Moisture curing polyurethane adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a moisture curing polyurethane adhesive and a preparation method thereof. The invention relates to a moisture-curable polyurethane adhesive. The moisture-curable polyurethane adhesive is prepared from the following raw materials in parts by weight: diisocyanate; organic silicon modified naphthenic polyether glycol; a modified naphthenic polyether polyol; polyether glycol; polyester glycol; a small molecule dihydric alcohol; an anti-aging agent; and a polyurethane catalyst. The moisture-cured polyurethane adhesive has the beneficial effects that the moisture-cured polyurethane adhesive contains a large number of isocyanate groups, so that a network structure is formed, and the crosslinking degree is high; the used modified naphthenic polyether polyol can be combined with an isocyanate group to provide good cross-linking performance for the polyurethane adhesive, the cross-linking degree is uniform, the elasticity is good, and the obtained moisture-cured polyurethane adhesive has good heat-resistant and rebound effects.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to a moisture-curing polyurethane adhesive and a preparation method thereof. Background Art

[0002] Traditional clothing, especially close-fitting fabrics, usually require elastic bands as clothing accessories to adjust the tightness of clothing. They are widely used in underwear, thermal trousers, sportswear, etc. Traditional elastic bands are generally made of rubber, are relatively thick, and need to be sewn into clothing. The wrinkles formed may affect the wearer's comfort. In addition, rubber is easy to age and is prone to breakage and creep after long-term use, causing the clothing to deform and become unwearable.

[0003] CN112030347A provides a novel method for preparing elastic bands, which directly prints silicone onto the cut pieces for making clothes to form a strip-shaped elastic pattern, and no longer needs to be sewn into a webbing, thereby reducing the thickness and providing a better user experience. However, since the elastic modulus of silicone is generally higher than that of rubber and the stretch length is lower, the elastic band made of silicone is apparently tight, which affects the wearing experience.

[0004] CN114957605A discloses a TPU film material for seamless underwear and a preparation method thereof. The TPU film material for seamless underwear prepared by the invention has excellent water washing peeling strength and excellent water resistance. It has high air permeability and excellent resilience when used in the underwear field. The invention uses TPU film, which needs to be cut according to the use scenario in subsequent molding, which not only wastes TPU film, but also makes the operation process inconvenient. Moreover, since the TPU film must have a thicker thickness to avoid stacking and unevenness during subsequent use, its application range in ultra-thin comfortable fabrics is limited. At the same time, the use temperature of linear TPU generally does not exceed 80°C, while the maximum temperature of underwear can reach 90°C when it is sterilized and washed at high temperature. The invention has not verified its performance characteristics during high-temperature washing.

[0005] CN104387560A discloses a thermoplastic polyurethane elastomer and a preparation method thereof. The TPU synthesized by the invention contains trace amounts of chemical crosslinking in its soft segment, soft segment and hard segment, which gives the TPU good comprehensive performance and low tensile permanent deformation characteristics; when the TPU is used to process products such as elastic bands or elastic cords, the low tensile permanent deformation characteristics greatly extend its dimensional stability and durability, and the products have good elasticity and processability. However, the trace amounts of chemical crosslinking in the TPU described in the invention may generate certain stresses in the process of preparing elastic bands or elastic cords, and the degree of chemical crosslinking is obviously insufficient, which may cause problems such as the elastic bands or elastic cords not fitting well enough and not being able to withstand high-temperature washing. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a moisture-curing polyurethane adhesive having heat resistance and good resilience effect and a preparation method thereof.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is: to provide a moisture-curing polyurethane adhesive, wherein the moisture-curing polyurethane adhesive is prepared from raw materials including the following weight ratios: 6-18 parts of diisocyanate; 18-34 parts of organosilicon-modified cycloalkyl polyether diol; 2-5 parts of modified cycloalkyl polyether polyol; 19-34 parts of polyether diol; 25-33 parts of polyester diol; 0.1-0.6 parts of small molecule diol; Anti-aging agent 0.6-1.3 parts; Polyurethane catalyst 0.02-0.08 parts.

[0008] Furthermore, in the above-mentioned moisture-curing polyurethane adhesive, the preparation method of the organosilicon-modified cycloalkyl polyether diol is as follows: (1) Add 3-allyloxy-1,2-propylene glycol to a reaction kettle, add boron trifluoride etherate and dichloromethane, stir and cool to 0-5°C; drip epoxide composition A into the reaction kettle at a uniform speed, react for a certain time, then drip epoxide composition B into the reaction kettle at a uniform speed, and continue to react for a certain time; add deionized water to terminate the reaction, wash the separated liquid and discard the water layer, and distill the organic layer under reduced pressure to remove dichloromethane and water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol; (2) The allyloxy polyether diol obtained in step (1) and the silicon hydride compound are mixed, stirred and heated to 80-100° C., a silicon hydrogen addition catalyst is added, and a colorless transparent viscous liquid is obtained after the reaction, which is the organosilicon-modified cycloalkyl polyether diol.

[0009] Furthermore, in the above-mentioned moisture-curing polyurethane adhesive, the preparation method of the modified cycloalkyl polyether polyol is as follows: The allyloxy polyether diol obtained in step (2) of claim 2 is dissolved in dichloromethane, and diluted bromine water is slowly added dropwise until the added bromine water does not fade within 30 seconds, and a small amount of isoascorbic acid aqueous solution is added dropwise until the solution fades, and the solution is allowed to stand for separation to remove the water layer, and a catalyst 4-dimethylaminopyridine is added to the organic layer, and hydroxylamine is added to a reaction kettle, stirred and heated to react, cooled, and water is added dropwise, and the solution is allowed to stand for separation, and the organic layer is distilled under reduced pressure to remove dichloromethane and remaining water to obtain a modified cycloalkyl polyether polyol.

[0010] Further, in the above-mentioned moisture-curing polyurethane adhesive, the epoxide composition A is a combination of one or more of 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, and 1,4-epoxycyclohexane and one or more of 1,2-epoxypropylene, 1,2-epoxybutylene, 1,4-epoxybutylene, 1,2-epoxypentane, 1,2-epoxyhexane, and 1,2-epoxyoctane; The epoxide composition B is a combination of two or more of 1,2-propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 1,2-pentene oxide, 1,2-cyclopentene oxide, 1,2-hexene oxide, 1,2-cyclohexene oxide, 1,2-octane oxide and 1,4-cyclohexene oxide.

[0011] Furthermore, in the above-mentioned moisture-curing polyurethane adhesive, the silicon hydride compound is a single-terminal hydrogen-containing silicone oil, and its general structural formula is HSi(CH3)2O[Si(CH3)2O] n Si(CH3)3, wherein n=1-10; the hydrosilylation catalyst is one of a 2wt% isopropanol solution of chloroplatinic acid or a 2wt% toluene solution of platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane.

[0012] Furthermore, in the above-mentioned moisture-curing polyurethane adhesive, the dilute bromine water is an aqueous solution of bromine with a concentration of about 0.5 wt %; and the hydroxylamine is one or a combination of two of 2-hydroxyethylamine and 2,2'-dihydroxydiethylamine.

[0013] Furthermore, in the above-mentioned moisture-curing polyurethane adhesive, the polyether diol is one or a combination of polyoxyethylene diol, polyoxypropylene diol, polytetrahydrofuran diol, polyoxyethylene polyoxypropylene diol, etc., having an average molecular weight of 2000-5000Da; The polyester diol is one or a combination of polycaprolactone diol, polyneopentyl adipate diol, poly1,4-butylene adipate diol, poly1,6-hexane adipate diol, polyneopentyl phthalate diol and polycarbonate diol with an average molecular weight of 1000-5000Da; The small molecule diol is one or a combination of 1,4-butanediol, 1,6-hexanediol and 1,8-octanediol; The anti-aging agent comprises an ultraviolet absorber and an antioxidant, wherein the ultraviolet absorber is one of Chisorb® 5411 or Chisorb® 770 with double bond chemistry; and the antioxidant is one of BASF's Irganox® 1010 or Irgafos® 168.

[0014] Furthermore, in the above-mentioned moisture-curing polyurethane adhesive, the diisocyanate is one or a combination of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; and the polyurethane catalyst is one of bismorpholinyl diethyl ether or bismuth isooctanoate.

[0015] Another technical solution provided by the present invention is to provide a method for preparing the above-mentioned moisture-curing polyurethane adhesive, comprising the following steps: Add organosilicon-modified cycloalkyl polyether diol, modified cycloalkyl polyether polyol, polyether diol, polyester diol and anti-aging agent into a reaction kettle, heat up to remove moisture, cool down to add diisocyanate, heat up to react for 2-5 hours, add small molecule diol and polyurethane catalyst, heat up to continue reacting for 2-5 hours, stop stirring and evacuate to remove bubbles, pour into an aluminum foil bag while hot, evacuate and seal, and cool down to obtain moisture-curing polyurethane adhesive.

[0016] Furthermore, the preparation method of the moisture-curing polyurethane adhesive specifically comprises the following steps: Add organosilicon-modified cycloalkyl polyether diol, modified cycloalkyl polyether polyol, polyether diol, polyester diol and anti-aging agent into a reaction kettle, heat up to 110-120°C, reduce the moisture in the materials to 0.05-0.1wt% by vacuuming, and cool down to 40-50°C; add diisocyanate, heat up to 80-100°C and react for 2-5 hours, add small molecule diol and polyurethane catalyst, heat up to 110-130°C and continue to react for 1-5 hours, stop stirring and vacuum to remove bubbles, pour into an aluminum foil bag while hot, evacuate and seal, and cool down to 20-30°C to obtain a moisture-curing polyurethane adhesive.

[0017] The beneficial effects of the present invention are as follows: the moisture-curing polyurethane adhesive obtained by the present invention contains a large number of isocyanate groups. In the presence of a trace amount of water vapor, the isocyanate groups can react with water to generate amine groups, and the amine groups can quickly form crosslinks with other isocyanate groups to form a network structure with a high degree of crosslinking; the modified cycloalkyl polyether polyol used includes a hydroxyl group at the end and a hydroxyl secondary amine group in the middle of the molecular chain on a single molecule, and the number of active hydrogens in the hydroxyl group and the secondary amine group is greater than 2, which can be combined with the isocyanate group to provide the polyurethane adhesive with good crosslinking performance, uniform crosslinking degree, good elasticity, and make the obtained moisture-curing polyurethane adhesive have good heat resistance and rebound effects.

[0018] The moisture-curing polyurethane adhesive obtained by the present invention uses epoxy cycloalkanes as the components of the special polyether, has good compatibility, improves the transparency and elastic modulus of the moisture-curing polyurethane adhesive, reduces the use of easily hydrolyzed polyester, and improves the high-temperature detergent washing resistance of the moisture-curing polyurethane adhesive while maintaining sufficient strength, thereby improving durability.

[0019] The moisture-curing polyurethane adhesive obtained by the invention contains an organosilicon-modified polyether segment, has good penetration into fabrics and the like, is beneficial to improving the adhesion to the fabrics, avoids the disadvantages of delamination, breakage and the like, and prolongs the service life.

[0020] Example 9 of the present invention verifies that the moisture-curing polyurethane adhesive obtained by the present invention has moderate peel strength for nylon cloth, adjustable mechanical properties such as elastic modulus, good elastic recovery rate, and high peel strength retention rate after high-temperature washing, and can replace elastic bands or elastic threads in fabrics such as clothing. DETAILED DESCRIPTION

[0021] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in conjunction with the implementation methods.

[0022] Example 1 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) Add 13.2 g of 3-allyloxy-1,2-propylene glycol into a reactor, add 2.5 g of boron trifluoride etherate and 600 g of dichloromethane, stir and cool the reactor to 0°C; A composition of 30 g of 1,2-propylene oxide, 45 g of 1,2-butylene oxide, 70 g of 1,4-butylene oxide and 20 g of 1,2-cyclohexene oxide at 0° C. was uniformly dripped into a reaction kettle within 1 hour. After reacting for 2 hours, 40 g of 1,2-cyclopentane oxide and 15 g of 1,2-hexene oxide at 0° C. were uniformly dripped into the reaction kettle within 1 hour. The reaction was continued for 1 hour while keeping the temperature not exceeding 10° C. 1000 g of deionized water was added to terminate the reaction. The water layer was washed and separated and discarded. The organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0023] (2) 115 g of the allyloxy polyether diol obtained in step (1) and 22.5 g of HSi(CH3)2O[Si(CH3)2O]4Si(CH3)3 were mixed, stirred and heated to 85°C, 0.25 g of a 2 wt% isopropanol solution of chloroplatinic acid was added, the mixture was reacted for 8 hours, and the temperature was lowered to 20°C to obtain a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol.

[0024] (3) 23 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the bromine water did not fade after 30 seconds. A small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation. A small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 0.8 g of 2-hydroxyethylamine was added to the reaction kettle, stirred at 55° C. for 4 hours, cooled to 20° C., a small amount of water was added dropwise, and the solution was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and remaining water to obtain a modified cycloalkyl polyether polyol.

[0025] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 8 g of the modified cycloalkyl polyether polyol obtained in step (3), 60 g of polyoxypropylene diol with an average molecular weight of 3000 Da, 70 g of polyoxyethylene polyoxypropylene diol with an average molecular weight of 3500 Da, 40 g of polycaprolactone diol with an average molecular weight of 2000 Da, 40 g of polyadipate neopentyl glycol ester diol with an average molecular weight of 2000 Da, 20 g of polycarbonate diol with an average molecular weight of 4000 Da, and 2 g of ultraviolet absorber Chisorb were added. ® 770 and 1g of antioxidant Irganox ® 1010 was added into the reactor, the temperature was raised to 115°C, the moisture in the material was reduced to 0.05wt% by vacuuming, and the temperature was lowered to 45°C; 43.5g of isophorone diisocyanate was added, the temperature was raised to 80°C and the reaction was continued for 5 hours, 1.5g of 1,4-butanediol and 0.1g of bismuth isooctanoate were added, the temperature was raised to 110°C and the reaction was continued for 5 hours, stirring was stopped and vacuuming was performed to remove bubbles, the mixture was poured into an aluminum foil bag while hot, the bag was evacuated and sealed, and the temperature was lowered to 20°C to obtain moisture-curing polyurethane adhesive A.

[0026] Example 2 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) Add 13.2 g of 3-allyloxy-1,2-propylene glycol to a reactor, add 2 g of boron trifluoride etherate and 600 g of dichloromethane, stir and cool the reactor to 3°C; within 1.5 hours, uniformly drip a composition of 90 g of 1,2-epoxycyclopentane, 40 g of 1,2-epoxybutylene oxide, 80 g of 1,4-epoxybutylene oxide and 40 g of 1,2-epoxypentane at 0°C into the reactor, react for 1.5 hours, and within 1 hour, drip 40 g of 1,2-epoxycyclohexane, 40 g of 1,2-epoxyhexane and 40 g of 1,2-epoxyhexane at 0°C. 1,2-Octyl oxide was uniformly added to the reactor, and the reaction was continued for 2 hours, with the temperature kept not exceeding 10°C; 1000 g of deionized water was added to terminate the reaction, the aqueous layer was washed and separated, and the organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0027] (2) 190 g of the allyloxy polyether diol obtained in step (1) and 45 g of HSi(CH3)2O[Si(CH3)2O] 10 Si(CH3)3 was mixed, stirred and heated to 100°C, 0.3g of 2wt% toluene solution of platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane was added, reacted for 8 hours, cooled to 30°C, and a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol was obtained.

[0028] (3) 38 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the bromine water did not fade after 30 seconds. A small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation. A small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 1.3 g of 2,2'-dihydroxydiethylamine was added to the reaction kettle, stirred at 60° C. for 2 hours, cooled to 20° C., a small amount of water was added dropwise, and the solution was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and remaining water to obtain a modified cycloalkyl polyether polyol.

[0029] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 12 g of the modified cycloalkyl polyether polyol obtained in step (3), 100 g of polyoxypropylene diol with an average molecular weight of 5000 Da, 20 g of polyoxyethylene diol with an average molecular weight of 5000 Da, 80 g of poly(neopentyl phthalate) diol with an average molecular weight of 1000 Da, 35 g of poly(caprolactone) diol with an average molecular weight of 2000 Da, 10 g of poly(neopentyl adipate) diol with an average molecular weight of 2500 Da, and 2 g of the ultraviolet absorber Chisorb were added. ® 770 and 1g of the antioxidant Irgafos ® 168 was added into the reaction kettle, the temperature was raised to 120°C, the moisture in the material was reduced to 0.1wt% by vacuuming, and the temperature was lowered to 40°C; 25g of hexamethylene diisocyanate was added, the temperature was raised to 95°C for reaction for 3 hours, 1.8g of 1,8-octanediol and 0.2g of bismorpholinyl diethyl ether were added, the temperature was raised to 120°C for further reaction for 3 hours, stirring was stopped and vacuuming was performed to remove bubbles, the mixture was poured into an aluminum foil bag while hot, the bag was evacuated and sealed, and the temperature was lowered to 30°C to obtain moisture-curing polyurethane adhesive B.

[0030] Example 3 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) Add 13.2 g of 3-allyloxy-1,2-propylene glycol to a reactor, add 3 g of boron trifluoride etherate and 600 g of dichloromethane, stir and cool the reactor to 5°C; within 2 hours, uniformly drip a composition of 50 g of 1,4-epoxycyclohexane, 80 g of 1,2-epoxypentane, 30 g of 1,2-epoxyhexane and 20 g of 1,2-epoxyoctane at 5°C into the reactor, react for 1 hour, and within 2 hours, drip 25 g of 1,4-epoxycyclohexane, 40 g of 1,2-epoxypentane, 15 g of 1,2-epoxyoctane at 5°C into the reactor. A composition of 1,2-epoxyhexane and 10 g of 1,2-epoxyoctane was uniformly dripped into the reaction kettle, and the reaction was continued for 1 hour, with the temperature maintained at no more than 10°C; 1000 g of deionized water was added to terminate the reaction, the aqueous layer was washed and separated, and the organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0031] (2) 140 g of the allyloxy polyether diol obtained in step (1) and 34 g of HSi(CH3)2O[Si(CH3)2O]7Si(CH3)3 were mixed, stirred and heated to 90°C, 0.2 g of a 2 wt% toluene solution of platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane was added, the mixture was reacted for 7 hours, and the temperature was lowered to 25°C to obtain a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol.

[0032] (3) 28 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the added bromine water did not fade after 30 seconds, and a small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation, and a small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 1.4 g of 2,2'-dihydroxydiethylamine was added to the reaction kettle, and the mixture was stirred at 55° C. for 3 hours. The mixture was cooled to 10-20° C., and a small amount of water was added dropwise. The mixture was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and the remaining water to obtain a modified cycloalkyl polyether polyol.

[0033] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 15 g of the modified cycloalkyl polyether polyol obtained in step (3), 60 g of polyoxyethylene diol with an average molecular weight of 2000 Da, 80 g of polycarbonate diol with an average molecular weight of 2500 Da, and 1 g of ultraviolet absorber Chisorb were added. ® 5411 and 1g of the antioxidant Irgafos ®168 was added into the reaction kettle, the temperature was raised to 120°C, the moisture in the material was reduced to 0.08wt% by vacuuming, and the temperature was lowered to 50°C; 49.5g of diphenylmethane diisocyanate was added, the temperature was raised to 100°C and the reaction was carried out for 3 hours, 1g of 1,6-hexanediol, 0.3g of 1,4-butanediol, and 0.2g of bismorpholinyl diethyl ether were added, the temperature was raised to 120°C and the reaction was continued for 4 hours, stirring was stopped and vacuuming was carried out to remove bubbles, the bag was poured into an aluminum foil bag while hot, the bag was evacuated and sealed, and the temperature was lowered to 30°C to obtain moisture-curing polyurethane adhesive C.

[0034] Example 4 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) 13.2 g of 3-allyloxy-1,2-propylene glycol was added to a reaction kettle, and 3.5 g of boron trifluoride etherate and 600 g of dichloromethane were added, and the reaction kettle was stirred and cooled to 0°C; within 2 hours, a composition A containing 75 g of 1,2-epoxycyclohexane, 40 g of 1,2-epoxypropylene and 35 g of 1,2-epoxybutylene at 0°C was uniformly dripped into the reaction kettle, and after reacting for 1 hour, within 1 hour, a composition B containing 10 g of 1,2-epoxybutylene and 30 g of 1,2-epoxyhexane at 0°C was uniformly dripped into the reaction kettle, and the reaction was continued for 3 hours, and the temperature was kept not higher than 10°C; 1000 g of deionized water was added to terminate the reaction, and the water layer was washed and separated, and the organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water, thereby obtaining a colorless, transparent, viscous liquid allyloxy polyether diol.

[0035] (2) 100 g of the allyloxy polyether diol obtained in step (1) and 11.6 g of HSi(CH3)2OSi(CH3)2OSi(CH3)3 were mixed, stirred and heated to 80°C, 0.1 g of a 2 wt% isopropanol solution of chloroplatinic acid was added, the mixture was reacted for 8 hours, and the temperature was lowered to 20°C to obtain a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol.

[0036] (3) 20 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the bromine water did not fade after 30 seconds. A small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The solution was allowed to stand for separation and the water layer was removed. A small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 0.7 g of 2-hydroxyethylamine was added to the reaction kettle, stirred at 50° C. for 2 hours, cooled to 10° C., a small amount of water was added dropwise, and the solution was allowed to stand for separation. The organic layer was distilled under reduced pressure to remove dichloromethane and remaining water to obtain a modified cycloalkyl polyether polyol.

[0037] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 20 g of the modified cycloalkyl polyether polyol obtained in step (3), 80 g of 2000 Da average molecular weight polyoxyethylene polyoxypropylene diol, 80 g of 2000 Da average molecular weight polytetrahydrofuran diol, 60 g of 2500 Da average molecular weight polyadipate-1,4-butanediol ester diol, 100 g of 2000 Da average molecular weight polyadipate-1,6-hexanediol ester diol, 3 g Chisorb ® 5411 and 1g Irganox ® 1010 was added into the reactor, the temperature was raised to 110°C, the moisture in the material was reduced to 0.05wt% by vacuuming, and the temperature was lowered to 40°C; 95g of 4,4'-dicyclohexylmethane diisocyanate was added, the temperature was raised to 80°C and the reaction was carried out for 5 hours, 1g of 1,4-butanediol and 0.1g of bismuth isooctanoate were added, the temperature was raised to 110°C and the reaction was continued for 5 hours, stirring was stopped and vacuuming was carried out to remove bubbles, the mixture was poured into an aluminum foil bag while hot, vacuumed and sealed, and the temperature was lowered to 20°C to obtain moisture-curing polyurethane adhesive D.

[0038] Example 5 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) Add 13.2 g of 3-allyloxy-1,2-propylene glycol to a reactor, add 3 g of boron trifluoride etherate and 600 g of dichloromethane, stir and cool the reactor to 2°C; within 1.5 hours, uniformly drip a composition of 50 g of 1,2-epoxycyclopentane, 55 g of 1,2-epoxybutylene oxide and 80 g of 1,4-epoxybutylene oxide into the reactor, react for 2 hours, and within 1.5 hours, drip 60 g of 1,2-epoxycyclopentane, 30 g of 1,2-epoxybutylene oxide, 10 g of 1,4-epoxybutylene oxide and 20 g of 2°C into the reactor. The composition of 1,2-octane oxide was uniformly dripped into the reactor, and the reaction was continued for 2.5 hours, and the temperature was kept not higher than 10°C; 1000g of deionized water was added to terminate the reaction, the aqueous layer was discarded after washing, and the organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0039] (2) 160 g of the allyloxy polyether diol obtained in step (1) and 40 g of HSi(CH3)2O[Si(CH3)2O] 8.5 Si(CH3)3 was mixed, stirred and heated to 95°C, 0.25g of 2wt% toluene solution of platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane was added, reacted for 5 hours, cooled to 26°C, and a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol was obtained.

[0040] (3) 32 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the bromine water did not fade after 30 seconds. A small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation. A small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 1.3 g of 2,2'-dihydroxydiethylamine was added to the reaction kettle, stirred at 60° C. for 2 hours, cooled to 15° C., a small amount of water was added dropwise, and the solution was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and remaining water to obtain a modified cycloalkyl polyether polyol.

[0041] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 17.5 g of the modified cycloalkyl polyether polyol obtained in step (3), 20 g of polyoxyethylene diol with an average molecular weight of 2000 Da, 50 g of polyoxypropylene diol with an average molecular weight of 5000 Da, 35 g of polytetrahydrofuran diol with an average molecular weight of 3000 Da, 25 g of polyoxyethylene polyoxypropylene diol with an average molecular weight of 2500 Da, 100 g of polycarbonate diol with an average molecular weight of 2250 Da, and 3 g of ultraviolet absorber Chisorb were added. ® 770 and 2g of the antioxidant Irgafos ® 168 was added into the reactor, the temperature was raised to 110°C, the moisture in the material was reduced to 0.1wt% by vacuuming, and the temperature was lowered to 40°C; 31g 4,4'-dicyclohexylmethane diisocyanate was added, the temperature was raised to 90°C and the reaction was carried out for 3 hours, 2g 1,8-octanediol and 0.1g bismuth isooctanoate were added, the temperature was raised to 130°C and the reaction was continued for 1 hour, stirring was stopped and vacuuming was carried out to remove bubbles, and the mixture was poured into an aluminum foil bag while hot, vacuumed and sealed, and the temperature was lowered to 25°C to obtain moisture-curing polyurethane adhesive E.

[0042] Example 6 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) 13.2 g of 3-allyloxy-1,2-propylene glycol was added to a reaction kettle, and 2.5 g of boron trifluoride etherate and 600 g of dichloromethane were added. The reaction kettle was stirred and the temperature was lowered to 5°C. A composition of 40 g of 1,4-epoxycyclohexane and 100 g of 1,2-epoxyhexane at 5°C was uniformly dripped into the reaction kettle within 2 hours. After reacting for 1 hour, a composition of 40 g of 1,4-epoxycyclohexane and 70 g of 1,2-epoxyhexane at 5°C was uniformly dripped into the reaction kettle within 2 hours. The reaction was continued for 2 hours, and the temperature was kept at no more than 10°C. 1000 g of deionized water was added to terminate the reaction. The aqueous layer was washed and separated, and the organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0043] (2) 130 g of the allyloxy polyether diol obtained in step (1) and 19 g of HSi(CH3)2O[Si(CH3)2O]3Si(CH3)3 were mixed, stirred and heated to 90°C, 0.2 g of a hydrosilylation catalyst was added, reacted for 5 hours, and cooled to 25°C to obtain a colorless, transparent, viscous liquid organosilicon-modified cycloalkyl polyether diol.

[0044] (3) 26 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the added bromine water did not fade after 30 seconds, and a small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation, and a small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 0.75 g of 2-hydroxyethylamine was added to the reaction kettle, and the mixture was stirred at 50° C. for 5 hours. The mixture was cooled to 10° C., and a small amount of water was added dropwise. The mixture was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and the remaining water to obtain a modified cycloalkyl polyether polyol.

[0045] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 10 g of the modified cycloalkyl polyether polyol obtained in step (3), 80 g of polyoxyethylene polyoxypropylene diol with an average molecular weight of 2000 Da, 60 g of polyadipate neopentyl glycol ester diol with an average molecular weight of 3000 Da, 50 g of polyadipate-1,4-butylene glycol ester diol with an average molecular weight of 2500 Da, and 1 g of ultraviolet absorber Chisorb were added. ® 5411 and 2g antioxidant Irganox ® 1010 was added into the reaction kettle, the temperature was raised to 115°C, and the moisture in the material was removed by vacuuming to 0.08wt%, and the temperature was lowered to 40°C; 35.5g of toluene diisocyanate was added, the temperature was raised to 100°C and the reaction was carried out for 4 hours, 1.2g of 1,4-butanediol and 0.3g of dimorpholino diethyl ether were added, the temperature was raised to 125°C and the reaction was continued for 2 hours, stirring was stopped and the bubbles were removed by vacuuming, and the mixture was poured into an aluminum foil bag while hot, and the bag was sealed by vacuuming, and the temperature was lowered to 30°C to obtain moisture-curing polyurethane adhesive F.

[0046] Example 7 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) 13.2 g of 3-allyloxy-1,2-propylene glycol was added to a reaction kettle, and 2.5 g of boron trifluoride etherate and 600 g of dichloromethane were added, and the reaction kettle was stirred and cooled to 0°C; within 1 hour, a composition of 30 g of 1,2-propylene oxide, 45 g of 1,2-butylene oxide, 70 g of 1,4-butylene oxide and 20 g of 1,2-cyclohexene oxide at 0°C was uniformly dripped into the reaction kettle, and after reacting for 2 hours, within 1 hour, 40 g of 1,2-cyclopentane oxide and 20 g of 1,2-hexene oxide at 0°C were uniformly dripped into the reaction kettle, and the reaction was continued for 1-3 hours, and the temperature was kept not higher than 10°C; 1000 g of deionized water was added to terminate the reaction, and the water layer was discarded after washing and separation, and the dichloromethane and a small amount of water were removed from the organic layer under reduced pressure to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0047] (2) 120 g of the allyloxy polyether diol obtained in step (1) and 27.2 g of HSi(CH3)2O[Si(CH3)2O] 5.3 Si(CH3)3 was mixed, stirred and heated to 85°C, 0.25g of 2wt% chloroplatinic acid isopropanol solution was added, reacted for 8 hours, and cooled to 20°C to obtain a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol.

[0048] (3) 24 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the added bromine water did not fade after 30 seconds, and a small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation, and a small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 0.8 g of 2-hydroxyethylamine was added to the reaction kettle, and the mixture was stirred at 55° C. for 4 hours. The mixture was cooled to 20° C., and a small amount of water was added dropwise. The mixture was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and the remaining water to obtain a modified cycloalkyl polyether polyol.

[0049] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 8 g of the modified cycloalkyl polyether polyol obtained in step (3), 60 g of polyoxypropylene diol with an average molecular weight of 3000 Da, 70 g of polyoxyethylene polyoxypropylene diol with an average molecular weight of 3500 Da, 40 g of polycaprolactone diol with an average molecular weight of 2000 Da, 40 g of polyadipate neopentyl glycol ester diol with an average molecular weight of 2000 Da, 20 g of polycarbonate diol with an average molecular weight of 4000 Da, and 2 g of ultraviolet absorber Chisorb were added. ® 770 and 1g of antioxidant Irganox ®1010 was added into the reactor, the temperature was raised to 115°C, the moisture in the material was reduced to 0.05wt% by vacuuming, and the temperature was lowered to 45°C; 51g of 4,4'-dicyclohexylmethane diisocyanate was added, the temperature was raised to 80°C and the reaction was carried out for 5 hours, 0.5g of 1,4-butanediol and 0.1g of bismuth isooctanoate were added, the temperature was raised to 115°C and the reaction was continued for 4 hours, stirring was stopped and vacuuming was carried out to remove bubbles, the mixture was poured into an aluminum foil bag while hot, the bag was evacuated and sealed, and the temperature was lowered to 25°C to obtain moisture-curing polyurethane adhesive G.

[0050] Example 8 A method for preparing a moisture-curing polyurethane adhesive comprises the following steps: (1) Add 13.2 g of 3-allyloxy-1,2-propylene glycol to a reactor, add 3 g of boron trifluoride etherate and 600 g of dichloromethane, stir and cool the reactor to 5°C; within 2 hours, uniformly drip a composition of 50 g of 1,4-epoxycyclohexane, 10 g of 1,2-epoxypentane, 30 g of 1,2-epoxyhexane and 20 g of 1,2-epoxyoctane at 5°C into the reactor, react for 1 hour, and within 2 hours, drip 15 g of 1,4-epoxycyclohexane, 10 g of 1,2-epoxypentane, 15 g of 1,2-epoxyoctane at 5°C into the reactor. A composition of 1,2-epoxyhexane and 10 g of 1,2-epoxyoctane was uniformly dripped into the reaction kettle, and the reaction was continued for 1 hour, with the temperature maintained at no more than 10°C; 1000 g of deionized water was added to terminate the reaction, the aqueous layer was washed and separated, and the organic layer was distilled under reduced pressure to remove dichloromethane and a small amount of water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol.

[0051] (2) 90 g of the allyloxy polyether diol obtained in step (1) and 13.2 g of HSi(CH3)2O[Si(CH3)2O]2Si(CH3)3 were mixed, stirred and heated to 90°C, 0.2 g of a 2 wt% toluene solution of platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane was added, the mixture was reacted for 7 hours, and the temperature was lowered to 25°C to obtain a colorless, transparent, viscous liquid silicone-modified cycloalkyl polyether diol.

[0052] (3) 18 g of the allyloxy polyether diol obtained in step (1) was dissolved in 100 g of dichloromethane, and diluted bromine water was slowly added dropwise until the added bromine water did not fade after 30 seconds, and a small amount of isoascorbic acid aqueous solution was added dropwise until the solution faded. The aqueous layer was removed by standing and separation, and a small amount of catalyst 4-dimethylaminopyridine was added to the organic layer. 1.4 g of 2,2'-dihydroxydiethylamine was added to the reaction kettle, and the mixture was stirred at 55° C. for 3 hours. The mixture was cooled to 10-20° C., and a small amount of water was added dropwise. The mixture was allowed to stand and separate. The organic layer was distilled under reduced pressure to remove dichloromethane and the remaining water to obtain a modified cycloalkyl polyether polyol.

[0053] (4) 100 g of the organosilicon-modified cycloalkyl polyether diol obtained in step (2), 14 g of the modified cycloalkyl polyether polyol obtained in step (3), 60 g of polyoxyethylene diol with an average molecular weight of 2000 Da, 80 g of polycarbonate diol with an average molecular weight of 2500 Da, and 1 g of ultraviolet absorber Chisorb were added. ® 5411 and 1g of the antioxidant Irgafos ® 168 was added into the reaction kettle, the temperature was raised to 120°C, the moisture in the material was reduced to 0.08wt% by vacuuming, and the temperature was lowered to 50°C; 43.5g of isophorone diisocyanate was added, the temperature was raised to 100°C for reaction for 3 hours, 1.3g of 1,6-hexanediol and 0.2g of bismorpholinyl diethyl ether were added, the temperature was raised to 120°C for reaction for 2 hours, stirring was stopped and vacuuming was performed to remove bubbles, the mixture was poured into an aluminum foil bag while hot, the bag was evacuated and sealed, and the temperature was lowered to 30°C to obtain moisture-curing polyurethane adhesive H.

[0054] Example 9 The moisture-curing polyurethane adhesives AH obtained in the above examples 1-8 were coated on cotton cloth respectively, with a coating thickness of 30 μm. After the coating was completed, another piece of cotton cloth was covered on the adhesive while it was hot, and it was quickly rolled 5 times with a 5kg roller, and then left to stand for 48 hours in an environment of 25°C and 90% humidity. The composite cloth was taken out and cut into strips with a width of 25 mm. One part was tested for the 180° peel strength of the moisture-curing polyurethane adhesive on a digital tensile machine, with a tensile speed of 100 mm / min, and each group of tests was repeated 5 times to take the average value; the other part of the composite cloth was placed in a washing machine, washed with washing powder at 90°C for 1 hour, and cycled 5 times. After the cycle, it was dried and left to stand for 48 hours in an environment of 25°C and 90% humidity, and the 180° peel strength of the moisture-curing polyurethane adhesive after washing was tested, with a tensile speed of 100 mm / min, and each group of tests was repeated 5 times to take the average value.

[0055] The test method for the elastic modulus of the above-mentioned moisture-curing polyurethane adhesive AH refers to "HG / T 3321-2012 Test method for elastic modulus of vulcanized rubber". The moisture-curing polyurethane adhesive AH of the present invention is prepared into a rectangular sheet of 90mm*10mm*2mm, placed in an environment of 25°C and 90% humidity. After standing for 48 hours, the long direction of the rectangular sheet is clamped on a digital tensile testing machine with a clamping distance of 50mm and a stretching speed of 100mm / min. The stress-strain value of the rectangular sheet is measured, and each group of tests is repeated 3 times, and the elastic modulus is obtained by taking the average value; the sample is stretched to fracture at the same speed, and the displayed value is the fracture strength of the sample. The ratio of the clamping distance to the original clamping distance at fracture is the elongation at fracture. Each group of tests is repeated 3 times, and the average value is taken.

[0056] Elastic recovery rate test conditions: clamping distance 50mm, stretching speed 100mm / min, set elongation value to 75mm. During the test, the sample is first stretched to the set elongation value, then returned to the origin after 1min, and then the second stretching is started after 3min. The first stretching process is repeated until the cycle is repeated 5 times. The length L2 of the sample clamping distance is measured, and then the elastic recovery rate result is calculated according to formula (1).

[0057] ρ = (75-L2) / (75-50)*100% Formula (1) The above mechanical properties test results are shown in Table 1.

[0058] Table 1. Mechanical properties test results of moisture-curing polyurethane adhesive AH samples As can be seen from Table 1, the moisture-curing polyurethane adhesive obtained by the present invention has moderate peel strength for nylon cloth, adjustable mechanical properties such as elastic modulus, good elastic recovery rate, high peel strength retention rate after high-temperature washing, and can replace elastic bands or elastic threads in fabrics such as clothing.

[0059] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A moisture curing polyurethane adhesive, characterized in that: The moisture-curing polyurethane adhesive is prepared from the following raw materials in parts by weight: 6-18 parts of diisocyanate; 18-34 parts of organosilicon-modified cycloalkyl polyether diol; 2-5 parts of modified cycloalkyl polyether polyol; 19-34 parts of polyether diol; 25-33 parts of polyester diol; 0.1-0.6 parts of small molecule diol; Anti-aging agent 0.6-1.3 parts; Polyurethane catalyst 0.02-0.08 parts.

2. The moisture-curing polyurethane adhesive according to claim 1, characterized in that: The preparation method of the organosilicon-modified cycloalkyl polyether diol is as follows: (1) Add 3-allyloxy-1,2-propylene glycol to a reaction kettle, add boron trifluoride etherate and dichloromethane, stir and cool to 0-5°C; drip epoxide composition A into the reaction kettle at a uniform speed, react for a certain time, then drip epoxide composition B into the reaction kettle at a uniform speed, and continue to react for a certain time; add deionized water to terminate the reaction, wash the separated liquid and discard the water layer, and distill the organic layer under reduced pressure to remove dichloromethane and water to obtain a colorless, transparent, viscous liquid allyloxy polyether diol; (2) The allyloxy polyether diol obtained in step (1) and the silicon hydride compound are mixed, stirred and heated to 80-100° C., a silicon hydrogen addition catalyst is added, and a colorless transparent viscous liquid is obtained after the reaction, which is the organosilicon-modified cycloalkyl polyether diol.

3. The moisture-curing polyurethane adhesive according to claim 2, characterized in that: The preparation method of the modified cycloalkyl polyether polyol is as follows: The allyloxy polyether diol obtained in step (2) of claim 2 is dissolved in dichloromethane, and diluted bromine water is slowly added dropwise until the added bromine water does not fade within 30 seconds, and a small amount of isoascorbic acid aqueous solution is added dropwise until the solution fades, and the solution is allowed to stand for separation to remove the water layer, and a catalyst 4-dimethylaminopyridine is added to the organic layer, and hydroxylamine is added to a reaction kettle, stirred and heated to react, cooled, and water is added dropwise, and the solution is allowed to stand for separation, and the organic layer is distilled under reduced pressure to remove dichloromethane and remaining water to obtain a modified cycloalkyl polyether polyol.

4. The moisture-curing polyurethane adhesive according to claim 2, characterized in that: The epoxide composition A is a combination of one or more of 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, and 1,4-epoxycyclohexane and one or more of 1,2-epoxypropylene, 1,2-epoxybutylene, 1,4-epoxybutylene, 1,2-epoxypentane, 1,2-epoxyhexane, and 1,2-epoxyoctane; The epoxide composition B is a combination of two or more of 1,2-propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 1,2-pentene oxide, 1,2-cyclopentene oxide, 1,2-hexene oxide, 1,2-cyclohexene oxide, 1,2-octane oxide and 1,4-cyclohexene oxide.

5. The moisture-curing polyurethane adhesive according to claim 2, characterized in that: The silicon hydrogen compound is a single-ended hydrogen-containing silicone oil, and its general structural formula is HSi(CH3)2O[Si(CH3)2O] n Si(CH3)3, wherein n=1-10; the hydrosilylation catalyst is one of a 2wt% isopropanol solution of chloroplatinic acid or a 2wt% toluene solution of platinum (0)-1,3-diethene-1,1,3,3-tetramethyldisiloxane.

6. The moisture-curing polyurethane adhesive according to claim 3, characterized in that: The dilute bromine water is a bromine aqueous solution with a concentration of 0.5 wt %; the hydroxylamine is one or a combination of 2-hydroxyethylamine and 2,2'-dihydroxydiethylamine.

7. The moisture-curing polyurethane adhesive according to claim 1, characterized in that: The polyether diol is one or a combination of polyoxyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran diol, polyoxyethylene polyoxypropylene glycol, etc., with an average molecular weight of 2000-5000Da; The polyester diol is one or a combination of polycaprolactone diol, polyneopentyl adipate diol, poly1,4-butylene adipate diol, poly1,6-hexane adipate diol, polyneopentyl phthalate diol and polycarbonate diol with an average molecular weight of 1000-5000Da; The small molecule diol is one or a combination of 1,4-butanediol, 1,6-hexanediol and 1,8-octanediol; The anti-aging agent comprises an ultraviolet absorber and an antioxidant, wherein the ultraviolet absorber is one of Chisorb® 5411 or Chisorb® 770 with double bond chemistry; and the antioxidant is one of BASF's Irganox® 1010 or Irgafos® 168.

8. The moisture-curing polyurethane adhesive according to claim 1, characterized in that: The diisocyanate is one of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate, or a combination of the two or more thereof; the polyurethane catalyst is one of bismorpholinyl diethyl ether and bismuth isooctanoate.

9. A method for preparing the moisture-curing polyurethane adhesive according to any one of claims 1 to 8, characterized in that: The steps include: Add organosilicon-modified cycloalkyl polyether diol, modified cycloalkyl polyether polyol, polyether diol, polyester diol and anti-aging agent into a reaction kettle, heat up to remove moisture, cool down to add diisocyanate, heat up to react for 2-5 hours, add small molecule diol and polyurethane catalyst, heat up to continue reacting for 2-5 hours, stop stirring and evacuate to remove bubbles, pour into an aluminum foil bag while hot, evacuate and seal, and cool down to obtain moisture-curing polyurethane adhesive.

10. The method for preparing the moisture-curing polyurethane adhesive according to claim 9, characterized in that: The specific steps include: Add organosilicon-modified cycloalkyl polyether diol, modified cycloalkyl polyether polyol, polyether diol, polyester diol and anti-aging agent into a reaction kettle, heat up to 110-120°C, reduce the moisture in the materials to 0.05-0.1wt% by vacuuming, and cool down to 40-50°C; add diisocyanate, heat up to 80-100°C and react for 2-5 hours, add small molecule diol and polyurethane catalyst, heat up to 110-130°C and continue to react for 1-5 hours, stop stirring and vacuum to remove bubbles, pour into an aluminum foil bag while hot, evacuate and seal, and cool down to 20-30°C to obtain a moisture-curing polyurethane adhesive.

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