A wet-heat latent curing one-component polyurethane pouring sealant of serinol derivative and preparation method thereof

Abstract

The present application belongs to the technical field of polyurethane adhesive preparation, and relates to a serinol derivative moisture-heat latent curing one-component polyurethane pouring sealant and a preparation method. The present application solves the problem of brittle cured adhesive layer affecting the bonding strength caused by the common technology. The serinol derivative moisture-heat latent curing one-component polyurethane pouring sealant is composed of a serinol derivative moisture-heat latent curing agent, a polyurethane prepolymer, a crosslinking agent and a catalyst. The pouring sealant prepared by the present application has no VOCs emission, is safe and environmentally friendly, and is convenient to use. After pre-curing at 100 DEG C for 1 h, the pouring sealant can continue to cure at room temperature by using the moisture in the air, the cured adhesive layer has no bubbles, has strong adhesion, is resistant to moisture and heat aging, and can meet the pouring requirements in the fields of electronic components and power battery assembly.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of polyurethane adhesive preparation, and relates to a serinol derivative moisture-heat latent curing one-component polyurethane pouring sealant and a preparation method thereof. BACKGROUND

[0002] In recent years, with the progress of industrial technology and the improvement of environmental protection requirements, traditional solvent-based and two-component adhesives are gradually eliminated by the market due to their complex use process and potential impact on the environment. One-component polyurethane adhesives have gradually become a research hotspot due to their convenient use and environmental protection characteristics. In particular, one-component moisture-heat curing type can be directly cured at a lower heating temperature or in an environment with a certain humidity, greatly improving the flexibility and reliability of its application. In addition, one-component moisture-vapor curing polyurethane pouring sealant has excellent mechanical strength and chemical resistance, can maintain good bonding performance in extreme environments, can strengthen the integrity of electronic devices, and improve the resistance to external impact and vibration, which makes them particularly concerned in the fields of electronic component encapsulation and power battery assembly.

[0003] The promotion and use of one-component polyurethane adhesives help to improve production efficiency and reduce production cost. At the same time, one-component polyurethane adhesives have the characteristics of not needing to add additional solvents and curing agents, which can effectively reduce the use of organic solvents, are environmentally friendly, and meet the current green chemistry and sustainable development strategy. Although one-component polyurethane adhesives have the above advantages, the generation of CO2 during the moisture curing process of one-component polyurethane can cause the foaming and swelling of the adhesive layer, and the formation of micropores, which further affects the bonding strength. Researchers mainly inhibit the generation of CO2 by adding latent curing agents. The common latent curing agents mainly include oxazolidine type and imine type, and the latent curing agent reacts with water in the air to generate -OH or -NH2, and then crosslinks and cures with isocyanate.

[0004] Imine latent curing agents can slowly react with isocyanate during the storage of the adhesive, which reduces the storage performance of one-component polyurethane adhesives. At the same time, imine latent curing agents also affect the bonding strength of the adhesive to metal substrates to some extent. The reaction rate of general oxazolidine latent curing agents with moisture is limited, so there are still many microbubbles in the adhesive layer after curing, in addition, the cured adhesive layer becomes brittle, which affects the bonding strength and reliability during use

[0005] Therefore, it is urgent to propose a serinol derivative moisture-heat latent curing one-component polyurethane pouring sealant and a preparation method thereof to solve the above technical problems. SUMMARY

[0006] The present application is to solve the problem of the cured adhesive layer becoming brittle and affecting the bonding strength formed by the common technology, and a brief summary of the present application is given below to provide a basic understanding of some aspects of the present application. It should be understood that this summary is not an exhaustive summary of the present application. It is not intended to determine the key or important parts of the present application, nor to limit the scope of the present application.

[0007] Technical scheme of the present application:

[0008] A serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant, the serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant is composed of serinol derivative moisture and heat latent curing agent, polyurethane prepolymer, crosslinking agent, catalyst;

[0009] The mass fraction of the serinol derivative moisture and heat latent curing agent is 6.65-15.21 parts, the mass fraction of the polyurethane prepolymer is 70-75 parts, the mass fraction of the crosslinking agent is 0.3-0.6 parts, and the catalyst is 0-0.1 parts.

[0010] Preferably, the serinol derivative moisture and heat latent curing agent is 4a,6a-dimethyl-hexahydro-1,4-dioxa-6-azacyclopent[cd]cyclopentadiene synthesized by the reaction of serinol and 2,5-hexanedione, and the reaction formula is as follows:

[0011]

[0012] Preferably, the polyurethane prepolymer is mixed by one or more of polybutylene adipate, polyhexylene adipate, and polyethylene glycol, and one or more of polyphenyl polymethylene polyisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and isophorone diisocyanate.

[0013] Preferably, the crosslinking agent is one or more of diethanolamine, triethanolamine, and trimethylolpropane.

[0014] Preferably, the catalyst is one or more of dimorpholine divinyl ether, dibutyl tin dilaurate, and stannous octoate.

[0015] A preparation method of a serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant, comprising the following steps:

[0016] Step one: put serinol and 2,5-hexanedione into a four-necked flask, set the reaction temperature and stirring speed, and after the reaction is completed, remove water by heating, reducing pressure, and holding temperature, and cool to room temperature to obtain the serinol derivative moisture and heat latent curing agent;

[0017] Step 2: Place the polyester polyol in an open reactor, heat it to remove water under vacuum, then cool it down to the reaction temperature, add polyisocyanate and stir to react. After the reaction is complete, cool it to room temperature to obtain an isocyanate-terminated polyurethane prepolymer.

[0018] Step 3: Mix the serine alcohol derivative wet heat latent curing agent and polyurethane prepolymer evenly to obtain the serine alcohol derivative wet heat latent curing single-component polyurethane potting compound.

[0019] Preferred method: In step one, the stirring rate is 100 r / min, the reaction temperature is 40℃, and the reaction time is 1.5 to 2 h.

[0020] Preferred settings include: a vacuum degree of 1000 Pa, a stirring rate of 150 r / min, a dehydration temperature of 125 ± 5 °C, and a reaction temperature of 75 ± 5 °C.

[0021] The present invention has the following beneficial effects:

[0022] This invention solves the problem of complex application process of traditional two-component polyurethane adhesives, and overcomes the inherent defects of existing one-component polyurethane adhesives.

[0023] The potting compound prepared by this invention has no VOC emissions, is safe and environmentally friendly, and is easy to use. After pre-curing at 100°C for 1 hour, it can continue to cure at room temperature using the moisture in the air. After curing, the adhesive layer is free of bubbles, has strong adhesion, and is resistant to damp heat aging. It can meet the potting needs of electronic components and power battery assembly. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described below through specific embodiments. However, it should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0025] Specific implementation method one: The serine alcohol derivative wet heat latent curing one-component polyurethane potting compound of this embodiment is composed of serine alcohol derivative wet heat latent curing agent, polyurethane prepolymer, crosslinking agent and catalyst.

[0026] The mass fraction of the serine alcohol derivative wet heat latent curing agent is 6.65 to 15.21 parts, the mass fraction of the polyurethane prepolymer is 70 to 75 parts, the mass fraction of the crosslinking agent is 0.3 to 0.6 parts, and the mass fraction of the catalyst is 0 to 0.1 parts.

[0027] The design of the formula makes the pouring sealant have good moisture and heat latent curing ability, which can be stably cured in a humid and hot environment, thereby forming a solid encapsulating material with high insulation and durability, suitable for use in electronic packaging and other similar fields.

[0028] Specific embodiment two: a serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant of the present embodiment, the serinol derivative moisture and heat latent curing agent is 4a, 6a-dimethyl-hexahydro-1, 4-dioxo-6-azacyclopentane [cd] and cyclopentadiene synthesized by the reaction of serinol and 2, 5-hexanedione, the reaction formula is as follows:

[0029]

[0030] The derivative can self-cure in a humid and hot environment, forming a more stable and solid crosslinked network. With this special moisture and heat latent curing agent, the curing speed and performance of the polyurethane pouring sealant in a humid environment can be significantly improved. Due to its special structure, the derivative may have good resistance to chemical corrosion, moisture erosion, etc.

[0031] Specific embodiment three: a serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant of the present embodiment, the polyurethane prepolymer is mixed by one or more of polybutylene adipate (PBA1000, M n = 1000), polyhexylene adipate (PHA1000, M n = 1000), polyethylene glycol (PEG800, M n = 800) and one or more of polyphenyl polyformaldehyde polyisocyanate (PM400), diphenyl methane diisocyanate (MDI-50), toluene diisocyanate (TDI-80), isophorone diisocyanate (IPDI). By selecting different polyols and isocyanates to synthesize polyurethane prepolymers, the performance of the pouring sealant can be adjusted according to the needs, so that it achieves the best effect in many aspects.

[0032] Specific embodiment four: a serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant of the present embodiment, the crosslinking agent is one or more of diethanolamine, triethanolamine, and trimethylolpropane, which can significantly improve the curing speed, mechanical properties, chemical stability, weather resistance, moisture and heat environment adaptability, flexibility and flowability of the serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant. This makes the pouring sealant have more excellent comprehensive performance in the field of electronic device packaging, sealing, protection, etc., and can provide efficient and reliable protection in various complex environments.

[0033] Embodiment five: the catalyst of the silinol derivative moisture and heat latent curing one-component polyurethane pouring sealant is one or several of dimorpholinodiethylenyl ether, dibutyltin dilaurate and stannous octoate, which can significantly improve the curing rate, physical properties, processability and chemical stability of the silinol derivative moisture and heat latent curing one-component polyurethane pouring sealant. This makes the pouring sealant be able to work stably in high-humidity and high-temperature environment and be able to provide good protection effect, especially suitable for packaging and sealing of electronic products.

[0034] Embodiment six: a preparation method of the silinol derivative moisture and heat latent curing one-component polyurethane pouring sealant, comprising the following steps:

[0035] Step one: put silinol and 2,5-hexanedione into a four-necked flask, set the reaction temperature and stirring speed, and then through temperature rising, pressure reduction, water removal and temperature preservation, cool to room temperature to obtain a silinol derivative moisture and heat latent curing agent;

[0036] Step two: put polyester polyol into an open reactor, remove water under vacuum at high temperature, then cool to the reaction temperature, add polyisocyanate and stir to react, and then cool to room temperature to obtain an isocyanate-terminated polyurethane prepolymer;

[0037] Step three: stir the silinol derivative moisture and heat latent curing agent and the polyurethane prepolymer uniformly to obtain a silinol derivative moisture and heat latent curing one-component polyurethane pouring sealant.

[0038] This method can prepare a one-component polyurethane pouring sealant with moisture and heat latent curing characteristics by controlling the reaction temperature, time and proportion of ingredients, which is suitable for packaging of electronic components. Through the addition of silinol derivative, the pouring sealant not only can be quickly cured in a humid environment, but also has excellent chemical stability and mechanical properties, and is widely used in high-performance packaging materials.

[0039] Embodiment seven: a preparation method of the silinol derivative moisture and heat latent curing one-component polyurethane pouring sealant, the stirring speed in step one is 100 r / min, the reaction temperature is 40℃, and the reaction time is 1.5-2h, which is helpful to control the temperature, time and stirring speed in the reaction process, ensure the complete and stable reaction and improve the product quality, and at the same time, optimize the energy consumption and equipment requirements. These favorable conditions can provide ideal raw materials for preparing high-performance moisture and heat latent curing one-component polyurethane pouring sealant.

[0040] Embodiment eight: a preparation method of the silinol derivative moisture and heat latent curing one-component polyurethane pouring sealant, the vacuum degree is 1000 Pa, the stirring speed is 150 r / min, the water removal temperature is 125±5℃, and the reaction temperature is 75±5℃.

[0041] The above parameters can effectively improve the efficiency of the preparation process and the quality of the product. Optimization of these parameters helps to ensure the removal of moisture and impurities, promote the full reaction of raw materials, avoid the occurrence of side reactions, and thus obtain a wet-heat latent curing single-component polyurethane pouring sealant with excellent performance and stability, suitable for high-performance packaging and protection applications.

[0042] Example 1

[0043] A preparation method of a serinol derivative wet-heat latent curing single-component polyurethane pouring sealant, comprising the following steps:

[0044] Step one: weigh 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stir at a rate of 100 r / min, and react at an oil bath temperature of 35℃ for 2 h, then increase the temperature to 55℃, remove water under reduced pressure to 100 Pa, and keep warm for 3 h, and then cool to room temperature to obtain a serinol derivative wet-heat latent curing agent;

[0045] Step two: weigh 50 parts of PBA1000 in an open reactor, start stirring, heat to 125℃, and keep warm under reduced pressure to 1000 Pa for 2 h to remove moisture in the polyester polyol, cool to 75℃, and then add 0.3 parts of triethanolamine, 0.1 parts of dibutyltin dilaurate, 20 parts of polyphenyl polymethylene polyisocyanate (PM400), and 5 parts of isophorone diisocyanate (IPDI) under the condition of connecting nitrogen, stir at a rate of 150 r / min for 2.5 h, and then cool to room temperature to obtain an isocyanate group terminated polyurethane prepolymer

[0046] Step three: weigh 75 parts of the isocyanate group terminated polyurethane prepolymer and 0.02 parts of bismorpholine divinyl ether, heat to 55℃, stir uniformly, slowly add 6.65 parts of the serinol derivative wet-heat latent curing agent, and continue to keep warm and stir for 1 h to obtain a serinol wet-heat latent curing single-component polyurethane pouring sealant.

[0047] Example 2

[0048] A preparation method of a serinol derivative wet-heat latent curing single-component polyurethane pouring sealant, comprising the following steps:

[0049] Step one: weigh 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stir at a rate of 100 r / min, and react at an oil bath temperature of 35℃ for 2 h, then increase the temperature to 55℃, remove water under reduced pressure to 100 Pa, and keep warm for 3 h, and then cool to room temperature to obtain a serinol derivative wet-heat latent curing agent;

[0050] Step 2: Weigh 35 parts of PHA1000 into an open reactor, turn on the stirrer, heat to 125℃, reduce the pressure to 1000Pa and keep at that temperature for 2 hours to remove the water in the polyester polyol, cool to 75℃, and add 0.6 parts of diethanolamine, 0.03 parts of stannous octoate, 30 parts of polyphenyl polymethylene polyisocyanate (PM400), and 5 parts of toluene diisocyanate (TDI-80) under nitrogen gas. Stir at 150 r / min and react for 2.5 hours. Cool to room temperature to obtain isocyanate-terminated polyurethane prepolymer.

[0051] Step 3: Weigh 70 parts of isocyanate-terminated polyurethane prepolymer, add 0.02 parts of bismorpholine divinyl ether, heat to 55°C and stir until homogeneous. Weigh 15.21 parts of serine alcohol derivative wet heat latent curing agent and slowly add to the system. Continue to heat and stir for 1 hour to obtain serine alcohol wet heat latent curing single-component polyurethane potting compound.

[0052] Example 3

[0053] A method for preparing a serine alcohol derivative moisture-heat latent curing one-component polyurethane potting compound includes the following steps:

[0054] Step 1: Weigh 28.5 parts of serine alcohol and 22.75 parts of 2,5-hexanedione into a 150mL four-necked flask, stir at 100r / min, react at 35℃ in an oil bath for 2h, then raise the temperature to 55℃, reduce the pressure to 100Pa to remove water and keep warm for 3h, and cool to room temperature to obtain a serine alcohol derivative wet heat latent curing agent;

[0055] Step 2: Weigh 25 parts of PBA1000 and 15 parts of PHA1000 into an open reactor, turn on the stirrer, heat to 125℃, reduce the pressure to 1000Pa and keep at that temperature for 2 hours to remove the water in the polyester polyol, cool to 75℃, and add 0.4 parts of trimethylolpropane, 0.03 parts of dibutyltin dilaurate, 25 parts of polyphenyl polymethylene polyisocyanate (PM400), and 5 parts of diphenylmethane diisocyanate (liquefied MDI-50) under nitrogen gas. Stir at 150 r / min and react for 2.5 hours. Cool to room temperature to obtain isocyanate-terminated polyurethane prepolymer.

[0056] Step 3: Weigh 70 parts of isocyanate-terminated polyurethane prepolymer, add 0.02 parts of bismorpholine diallyl ether, heat to 55°C and stir until homogeneous. Weigh 11.35 parts of serine alcohol derivative wet heat latent curing agent and slowly add to the system. Continue to heat and stir for 1 hour to obtain serine alcohol wet heat latent curing single-component polyurethane potting compound.

[0057] Example 4

[0058] A method for preparing a serine alcohol derivative moisture-heat latent curing one-component polyurethane potting compound includes the following steps:

[0059] Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the pressure is reduced to 100 Pa to remove water for 3h, and then cooled to room temperature to obtain the serinol derivative moisture-curing curing agent;

[0060] Step two: take 38 parts of PBA1000 and 2 parts of PEG800 in an open reactor, start stirring, heat to 125℃, reduce the pressure to 1000 Pa for 2h, remove the water in the polyester polyol, cool to 75℃, add 0.5 parts of trimethylolpropane, 25 parts of polyphenyl polyformaldehyde polyisocyanate (PM400), 5 parts of diphenyl methane diisocyanate (liquefied MDI-50) under the condition of connecting nitrogen, stirring rate 150 r / min, reaction for 2.5h, and then cooled to room temperature to obtain the isocyanate-terminated polyurethane prepolymer;

[0061] Step three: take 70 parts of the isocyanate-terminated polyurethane prepolymer, heat to 55℃ and stir uniformly, then slowly add 11.35 parts of the serinol derivative moisture-curing curing agent into the system, continue to heat and stir for 1h to obtain the serinol moisture-curing single-component polyurethane pouring sealant.

[0062] Example 5

[0063] A method for preparing a serinol derivative moisture-curing single-component polyurethane pouring sealant, comprising the following steps:

[0064] Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the pressure is reduced to 100 Pa to remove water for 3h, and then cooled to room temperature to obtain the serinol derivative moisture-curing curing agent;

[0065] Step two: take 40 parts of PBA1000 in an open reactor, start stirring, heat to 125℃, reduce the pressure to 1000 Pa for 2h, remove the water in the polyester polyol, cool to 75℃, add 0.5 parts of trimethylolpropane, 25 parts of diphenyl methane diisocyanate (liquefied MDI-50) under the condition of connecting nitrogen, stirring rate 150 r / min, reaction for 2.5h, and then cooled to room temperature to obtain the isocyanate-terminated polyurethane prepolymer;

[0066] Step three: take 70 parts of the isocyanate-terminated polyurethane prepolymer, heat to 55℃ and stir uniformly, then slowly add 9.5 parts of the serinol derivative moisture-curing curing agent into the system, continue to heat and stir for 1h to obtain the serinol moisture-curing single-component polyurethane pouring sealant.

[0067] Example 6

[0068] A preparation method of a serinol derivative moisture and heat latent curing one-component polyurethane pouring sealant, comprising the following steps:

[0069] Step one: weigh 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stir at a speed of 100 r / min, and react at an oil bath temperature of 35℃ for 2 h, then increase the temperature to 55℃, remove water under reduced pressure to 100 Pa, and keep for 3 h, and then cool to room temperature to obtain a serinol derivative moisture and heat latent curing agent;

[0070] Step two: weigh 35 parts of PBA1000 in an open reactor, start stirring, increase the temperature to 125℃, remove water in the polyester polyol under reduced pressure to 1000 Pa for 2 h, cool to 75℃, add 0.3 parts of diethanolamine, 0.1 parts of dibutyltin dilaurate, 35 parts of polyphenyl polymethylene polyisocyanate (PM400) under the condition of connecting nitrogen, stir at a speed of 150 r / min for 2.5 h, and then cool to room temperature to obtain an isocyanate group terminated polyurethane prepolymer;

[0071] Step three: weigh 70 parts of the isocyanate group terminated polyurethane prepolymer, 0.02 parts of bismorpholine divinyl ether, and 15.21 parts of the serinol derivative moisture and heat latent curing agent, stir uniformly at an increased temperature of 55℃, slowly add the serinol derivative moisture and heat latent curing agent into the system, and continue to keep stirring for 1 h to obtain a serinol moisture and heat latent curing one-component polyurethane pouring sealant.

[0072] Comparative Example 1

[0073] Weigh 25 parts of PBA1000, 15 parts of PHA1000 in an open reactor, start stirring, increase the temperature to 125℃, remove water in the polyester polyol under reduced pressure to 1000 Pa for 2 h, cool to 75℃, add 0.4 parts of trimethylolpropane, 0.03 parts of dibutyltin dilaurate, 25 parts of polyphenyl polymethylene polyisocyanate (PM400), and 5 parts of diphenylmethane diisocyanate (liquefied MDI-50) under the condition of connecting nitrogen, stir at a speed of 150 r / min for 2.5 h, add 0.02 parts of bismorpholine divinyl ether, and then cool to room temperature to obtain an isocyanate group terminated polyurethane prepolymer.

[0074] Comparative Example 2

[0075] Take 25 parts of PBA1000, 15 parts of PHA1000 in the open reactor, open stirring, heating to 125℃, reduced pressure to 1000Pa for 2h, remove the moisture in polyester polyols, cooling to 75℃, under the condition of connecting nitrogen, add 0.4 parts of trimethylolpropane, 0.03 parts of dibutyltin dilaurate, 25 parts of polyphenyl poly methylene polyisocyanate (PM400), 5 parts of diphenyl methane diisocyanate (liquefied MDI-50), stirring rate 150r / min reaction 2.5h, add 0.02 parts of dimorpholine divinyl ether continue to stir and cool to room temperature, get isocyanate group terminated polyurethane prepolymer;

[0076] Take 20 parts of aldehyde imine latent curing agent into the polyurethane prepolymer, stirring and dispersing uniformly to get aldehyde imine latent curing one-component polyurethane adhesive.

[0077] Comparative example 3

[0078] Take 25 parts of PBA1000, 15 parts of PHA1000 in the open reactor, open stirring, heating to 125℃, reduced pressure to 1000Pa for 2h, remove the moisture in polyester polyols, cooling to 75℃, under the condition of connecting nitrogen, add 0.4 parts of trimethylolpropane, 0.03 parts of dibutyltin dilaurate, 25 parts of polyphenyl poly methylene polyisocyanate (PM400), 5 parts of diphenyl methane diisocyanate (liquefied MDI-50), stirring rate 150r / min reaction 2.5h, add 0.02 parts of dimorpholine divinyl ether continue to stir and cool to room temperature, get isocyanate group terminated polyurethane prepolymer;

[0079] Take 20 parts of aldehyde imine latent curing agent into the polyurethane prepolymer, stirring and dispersing uniformly to get aldehyde imine latent curing one-component polyurethane adhesive. Take 20 parts of oxazolidine latent curing agent into the polyurethane prepolymer, stirring and dispersing uniformly to get aldehyde imine latent curing one-component polyurethane adhesive.

[0080] Comparative example 4

[0081] The preparation of polyurethane adhesive with traditional curing agent, including A component and B component, the preparation of the A component includes the following methods: take 55 parts of PBA1000, 15 parts of PHA1000 in the open reactor, open stirring, heating to 125℃, reduced pressure to 1000Pa for 2h, remove the moisture in polyester polyols. Cooling to 75℃, under the condition of connecting nitrogen, add 0.4 parts of trimethylolpropane, 0.03 parts of dibutyltin dilaurate, 10 parts of polyphenyl poly methylene polyisocyanate (PM400), 5 parts of diphenyl methane diisocyanate (liquefied MDI-50), stirring rate 150r / min reaction 2.5h;

[0082] The B component is an aromatic isocyanate curing agent TMP-TDI adduct, and the A, B component usage is 4.5-5:1.

[0083] The products prepared in Examples 1-6 and Comparative Examples 1-4 were detected, and the performance indicators are as follows:

[0084]

[0085]

[0086] Examples 1-4 and Comparative Examples 1-3 all used 120°C curing for 1h and room temperature curing for 7 days. As can be seen from the above table, Examples 1-4 all achieved surface dryness at 120°C for 1h, while Comparative Examples 1-3 without the addition of serinol wet-heat latent curing agent all needed to continue room temperature curing for 12h to achieve surface dryness. Only Comparative Example 1 without the addition of latent curing agent had more bubbles after curing, indicating that the addition of latent curing agent can effectively inhibit the generation of carbon dioxide during curing.

[0087] Thermal stability test: The cured adhesive was tested using a differential scanning calorimeter produced by Germany NETZSCH company. Test conditions: under nitrogen, -70°C to 180°C, heating rate 10°C / min. As can be seen from the above table, the addition of serinol derivative wet-heat latent curing agent does not cause changes in the thermal stability of the adhesive, while the addition of traditional aldehyde imine and oxazolidine latent curing agent causes the initial thermal decomposition temperature of the adhesive to decrease.

[0088] The AI-Al, PET-PET and PC-PC bonded after complete curing of Examples 1-4 and Comparative Examples 1-3 were respectively subjected to shear test, and the results are as follows:

[0089]

[0090] After 1h of curing at 120°C and then 7 days of continued curing at room temperature and air humidity of 40%, the shear strength was tested according to GB / T7124-2008.

[0091] As can be seen from the above table, the addition of serinol derivative wet-heat latent curing agent significantly improves the bonding strength of single-component polyurethane pouring sealant to various substrates. Compared with traditional aldehyde imine and oxazolidine latent curing agent, it not only effectively inhibits the generation of carbon dioxide but also does not affect the bonding strength of the adhesive to the substrate.

[0092] After 30 days of storage and 1000 hours of double 85 aging of Examples 1-6 and Comparative Examples 1-4, Al-PET bonding shear strength test was performed, and the results are shown in the following table:

[0093]

[0094] The addition of the serinol derivative moisture and heat latent curing agent improves the storage performance of the single-component polyurethane pouring sealant, and the adhesive shear strength attenuation is less than 20% after 1000h of double 85 aging.

[0095] From the above test results, it can be seen that the prepared serinol derivative moisture and heat latent curing single-component polyurethane adhesive has good bonding performance and excellent moisture and heat aging resistance in use. The serinol derivative is used as a latent curing agent of single-component polyurethane for the first time, and a pouring sealant that can meet the application in a relatively complex environment is prepared.

[0096] It should be noted that in the above examples, as long as the technical solutions are not contradictory, they can be arranged and combined. Those skilled in the art can exhaust all possibilities according to the mathematical knowledge of arrangement and combination, and therefore the technical solutions after arrangement and combination will not be described one by one, but it should be understood that the technical solutions after arrangement and combination have been disclosed by the present application.

[0097] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Those skilled in the art can make various modifications and changes to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a serine alcohol derivative latently curing one-component polyurethane potting compound, characterized in that... Comprising the following steps: Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the water is removed under reduced pressure to 100 Pa for 3h, and then cooled to room temperature to obtain the serinol derivative moisture curing agent, which is 4a,6a-dimethyl-hexahydro-1,4-dioxo-6-azacyclopentane[cd]cyclopentadiene synthesized by reaction of serinol and 2,5-hexanedione, and the reaction formula is as follows: ； Step two: take 50 parts of PBA1000 in an open reactor, start stirring, heat to 125℃, reduce pressure to 1000 Pa for 2h, remove water in polyester polyol, cool to 75℃, add 0.3 parts of triethanolamine, 0.1 parts of dibutyltin dilaurate, 20 parts of polyphenyl polymethylene polyisocyanate PM400, 5 parts of isophorone diisocyanate IPDI under the condition of connecting nitrogen, stirring rate 150 r / min for 2.5h, and then cooled to room temperature to obtain isocyanate-terminated polyurethane prepolymer; Step three: take 75 parts of isocyanate-terminated polyurethane prepolymer, 0.02 parts of bismorpholine divinyl ether, heat to 55℃ and stir uniformly, take 6.65 parts of serinol derivative moisture curing agent, slowly add to the system, continue to heat and stir for 1h to obtain serinol moisture curing one-component polyurethane pouring sealant.

2. A method for preparing a serinol derivative moisture heat latent curing one-component polyurethane pouring sealant, characterized in that Comprising the following steps: Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the water is removed under reduced pressure to 100 Pa for 3h, and then cooled to room temperature to obtain the serinol derivative moisture curing agent, which is 4a,6a-dimethyl-hexahydro-1,4-dioxo-6-azacyclopentane[cd]cyclopentadiene synthesized by reaction of serinol and 2,5-hexanedione, and the reaction formula is as follows: ； Step two: take 35 parts of PHA1000 in an open reactor, start stirring, heat to 125℃, reduce pressure to 1000 Pa for 2h, remove water in polyester polyol, cool to 75℃, add 0.6 parts of diethanolamine, 0.03 parts of stannous octoate, 30 parts of polyphenyl polymethylene polyisocyanate PM400, 5 parts of toluene diisocyanate TDI-80 under the condition of connecting nitrogen, stirring rate 150 r / min for 2.5h, and then cooled to room temperature to obtain isocyanate-terminated polyurethane prepolymer; Step three: take 70 parts of isocyanate-terminated polyurethane prepolymer, 0.02 parts of bismorpholine divinyl ether, heat to 55℃ and stir uniformly, take 15.21 parts of serinol derivative moisture curing agent, slowly add to the system, continue to heat and stir for 1h to obtain serinol moisture curing one-component polyurethane pouring sealant.

3. A process for the preparation of a serinol derivative moisture heat latent curing one component polyurethane pouring sealant, characterized by Comprising the following steps: Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the water is removed under reduced pressure to 100 Pa for 3h, and then cooled to room temperature to obtain the serinol derivative moisture curing agent, which is 4a,6a-dimethyl-hexahydro-1,4-dioxo-6-azacyclopentane[cd]cyclopentadiene synthesized by reaction of serinol and 2,5-hexanedione, the reaction formula is as follows: ； Step two: take 25 parts of PBA1000, 15 parts of PHA1000 in an open reactor, start stirring, heat to 125℃, reduce pressure to 1000 Pa for 2h, remove water in polyester polyol, cool to 75℃, under the condition of connecting nitrogen, add 0.4 parts of trimethylolpropane, 0.03 parts of dibutyltin dilaurate, 25 parts of polyphenyl poly-methylene polyisocyanate PM400, 5 parts of diphenylmethane diisocyanate liquefied MDI-50, stirring rate 150 r / min, reaction for 2.5h, and then cooled to room temperature to obtain isocyanate-terminated polyurethane prepolymer; Step three: take 70 parts of isocyanate-terminated polyurethane prepolymer, 0.02 parts of dimorpholine divinyl ether, heat to 55℃ and stir uniformly, take 11.35 parts of serinol derivative moisture curing agent, slowly add to the system, continue to heat and stir for 1h to obtain serinol moisture curing one-component polyurethane pouring sealant.

4. A method for preparing a serinol derivative moisture heat latent curing one-component polyurethane pouring sealant, characterized in that Comprising the following steps: Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the water is removed under reduced pressure to 100 Pa for 3h, and then cooled to room temperature to obtain the serinol derivative moisture curing agent, which is 4a,6a-dimethyl-hexahydro-1,4-dioxo-6-azacyclopentane[cd]cyclopentadiene synthesized by reaction of serinol and 2,5-hexanedione, the reaction formula is as follows: ； Step two: take 38 parts of PBA1000 and 2 parts of PEG800 in an open reactor, start stirring, heat to 125℃, reduce pressure to 1000 Pa for 2h, remove water in polyester polyol, cool to 75℃, under the condition of connecting nitrogen, add 0.5 parts of trimethylolpropane, 25 parts of polyphenyl poly-methylene polyisocyanate PM400, 5 parts of diphenylmethane diisocyanate liquefied MDI-50, stirring rate 150 r / min, reaction for 2.5h, and then cooled to room temperature to obtain isocyanate-terminated polyurethane prepolymer; Step three: take 70 parts of isocyanate-terminated polyurethane prepolymer, heat to 55℃ and stir uniformly, take 11.35 parts of serinol derivative moisture curing agent, slowly add to the system, continue to heat and stir for 1h to obtain serinol moisture curing one-component polyurethane pouring sealant.

5. A process for preparing a serinol derivative moisture heat latent curing one component polyurethane pouring sealant, characterized in that Comprising the following steps: Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the water is removed under reduced pressure to 100 Pa for 3h, and then cooled to room temperature to obtain the serinol derivative moisture curing agent, which is 4a,6a-dimethyl-hexahydro-1,4-dioxo-6-azacyclopent[cd]pentalene synthesized by the reaction of serinol and 2,5-hexanedione, and the reaction formula is as follows: ； Step two: take 40 parts of PBA1000 in an open reactor, start stirring, heat to 125℃, reduce pressure to 1000 Pa for 2h, remove water in polyester polyol, cool to 75℃, add 0.5 parts of trimethylolpropane, 25 parts of diphenyl methane diisocyanate liquid MDI-50 under the condition of connecting nitrogen, stirring rate 150 r / min for 2.5h, and then cool to room temperature to obtain isocyanate-terminated polyurethane prepolymer; Step three: take 70 parts of isocyanate-terminated polyurethane prepolymer, heat to 55℃ and stir uniformly, take 9.5 parts of serinol derivative moisture curing agent and slowly add to the system, continue to heat and stir for 1h to obtain serinol moisture curing one-component polyurethane pouring sealant.

6. A process for the preparation of a serinol derivative moisture heat latent curing one component polyurethane pouring sealant, characterized by Comprising the following steps: Step one: take 28.5 parts of serinol and 22.75 parts of 2,5-hexanedione in a 150 mL four-necked flask, stirring rate 100 r / min, oil bath temperature 35℃ for 2h, then the temperature is raised to 55℃, and the water is removed under reduced pressure to 100 Pa for 3h, and then cooled to room temperature to obtain the serinol derivative moisture curing agent, which is 4a,6a-dimethyl-hexahydro-1,4-dioxo-6-azacyclopent[cd]pentalene synthesized by the reaction of serinol and 2,5-hexanedione, and the reaction formula is as follows: ； Step two: take 35 parts of PBA1000 in an open reactor, start stirring, heat to 125℃, reduce pressure to 1000 Pa for 2h, remove water in polyester polyol, cool to 75℃, add 0.3 parts of diethanolamine, 0.1 parts of dibutyltin dilaurate, 35 parts of polyphenyl polymethylene polyisocyanate PM400 under the condition of connecting nitrogen, stirring rate 150 r / min for 2.5h, and then cool to room temperature to obtain isocyanate-terminated polyurethane prepolymer; Step three: take 70 parts of isocyanate-terminated polyurethane prepolymer, 0.02 parts of bis-morpholine divinyl ether, heat to 55℃ and stir uniformly, take 15.21 parts of serinol derivative moisture curing agent and slowly add to the system, continue to heat and stir for 1h to obtain serinol moisture curing one-component polyurethane pouring sealant.

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