CN108285524B - Anti-slip polyurethane elastomer stock solution and preparation method and application thereof - Google Patents
Anti-slip polyurethane elastomer stock solution and preparation method and application thereof Download PDFInfo
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- CN108285524B CN108285524B CN201711500957.2A CN201711500957A CN108285524B CN 108285524 B CN108285524 B CN 108285524B CN 201711500957 A CN201711500957 A CN 201711500957A CN 108285524 B CN108285524 B CN 108285524B
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Abstract
The invention discloses a slip-resistant polyurethane elastomer stock solution and a preparation method and application thereof, wherein the slip-resistant polyurethane elastomer stock solution comprises a polyurethane stock solution A component and a polyurethane stock solution B component; the component A of the polyurethane stock solution contains polyether ester dihydric alcohol and polyester polyol; the component B of the polyurethane stock solution contains hydroxyl-terminated liquid rubber modified polyester polyol. The anti-slip polyurethane elastomer stock solution can be applied to safety protection soles, non-slip mats and the like, and the safety protection effect is improved.
Description
Technical Field
The invention relates to a polyurethane elastomer stock solution and a preparation method and application thereof.
Background
Polyurethanes are polymers having repeating structural units of urethane segments made by reacting an isocyanate with a polyol. Compared with the common rubber sole, the polyurethane sole has the characteristics of light weight, good wear resistance and the like. The polyurethane sole takes polyurethane stock solution as a main raw material, and solves the problems that the prior domestic plastic sole and the regenerated rubber sole are easy to break and the like and the rubber sole is easy to open glue. By adding various additives, the wear resistance, oil resistance, electric insulation, static resistance and acid and alkali resistance of the polyurethane sole are greatly improved. However, due to the characteristics of polyurethane materials, the anti-slip performance of the polyurethane materials is a barrier to the extensive and extensive application of polyurethane in the field of shoe soles. The limited slip of the sole directly affects the comfort and safety of the shoe when worn. The anti-skid property is poor, and the road is easy to slip and fall when walking, especially on wet, smooth and slippery road surfaces. With the development of the global construction industry, particularly the construction of public places, the ground of a building is more and more high-grade, gorgeous, beautiful and magnificent, but the problem of ground skid resistance is mostly ignored, so that accidents of skid, fall and fall damage frequently occur.
At the present stage, the main material of the anti-slip sole is mainly produced, and the anti-slip sole is mainly made of rubber, TPR and the like, so that the production cost is high, the production process is complex, the sole is heavy, and the wearing comfort is reduced. And the material also has certain pollution to the environment, which is not beneficial to the sustainable development of the environment. Therefore, the anti-slip polyurethane elastomer stock solution is developed to meet the market demand, is a green and environment-friendly product, and has good anti-slip performance, simple processing and forming process, low production cost and high wearing comfort.
Disclosure of Invention
The invention aims to provide a non-slip polyurethane elastomer stock solution, a preparation method and application thereof, and aims to solve the problems in the prior art.
The anti-slip polyurethane elastomer stock solution comprises a polyurethane stock solution A component and a polyurethane stock solution B component;
the polyurethane stock solution A component consists of the following raw materials in parts by weight:
the polyether ester dihydric alcohol is an esterification and polycondensation reaction product of polytetrahydrofuran ether dihydric alcohol with the number average molecular weight of 100-800, micromolecular dihydric alcohol and adipic acid;
the number average molecular weight of the polyether ester dihydric alcohol is 3000-6000;
the polyether ester dihydric alcohol comprises the following raw materials in parts by weight:
20-40 parts of polytetrahydrofuran ether dihydric alcohol;
10-30 parts of micromolecular dihydric alcohol;
40-85 parts of adipic acid;
the molar ratio of hydroxyl in the polytetrahydrofuran ether dihydric alcohol and the micromolecular dihydric alcohol to carboxyl in the adipic acid is (1.2-1.3) to 1.
The micromolecular dihydric alcohol is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and neopentyl glycol.
The preparation method of the polyether ester dihydric alcohol comprises the steps of sequentially adding polytetrahydrofuran ether dihydric alcohol, micromolecular dihydric alcohol and adipic acid into a reaction kettle, starting stirring, starting heating, keeping the temperature at 120-150 ℃ for 1-2 h, stabilizing the dehydration speed (the temperature at the top of a distillation tower is kept at 90-100 ℃) and then continuously heating, introducing nitrogen from the lower part when the temperature is raised to 160-190 ℃ and gradually increasing the nitrogen amount for dehydration. Heating to 210-240 ℃, keeping the temperature for 1-2 h, adding 40-160ppm of titanium catalyst, starting to vacuumize, performing ester exchange, taking samples every 2h from vacuumization for 4-6 h, performing central control analysis until the acid value is less than or equal to 0.5, the hydroxyl value is 18-36 mgKOH/g, recovering the normal pressure, introducing nitrogen at the upper part, starting to cool, cooling to 100-120 ℃, starting to sample, performing final analysis and discharging, and storing.
The titanium catalyst is one or a mixture of tetraisopropyl titanate and n-butyl titanate.
The polyester polyol is a polyester adipate polyester polyol, the functionality is 2-4, and the number average molecular weight is 1000-5000.
The chain extender is one or more than one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 6-hexanediol and cyclohexanedimethanol;
the anti-slip agent contains rosin, liquid rubber, zinc oxide and a plasticizer;
the anti-slip agent comprises the following raw materials in parts by weight:
the rosin is one or two of natural rosin and rosin resin;
the liquid rubber is one or more of hydroxyl-terminated poly-acrylonitrile butadiene liquid rubber, hydroxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated polychloroprene liquid rubber, hydroxyl-terminated butylbenzene liquid rubber, hydroxyl-terminated polyisoprene liquid rubber, carboxyl-terminated poly-acrylonitrile butadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber and carboxyl-terminated polyisoprene liquid rubber, the functionality is 1.9-2.4, and the number average molecular weight is 250-500;
the oxidant is nano zinc oxide, and the particle size is 1-100 nm;
the plasticizer is one or more of butyrolactone, acylated tributyl citrate, mixed dibasic acid dimethyl ester, propylene carbonate and diisooctyl adipate;
the preparation method of the anti-skid agent comprises the following steps:
(1) adding 1-10 parts of zinc oxide into 5-10 parts of plasticizer, and grinding in a ball mill for 240-300 min to obtain zinc oxide slurry;
(2) adding the zinc oxide slurry obtained in the step (1), 40-50 parts of rosin and 0-10 parts of liquid rubber into 35-40 parts of plasticizer, placing the mixture into an oven at 80-100 ℃ for 1-3 h, taking out, and stirring for 20-40 min by using a stirrer to obtain the anti-slip agent.
The catalyst is a tertiary amine catalyst or an organic tin catalyst;
the tertiary amine catalyst is one of triethylene diamine, tetramethyl diethylene triamine and dibutyltin dilaurate.
The polyurethane stock solution B comprises the following raw materials in parts by weight:
20-60 parts of hydroxyl-terminated liquid rubber modified polyester polyol;
50-75 parts of diisocyanate.
The NCO content of the polyurethane stock solution B component is 15-18 wt%.
The diisocyanate is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate and naphthalene diisocyanate;
the hydroxyl-terminated liquid rubber modified polyester polyol is an esterification and polycondensation reaction product of hydroxyl-terminated liquid rubber, micromolecular dihydric alcohol and adipic acid;
the hydroxyl value of the liquid rubber modified polyester polyol is (28.0-112.0) mgKOH/g, and the acid value is (0.1-0.6) mgKOH/g;
the hydroxyl-terminated liquid rubber is one or more of hydroxyl-terminated butyronitrile liquid rubber, hydroxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated polychloroprene liquid rubber, hydroxyl-terminated butylbenzene liquid rubber and hydroxyl-terminated polyisoprene liquid rubber;
the functionality of the hydroxyl-terminated liquid rubber is 1.9-2.4, and the number average molecular weight is 250-500;
the micromolecular dihydric alcohol is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and neopentyl glycol;
the mass ratio of the hydroxyl-terminated liquid rubber to the micromolecular dihydric alcohol is 2: 1-1: 3;
the molar ratio of hydroxyl in the hydroxyl-terminated liquid rubber and the micromolecular dihydric alcohol to carboxyl in the adipic acid is (1.2-1.6) to 1.
The preparation method of the liquid rubber modified polyester polyol comprises the steps of sequentially adding micromolecular dihydric alcohol, hydroxyl-terminated liquid rubber and 40-160ppm of titanium catalyst into a reaction kettle, starting stirring, keeping the temperature constant for 1-2 hours when the temperature is raised to 140-160 ℃, stabilizing the dehydration speed (keeping the temperature at the top of a tower to be 90-105 ℃ through a rectifying tower), raising the temperature to 170-190 ℃, starting a vacuum pump, controlling the vacuum degree to be gradually increased, raising the temperature to 215-235 ℃ for ester exchange reaction, introducing nitrogen to take away surplus polyalcohol and micromolecular alcohol, taking a sample every 2 hours after the vacuum pumping is started and timed for 5 hours, carrying out central control analysis to the final acid value and hydroxyl value, recovering the normal pressure, reducing the temperature to room temperature, and discharging and storing.
The titanium catalyst is one or a mixture of tetraisopropyl titanate and n-butyl titanate.
The preparation method of the anti-slip polyurethane elastomer stock solution A comprises the steps of adding polyether ester dihydric alcohol, polyester polyol, a chain extender and a plasticizer into a reaction kettle with a temperature control and stirring device, mixing for 2.5-3.5 hours at the controlled temperature of (45-55 ℃), cooling to (25-35 ℃), adding water, a catalyst and an anti-slip agent, fully stirring for 2-3 hours, uniformly mixing, discharging, sealing and storing.
The preparation method of the anti-slip polyurethane elastomer stock solution B component comprises the steps of adding the liquid rubber modified polyester polyol and the diisocyanate into a reaction kettle with a temperature control and stirring device for mixing reaction at the temperature of (55-65 ℃) for 2-3 h, cooling, discharging, sealing and storing.
The anti-slip polyurethane stock solution can be used for preparing an anti-slip polyurethane elastomer, and the preparation method comprises the following steps:
mixing a polyurethane stock solution A component with the temperature of 48-52 ℃ and a polyurethane stock solution B component with the temperature of 43-47 ℃ in a two-component casting machine, injecting the A component and the B component into a (45-50) DEG C mold for reaction (5-7) min for molding after the A component and the B component have the molar ratio of 1: 1, demolding, and curing in a (60-70) DEG C oven for (22-24) h to obtain the anti-slip polyurethane elastomer.
Compared with the prior art, the invention has the following advantages:
(1) rosin, zinc oxide, liquid rubber and a plasticizer are mixed to prepare a slip stopping agent, and the slip stopping agent is added into a stock solution of a polyurethane elastomer, so that the slip stopping effect of the polyurethane elastomer is improved;
(2) the hydroxyl-terminated liquid rubber modified polyester polyol is utilized to improve the low-temperature resistance of the polyurethane elastomer, the hardness of the polyurethane elastomer is less increased in a low-temperature environment, and the slip resistance and the use comfort are improved;
(3) the anti-slip polyurethane elastomer stock solution can be applied to safety protection soles, anti-slip pads and the like, and the safety protection effect is improved.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood that the specific materials, process conditions and results described in the examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Preparation of polyether ester dihydric alcohol
Example 1
Adding 16.4kg of polytetrahydrofuran ether dihydric alcohol (the number average molecular weight is 100), 8.2kg of ethylene glycol and 35.4kg of adipic acid into a reaction kettle in sequence, opening and stirring, starting heating, keeping the temperature at 120 ℃ for 2h, stabilizing the dehydration speed (keeping the temperature at the top of a distillation tower at 90 ℃), continuing heating, introducing nitrogen from the lower part when heating to 160 ℃, and gradually increasing the nitrogen amount for dehydration. Heating to 210 ℃, keeping the temperature for 2 hours, adding 2.4g of tetraisopropyl titanate, starting to vacuumize, carrying out ester exchange, taking a sample every 2 hours from the beginning of vacuumization for carrying out central control analysis until the acid value is less than or equal to 0.5mgKOH/g and the hydroxyl value is 37.4 mgKOH/g, recovering to normal pressure, introducing nitrogen at the upper part by switching, starting to cool, starting to sample when the temperature is reduced to 100 ℃, carrying out final analysis and discharging, and storing to obtain the polyether ester dihydric alcohol 1.
Example 2
Adding 11.5kg of polytetrahydrofuran ether dihydric alcohol (the number average molecular weight is 400), 15.3kg of ethylene glycol and 33.2kg of adipic acid into a reaction kettle in sequence, opening and stirring, starting heating, keeping the temperature at 150 ℃ for 1h, stabilizing the dehydration speed (keeping the temperature at the top of the tower at 100 ℃ through a distillation tower), then continuing heating, introducing nitrogen from the lower part when heating to 190 ℃, and gradually increasing the nitrogen amount for dehydration. Heating to 240 ℃, keeping the temperature for 1h, adding 5.4g of tetraisopropyl titanate, starting to vacuumize, carrying out ester exchange, taking a sample every 2h from 4h after vacuumizing for central control analysis until the acid value is less than or equal to 0.5mgKOH/g and the hydroxyl value is 28.0mgKOH/g, recovering the normal pressure, introducing nitrogen gas at the upper part by switching, starting to cool, cooling to 120 ℃, starting to sample, carrying out final analysis and discharging, and storing to obtain the polyether ester dihydric alcohol 2.
Example 3
Adding 14.6kg of polytetrahydrofuran ether dihydric alcohol (the number average molecular weight is 800), 14.6kg of ethylene glycol and 30.8kg of adipic acid into a reaction kettle in sequence, opening and stirring, starting heating, keeping the temperature at 150 ℃ for 1h, stabilizing the dehydration speed (keeping the temperature at the top of a distillation tower at 100 ℃), continuing heating, introducing nitrogen from the lower part when heating to 180 ℃, and gradually increasing the nitrogen amount for dehydration. Heating to 230 ℃, keeping the temperature for 1h, adding 9.6g of tetraisopropyl titanate, starting to vacuumize, carrying out ester exchange, taking a sample every 2h from 4h after vacuumizing for central control analysis until the acid value is less than or equal to 0.5mgKOH/g and the hydroxyl value is 18.7mgKOH/g, recovering the normal pressure, introducing nitrogen gas at the upper part by switching, starting to cool, cooling to 120 ℃, starting to sample, carrying out final analysis and discharging, and storing to obtain the polyether ester dihydric alcohol 3.
Preparation of anti-skid agent
Example 4
(1) Adding 100g of nano zinc oxide into 500g of butyrolactone, and putting the butyrolactone into a ball mill for grinding for 300min to obtain zinc oxide slurry;
(2) and (2) adding the zinc oxide slurry obtained in the step (1) and 4000g of natural rosin into 3500g of butyrolactone, placing the mixture into an oven at the temperature of 80 ℃ for 3h, taking out the mixture, and stirring the mixture for 40min by using a stirrer to obtain the anti-slip agent 1.
Example 5
(1) Adding 100g of nano zinc oxide into 100g of butyrolactone, and grinding for 240min in a ball mill to obtain zinc oxide slurry;
(2) and (2) adding the zinc oxide slurry obtained in the step (1), 5000g of natural rosin and 100g of polybutadiene liquid rubber into 4000g of butyrolactone, placing the mixture into a 100 ℃ oven, standing the mixture for 1 hour, taking the mixture out, and stirring the mixture for 20 minutes by using a stirrer to obtain the anti-slip agent 2.
Example 6
(1) Adding 100g of nano zinc oxide into 80g of butyrolactone, and putting the butyrolactone into a ball mill for grinding for 260min to obtain zinc oxide slurry;
(2) and (2) adding the zinc oxide slurry obtained in the step (1), 5000g of natural rosin and 50g of polybutadiene liquid rubber into 4000g of butyrolactone, placing the mixture into a 100 ℃ oven, standing for 1h, taking out, and stirring for 30min by using a stirrer to obtain the anti-slip agent 3.
Preparation of hydroxyl-terminated liquid rubber modified polyester polyol
Example 7
6.0kg of ethylene glycol, 6.0kg of 1, 4-butanediol, 24.0kg of hydroxyl-terminated polybutadiene liquid rubber (molecular weight is 250, functionality is 1.9), 24.0kg of adipic acid and 2.4g of titanium catalyst are sequentially added into a reaction kettle, stirring is started, the temperature is kept constant for 2 hours when the temperature is raised to 140 ℃, the dehydration speed is stabilized (the temperature at the top of the tower is kept at 90 ℃ through a rectifying tower), the temperature is continuously raised to 170 ℃, a vacuum pump is started, and the vacuum degree is controlled to be gradually increased. Heating to 215 ℃ for ester exchange reaction, introducing nitrogen to carry away excessive polyol and small molecular alcohol, taking a sample every 2 hours after timing 5 hours from the beginning of vacuum pumping, performing central control analysis until the final acid value is about (0.1-0.6) mgKOH/g and the hydroxyl value is 112.0mgKOH/g, recovering to normal pressure, cooling to room temperature, discharging and storing to obtain the liquid rubber modified polyester polyol 1.
Example 8
13.8kg of ethylene glycol, 13.8kg of hydroxyl-terminated polybutyronitrile liquid rubber (molecular weight is 500, functionality is 2.4), 32.4kg of adipic acid and 5.6g of titanium catalyst are sequentially added into a reaction kettle, stirring is started, the temperature is kept constant for 2 hours when the temperature is raised to 160 ℃, the dehydration speed is stabilized (the temperature at the top of a rectifying tower is kept at 105 ℃ through a rectifying tower), the temperature is continuously raised to 190 ℃, a vacuum pump is started, and the vacuum degree is controlled to be gradually increased. Heating to 235 ℃ for ester exchange reaction, introducing nitrogen to take away excessive polyol and small molecular alcohol, taking a sample every 2 hours after timing for 5 hours from the beginning of vacuum pumping, performing central control analysis until the final acid value is (0.1-0.6) mgKOH/g and the hydroxyl value is 56.0mgKOH/g, recovering the normal pressure, cooling to room temperature, discharging and storing to obtain the liquid rubber modified polyester polyol 2.
Example 9
6.5kg of ethylene glycol, 13.0kg of 1, 4-butanediol, 6.5kg of hydroxyl-terminated polybutadiene liquid rubber (molecular weight is 500, functionality is 2.4), 34.0kg of adipic acid and 9.6g of titanium catalyst are sequentially added into a reaction kettle, stirring is started, the temperature is kept constant for 2 hours when the temperature is raised to 160 ℃, the dehydration speed is stabilized (the temperature at the top of the tower is kept at 105 ℃ through a rectifying tower), the temperature is continuously raised to 190 ℃, a vacuum pump is started, and the vacuum degree is controlled to be gradually increased. Heating to 230 ℃ for ester exchange reaction, introducing nitrogen to carry away excessive polyhydric alcohol and small molecular alcohol, taking a sample every 2 hours after timing 5 hours from the beginning of vacuum pumping, performing central control analysis until the final acid value is (0.1-0.6) mgKOH/g and the hydroxyl value is 28.0mgKOH/g, recovering to normal pressure, cooling to room temperature, discharging and storing to obtain the liquid rubber modified polyester polyol 3.
Example 10
6.0kg of polyether ester dihydric alcohol 1, 0.30kg of polyethylene glycol adipate dihydric alcohol (the number average molecular weight is 4000), 0.30kg of ethylene glycol and 0.20kg of butyrolactone are added into a reaction kettle with a temperature control and stirring device, the temperature is controlled to 45 ℃, after mixing for 3.5 hours, the temperature is reduced to 25 ℃, 0.14kg of triethylene diamine catalyst and 0.50kg of anti-slip agent 1 are added, the mixture is fully stirred for 3 hours, and the component A of the polyurethane stock solution is obtained after uniform mixing.
2.0kg of liquid rubber modified polyester polyol 1, 3.0kg of MDI and 0.1kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at the reaction temperature of 55 ℃ for 3h to obtain the component B of the polyurethane stock solution.
Mixing the component A of the polyurethane stock solution with the temperature of 48 ℃ and the component B of the polyurethane stock solution with the temperature of 43 ℃ in a two-component casting machine according to the mass ratio of 1.8: 1, injecting the mixture into a 45 ℃ mold for reaction for 7min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the anti-slip polyurethane elastomer.
Example 11
9.0kg of polyether ester dihydric alcohol 2, 1.0kg of polyethylene glycol adipate trihydric alcohol (the number average molecular weight is 3000), 1.0kg of ethylene glycol and 1.0kg of butyrolactone are added into a reaction kettle with a temperature control and stirring device, the temperature is controlled to be 55 ℃, after mixing is carried out for 2.5 hours, the temperature is reduced to 35 ℃, 0.020kg of water, 0.25kg of triethylene diamine catalyst and 1.5kg of anti-slip agent 2 are added, the mixture is fully stirred for 2 hours, and the component A of the polyurethane stock solution is obtained after uniform mixing.
6.0kg of liquid rubber modified polyester polyol 2, 7.0kg of MDI and 0.5kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at 65 ℃ for 2h to obtain the component B of the polyurethane stock solution.
Mixing the component A of the polyurethane stock solution with the temperature of 52 ℃ and the component B of the polyurethane stock solution with the temperature of 47 ℃ in a two-component casting machine according to the mass ratio of 1.2: 1, injecting the mixture into a 50 ℃ mold for reaction for 5min for molding, demolding, and curing in a 70 ℃ oven for 22h to obtain the anti-slip polyurethane elastomer.
Example 12
Adding 8.0kg of polyether ester dihydric alcohol 3, 0.80kg of polyethylene glycol adipate tetrahydric alcohol (with the number average molecular weight of 5000), 0.40kg of ethylene glycol and 0.60kg of butyrolactone into a reaction kettle with a temperature control and stirring device, mixing for 3 hours at the controlled temperature of 50 ℃, cooling to 30 ℃, adding 0.010kg of water, 0.20kg of triethylene diamine catalyst and 1.0kg of anti-slip agent 3, fully stirring for 2 hours, and uniformly mixing to obtain the component A of the polyurethane stock solution.
5.5kg of liquid rubber modified polyester polyol 3, 6.0kg of MDI and 0.3kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at the reaction temperature of 60 ℃ for 3h to obtain the component B of the polyurethane stock solution.
Mixing the polyurethane stock solution A component with the temperature of 50 ℃ and the polyurethane stock solution B component with the temperature of 45 ℃ in a two-component casting machine according to the mass ratio of 2.1: 1, injecting the mixture into a 50 ℃ mold for reaction for 5min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the anti-slip polyurethane elastomer.
Comparative example 1
6.0kg of polyether ester dihydric alcohol 1, 0.30kg of polyethylene glycol adipate dihydric alcohol (the number average molecular weight is 4000), 0.30kg of ethylene glycol and 0.20kg of butyrolactone are added into a reaction kettle with a temperature control and stirring device, the temperature is controlled to 45 ℃, after mixing for 3.5 hours, the temperature is reduced to 25 ℃, 0.14kg of triethylene diamine catalyst, 6.2g of zinc oxide and 0.25kg of natural rosin are added, fully stirred for 3 hours, and uniformly mixed, and the component A of the polyurethane stock solution is obtained.
2.0kg of liquid rubber modified polyester polyol 1, 5.0kg of MDI and 0.1kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at the reaction temperature of 55 ℃ for 3h to obtain the component B of the polyurethane stock solution.
Mixing the component A of the polyurethane stock solution with the temperature of 48 ℃ and the component B of the polyurethane stock solution with the temperature of 43 ℃ in a two-component casting machine according to the mass ratio of 2.3: 1, injecting the mixture into a 45 ℃ mold for reaction for 7min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the anti-slip polyurethane elastomer.
Comparative example 2
9.0kg of polytetrahydrofuran dihydric alcohol (with the number average molecular weight of 4000), 1.0kg of polyethylene glycol adipate trihydric alcohol (with the number average molecular weight of 3000), 1.0kg of ethylene glycol and 1.0kg of butyrolactone are added into a reaction kettle with a temperature control and stirring device, the temperature is controlled to 55 ℃, after mixing is carried out for 2.5 hours, the temperature is reduced to 35 ℃, 0.020kg of water, 0.25kg of triethylene diamine catalyst and 1.5kg of anti-slip agent 2 are added, and the mixture is fully stirred for 2 hours and uniformly mixed, so that the component A of the polyurethane stock solution is obtained.
4.0kg of liquid rubber modified polyester polyol 2, 7.0kg of MDI and 0.5kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at 65 ℃ for 2h to obtain the component B of the polyurethane stock solution.
Mixing the component A of the polyurethane stock solution with the temperature of 52 ℃ and the component B of the polyurethane stock solution with the temperature of 47 ℃ in a two-component casting machine according to the mass ratio of 1.1: 1, injecting the mixture into a 50 ℃ mold for reaction for 5min for molding, demolding, and curing in a 70 ℃ oven for 22h to obtain the anti-slip polyurethane elastomer.
Comparative example 3
9.0kg of polyethylene glycol adipate dihydric alcohol (with the number average molecular weight of 4000), 1.0kg of polyethylene glycol adipate trihydric alcohol (with the number average molecular weight of 3000), 1.0kg of ethylene glycol and 1.0kg of butyrolactone are added into a reaction kettle with a temperature control and stirring device, the temperature is controlled to 55 ℃, after mixing is carried out for 2.5 hours, the temperature is reduced to 35 ℃, 0.020kg of water, 0.25kg of triethylene diamine catalyst and 1.5kg of anti-slip agent are added, and the mixture is fully stirred for 2 hours and uniformly mixed, so that the component A of the polyurethane stock solution is obtained.
4.0kg of liquid rubber modified polyester polyol 2, 7.0kg of MDI and 0.5kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at 65 ℃ for 2h to obtain the component B of the polyurethane stock solution.
Mixing the component A of the polyurethane stock solution with the temperature of 52 ℃ and the component B of the polyurethane stock solution with the temperature of 47 ℃ in a two-component casting machine according to the mass ratio of 1.1: 1, injecting the mixture into a 50 ℃ mold for reaction for 5min for molding, demolding, and curing in a 70 ℃ oven for 22h to obtain the anti-slip polyurethane elastomer.
Comparative example 4
Adding 8.0kg of polyether ester dihydric alcohol 3, 0.80kg of polyethylene glycol adipate tetrahydric alcohol (with the number average molecular weight of 5000), 0.60kg of ethylene glycol and 0.60kg of butyrolactone into a reaction kettle with a temperature control and stirring device, mixing for 3 hours at the controlled temperature of 50 ℃, cooling to 30 ℃, adding 0.010kg of water, 0.20kg of triethylene diamine catalyst and 1.0kg of anti-slip agent 3, fully stirring for 2 hours, and uniformly mixing to obtain the component A of the polyurethane stock solution.
3.0kg of hydroxyl-terminated polybutadiene liquid rubber (with the number average molecular weight of 4000), 6.0kg of MDI and 0.3kg of carbodiimide modified MDI are added into a reaction kettle with a temperature control and stirring device for mixing reaction at the reaction temperature of 60 ℃ for 3 hours to obtain the component B of the polyurethane stock solution.
Mixing the component A of the polyurethane stock solution with the temperature of 50 ℃ and the component B of the polyurethane stock solution with the temperature of 45 ℃ in a two-component casting machine according to the mass ratio of 1.2: 1, injecting the mixture into a 50 ℃ mold for reaction for 5min for molding, demolding, and curing in a 60 ℃ oven for 24h to obtain the anti-slip polyurethane elastomer.
The results of the physical property tests of the polyurethane elastomers obtained in application examples 10 to 12 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
The density test method refers to GB/T1033, the hardness test method refers to ASTM D2240, the resilience test method refers to GB/T1681, the hydrolysis resistance test method refers to SATRATM344, the folding resistance test method refers to ASTM D1790, the DIN abrasion resistance test method refers to GB/T9867, and the slip resistance test method refers to ISO 13287.
In summary, although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the above embodiments, and equivalent changes or modifications made within the scope of the claims of the present invention should be considered to be the technical scope of the present invention without departing from the spirit and the scope of the present invention.
Claims (12)
1. The anti-slip polyurethane elastomer stock solution is characterized by comprising a polyurethane stock solution A component and a polyurethane stock solution B component;
the polyurethane stock solution A component consists of the following raw materials in parts by weight:
the polyether ester dihydric alcohol is an esterification and polycondensation reaction product of polytetrahydrofuran ether dihydric alcohol with the number average molecular weight of 100-800, micromolecular dihydric alcohol and adipic acid;
the anti-slip agent contains rosin, liquid rubber, zinc oxide and a plasticizer;
the anti-slip agent comprises the following raw materials in parts by weight:
the rosin is one or two of natural rosin and rosin resin;
the oxidant is nano zinc oxide, and the particle size is 1-100 nm;
the plasticizer is one or more of butyrolactone, acylated tributyl citrate, mixed dibasic acid dimethyl ester, propylene carbonate and diisooctyl adipate;
the polyurethane stock solution B comprises the following raw materials in parts by weight:
20-60 parts of hydroxyl-terminated liquid rubber modified polyester polyol;
50-75 parts of diisocyanate;
the hydroxyl-terminated liquid rubber modified polyester polyol is an esterification and polycondensation reaction product of hydroxyl-terminated liquid rubber, micromolecular dihydric alcohol and adipic acid;
the hydroxyl-terminated liquid rubber is one or more of hydroxyl-terminated poly-acrylonitrile-butadiene liquid rubber, hydroxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated polychloroprene liquid rubber, hydroxyl-terminated butylbenzene liquid rubber, hydroxyl-terminated polyisoprene liquid rubber, carboxyl-terminated poly-acrylonitrile-butadiene liquid rubber, carboxyl-terminated polybutadiene liquid rubber and carboxyl-terminated polyisoprene liquid rubber, the functionality is 1.9-2.4, and the number average molecular weight is 250-500;
the micromolecular dihydric alcohol is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and neopentyl glycol;
the mass ratio of the hydroxyl-terminated liquid rubber to the micromolecular dihydric alcohol is 2: 1-1: 3;
the molar ratio of hydroxyl in the hydroxyl-terminated liquid rubber and the micromolecular dihydric alcohol to carboxyl in the adipic acid is 1.2-1.6: 1;
the NCO content of the polyurethane stock solution B component is 15-18 wt%.
2. The slip-resistant polyurethane elastomer stock solution as claimed in claim 1, wherein the polyether ester diol has a number average molecular weight of 3000 to 6000.
3. The slip-resistant polyurethane elastomer stock solution as claimed in claim 2, wherein the polyether ester diol comprises the following raw materials in parts by weight,
20-40 parts of polytetrahydrofuran ether dihydric alcohol;
10-30 parts of micromolecular dihydric alcohol;
40-85 parts of adipic acid;
the molar ratio of hydroxyl in the polytetrahydrofuran ether dihydric alcohol and the micromolecular dihydric alcohol to carboxyl in the adipic acid is 1.2-1.3: 1;
the micromolecular dihydric alcohol is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and neopentyl glycol.
4. The non-slip polyurethane elastomer stock solution as claimed in claim 2 or 3, wherein the preparation method of the polyether ester diol comprises the steps of sequentially adding polytetrahydrofuran ether diol, small molecular diol and adipic acid into a reaction kettle, opening stirring, starting heating, keeping the temperature constant for 1-2 hours when the temperature is 120-150 ℃, stabilizing the dehydration speed through a distillation tower, keeping the temperature at the top of the distillation tower at 90-100 ℃, continuing heating, introducing nitrogen from the lower part when the temperature is 160-190 ℃, gradually increasing the nitrogen amount for dehydration, heating to 210-240 ℃, keeping the temperature constant for 1-2 hours, adding 40-160ppm of tetraisopropyl titanate or n-butyl titanate catalyst, starting vacuum pumping, performing ester exchange, taking samples every 2 hours from 4-6 hours after vacuum pumping, performing center control analysis until the acid value is less than or equal to 0.5 and the hydroxyl value is 18-36 mgKOH/g, recovering the normal pressure, and (4) switching the upper part of the nitrogen to be introduced, starting cooling, starting sampling when the temperature is reduced to 100-120 ℃, performing final analysis and discharging, and storing.
5. The slip-resistant polyurethane elastomer stock solution as claimed in claim 1, wherein the polyester polyol is a polyester adipate, has a functionality of 2 to 4 and a number average molecular weight of 1000 to 5000;
the chain extender is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 6-hexanediol and cyclohexanedimethanol.
6. The slip-resistant polyurethane elastomer stock solution of claim 1, wherein the slip agent is prepared by a method comprising the steps of:
(1) adding 1-10 parts of zinc oxide into 5-10 parts of plasticizer, and grinding in a ball mill for 240-300 min to obtain zinc oxide slurry;
(2) adding the zinc oxide slurry obtained in the step (1), 40-50 parts of rosin and 0-10 parts of liquid rubber into 35-40 parts of plasticizer, placing the mixture into an oven at 80-100 ℃ for 1-3 h, taking out, and stirring for 20-40 min by using a stirrer to obtain the anti-slip agent.
7. The slip-resistant polyurethane elastomer stock solution of claim 1, wherein the catalyst is a tertiary amine-based catalyst or an organotin-based catalyst;
the diisocyanate is one or more of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and naphthalene diisocyanate.
8. The non-slip polyurethane elastomer stock solution as claimed in claim 1, wherein the liquid rubber-modified polyester polyol has a hydroxyl value of 28.0 to 112.0mgKOH/g and an acid value of 0.1 to 0.6 mgKOH/g.
9. The non-slip polyurethane elastomer stock solution as claimed in claim 8, wherein the preparation method of the liquid rubber modified polyester polyol comprises the steps of sequentially adding micromolecule dihydric alcohol, hydroxyl-terminated liquid rubber, adipic acid and 40-160ppm of tetraisopropyl titanate or n-butyl titanate catalyst into a reaction kettle, opening and stirring, keeping the temperature constant for 1-2 hours when the temperature is raised to 140-160 ℃, stabilizing the dehydration speed through a rectifying tower, keeping the temperature at the top of the tower at 90-105 ℃, raising the temperature to 170-190 ℃, opening a vacuum pump, controlling the vacuum degree to be gradually increased, raising the temperature to 215-235 ℃ to perform ester exchange reaction, introducing nitrogen to take away surplus polyalcohol and micromolecule alcohol, taking a sample every 2 hours after the vacuum pumping is started for 5 hours, carrying out central control analysis to the final acid value and hydroxyl value, recovering the normal pressure, reducing the sample to the room temperature, discharging and storing the sample.
10. The preparation method of the anti-slip polyurethane elastomer stock solution according to any one of claims 1 to 9, wherein the preparation method of the component A of the anti-slip polyurethane elastomer stock solution comprises the steps of adding polyether ester diol, polyester polyol, a chain extender and a plasticizer into a reaction kettle with a temperature control and stirring device, mixing for 2.5-3.5 hours at a controlled temperature of 45-55 ℃, cooling to 25-35 ℃, adding water, a catalyst and an anti-slip agent, fully stirring for 2-3 hours, uniformly mixing, discharging, sealing and storing;
the preparation method of the anti-slip polyurethane elastomer stock solution B component comprises the steps of adding liquid rubber modified polyester polyol and diisocyanate into a reaction kettle with a temperature control and stirring device for mixing reaction at 55-65 ℃ for 2-3 h, cooling, discharging, and sealing for storage.
11. Use of the slip-resistant polyurethane elastomer stock solution according to any one of claims 1 to 9 for preparing a slip-resistant polyurethane elastomer.
12. The application of the slip-resistant polyurethane elastomer stock solution as claimed in claim 11, wherein the application method comprises the following steps of mixing a polyurethane stock solution A component with the temperature of 48-52 ℃ and a polyurethane stock solution B component with the temperature of 43-47 ℃ in a two-component casting machine, injecting the mixture into a mold with the temperature of 45-50 ℃ to react for 5-7 min for forming after the mole ratio of active hydrogen of the A component to isocyanate group of the B component is 1: 1, demolding, and curing in an oven with the temperature of 60-70 ℃ for 22-24 h to obtain the slip-resistant polyurethane elastomer.
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| US6359100B1 (en) * | 1998-01-28 | 2002-03-19 | Bristol-Myers Squibb Company | Methods of preparing polyurethane adhesives, adhesives produced thereby and medical devices employing the same |
| CN1100840C (en) * | 1999-12-24 | 2003-02-05 | 中国科学院感光化学研究所 | Spray anti-slip agent and its preparing method |
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