylmethane-4,4′-diisocyanate; and the polyether polyol is polyether polyol 450.

[0023] Further preferably, the plasticizer is phthalate; the silane coupling agent is KH-560; and the anti-aging agent is antioxidant 1010.

[0024] In the present invention, the preferred embodiment is that the TDI-modified Ti3C2T x The preparation method of the / MoS2 composite material comprises the following steps:

[0025] (1) Etch the Ti3AlC2 precursor with concentrated HF solution to obtain Ti3C2T x Dispersion, separation, washing, drying to Ti3C2T x ;

[0026] (2) Ti3C2T obtained in step (1) x Disperse in deionized water, ultrasonicate for 20-40 min, then add molybdate and continue ultrasonication for 10-20 min, then add sulfur source and continue ultrasonication for 10-30 min, then transfer to a hydrothermal reactor lined with polytetrafluoroethylene and seal, perform hydrothermal reaction, cool to room temperature, wash, and vacuum dry to constant weight to obtain Ti3C2T x / MoS2 composite materials;

[0027] (3) Ti3C2T obtained in step (2) xThe Ti3C2T / MoS2 composite material was dispersed in DMF and stirred for 20-40 min. Then, toluene-2,4-diisocyanate (TDI) was added under nitrogen protection and stirred at 70-80 °C for 5-9 h. The mixture was centrifuged, washed, and vacuum dried to constant weight to obtain TDI-modified Ti3C2T x / MoS2 composite materials.

[0028] Preferably, in step (1), the drying is performed by vacuum drying at 60 to 90° C. for 10 to 14 hours.

[0029] Further preferably, in step (2), the molybdate is one of ammonium molybdate, potassium molybdate, and sodium molybdate; the sulfur source is thiourea; the Ti3C2T x , molybdate and thiourea ratio is: 100g:30mmol:15~30mmol.

[0030] Further preferably, in step (2), the hydrothermal reaction is carried out at 180-220°C for 16-24 hours; and the vacuum drying temperature is 60-90°C.

[0031] More preferably, in step (3), the Ti3C2T x The mass ratio of / MoS2 composite material to TDI is 1:8~12.

[0032] Based on the above-mentioned method for preparing an anti-aging and low-temperature resistant glue, the preparation method comprises the following steps:

[0033] Add polyether polyol, castor oil and 2-hydroxyethyl ricinoleate to the reactor, stir evenly, then add plasticizer and isocyanate and continue stirring for 20-40 minutes, then add half of dibutyltin dilaurate under nitrogen protection, continue stirring, control the reaction temperature at 75-85℃, react for 2-4 hours to obtain polyurethane prepolymer; then add TDI-modified Ti3C2T x The / MoS2 composite material and the silane coupling agent are stirred at a speed of 500-700 rpm for 20-40 minutes, and then the remaining dibutyltin dilaurate is added and the stirring is continued for 10-30 minutes to obtain an anti-aging and low-temperature resistant glue.

[0034] Based on the application of the above-mentioned anti-aging and low-temperature resistant glue in pasting materials.

[0035] The present invention has the following beneficial effects:

[0036] By adding castor oil and 2-hydroxyethyl ricinoleate to the glue, the low temperature resistance of the glue is improved through the compounding of the two, and the low temperature resistance of the glue is improved by combining the TDI modified Ti3C2T x / MoS2 composite material improves the mechanical properties of the glue, among which Ti3C2T x / MoS2 is modified by TDI to improve its dispersion performance in the glue, and the interaction between TDI and the base material further improves the mechanical properties. The anti-aging and low-temperature resistant glue prepared by the present invention has excellent low-temperature resistance and strong mechanical properties. DETAILED DESCRIPTION

[0037] The present invention is further described below with reference to specific examples, which, however, are not intended to limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the art.

[0038] The isocyanate is diphenylmethane-4,4′-diisocyanate, the polyether polyol is polyether polyol 450, the plasticizer is phthalate, the silane coupling agent is KH-560, and the anti-aging agent is antioxidant 1010.

[0039] Unless otherwise specified, the reagents and materials used in the following examples were commercially available.

[0040] Example 1

[0041] An anti-aging and low-temperature resistant glue, comprising the following components in parts by weight:

[0042] 70 parts of isocyanate;

[0043] 80 parts of polyether polyol;

[0044] TDI modified Ti3C2T x / MoS2 composite material 5 parts;

[0045] 4 parts castor oil;

[0046] 2 parts of 2-hydroxyethyl ricinoleate;

[0047] 35 parts of plasticizer;

[0048] 4 parts of dibutyltin dilaurate;

[0049] 6 parts of silane coupling agent;

[0050] 2 parts of anti-aging agent;

[0051] TDI modified Ti3C2T x The preparation method of the / MoS2 composite material comprises the following steps:

[0052] (1) Weigh 50 g Ti3AlC2 and add it to 80 mL 45 wt% HF solution, stir for 20 h, filter, wash, and vacuum dry at 80 ° C for 12 h to obtain Ti3C2T x ;

[0053] (2) 100g of Ti3C2T obtained in step (1) x Disperse into 250 mL deionized water, ultrasonicate for 30 min, then add 30 mmol ammonium molybdate and continue ultrasonication for 15 min, then add 25 mmol thiourea and continue ultrasonication for 20 min, then transfer to a hydrothermal reactor lined with polytetrafluoroethylene, seal, hydrothermally react at 200 ° C for 20 h, cool to room temperature, wash, and vacuum dry at 80 ° C to constant weight to obtain Ti3C2T x / MoS2 composite materials;

[0054] (3) 10g of Ti3C2T obtained in step (2) was added x The Ti3C2T / MoS2 composite material was dispersed in 250 mL of DMF and stirred for 30 min. Then, 100 g of toluene-2,4-diisocyanate (TDI) was added under nitrogen protection and stirred at 75 °C for 7 h. The mixture was centrifuged, washed, and dried in vacuum at 80 °C to constant weight to obtain TDI-modified Ti3C2T x / MoS2 composite materials.

[0055] A method for preparing an anti-aging and low-temperature resistant glue comprises the following steps:

[0056] Add polyether polyol, castor oil and 2-hydroxyethyl ricinoleate to the reactor, stir evenly, then add plasticizer and isocyanate and continue stirring for 30 minutes. Then, add half of dibutyltin dilaurate under nitrogen protection, continue stirring, control the reaction temperature to 80℃, and react for 3 hours to obtain polyurethane prepolymer. Then add TDI-modified Ti3C2T x / MoS2 composite material and silane coupling agent were stirred at 600 rpm for 30 min, and then the remaining dibutyltin dilaurate was added and stirred for 20 min to obtain an anti-aging and low-temperature resistant glue.

[0057] Example 2

[0058] An anti-aging and low-temperature resistant glue, comprising the following components in parts by weight:

[0059] 80 parts of isocyanate;

[0060] 70 parts of polyether polyol;

[0061] TDI modified Ti3C2T x / MoS2 composite material 7 parts;

[0062] 3 parts castor oil;

[0063] 3 parts of 2-hydroxyethyl ricinoleate;

[0064] 30 parts of plasticizer;

[0065] 5 parts of dibutyltin dilaurate;

[0066] 4 parts of silane coupling agent;

[0067] 3 parts of anti-aging agent;

[0068] TDI modified Ti3C2T x The preparation method of the / MoS2 composite material comprises the following steps:

[0069] (1) Same as Example 1;

[0070] (2) 100g of Ti3C2T obtained in step (1) x Disperse into 250 mL deionized water, ultrasonicate for 40 min, then add 30 mmol potassium molybdate and continue ultrasonication for 10 min, then add 30 mmol thiourea and continue ultrasonication for 30 min, then transfer to a hydrothermal reactor lined with polytetrafluoroethylene and seal, hydrothermally react at 220 ° C for 16 h, cool to room temperature, wash, and vacuum dry at 90 ° C to constant weight to obtain Ti3C2T x / MoS2 composite materials;

[0071] (3) 10g of Ti3C2T obtained in step (2) was added x The Ti3C2T / MoS2 composite material was dispersed in 250 mL of DMF and stirred for 40 min. Then, 120 g of toluene-2,4-diisocyanate (TDI) was added under nitrogen protection and stirred at 80 °C for 5 h. The mixture was centrifuged, washed, and dried in vacuum at 90 °C to constant weight to obtain TDI-modified Ti3C2T x / MoS2 composite materials.

[0072] The preparation method of an anti-aging and low-temperature resistant glue is the same as that of Example 1.

[0073] Example 3

[0074] An anti-aging and low-temperature resistant glue, comprising the following components in parts by weight:

[0075] 60 parts of isocyanate;

[0076] 90 parts of polyether polyol;

[0077] TDI modified Ti3C2T x / MoS2 composite material 3 parts;

[0078] 5 parts castor oil;

[0079] 1 part of 2-hydroxyethyl ricinoleate;

[0080] 40 parts of plasticizer;

[0081] 3 parts of dibutyltin dilaurate;

[0082] 8 parts of silane coupling agent;

[0083] 1 part of anti-aging agent;

[0084] TDI modified Ti3C2T x The preparation method of the / MoS2 composite material comprises the following steps:

[0085] (1) Same as Example 1;

[0086] (2) 100g of Ti3C2T obtained in step (1) x Disperse into 250 mL deionized water, ultrasonicate for 20 min, then add 30 mmol sodium molybdate and continue ultrasonication for 20 min, then add 15 mmol thiourea and continue ultrasonication for 10 min, then transfer to a hydrothermal reactor lined with polytetrafluoroethylene and seal, hydrothermally react at 180 ° C for 24 h, cool to room temperature, wash, and vacuum dry at 60 ° C to constant weight to obtain Ti3C2T x / MoS2 composite materials;

[0087] (3) 10g of Ti3C2T obtained in step (2) was added x The Ti3C2T / MoS2 composite material was dispersed in 250 mL of DMF and stirred for 20 min. Then, 80 g of toluene-2,4-diisocyanate (TDI) was added under nitrogen protection and stirred at 70 °C for 9 h. The mixture was centrifuged, washed, and dried in vacuum at 60 °C to constant weight to obtain TDI-modified Ti3C2T x / MoS2 composite materials.

[0088] The preparation method of an anti-aging and low-temperature resistant glue is the same as that of Example 1.

[0089] Comparative Example 1

[0090] The difference between Comparative Example 1 and Example 1 is that an equal amount of castor oil is used instead of 2-hydroxyethyl ricinoleate.

[0091] Comparative Example 2

[0092] The difference between Comparative Example 2 and Example 1 is that the same amount of Ti3C2T x / MoS2 composite materials replacing TDI modified Ti3C2T x / MoS2 composite materials, the Ti3C2T x The preparation method of the / MoS2 composite material comprises the following steps:

[0093] (1) Weigh 50 g Ti3AlC2 and add it to 80 mL 45 wt% HF solution, stir for 20 h, filter, wash, and vacuum dry at 80 ° C for 12 h to obtain Ti3C2T x ;

[0094] (2) 100g of Ti3C2T obtained in step (1) x Disperse into 250 mL deionized water, ultrasonicate for 30 min, then add 30 mmol ammonium molybdate and continue ultrasonication for 15 min, then add 25 mmol thiourea and continue ultrasonication for 20 min, then transfer to a hydrothermal reactor lined with polytetrafluoroethylene, seal, hydrothermally react at 200 ° C for 20 h, cool to room temperature, wash, and vacuum dry at 80 ° C to constant weight to obtain Ti3C2T x / MoS2 composite materials.

[0095] Comparative Example 3

[0096] The difference between Comparative Example 3 and Example 1 is that the same amount of TDI modified Ti3C2T x Composite materials replace TDI modified Ti3C2T x / MoS2 composite material, the TDI modified Ti3C2T x The preparation method of the composite material comprises the following steps:

[0097] (1) Same as Example 1;

[0098] (2) 10g of Ti3C2T obtained in step (1) was added x The composite material was dispersed in 250 mL of DMF and stirred for 40 min. Then, 120 g of toluene-2,4-diisocyanate (TDI) was added under nitrogen protection and stirred at 80 °C for 5 h. The mixture was centrifuged, washed, and dried in vacuum at 90 °C to constant weight to obtain TDI-modified Ti3C2T x Composite materials.

[0099] The comprehensive performance of Examples 1-3 and Comparative Examples 1-3 was tested, and the specific test results are shown in Table 1.

[0100] Among them, peel strength: GB / T 532-2008;

[0101] Table 1

[0102]

[0103]

[0104] It can be seen from Table 1 that the anti-aging and low-temperature resistant glue prepared by the present invention has excellent low-temperature resistance. Moreover, by comparing Example 1 with Comparative Example 1, it can be seen that the present invention improves the low-temperature resistance of the glue by adding castor oil and 2-hydroxyethyl ricinoleate and utilizing the mutual relationship between the two. Moreover, by adding TDI-modified Ti3C2T x / MoS2 composite material improves the performance of the glue. It can be seen that the anti-aging and low-temperature resistant glue prepared by the present invention has strong low-temperature resistance and is widely used.

[0105] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. An anti-aging and low-temperature resistant glue, characterized by: Calculated by weight, it includes the following components: 60-80 parts of isocyanate; 70-90 parts of polyether polyol; TDI modified Ti3C2T x / MoS2 composite material 3~7 parts; 3-5 parts castor oil; 1-3 parts of 2-hydroxyethyl ricinoleate; 30~40 parts of plasticizer; 3-5 parts of dibutyltin dilaurate; 4-8 parts of silane coupling agent; 1~3 parts of anti-aging agent; The TDI-modified Ti3C2T x The preparation method of the / MoS2 composite material comprises the following steps: (1) Etch the Ti3AlC2 precursor with concentrated HF solution to obtain Ti3C2T x Dispersion, separation, washing, drying to Ti3C2T x ; (2) Ti3C2T obtained in step (1) x Disperse in deionized water, ultrasonicate for 20-40 min, then add molybdate and continue ultrasonication for 10-20 min, then add sulfur source and continue ultrasonication for 10-30 min, then transfer to a hydrothermal reactor lined with polytetrafluoroethylene and seal, perform hydrothermal reaction, cool to room temperature, wash, and vacuum dry to constant weight to obtain Ti3C2T x / MoS2 composite materials; (3) Ti3C2T obtained in step (2) x The / MoS2 composite material was dispersed in DMF and stirred for 20-40 min. Then, toluene-2,4-diisocyanate (TDI) was added under nitrogen protection and stirred at 70-80 °C for 5-9 h. The mixture was centrifuged, washed, and vacuum dried to constant weight to obtain TDI-modified Ti3C2T x / MoS2 composite materials.

2. The anti-aging and low-temperature resistant glue according to claim 1, characterized in that: The isocyanate is diphenylmethane-4,4'-diisocyanate; and the polyether polyol is polyether polyol 450.

3. The anti-aging and low-temperature resistant glue according to claim 1, characterized in that: The plasticizer is phthalate; the silane coupling agent is KH-560; and the anti-aging agent is antioxidant 1010.

4. The anti-aging and low-temperature resistant glue according to claim 1, characterized in that: In step (1), the drying is performed by vacuum drying at 60-90° C. for 10-14 hours.

5. The anti-aging and low-temperature resistant glue according to claim 1, characterized in that: In step (2), the molybdate is one of ammonium molybdate, potassium molybdate, and sodium molybdate; the sulfur source is thiourea; the Ti3C2T x , molybdate and thiourea ratio is: 100g:30mmol:15~30mmol.

6. The anti-aging and low-temperature resistant glue according to claim 1, characterized in that: In step (2), the hydrothermal reaction is carried out at 180-220°C for 16-24 hours; and the vacuum drying temperature is 60-90°C.

7. The anti-aging and low-temperature resistant glue according to claim 1, characterized in that: In step (3), the Ti3C2T x The mass ratio of / MoS2 composite material to TDI is 1:8~12.

8. The method for preparing an anti-aging and low-temperature resistant glue according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: Add polyether polyol, castor oil and 2-hydroxyethyl ricinoleate to the reactor, stir evenly, then add plasticizer and isocyanate and continue stirring for 20-40 minutes. Then, add half of dibutyltin dilaurate under nitrogen protection, continue stirring, control the reaction temperature at 75-85℃, and react for 2-4 hours to obtain polyurethane prepolymer. Then add TDI-modified Ti3C2T x / MoS2 composite material and silane coupling agent, stir at a speed of 500-700 rpm for 20-40 min, then add the remaining dibutyltin dilaurate, and continue stirring for 10-30 min to obtain anti-aging and low-temperature resistant glue.

9. Use of the anti-aging and low-temperature resistant glue according to any one of claims 1 to 8 in pasting materials.

Images