CN109468114B - High-performance polyurethane adhesive - Google Patents
High-performance polyurethane adhesive Download PDFInfo
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- CN109468114B CN109468114B CN201811522313.8A CN201811522313A CN109468114B CN 109468114 B CN109468114 B CN 109468114B CN 201811522313 A CN201811522313 A CN 201811522313A CN 109468114 B CN109468114 B CN 109468114B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention provides a high-performance polyurethane adhesive, which comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1 to obtain the high-performance polyurethane adhesive. Compared with the traditional high-performance polyurethane adhesive, the high-performance polyurethane adhesive has wide application range, can be coated at high concentration (50%), is suitable for aluminized films, aluminum foils, water boiling and the like, has good appearance effect after use, has long service life of a rubber disc, and meets the requirements of energy conservation, environmental protection, upgrading and updating.
Description
Technical Field
The invention relates to the technical field of composite film flexible packaging, in particular to a high-performance polyurethane adhesive.
Background
The adhesive is suitable for bonding different materials, different thicknesses, different specifications and different components. The polyurethane adhesive has excellent low temperature resistance, water resistance, oil resistance and flexibility, and high bonding strength, and is widely applied to the industries of synthetic leather, composite films and the like. However, the existing polyurethane adhesive can not meet the adhesion of multiple materials at the same time, and can only be used pertinently, especially for flexible packaging materials, the existing polyurethane adhesive which can meet multiple flexible packaging materials at the same time does not exist, different components are required to be added for realizing the bonding effect aiming at different flexible packaging materials, so that the multiple switching sequence of the glue in the composite work is increased, a large amount of manpower is wasted, the labor production efficiency is reduced, meanwhile, because different adhesives are used, the cost is increased, the storage area is increased, and the convenience of composite production is reduced. Meanwhile, the problems of poor peel strength and the like easily occur in the use of the polyurethane adhesive, and the existing polyurethane adhesive also has the problem of pressure brought to environmental protection due to overhigh discharge of VOCs (volatile organic chemicals) caused by low gluing concentration.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-performance polyurethane adhesive, which solves the problems that the existing polyurethane adhesive can not simultaneously meet the adhesion of various materials, has poor peel strength in use and low gluing concentration, and causes large environmental protection pressure.
In order to achieve the purpose, the invention adopts the following technical scheme: the high-performance polyurethane adhesive comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1, and then obtaining the high-performance polyurethane adhesive;
the component A and the component B comprise the following raw materials in parts by weight:
the component A comprises:
12-19 parts of ethylene glycol, 18-25 parts of 1-4 butanediol, 32-40 parts of diethylene glycol, 31-41 parts of neopentyl glycol, 42-48 parts of isophthalic acid, 0.005-0.01 part of catalyst A, 60-80 parts of dibasic acid, 44-59 parts of adipic acid, 0.01-0.02 part of antioxidant, 5-10 parts of castor oil polyol, 60-70 parts of ethyl acetate, 10-15 parts of chain extender, 1.8-2.7 parts of carbodiimide and 1.8-2.7 parts of organosilicon coupling agent;
and B component:
48-52 parts of trimethylolpropane, 14-18 parts of trimethylpentane diol, 230 parts of a chain extender, 95-105 parts of ethyl acetate, 0.003-0.005 part of a catalyst B and 10-15 parts of a hexamethylene diisocyanate derivative.
Further, the dibasic acid is one or more of sebacic acid and azelaic acid.
Further, the hexamethylene diisocyanate derivative is one or more of HDI tripolymer and HDI biuret. The polyurethane adhesive produced by taking HDI tripolymer and HDI biuret as raw materials has the characteristics of no yellowing, strong weather resistance and the like.
Further, the chain extender is one or more of MDI-50, MDI-100, MDI-103C, MDI-100LL and TDI-80.
Further, the catalyst A is one or more of tetra-n-butyl titanate and zinc acetate, and the catalyst B is one or more of organic tin and organic bismuth.
Further, the antioxidant is triphenyl phosphite.
Further, the castor oil polyol is HF-1300 produced by Ivy Japan.
The invention also adopts the following technical scheme:
the production method of the high-performance polyurethane adhesive comprises the following steps:
s1: preparation of component A: adding ethylene glycol, 1-4 butanediol, diethylene glycol, neopentyl glycol, isophthalic acid, a catalyst A, dibasic acid, adipic acid, an antioxidant, castor oil polyol, ethyl acetate, a chain extender, carbodiimide and an organic silicon coupling agent into a reaction kettle according to the formula amount, and uniformly mixing to obtain a component A;
s2: preparation of the component B: adding trimethylolpropane, trimethylpentane diol, a chain extender, ethyl acetate, a catalyst B and a hexamethylene diisocyanate derivative into a reaction kettle according to the formula amount, and uniformly mixing to obtain a component B;
s3: mixing the component A and the component B according to the proportion of 5: 1 to obtain the high-performance polyurethane adhesive.
Further, the preparation of the A component in S1 comprises the following steps:
s11: mixing and uniformly stirring ethylene glycol, 1-4 butanediol, diethylene glycol, neopentyl glycol and isophthalic acid to form a mixture A, and then placing the mixture A into a reaction kettle;
s12: heating the mixture A in the S11 to 190 ℃ and stopping heating, and then adding a catalyst A for reaction to form a mixture B;
s13: when the mixture B in the S12 reacts to generate water to a theoretical amount, adding dibasic acid, and continuously heating to 150 ℃ for mixed esterification to form a mixture C;
s14: when the mixture C in the S13 reacts to generate water to a theoretical amount, adding adipic acid, continuously heating to 210 ℃, and then adding an antioxidant to form a mixture D;
s15: continuously heating the mixture D in the S14 to 235 ℃ for polycondensation reaction for 4 hours until the hydroxyl value of sampling analysis is 50-55mgKOH/g and the acid value is less than or equal to 2.0mgKOH/g, and cooling and discharging to obtain polyester polyol;
s16: adding castor oil polyol and ethyl acetate into the polyester polyol in the S15, uniformly stirring, and heating to 60 ℃ to form a mixture E;
s17: dropwise adding a chain extender into the mixture E in the S16, heating to 80 ℃, and continuously reacting for 2 hours to form a mixture F;
s18: sampling mixture F in test S17, cooling and adding ethyl acetate, carbodiimide and organosilicon coupling agent for stirring thoroughly for 30 minutes when the viscosity is 2500 +/-500 mPa & S (25 ℃), so as to form mixture G;
s19: the mixture G in S18 was further stirred and subjected to sampling test, and filtered when the viscosity was 200-500 mPa. multidot.S (25 ℃ C.) and the solid content was 50%. + -. 1, to obtain component A.
Further, the preparation of the B component in S2 comprises the following steps:
s21: mixing trimethylolpropane and trimethylpentane diol at 120 ℃ for 1.5 hours, and dehydrating to form a mixture H;
s22: mixing a chain extender and ethyl acetate, heating to 60 ℃, and dropwise adding the mixture H in S21 to form a mixture I;
s23: heating the mixture I in the S22 to 80 +/-2 ℃, and carrying out reflux heat preservation for 4 hours to form a mixture J;
s24: sampling and testing the mixture J in S24, and adding the catalyst B into the mixture J to react for 1 hour when NCO is 13 +/-0.8 to form a mixture K;
s25: after the mixture K was cooled to 60 ℃ and was then added with hexamethylene diisocyanate derivative and ethyl acetate to form a mixture L, and the mixture L was sampled while adding hexamethylene diisocyanate derivative and ethyl acetate and tested to obtain the B component when its NCO was 6.0-6.5% and the viscosity was 100-300 mPa. multidot.S (25 ℃ C.).
Compared with the prior art, the invention has the following beneficial effects:
the adhesive is suitable for adhering various materials: the high-performance polyurethane adhesive disclosed by the invention can be suitable for bonding of various materials, and can simultaneously meet the bonding of most flexible packaging materials on the market, so that repeated switching of glue in the compounding work of the traditional adhesive is not needed, the manpower resource is saved, the production efficiency is improved, the cost is reduced, an overlarge storage area is not needed, and the convenience of compounding production is greatly improved;
②, the performance is excellent: the high-performance polyurethane adhesive has extremely strong heat-seal strength and peel strength, can effectively reduce the broken bag rate, has tensile strength and elongation at break which are more than 2 times of those of the traditional adhesive, has less than 3mg of residual solvent, can enhance the barrier property of the product after compounding, and has oxygen and moisture resistance completely reaching the national standard;
thirdly, the energy-saving and emission-reducing performance is good: the high-performance polyurethane adhesive disclosed by the invention is in the beginning of dry compounding in China, high-concentration high-network-wire gluing is realized, the discharge of VOCs (volatile organic compounds) is reduced by 60% compared with that of the traditional glue, the curing temperature is low, the curing time is short, the power consumption is effectively reduced, and the working efficiency is improved;
fourthly, the composite cost is reduced by 10 to 20 percent: the high-performance polyurethane adhesive disclosed by the invention has excellent bonding force and can realize high-solid-content gluing, the gluing amount on a dry basis is 15-20% less than that of the traditional adhesive, 1-1.2 tons of diluting solvent can be used for each ton of glue, and the composite cost per square meter is comprehensively reduced by about 2 min;
fifthly, reducing enterprise tax: because the high-performance polyurethane adhesive realizes high-concentration gluing, the using amount of a solvent is greatly reduced, and the VOSs (volatile organic Compounds) emission cost (tax) of each dry compound machine is reduced by about 8 ten thousand yuan (1.2 yuan per equivalent);
sixthly, the production mode of the high-performance polyurethane adhesive disclosed by the invention is a complete combination of the components and the weight ratio of the high-performance polyurethane adhesive disclosed by the invention, the components and the weight ratio are related and restricted, and the effect of a final product can be influenced by the change of any component or weight ratio and the change of the production mode.
Compared with the traditional high-performance polyurethane adhesive, the high-performance polyurethane adhesive has the advantages that the application range is wide, the high-concentration (50%) coating can be realized, the high-performance polyurethane adhesive is suitable for aluminizing films, aluminum foils, water boiling and the like, the appearance effect is good after the high-performance polyurethane adhesive is used, the service life of an adhesive disc is long, and the requirements of energy conservation, environmental protection, upgrading and updating are met.
Detailed Description
The present invention is further described below.
Example one
The high-performance polyurethane adhesive comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1, and then obtaining the high-performance polyurethane adhesive;
the component A and the component B comprise the following raw materials in parts by weight:
the component A comprises:
12 parts of ethylene glycol, 18 parts of 1-4 butanediol, 32 parts of diethylene glycol, 31 parts of neopentyl glycol, 42 parts of isophthalic acid, 0.005 part of catalyst A, 60 parts of dibasic acid, 44 parts of adipic acid, 0.01 part of triphenyl phosphite, 13005 parts of castor oil polyol produced by Japan ita, 60 parts of ethyl acetate, 10 parts of a chain extender, 1.8 parts of carbodiimide and 1.8 parts of an organosilicon coupling agent;
and B component:
48 parts of trimethylolpropane, 14 parts of trimethylpentane diol, 230 parts of a chain extender, 95 parts of ethyl acetate, 0.003 part of a catalyst B and 10 parts of a hexamethylene diisocyanate derivative.
The dibasic acid is sebacic acid, the hexamethylene diisocyanate derivative is HDI trimer, the chain extender is MDI-50, the catalyst A is tetra-n-butyl titanate, the catalyst B is organic bismuth, and the organic silicon coupling agent is vinyl silane coupling agent.
Adding ethylene glycol, 1-4 butanediol, diethylene glycol, neopentyl glycol, isophthalic acid, tetra-n-butyl titanate, sebacic acid, adipic acid, triphenyl phosphite, HF-1300, ethyl acetate, MDI-50, carbodiimide and an organic silicon coupling agent into a reaction kettle according to the formula amount, and uniformly mixing to obtain a component A, wherein the step of preparing the component A specifically comprises the following steps:
s11: mixing and uniformly stirring 12 parts of ethylene glycol, 18 parts of 1-4 butanediol, 32 parts of diethylene glycol, 31 parts of neopentyl glycol and 42 parts of isophthalic acid to form a mixture A, and placing the mixture A into a reaction kettle;
s12: heating the mixture A in S11 to 190 ℃ and stopping heating, and then adding 0.005 part of tetra-n-butyl titanate for reaction to form a mixture B;
s13: when the mixture B in the S12 reacts to obtain water with the theoretical amount of 10.3 parts by weight, 60 parts of sebacic acid is added, and the temperature is continuously raised to 150 ℃ for mixed esterification to form a mixture C;
s14: when the mixture C in S13 reacts to yield water with a theoretical amount of 10.6 parts by weight, 44 parts of adipic acid is added, the temperature is continuously raised to 210 ℃, and then 0.01 part of triphenyl phosphite is added to form a mixture D;
s15: continuously heating the mixture D in the S14 to 235 ℃ for polycondensation reaction for 4 hours until the sampling analysis hydroxyl value is 50mgKOH/g and the acid value is 1.0mgKOH/g, and cooling and discharging to obtain polyester polyol;
s16: adding HF-13005 parts and 20 parts of ethyl acetate into the polyester polyol in the S15, uniformly stirring, and heating to 60 ℃ to form a mixture E;
s17: dropwise adding MDI-5010 parts of the mixture E in the S16, heating to 80 ℃, and continuously reacting for 2 hours to form a mixture F;
s18: the mixture F in test S17 was sampled, and when its viscosity was 2000 mPaS (25 ℃ C.), it was cooled and added with 40 parts of ethyl acetate, 1.8 parts of carbodiimide and 1.8 parts of a vinyl silane coupling agent and sufficiently stirred for 30 minutes to form a mixture G;
s19: the mixture G in S18 was further stirred and subjected to sampling test, and filtered when it had a viscosity of 200 mPaS (25 ℃ C.) and a solid content of 49% to obtain A fraction.
Adding trimethylolpropane, trimethylpentane diol, MDI-50, ethyl acetate, organic bismuth and HDI trimer into a reaction kettle according to the formula amount, and uniformly mixing to obtain a component B, wherein the step of preparing the component B specifically comprises the following steps:
s21: mixing 48 parts of trimethylolpropane and 14 parts of trimethylpentanediol in an environment of 120 ℃ for 1.5 hours for dehydration to form a mixture H, wherein the water content of the mixture H is 0.002%;
s22: mixing 230 parts of MDI-50 and 32 parts of ethyl acetate, heating to 60 ℃, and dropwise adding the mixture H in S21 to form a mixture I;
s23: heating the mixture I in the S22 to 78 ℃, and carrying out reflux heat preservation for 4 hours to form a mixture J;
s24: sampling mixture J in S24, and adding 0.003 part of organic bismuth to the mixture J for reaction for 1 hour when NCO is 12.2 to form mixture K;
s25: after cooling the mixture K to 60 ℃, 10 parts of HDI trimer and 63 parts of ethyl acetate were added to form a mixture L, and the mixture L was sampled and tested while adding HDI trimer and ethyl acetate to obtain a component B when the NCO content was 6.0% and the viscosity was 100mPa · S (25 ℃).
The A component and the B component are mixed according to the proportion of 5: 1 to obtain the high-performance polyurethane adhesive.
Example two
The high-performance polyurethane adhesive comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1, and then obtaining the high-performance polyurethane adhesive;
the component A and the component B comprise the following raw materials in parts by weight:
the component A comprises:
19 parts of ethylene glycol, 25 parts of 1-4 butanediol, 40 parts of diethylene glycol, 41 parts of neopentyl glycol, 48 parts of isophthalic acid, 0.01 part of a catalyst A, 80 parts of dibasic acid, 59 parts of adipic acid, 0.02 part of triphenyl phosphite, 0.3532 parts of castor oil polyol HF-130010 parts produced by Japan ita, 70 parts of ethyl acetate, 15 parts of a chain extender, 2.7 parts of carbodiimide and 2.7 parts of an organosilicon coupling agent;
and B component:
52 parts of trimethylolpropane, 18 parts of trimethylpentane diol, 230 parts of a chain extender, 105 parts of ethyl acetate, 0.005 part of a catalyst B and 15 parts of a hexamethylene diisocyanate derivative.
The binary acid is azelaic acid, the hexamethylene diisocyanate derivative is HDI biuret, the chain extender is MDI-100, the catalyst A is zinc acetate, the catalyst B is organic tin, and the organic silicon coupling agent is a vinyl silane coupling agent.
Adding ethylene glycol, 1-4 butanediol, diethylene glycol, neopentyl glycol, isophthalic acid, tetra-n-butyl titanate, azelaic acid, adipic acid, triphenyl phosphite, HF-1300, ethyl acetate, MDI-100, carbodiimide and an organic silicon coupling agent into a reaction kettle according to the formula amount, and uniformly mixing to obtain a component A, wherein the preparation method of the component A specifically comprises the following steps:
s11: mixing 19 parts of ethylene glycol, 25 parts of 1-4-butanediol, 40 parts of diethylene glycol, 41 parts of neopentyl glycol and 48 parts of isophthalic acid, uniformly stirring to form a mixture A, and placing the mixture A into a reaction kettle;
s12: heating the mixture A in the S11 to 190 ℃ and stopping heating, and then adding 0.01 part of zinc acetate for reaction to form a mixture B;
s13: when the mixture B in the S12 reacts to obtain 11.8 parts of theoretical water by weight, adding 80 parts of azelaic acid and continuously heating to 150 ℃ for mixed esterification to form a mixture C;
s14: when the mixture C in S13 reacts to yield water with theoretical amount of 14.2 parts by weight, 59 parts of adipic acid is added, the temperature is continuously raised to 210 ℃, and then 0.02 part of triphenyl phosphite is added to form a mixture D;
s15: continuously heating the mixture D in the S14 to 235 ℃ for polycondensation reaction for 4 hours until the sampling analysis hydroxyl value is 55mgKOH/g and the acid value is 2.0mgKOH/g, and cooling and discharging to obtain polyester polyol;
s16: adding HF-130010 parts and ethyl acetate 20 parts into polyester polyol in S15, uniformly stirring, and heating to 60 ℃ to form a mixture E;
s17: dropwise adding MDI-10015 parts of the mixture E in the S16, heating to 80 ℃, and continuously reacting for 2 hours to form a mixture F;
s18: the mixture F in test S17 was sampled, and when its viscosity was 3000 mPaS (25 ℃ C.), it was cooled and added with 50 parts of ethyl acetate, 2.7 parts of carbodiimide and 2.7 parts of vinyl silane coupling agent and sufficiently stirred for 30 minutes to form a mixture G;
s19: the mixture G in S18 was further stirred and subjected to sampling test, and filtered when its viscosity was 500 mPaS (25 ℃ C.) and solid content was 51% to obtain A component.
According to the formula, trimethylolpropane, trimethylpentane diol, MDI-100, ethyl acetate, organic tin and HDI biuret are added into a reaction kettle and uniformly mixed to prepare a component B, and specifically, the step of preparing the component B is as follows:
s21: mixing 52 parts of trimethylolpropane and 18 parts of trimethylpentane diol at 120 ℃ for 1.5 hours for dehydration to form a mixture H with the water content of 0.05%;
s22: mixing 230 parts of MDI-100 and 35 parts of ethyl acetate, heating to 60 ℃, and dropwise adding the mixture H in S21 to form a mixture I;
s23: heating the mixture I in the S22 to 82 ℃, and carrying out reflux heat preservation for 4 hours to form a mixture J;
s24: sampling and testing the mixture J in S24, and adding 0.005 part of organic tin to the mixture J for reaction for 1 hour when NCO is 13.8 to form a mixture K;
s25: after the mixture K was cooled to 60 ℃, 15 parts of HDI biuret and 70 parts of ethyl acetate were added to form a mixture L, and the mixture L was sampled while HDI biuret and ethyl acetate were added and tested to obtain a B component when the NCO thereof was 6.5% and the viscosity was 300 mPa. multidot.S (25 ℃).
The A component and the B component are mixed according to the proportion of 5: 1 to obtain the high-performance polyurethane adhesive.
EXAMPLE III
The high-performance polyurethane adhesive comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1, and then obtaining the high-performance polyurethane adhesive;
the component A and the component B comprise the following raw materials in parts by weight:
the component A comprises:
15 parts of ethylene glycol, 22 parts of 1-4 butanediol, 37 parts of diethylene glycol, 36 parts of neopentyl glycol, 44 parts of isophthalic acid, 0.007 part of catalyst A, 70 parts of dibasic acid, 51 parts of adipic acid, 0.015 part of triphenyl phosphite, 13007 parts of castor oil polyol produced by Ivy Japan, 65 parts of ethyl acetate, 13 parts of a chain extender, 2.3 parts of carbodiimide and 2.3 parts of an organosilicon coupling agent;
and B component:
50 parts of trimethylolpropane, 16 parts of trimethylpentane diol, 230 parts of a chain extender, 100 parts of ethyl acetate, 0.004 part of a catalyst B and 13 parts of hexamethylene diisocyanate derivatives.
The dibasic acid comprises sebacic acid and azelaic acid, and specifically comprises 30 parts of sebacic acid and 40 parts of azelaic acid; the hexamethylene diisocyanate derivative comprises an HDI trimer and an HDI biuret, and specifically comprises 6 parts of the HDI trimer and 7 parts of the HDI biuret; the chain extender is MDI-103C, and the catalyst A comprises tetrabutyl titanate and zinc acetate, specifically comprises 0.003 part of tetrabutyl titanate and 0.004 part of zinc acetate; the catalyst B comprises organic tin and organic bismuth, and specifically comprises 0.002 part of organic tin and 0.002 part of organic bismuth; the organic silicon coupling agent is a vinyl silane coupling agent.
Adding ethylene glycol, 1-4 butanediol, diethylene glycol, neopentyl glycol, isophthalic acid, a catalyst A, dibasic acid, adipic acid, an antioxidant, castor oil polyol, ethyl acetate, a chain extender, carbodiimide and an organic silicon coupling agent into a reaction kettle according to the formula amount, and uniformly mixing to obtain a component A, wherein the preparation method of the component A specifically comprises the following steps:
s11: mixing 15 parts of ethylene glycol, 22 parts of 1-4 butanediol, 37 parts of diethylene glycol, 36 parts of neopentyl glycol and 44 parts of isophthalic acid, uniformly stirring to form a mixture A, and placing the mixture A into a reaction kettle;
s12: heating the mixture A in the S11 to 190 ℃ and stopping heating, and then adding 0.003 part of tetrabutyl titanate and 0.004 part of zinc acetate for reaction to form a mixture B;
s13: when the mixture B in the S12 reacts to generate water with the theoretical amount of 11.0 parts by weight, adding 30 parts of sebacic acid and 40 parts of azelaic acid, continuously heating to 150 ℃ for mixed esterification to form a mixture C;
s14: when the mixture C in S13 reacts with water to a theoretical amount of 12.4 parts by weight, adding adipic acid and continuously heating to 210 ℃, and then adding 0.015 part of triphenyl phosphite to form a mixture D;
s15: continuously heating the mixture D in the S14 to 235 ℃ for polycondensation reaction for 4 hours until the sampling analysis hydroxyl value is 53mgKOH/g and the acid value is 1.5mgKOH/g, and cooling and discharging to obtain polyester polyol;
s16: adding HF-13007 parts and 20 parts of ethyl acetate into polyester polyol in S15, uniformly stirring, and heating to 60 ℃ to form a mixture E;
s17: dropwise adding 13 parts of MDI-103C into the mixture E in the S16, heating to 80 ℃, and continuously reacting for 2 hours to form a mixture F;
s18: the mixture F in test S17 was sampled, and when its viscosity was 2500 mPaS (25 ℃ C.), it was cooled and added with 45 parts of ethyl acetate, 2.3 parts of carbodiimide and 2.3 parts of a vinyl silane coupling agent and sufficiently stirred for 30 minutes to form a mixture G;
s19: the mixture G in S18 was further stirred and subjected to sampling test, and filtered when its viscosity was 350 mPaS (25 ℃ C.) and its solid content was 50% to obtain A component.
According to the formula, trimethylolpropane, trimethylpentane diol, MDI-103C, ethyl acetate, organic tin, organic bismuth, HDI tripolymer and HDI biuret are added into a reaction kettle and uniformly mixed to prepare a component B, and specifically, the step of preparing the component B is as follows:
s21: 50 parts of trimethylolpropane and 16 parts of trimethylpentane diol are mixed for 1.5 hours at 120 ℃ for dehydration to form a mixture H, and the water content of the mixture H is 0.02%;
s22: mixing 230 parts of MDI-103C and 33 parts of ethyl acetate, heating to 60 ℃, and dropwise adding the mixture H in S21 to form a mixture I;
s23: heating the mixture I in the S22 to 80 ℃, and carrying out reflux heat preservation for 4 hours to form a mixture J;
s24: sampling and testing the mixture J in S24, and adding 0.002 part of organic tin and 0.002 part of organic bismuth into the mixture J for reaction for 1 hour when NCO is 13 to form a mixture K;
s25: after cooling the mixture K to 60 ℃, 6 parts of HDI trimer, 7 parts of HDI biuret, and 67 parts of ethyl acetate were added to form a mixture L, and the mixture L was sampled while adding hexamethylene diisocyanate derivative and ethyl acetate to test, and when the NCO was 6.3% and the viscosity was 200mPa · S (25 ℃), the component B was obtained.
Example four
This example is the same as the protocol of example one except that the chain extender is replaced with MDI-100 LL.
EXAMPLE five
This example is the same as the protocol of example two, except that the chain extender is replaced with TDI-80.
EXAMPLE six
This example is the same as the third example except that the chain extender was replaced with a composition comprising MDI-50, MDI-100LL, and TDI-80, wherein 5 parts by weight of MDI-50, 5 parts by weight of MDI-100LL, and 3 parts by weight of TDI-80 were required in the formulation of the A component, and 100 parts by weight of MDI-50, 100 parts by weight of MDI-100LL, and 30 parts by weight of TDI-80 were required in the formulation of the B component.
EXAMPLE seven
The high-performance polyurethane adhesive comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1, and then obtaining the high-performance polyurethane adhesive;
the component A and the component B comprise the following raw materials in parts by weight:
the component A comprises:
14 parts of ethylene glycol, 23 parts of 1-4 butanediol, 38 parts of diethylene glycol, 33 parts of neopentyl glycol, 45 parts of isophthalic acid, 0.008 parts of catalyst A, 77 parts of dibasic acid, 48 parts of adipic acid, 0.013 part of triphenyl phosphite, 13008 parts of castor oil polyol produced by Ivy Japan, 66 parts of ethyl acetate, 12 parts of a chain extender, 2.1 parts of carbodiimide, 2.6 parts of an organosilicon coupling agent, 6 parts of silicon dioxide and 3 parts of dimethyl carbonate;
and B component:
52 parts of trimethylolpropane, 15 parts of trimethylpentane diol, 230 parts of a chain extender, 102 parts of ethyl acetate, 0.003 part of a catalyst B and 12 parts of a hexamethylene diisocyanate derivative.
The dibasic acid is sebacic acid; the hexamethylene diisocyanate derivative is HDI trimer; the chain extender is TDI-80, and the catalyst A is tetrabutyl titanate; the catalyst B is organic tin; the organic silicon coupling agent is a vinyl silane coupling agent.
The preparation steps of the component A are as follows:
s11: mixing 14 parts of ethylene glycol, 23 parts of 1-4 butanediol, 38 parts of diethylene glycol, 33 parts of neopentyl glycol, 45 parts of isophthalic acid and 3 parts of dimethyl carbonate, uniformly stirring to form a mixture A, and then placing the mixture A into a reaction kettle;
s12: heating the mixture A in the S11 to 190 ℃ and stopping heating, and then adding 0.008 part of tetra-n-butyl titanate for reaction to form a mixture B;
s13: when the mixture B in the S12 reacts to generate water with the theoretical amount of 11.0 parts by weight, 77 parts of sebacic acid is added, and the temperature is continuously raised to 150 ℃ for mixed esterification to form a mixture C;
s14: adding 6 parts of silicon dioxide into the mixture C, dispersing for 5min at 500r/min by using a dispersing machine, adding 0.04 part of TDI, reacting for 1h to obtain a mixture X, heating the mixture X to 50 ℃, adding dibutyltin dilaurate, reacting for 1h to obtain a mixture Y, adding 48 parts of adipic acid, continuously heating to 210 ℃, and then adding 0.013 part of triphenyl phosphite to form a mixture D;
s15: continuously heating the mixture D in the S14 to 235 ℃ for polycondensation reaction for 4 hours until the sampling analysis hydroxyl value is 53mgKOH/g and the acid value is 1.5mgKOH/g, and cooling and discharging to obtain polyester polyol;
s16: adding HF-13008 parts and 20 parts of ethyl acetate into the polyester polyol in the S15, uniformly stirring, and heating to 60 ℃ to form a mixture E;
s17: dropwise adding TDI-8012 parts of the mixture E in S16, heating to 80 ℃, and continuously reacting for 2 hours to form a mixture F;
s18: the mixture F in test S17 was sampled, and when the viscosity thereof was 2500 mPaS (25 ℃ C.), the temperature was lowered and 46 parts of ethyl acetate, 2.1 parts of carbodiimide and 2.6 parts of a vinyl silane coupling agent were added thereto and sufficiently stirred for 30 minutes to form a mixture G;
s19: the mixture G in S18 was further stirred and subjected to sampling test, and filtered when its viscosity was 350 mPaS (25 ℃ C.) and its solid content was 50% to obtain A component.
The preparation method of the component B comprises the following steps:
s21: mixing 52 parts of trimethylolpropane and 15 parts of trimethylpentane diol at 120 ℃ for 1.5 hours for dehydration to form a mixture H with the water content of 0.02%;
s22: mixing TDI-80230 parts and 32 parts of ethyl acetate, heating to 60 ℃, and dropwise adding the mixture H in S21 to form a mixture I;
s23: heating the mixture I in the S22 to 80 ℃, and carrying out reflux heat preservation for 4 hours to form a mixture J;
s24: sampling and testing the mixture J in S24, and adding 0.003 part of organic tin to the mixture J for reaction for 1 hour when NCO is 13 to form a mixture K;
s25: after the mixture K was cooled to 60 ℃ and 12 parts of HDI trimer and 70 parts of ethyl acetate were added to form a mixture L, and the mixture L was sampled while adding the hexamethylene diisocyanate derivative and ethyl acetate to test it, to obtain a B component when its NCO was 6.3% and viscosity was 200 mPaS (25 ℃).
The high-performance polyurethane adhesives obtained in the first to seventh examples are used for bonding PET12/VMPET12/CPE40, and the data of the bonded finished products are subjected to performance tests, and the results are shown in the following table:
it can be seen that the data of the finished products after the first to seventh embodiments are bonded have extremely strong heat seal strength and peel strength, the bag breaking rate can be effectively reduced, and the tensile strength and the elongation at break are more than 2 times of those of the conventional glue, the finished products after the high-performance polyurethane adhesive obtained in the seventh embodiment are bonded all meet the requirements of QB/T2358 on the heat seal strength and GB13022 on the tensile strength and the elongation at break, the heat seal strength reaches more than 3 times of that of QB/T2358, and the tensile strength and the elongation at break also reach more than 2-3 times of that of GB 13022. Particularly, the polyurethane adhesive prepared in the seventh embodiment has no free isocyanate in the adhesive solution, is more environment-friendly, can improve the hardness and tensile strength of the adhesive film of the polyurethane adhesive again, and can also obviously reduce the water absorption of the adhesive film.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (1)
1. The high-performance polyurethane adhesive comprises a component A and a component B, wherein the component A and the component B are mixed according to the proportion of 5: 1, and then obtaining the high-performance polyurethane adhesive;
the preparation method comprises the following steps of:
s11: mixing 14 parts of ethylene glycol, 23 parts of 1, 4-butanediol, 38 parts of diethylene glycol, 33 parts of neopentyl glycol, 45 parts of isophthalic acid and 3 parts of dimethyl carbonate, uniformly stirring to form a mixture A, and putting the mixture A into a reaction kettle;
s12: heating the mixture A in the S11 to 190 ℃ and stopping heating, and then adding 0.008 part of tetra-n-butyl titanate for reaction to form a mixture B;
s13: when the mixture B in the S12 reacts to generate water with the theoretical amount of 11.0 parts by weight, 77 parts of sebacic acid is added, and the temperature is continuously raised to 150 ℃ for mixed esterification to form a mixture C;
s14: adding 6 parts of silicon dioxide into the mixture C, dispersing for 5min at 500r/min by using a dispersing machine, adding 0.04 part of TDI, reacting for 1h to obtain a mixture X, heating the mixture X to 50 ℃, adding dibutyltin dilaurate, reacting for 1h to obtain a mixture Y, adding 48 parts of adipic acid, continuously heating to 210 ℃, and then adding 0.013 part of triphenyl phosphite to form a mixture D;
s15: continuously heating the mixture D in the S14 to 235 ℃ for polycondensation reaction for 4 hours until the sampling analysis hydroxyl value is 53mgKOH/g and the acid value is 1.5mgKOH/g, and cooling and discharging to obtain polyester polyol;
s16: adding castor oil polyol HF-13008 parts and ethyl acetate 20 parts into the polyester polyol in S15, uniformly stirring, and heating to 60 ℃ to form a mixture E;
s17: dropwise adding chain extender TDI-8012 parts of the mixture E in S16, heating to 80 ℃, and continuously reacting for 2 hours to form a mixture F;
s18: sampling the mixture F in the test S17, cooling and adding 46 parts of ethyl acetate, 2.1 parts of carbodiimide and 2.6 parts of vinyl silane coupling agent for fully stirring for 30 minutes when the viscosity of the mixture F is 2500mPa & S at 25 ℃ to form a mixture G;
s19: continuing to stir the mixture G in the S18, sampling and testing the mixture G, and filtering the mixture G when the viscosity of the mixture G is 350mPa & S at 25 ℃ and the solid content of the mixture G is 50% to obtain a component A;
the preparation method comprises the following steps of:
s21: mixing 52 parts of trimethylolpropane and 15 parts of trimethylpentane diol at 120 ℃ for 1.5 hours for dehydration to form a mixture H with the water content of 0.02%;
s22: mixing and heating chain extender TDI-80230 parts and 32 parts of ethyl acetate to 60 ℃, and dropwise adding the mixture H in S21 to form a mixture I;
s23: heating the mixture I in the S22 to 80 ℃, and carrying out reflux heat preservation for 4 hours to form a mixture J;
s24: sampling and testing the mixture J in S24, and adding 0.003 part of organic tin to the mixture J for reaction for 1 hour when the NCO is 13 percent to form a mixture K;
s25: after cooling the mixture K to 60 ℃, 12 parts of HDI trimer and 70 parts of ethyl acetate were added to form a mixture L, and the mixture L was sampled and tested while adding the hexamethylene diisocyanate derivative and ethyl acetate to obtain a B component when the NCO content was 6.3% and the viscosity was 200 mPas at 25 ℃.
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| CN111171775B (en) * | 2020-02-20 | 2021-09-03 | 南京玄思新材料有限公司 | Preparation method of low-VOC polyurethane adhesive for flexible package |
| CN111621258A (en) * | 2020-06-05 | 2020-09-04 | 美邦（黄山）胶业有限公司 | Low-friction-coefficient bi-component solvent-free polyurethane adhesive |
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| CA2706455A1 (en) * | 2007-12-03 | 2009-06-11 | Mitsui Chemicals, Inc. | Laminating adhesive |
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