High-temperature-resistant adhesive as well as preparation method and application thereof

Abstract

The invention belongs to the field of water treatment, and relates to a high-temperature-resistant adhesive as well as a preparation method and application thereof. The high-temperature-resistant adhesive contains polyisocyanate, polymer polyol, acrylate resin with a specific structure, tackifying resin, modified high-temperature-resistant filler particles, a free radical initiator, a photoinitiator and a polymerization inhibitor. The modified high-temperature-resistant filler particles comprise high-temperature-resistant filler particles and polyester polyol which is coated on the surfaces of the high-temperature-resistant filler particles and has a specific structure. The polyurethane adhesive provided by the invention has very excellent long-term high temperature resistance and wide industrial application prospect.

Description

Technical Field

[0001] This invention belongs to the field of water treatment and relates to a high-temperature resistant adhesive, its preparation method, and its application. Background Technology

[0002] Spiral wound membranes are specialized membrane elements used in the water treatment industry. They possess functions such as separation, concentration, and purification, and are primarily used in food, electrophoretic coating, medical, biopharmaceutical, environmental protection, and chemical fields. In practical applications, spiral wound membranes are often used in high-temperature sterilization, high-temperature concentration, or high-temperature separation processes, thus frequently requiring them to withstand high temperatures. For example, fruit juice concentration requires high-temperature evaporation to remove water; if the membrane material is not heat-resistant, it can lead to membrane element deformation, swelling, or performance degradation, affecting separation accuracy and product quality. In the chemical industry, some reactions require high temperatures, and spiral wound membranes must withstand these temperatures to maintain separation efficiency. The medical and biopharmaceutical industries have extremely high hygiene requirements, and spiral wound membranes need to be sterilized with high-temperature steam (e.g., above 121°C) to kill microorganisms; if the membrane material is not heat-resistant, it can cause membrane detachment or seal failure.

[0003] The high-temperature resistance of adhesives used in spiral wound membranes is a core functional indicator, directly determining the applicability of membrane elements in high-temperature sterilization, environmental protection, chemical concentration, and separation. The heat resistance of spiral wound membranes depends not only on the membrane sheet performance but also, and more importantly, on the sealing adhesive. Therefore, high-temperature resistance of the adhesive is crucial. Existing high-temperature resistant adhesives typically perform well in the initial stages of membrane element operation, but gradually lose their effectiveness over time, exhibiting poor long-term high-temperature resistance. Therefore, there is an urgent need to develop adhesives with long-term high-temperature resistance to enable membrane modules to operate stably in high-temperature environments. Summary of the Invention

[0004] The primary objective of this invention is to provide an adhesive with long-term high-temperature resistance.

[0005] A second objective of this invention is to provide a method for preparing the above-mentioned high-temperature resistant adhesive.

[0006] A third objective of this invention is to provide the application of the above-mentioned high-temperature resistant adhesive in membrane module bonding.

[0007] The high-temperature resistant adhesive provided by the present invention contains polyisocyanate, polymer polyol, acrylate resin, tackifying resin, modified high-temperature resistant filler particles, photoinitiator, catalyst and polymerization inhibitor; the acrylate resin has the structure shown in formula (1); the modified high-temperature resistant filler particles include high-temperature resistant filler particles and polyester polyol coated on the surface of the high-temperature resistant filler particles, the polyester polyol has the structure shown in formula (2).

[0008]

[0009] In equation (1), R 11 R 12 R 13 R 21 R 22 R 23 R 31 R 32 and R 33 Each independently is H or Cl-C 10 alkyl, R 14 For C1-C 10 Alkyl groups; m, n, and p represent the molar amounts of each structural unit, with m:n:p being 1:(0.1–0.3):(0.5–0.8);

[0010]

[0011] In equation (2), n is an integer from 1 to 100.

[0012] The method for preparing the high-temperature resistant adhesive provided by the present invention includes mixing polyisocyanate, polymer polyol, acrylate resin, tackifying resin, modified high-temperature resistant filler particles, photoinitiator, catalyst and polymerization inhibitor evenly to obtain the high-temperature resistant adhesive.

[0013] The key to this invention lies in adding an acrylate resin with a specific structure and high-temperature resistant filler particles coated with a polyester polyol with a specific structure to a polyurethane adhesive. The acrylate resin contains both diphenyl groups and isoborneol groups, and the polyester polyol contains both isosorbide and itaconic acid structural units. The resulting polyurethane adhesive exhibits excellent long-term high-temperature resistance. This is presumably because the diphenyl and isoborneol groups in the acrylate resin can enhance the adhesive's long-term high-temperature resistance through molecular structure optimization and chemical bond strengthening mechanisms. Specifically, the diphenyl group is formed by two benzene rings connected by a single bond. Its structure is stable at high temperatures, preventing molecular chain breakage. Its planar conjugated structure effectively restricts the thermal motion of the molecular chain, reducing the risk of molecular chain slippage at high temperatures. Furthermore, the conjugation effect of the diphenyl group can disperse thermal stress at high temperatures, delaying thermal degradation reactions. The diphenyl group can also act as a crosslinking point, increasing cohesive strength at high temperatures and forming a stable chemical bond network. The isoborneol ester group contains a cyclic structure, which can impart a certain degree of flexibility to the adhesive, offsetting the embrittlement problem caused by the increased rigidity of the molecular chain at high temperatures, and reducing high-temperature shrinkage. The ester bonds and cyclic structure in the isoborneol ester group have high bond energy, which can resist oxidative degradation at high temperatures. The low surface energy of the isoborneol ester group can enhance the wettability of the adhesive to the substrate, forming a denser adhesive interface. The polyester polyol is a condensation product of itaconic acid and isosorbide, which improves the long-term high-temperature resistance of the adhesive through a triple mechanism of rigid cyclic structure, high crosslinking density, and antioxidant properties. Specifically, isosorbide contains both a rigid cyclic structure of dioxane and dihydroxyl groups, while itaconic acid contains both unsaturated double bonds and dicarboxyl groups. The unsaturated double bonds in itaconic acid can participate in free radical polymerization reactions, and the dicarboxyl groups in itaconic acid can undergo condensation reactions with the hydroxyl groups in isosorbide to form a polyester network structure containing a rigid cyclic structure. The dioxane structure exhibits high thermal stability, and its introduction significantly improves the glass transition stability of the condensate. Simultaneously, it restricts the close packing of molecular chains, forming a loose coating layer on the filler surface. This structure reduces direct contact between filler particles, lowers the tendency for aggregation caused by van der Waals forces, and improves dispersibility. The formation of the polyester network structure not only reduces molecular chain slippage and breakage at high temperatures, slowing down thermal degradation, but also effectively disperses thermal stress, preventing cracking caused by localized overheating. The cyclic structure of isosorbide further hinders oxygen molecule penetration through steric hindrance, delaying the oxidation induction period and avoiding the adverse effects of oxygen on high-temperature resistance.Furthermore, the high-temperature resistant adhesive provided by this invention contains both acrylate resin and polyester polyol. The unsaturated double bonds in the acrylate resin can undergo free radical polymerization, while the polyester polyol can react with polyisocyanate to form an interpenetrating network system. The acrylate resin branches, polyester polyol branches, and high-temperature resistant fillers in the interpenetrating network structure can all effectively play a role in high-temperature resistance. If one or both of them fail thermally, the remaining structure can still maintain heat resistance, thus giving the adhesive long-term high-temperature resistance through synergistic effect. Detailed Implementation

[0014] The high-temperature resistant adhesive provided by this invention contains polyisocyanate, polymeric polyol, acrylate resin, tackifying resin, modified high-temperature resistant filler, photoinitiator, catalyst, and polymerization inhibitor. Based on the total weight of the high-temperature resistant adhesive, the total weight of the polyisocyanate and polymeric polyol is preferably 50-80 wt%, such as 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, or any value between them; the content of the acrylate resin is preferably 5-40 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or any value between them; the content of the tackifying resin is preferably 1-10 wt%, such as 1 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, or any value between them; the modified high-temperature resistant filler particles... The preferred content is 5-30 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any value between them; the preferred content of the photoinitiator is 0.5-5 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any value between them; the preferred content of the catalyst is 0.5-5 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any value between them; the preferred content of the polymerization inhibitor is 0.5-5 wt%, such as 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, or any value between them. Furthermore, the molar ratio of isocyanate in the polyisocyanate to hydroxyl in the polymer polyol is preferably (2-2.5):1, such as 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1 or any value between them.

[0015] In this invention, the acrylate resin has the structure shown in formula (1).

[0016]

[0017] In equation (1), R 11R 12 R 13 R 21 R 22 R 23 R 31 R 32 and R 33 Each independently is H or Cl-C 10 The alkyl group, preferably H or C1-C5 alkyl group; R 14 For C1-C 10 The alkyl group is preferably a C1-C5 alkyl group. Examples of C1-C5 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl. m, n, and p represent the molar amounts of each structural unit, and m:n:p is 1:(0.1-0.3):(0.5-0.8). Specifically, m:p can be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, or any value between them. m:p can be 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, or any value between them. It should be noted that formula (1) is only used to represent the types and proportions of each structural unit and does not reflect the copolymerization reaction type or the connection relationship between the structural units. The acrylate resin can be a random copolymer or a block copolymer.

[0018] In this invention, the acrylic resin can be obtained commercially or prepared by various existing methods. In a preferred embodiment, the acrylic resin is prepared by the following method: unsaturated acrylic monomer having the structure shown in formula (3), unsaturated biphenyl monomer having the structure shown in formula (4), and unsaturated isobornyl acrylate monomer having the structure shown in formula (5) are subjected to free radical polymerization reaction at a molar ratio of 1:(0.1~0.3):(0.5~0.8), and the resulting free radical polymerization product is the acrylic resin;

[0019]

[0020] In equation (3), R 11 R 12 and R 13 Each independently is H or Cl-C 10 alkyl, R 14 For C1-C 10 Alkyl groups; in formula (4), R 21 R 22 and R 23 Each independently is H or Cl-C 10 Alkyl groups; in formula (5), R 31 R32 and R 33 Each independently is H or Cl-C 10 Alkyl groups.

[0021] In the preparation process of the above-mentioned acrylate resin, the unsaturated acrylate monomer may include at least one of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate.

[0022] In the preparation process of the above-mentioned acrylate resin, the molar ratio of the unsaturated acrylate monomer, the unsaturated biphenyl monomer, and the unsaturated isobornyl acrylate monomer is preferably 1:(0.1-0.3):(0.5-0.8). Specifically, the molar ratio of the unsaturated acrylate monomer to the unsaturated biphenyl monomer can be 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, or any value between them. The molar ratio of the unsaturated acrylate monomer to the unsaturated isobornyl acrylate monomer can be 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.75, 1:0.8, or any value between them.

[0023] In the preparation process of the above-mentioned acrylate resin, the conditions of the free radical polymerization reaction preferably include a temperature of 15-40°C, such as 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or any value between them; and a reaction time of 20-60 min, such as 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min or any value between them.

[0024] In this invention, the modified high-temperature resistant filler particles comprise high-temperature resistant filler particles and a polyester polyol coated on the surface of the high-temperature resistant filler particles. The polyester polyol has the structure shown in formula (2);

[0025]

[0026] In equation (1), n ​​is an integer from 1 to 100, such as 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or any value between them.

[0027] In a preferred embodiment, the modified high-temperature resistant filler particles are prepared by the following method: the high-temperature resistant filler particles are stirred and dispersed in an organic solvent, and under stirring conditions, itaconic acid, isosorbide and esterification catalyst are added to the resulting dispersion, and then the esterification reaction is carried out under esterification reaction conditions. After the reaction is completed, the particles are centrifuged and separated, and the resulting solid product is washed with water and dried to obtain the modified high-temperature resistant filler particles.

[0028] In the preparation process of the modified high-temperature resistant filler particles described above, the carboxyl groups in itaconic acid can be adsorbed onto the surface of the high-temperature resistant filler particles via van der Waals forces or hydrogen bonds through micropores or active sites on the particle surface. Subsequently, it undergoes an esterification reaction with isosorbide to form a polyester polyol coating the surface of the high-temperature resistant filler particles. The preferred molar ratio of itaconic acid to isosorbide is 1:(1.1–1.3), such as 1:1.1, 1:1.15, 1:1.2, 1:1.25, 1:1.3, or any value between them. The preferred mass ratio of the high-temperature resistant filler particles to the total amount of itaconic acid and isosorbide is 100:(10-50), such as 100:10, 100:15, 100:20, 100:25, 100:30, 100:35, 100:40, 100:45, 100:50 or any value between them.

[0029] In the preparation process of the above-mentioned modified high-temperature resistant filler particles, the high-temperature resistant filler particles may include at least one of the following: silica particles, alumina particles, graphite particles, titanate whiskers, montmorillonite, and vermiculite.

[0030] In the preparation process of the above-mentioned modified high-temperature resistant filler particles, the esterification catalyst can be concentrated sulfuric acid and / or organic sulfonic acid. Examples of organic sulfonic acids include at least one of methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. The amount of catalyst used is preferably 1% to 3% of the total mass of itaconic acid and isosorbide, such as 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, or any value between them.

[0031] In the preparation of the modified high-temperature resistant filler particles described above, specific examples of the polymerization inhibitor include, but are not limited to, at least one of p-hydroxyanisole, hydroquinone, and phenothiazine. The amount of the polymerization inhibitor is preferably 0.1% to 2% of the total mass of itaconic acid and isosorbide, such as 1%, 1.2%, 1.5%, 1.8%, 2%, or any value between them.

[0032] In the preparation process of the above-mentioned modified high-temperature resistant filler particles, the esterification reaction conditions preferably include a temperature of 50℃ to 100℃, such as 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃ or any value between them; and a time of 1 to 5h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or any value between them.

[0033] In this invention, the polyisocyanate is a compound with two or more isocyanate groups at the molecular chain terminal, and can be an aromatic isocyanate and / or an aliphatic isocyanate. Specific examples include, but are not limited to: isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, and polymerized diphenylmethane-4,4'-diisocyanate. The following is a list of at least one of the following: cyanate, 1,5-naphthalene diisocyanate, norbornene diisocyanate, bitoluidine diisocyanate, phenyldimethyl diisocyanate, hydrogenated phenyldimethyl diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tri(isocyanate phenyl)thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, dicyclohexylmethane diisocyanate, L-lysine triisocyanate, hexamethylene diisocyanate trimer, and polymethylene polyphenyl polyisocyanate.

[0034] In this invention, the polymeric polyol is a polyester polyol and / or a polyether polyol. The polyester polyol can be obtained by esterification of a polycarboxylic acid with a polyol. Specific examples of the polycarboxylic acid include, but are not limited to, at least one of: terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, decamethyldicarboxylic acid, and dodecamethyldicarboxylic acid. Specific examples of the polyol include, but are not limited to, at least one of: ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, and cyclohexanediol. The polyether polyol is preferably at least one of: polypropylene glycol, polypropylene triol, polytetrahydrofuran glycol, bisphenol A-modified polyether polyol, and polyethylene oxide polyol.

[0035] In this invention, the tackifying resin may include at least one of the following: C5 petroleum resin, C9 petroleum resin, dicyclopentadiene DCPD resin, coumarone-indene resin, styrene series resins, condensation resins, hydrocarbon petroleum resins, and hydrogenated petroleum resins.

[0036] In this invention, the photoinitiator may include at least one of the following: 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone.

[0037] In this invention, the catalyst may include at least one of 2,2-dimorpholinodiethyl ether, organic bismuth catalyst, dibutyltin dilaurate, and stannous octoate.

[0038] The method for preparing the high-temperature resistant adhesive provided by this invention includes uniformly mixing polyisocyanate, polymeric polyol, acrylate resin, tackifying resin, modified high-temperature resistant filler particles, photoinitiator, catalyst, and polymerization inhibitor to obtain the high-temperature resistant adhesive. The mixing method is not particularly limited; the ingredients can be added in any order and then stirred.

[0039] Furthermore, the present invention also provides the application of the above-mentioned high-temperature resistant adhesive in membrane module bonding.

[0040] The present invention will be described in detail below through embodiments.

[0041] In the following examples and comparative examples, polycaprolactone polyol was purchased from Daicel Inc. of Japan, brand name PLACEL220EB, Mn = 2000 g / mol; polytetrahydrofuran diol was purchased from BASF of Germany, brand name THF-20P, Mn = 2000 g / mol; and the tackifying resin was ExxonMobil's Escorez™ 5300.

[0042] Preparation Example 1-1 This preparation example illustrates acrylate resins and their preparation.

[0043] 1 mol of methyl acrylate, 0.5 mol of isobornyl methacrylate, and 1 g of hydrogen peroxide were dissolved in 300 mL of water to form a base solution. 0.1 mol of 4,4'-divinyl-1,1'-biphenyl was dissolved in 100 mL of ethanol to form an unsaturated biphenyl monomer solution. The unsaturated biphenyl monomer solution was added dropwise to the base solution. The initial addition temperature was controlled at 40℃, and the addition time was controlled at 20 min. After the addition was completed, the reaction was continued for 30 min to obtain acrylate resin PCE-1.

[0044] Preparation Examples 1-2 illustrate acrylate resins and their preparation.

[0045] 1 mol of ethyl acrylate, 0.8 mol of isobornyl methacrylate, and 1 g of hydrogen peroxide were dissolved in 300 mL of water to form a base solution. 0.3 mol of 4,4'-divinyl-1,1'-biphenyl was dissolved in 100 mL of ethanol to form an unsaturated biphenyl monomer solution. The unsaturated biphenyl monomer solution was added dropwise to the base solution. The initial addition temperature was controlled at 30℃, and the addition time was controlled at 20 min. After the addition was completed, the reaction continued for 40 min to obtain acrylate resin PCE-2.

[0046] Preparation Examples 1-3 illustrate acrylate resins and their preparation.

[0047] 1 mol of methyl methacrylate, 0.6 mol of isobornyl methacrylate, and 1 g of hydrogen peroxide were stirred and dissolved in 300 mL of water to form a base solution. 0.2 mol of 4,4'-divinyl-1,1'-biphenyl was stirred and dissolved in 100 mL of ethanol to form an unsaturated biphenyl monomer solution. The unsaturated biphenyl monomer solution was added dropwise to the base solution. The initial addition temperature was controlled at 35℃, and the addition time was controlled at 20 min. After the addition was completed, the reaction continued for 60 min to obtain acrylate resin PCE-3.

[0048] Comparative Preparation Example 1-1 This preparation example is used to illustrate the reference acrylic resin and its preparation.

[0049] Acrylic resin was prepared according to the method of Preparation Example 1-1, except that isobornyl methacrylate was replaced with the same molar amount of ethyl acrylate, and the other conditions were the same as in Preparation Example 1-1, to obtain reference acrylate resin DPCE-1.

[0050] Comparative Preparation Examples 1-2: These preparation examples illustrate the reference acrylic resin and its preparation.

[0051] Acrylic resin was prepared according to the method of Preparation Example 1-1, except that 4,4'-divinyl-1,1'-biphenyl was replaced with the same molar amount of 4-vinylbiphenyl, and the other conditions were the same as in Preparation Example 1-1, to obtain reference acrylate resin DPCE-2.

[0052] Preparation Example 2-1 This preparation example illustrates the modified high-temperature resistant filler particles and their preparation.

[0053] 100g of silica particles (particle size D90 of 0.8μm) were stirred and dispersed in 500mL of dichloromethane. Under nitrogen protection and stirring, 10g (0.077mol) itaconic acid, 12.4g (0.085mol) isosorbide, 0.5g concentrated sulfuric acid and 1g hydroquinone were added to the resulting dispersion. The temperature was then raised to 50℃ and reacted for 5h. After the reaction was completed, the mixture was centrifuged, and the resulting solid product was washed with water and dried to obtain the modified high-temperature resistant filler GT-1.

[0054] Preparation Example 2-2 This preparation example illustrates the modified high-temperature resistant filler particles and their preparation.

[0055] 100g of silica particles (particle size D90 of 1μm) were stirred and dispersed in 500mL of dichloromethane. Under nitrogen protection and stirring, 10g (0.077mol) of itaconic acid, 14.6g (0.01mol) of isosorbide, 0.5g of concentrated sulfuric acid and 1g of hydroquinone were added to the resulting dispersion. The temperature was then raised to 80℃ and reacted for 1h. After the reaction was completed, the particles were centrifuged, and the resulting solid product was washed with water and dried to obtain modified high-temperature resistant filler particles GT-2.

[0056] Preparation Examples 2-3 illustrate the modified high-temperature resistant filler particles and their preparation.

[0057] 100g of silica particles (particle size D90 of 1.5μm) were stirred and dispersed in 500mL of dichloromethane. Under nitrogen protection and stirring, 10g (0.077mol) of itaconic acid, 13.4g (0.092mol) of isosorbide, 0.5g of concentrated sulfuric acid and 1g of hydroquinone were added to the resulting dispersion. The temperature was then raised to 65℃ and reacted for 2h. After the reaction was completed, the particles were centrifuged, and the resulting solid product was washed with water and dried to obtain modified high-temperature resistant filler particles GT-3.

[0058] Comparative Preparation Example 2-1: This preparation example is used to illustrate the reference modified high-temperature resistant filler particles and their preparation.

[0059] Modified high-temperature resistant filler particles were prepared according to the method of Preparation Example 2-1, except that isosorbide was replaced with the same molar amount of 1,4-butanediol, and the other conditions were the same as in Preparation Example 2-1, to obtain reference modified high-temperature resistant filler particles DGT-1.

[0060] Comparative Preparation Example 2-2: This preparation example is used to illustrate the reference modified high-temperature resistant filler particles and their preparation.

[0061] Modified high-temperature resistant filler particles were prepared according to the method of Preparation Example 2-1, except that itaconic acid was replaced with the same molar amount of oxalic acid, and the other conditions were the same as in Preparation Example 2-1, to obtain reference modified high-temperature resistant filler particles DGT-2.

[0062] Example 1

[0063] According to the proportions in Table 1, polyisocyanate (isophorone diisocyanate), polymer polyol (polycaprolactone polyol), acrylate resin (PCE-1), tackifying resin, modified high-temperature resistant filler particles (GT-1), photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), catalyst (dibutyltin dilaurate), and polymerization inhibitor (hydroquinone) are mixed evenly. The molar ratio of isocyanate in the polyisocyanate to hydroxyl in the polymer polyol is 2:1, thus obtaining the high-temperature resistant adhesive.

[0064] Example 2

[0065] According to the proportions in Table 1, polyisocyanate (isophorone diisocyanate), polymer polyol (polytetrahydrofuran diol), acrylate resin (PCE-2), tackifying resin, modified high-temperature resistant filler particles (GT-2), photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), catalyst (dibutyltin dilaurate), and polymerization inhibitor (hydroquinone) are mixed evenly. The molar ratio of isocyanate in the polyisocyanate to hydroxyl in the polymer polyol is 2.5:1, thus obtaining the high-temperature resistant adhesive.

[0066] Example 3

[0067] According to the proportions in Table 1, polyisocyanate (isophorone diisocyanate), polymer polyol (polycaprolactone polyol), acrylate resin (PCE-3), tackifying resin, modified high-temperature resistant filler particles (GT-3), photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone), catalyst (dibutyltin dilaurate), and polymerization inhibitor (hydroquinone) are mixed evenly. The molar ratio of isocyanate in the polyisocyanate to hydroxyl in the polymer polyol is 2.2:1, thus obtaining the high-temperature resistant adhesive.

[0068] Comparative Example 1

[0069] A high-temperature resistant adhesive was prepared according to the method of Example 1, except that the acrylate resin (PCE-3) was replaced with the same part by weight of the reference acrylate resin (DPCE-1), and the other conditions were the same as in Example 1, to obtain a reference high-temperature resistant adhesive.

[0070] Comparative Example 2

[0071] A high-temperature resistant adhesive was prepared according to the method of Example 1, except that the acrylate resin (PCE-3) was replaced with the same part by weight of the reference acrylate resin (DPCE-2), and the other conditions were the same as in Example 1, to obtain a reference high-temperature resistant adhesive.

[0072] Comparative Example 3

[0073] The high-temperature resistant adhesive was prepared according to the method of Example 1, except that the modified high-temperature resistant filler particles (GT-1) were replaced with the same parts by weight of the reference modified high-temperature resistant filler particles (DGT-1), and the other conditions were the same as in Example 1, to obtain the reference high-temperature resistant adhesive.

[0074] Comparative Example 4

[0075] The high-temperature resistant adhesive was prepared according to the method of Example 1, except that the modified high-temperature resistant filler particles (GT-1) were replaced with the same parts by weight of the reference modified high-temperature resistant filler particles (DGT-2), and the other conditions were the same as in Example 1, to obtain the reference high-temperature resistant adhesive.

[0076] Table 1

[0077]

[0078] Test Case

[0079] (1) Initial bonding strength: The high-temperature resistant adhesives obtained in the above embodiments and the reference high-temperature resistant adhesives obtained in the comparative examples were applied to the surface of the PP substrate. The length, width, and height of the adhesive lines were controlled to be 10 mm, 2 mm, and 1 mm, respectively. The glass substrate was then bonded to the adhesive-coated surface of the PP substrate. The two substrates were pressed together with a pressure of 1 kg and cured at room temperature (35°C) for 2 min. Then, a 365 nm ultraviolet light source with a wavelength of 600 mW / cm² was used. 2 The sample was irradiated with the specified intensity for 5 seconds, and then stretched along the shear direction using a tensile testing machine at a moving speed of 10 mm / min. The maximum load that the sample could withstand when it failed was the initial bond strength. The results are shown in Table 2.

[0080] (2) 1-day high-temperature adhesive strength: The high-temperature adhesives obtained in the above embodiments and the reference high-temperature adhesives obtained in the comparative examples were applied to the surface of the PP substrate. The length, width, and height of the adhesive lines were controlled to be 10 mm, 2 mm, and 1 mm, respectively. The glass substrate was then bonded to the adhesive-coated surface of the PP substrate. The two substrates were pressed together with a pressure of 1 kg and cured at room temperature (35°C) for 2 minutes. Then, a 365 nm ultraviolet light source with a wavelength of 600 mW / cm² was used. 2 The sample was irradiated with high intensity for 5 seconds, then placed in an 80℃ oven for 1 day. After removal, it was stretched along the shear direction using a tensile testing machine at a moving speed of 10 mm / min. The maximum load that the sample could withstand when it failed was the 1-day high-temperature adhesive strength. The results are shown in Table 2.

[0081] (3) 30-day high-temperature adhesive strength: The high-temperature resistant adhesives obtained in the above embodiments and the reference high-temperature resistant adhesives obtained in the comparative examples were applied to the surface of the PP substrate. The length, width, and height of the adhesive lines were controlled to be 10 mm, 2 mm, and 1 mm, respectively. The glass substrate was then bonded to the adhesive-coated surface of the PP substrate. The two substrates were pressed together with a pressure of 1 kg and cured at room temperature (35°C) for 2 minutes. Then, a 365 nm ultraviolet light source with a wavelength of 600 mW / cm² was used. 2 The samples were irradiated with high intensity for 5 seconds, then placed in an 80℃ oven for 30 days. After removal, they were stretched along the shear direction using a tensile testing machine at a moving speed of 10 mm / min. The maximum load that the sample could withstand when it failed was the 30-day high-temperature adhesive strength. The results are shown in Table 2.

[0082] Table 2

[0083]

[0084] As can be seen from the results in Table 2, the polyurethane adhesive provided by the present invention has excellent long-term high-temperature resistance.

[0085] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. A high-temperature resistant adhesive, characterized in that, The high-temperature resistant adhesive contains polyisocyanate, polymer polyol, acrylate resin, tackifying resin, modified high-temperature resistant filler particles, photoinitiator, catalyst and polymerization inhibitor; the acrylate resin has the structure shown in formula (1); the modified high-temperature resistant filler particles include high-temperature resistant filler particles and polyester polyol coated on the surface of the high-temperature resistant filler particles, the polyester polyol has the structure shown in formula (2). In equation (1), R 11 R 12 R 13 R 21 R 22 R 23 R 31 R 32 and R 33 Each independently is H or Cl-C 10 alkyl, R 14 For C1-C 10 Alkyl groups; m, n, and p represent the molar amounts of each structural unit, with m:n:p being 1:(0.1–0.3):(0.5–0.8); In equation (2), n is an integer from 1 to 100.

2. The high-temperature resistant adhesive according to claim 1, characterized in that, The acrylate resin is prepared by the following method: unsaturated acrylate monomers having the structure shown in formula (3), unsaturated biphenyl monomers having the structure shown in formula (4), and unsaturated isoborneol acrylate monomers having the structure shown in formula (5) are subjected to free radical polymerization reaction in a molar ratio of 1:(0.1~0.3):(0.5~0.8), and the resulting free radical polymerization product is the acrylate resin. In equation (3), R 11 R 12 and R 13 Each independently is H or Cl-C 10 alkyl, R 14 For C1-C 10 Alkyl groups; In equation (4), R 21 R 22 and R 23 Each independently is H or Cl-C 10 Alkyl groups; In equation (5), R 31 R 32 and R 33 Each independently is H or Cl-C 10 Alkyl groups.

3. The high-temperature resistant adhesive according to claim 1, characterized in that, The modified high-temperature resistant filler particles are prepared by the following method: the high-temperature resistant filler particles are stirred and dispersed in an organic solvent. Under stirring conditions, itaconic acid, isosorbide, and an esterification catalyst are added to the resulting dispersion. The molar ratio of itaconic acid and isosorbide is controlled at 1:(1.1~1.3). Then, the esterification reaction is carried out under esterification reaction conditions. After the reaction is completed, the particles are centrifuged and separated. The resulting solid product is washed with water and dried to obtain the modified high-temperature resistant filler particles. Preferably, the mass ratio of the amount of the high-temperature resistant filler particles to the total amount of itaconic acid and isosorbide is 100:(10-50); Preferably, the esterification reaction conditions include a temperature of 50°C to 100°C and a time of 1 hour to 5 hours.

4. The high-temperature resistant adhesive according to claim 1, characterized in that, The molar ratio of isocyanate in the polyisocyanate to hydroxyl in the polymer polyol is (2-2.5):1; Preferably, the polyisocyanate is selected from at least one of isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, polymerized diphenylmethane-4,4'-diisocyanate, 1,5-naphthalene diisocyanate, norbornene diisocyanate, bitoluidine diisocyanate, phenylmethylene diisocyanate, hydrogenated phenylmethylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tri(isocyanate phenyl)thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, dicyclohexylmethane diisocyanate, L-lysine triisocyanate, hexamethylene diisocyanate trimer, and polymethylene polyphenyl polyisocyanate; Preferably, the polymeric polyol is a polyester polyol and / or a polyether polyol.

5. The high-temperature resistant adhesive according to claim 1, characterized in that, Based on the total weight of the high-temperature resistant adhesive, the total weight of the polyisocyanate and polymeric polyol is 50-80 wt%, the content of the acrylate resin is 5-40 wt%, the content of the tackifying resin is 1-10 wt%, the content of the modified high-temperature resistant filler particles is 5-30 wt%, the content of the photoinitiator is 0.5-5 wt%, the content of the catalyst is 0.5-5 wt%, and the content of the polymerization inhibitor is 0.5-5 wt%.

6. The high-temperature resistant adhesive according to claim 1, characterized in that, The tackifying resin is selected from at least one of C5 petroleum resin, C9 petroleum resin, dicyclopentadiene DCPD resin, coumarone-indene resin, styrene series resins, condensation resins, hydrocarbon petroleum resins, and hydrogenated petroleum resins.

7. The high-temperature resistant adhesive according to claim 1, characterized in that, The high-temperature resistant filler particles are selected from at least one of silica particles, alumina particles, graphite particles, titanate whiskers, montmorillonite, and vermiculite.

8. The high-temperature resistant adhesive according to claim 1, characterized in that, The photoinitiator is selected from at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone; the catalyst is selected from at least one of 2,2-dimorpholinyl diethyl ether, organobismuth catalyst, dibutyltin dilaurate, and stannous octoate; the polymerization inhibitor is selected from at least one of p-hydroxyanisole, hydroquinone, and phenothiazine.

9. A method for preparing the high-temperature resistant adhesive according to any one of claims 1 to 8, characterized in that, The method involves uniformly mixing polyisocyanate, polymeric polyol, acrylate resin, tackifying resin, modified high-temperature resistant filler particles, photoinitiator, catalyst, and polymerization inhibitor to obtain a high-temperature resistant adhesive.

10. The application of the high-temperature resistant adhesive according to any one of claims 1 to 8 in the bonding of membrane modules.

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