CN107459960B - Bi-component polyurethane adhesive and preparation and application thereof - Google Patents
Bi-component polyurethane adhesive and preparation and application thereof Download PDFInfo
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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
- C09J175/06—Polyurethanes from polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
- B65G15/30—Belts or like endless load-carriers
- B65G15/32—Belts or like endless load-carriers made of rubber or plastics
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a bi-component polyurethane adhesive and preparation and application thereof, the adhesive is formed by mixing a component A and a component B, the component A is an isocyanate-terminated polyurethane prepolymer, the component B is a catalytic component containing a hydroxyl-terminated chain extender, and the component A and the component B are mixed according to the mol ratio of NCO to OH of 0.85-2.5 to 1 of functional groups; the polyurethane adhesive is used for preparing industrial belts. Compared with the prior art, the bi-component polyurethane adhesive is applied to interlayer adhesion of industrial belts, has the advantages of high curing speed, low viscosity, high peel strength, good low temperature resistance, water resistance and heat resistance, and can effectively solve the technical problem that the edge warping is easily caused when the industrial belts are attached at high temperature.
Description
Technical Field
The invention belongs to the technical field of industrial belt material processing, and relates to a bi-component polyurethane adhesive, and preparation and application thereof.
Background
The industrial belt is divided into a conveyor belt and a conveyor belt, so that convenience is provided for material transportation of various industries, and along with the fine development of various industries, the demand on the industrial belt is more and more great. The industrial belt is mainly formed by compositely bonding covering glue and base cloth (framework material), and can be bonded by one layer or multiple layers of adhesive according to different purposes, the interlayer bonding force can directly influence the peeling strength of the material, and the use performance of the industrial belt is determined, namely, if the bonding force is too low, the abrasion resistance of the product is seriously reduced, and the interlayer separation is easy.
At present, the interlayer bonding of the industrial belt is mainly a solvent type adhesive, for example, the solvent type bi-component Polyurethane (PU) adhesive used at present, the solvent proportion is up to 70%, which causes environmental pollution and potential safety hazard, and the solvent type adhesive needs to be baked at high temperature after being coated to remove the solvent and then be attached, which not only causes energy waste, but also causes the base cloth to expand with heat and contract with cold after being baked at high temperature, so that the produced industrial belt is easy to have raised edges and the quality is affected. In addition, in the production process of the industrial belt, the initial peel strength of about 1N/mm needs to be achieved within 1-5 minutes after coating and attaching so as to prevent glue failure and dislocation during rolling. Therefore, the solvent-free adhesive is developed and can be subjected to interlayer bonding at low temperature, so that higher initial and final peel strength is obtained, and good economic and social benefits are achieved.
The invention discloses a 201010249896.9 Chinese patent application number 201010249896.9 a normal temperature curable two-component adhesive and a synthesis method thereof, wherein the adhesive is prepared from 35-75 parts by weight of epoxy-terminated polyurethane prepolymer, 5-15 parts by weight of epoxy-terminated hyperbranched polyurethane prepolymer and 10-60 parts by weight of polyurethane grafted epoxy resin, and the component B is selected from ethylenediamine, β -hydroxyethylenediamine, diethylenetriamine, triethylenetetramine, an addition product of diethylenetriamine and propylene oxide butyl ether, low molecular weight polyamide or low molecular weight terminal amino polyether, and the component A and the component B are uniformly mixed at room temperature to obtain the product.
It is well known that the bonding performance of PU adhesives is closely related to the molecular structure of polyols. The bi-component PU adhesive synthesized by polyester polyol with higher rigidity has higher heat resistance, bonding strength and oil resistance, but has poorer hydrolysis resistance and stability; polyether polyol has good ether group rotation property, and the synthesized PU adhesive has good flexibility, low temperature resistance and water resistance, but poor strength and aging resistance due to weak ether group rigidity.
The hyperbranched polyether not only has a highly branched structure and a large number of active end groups, and has low melt viscosity, but also retains the flexibility of the linear polyether polyol. Researches show that the hyperbranched polyether is added into the copolymerization reaction of hydroxyl-terminated polybutadiene and isophorone diisocyanate to obtain the modified polyurethane interpenetrating polymer network. Due to the approximately spherical structure and the intramolecular cavity in the hyperbranched polyether, part of energy is absorbed during single-phase stretching; and molecules contain a large number of ether bonds, and can form hydrogen bonds with amino groups of the urethane groups of the modified PU phase, so that the effect of strengthening and toughening is achieved. Therefore, the unique structure of the hyperbranched polyether can make up the defect of poor strength of the linear polyether. Supposing that if the hyperbranched polyether contains a large amount of rigid benzene rings, namely the hyperbranched polyphenylene oxide, the hyperbranched polyether can endow the hyperbranched polyether with better mechanical strength and heat resistance compared with the hyperbranched polyether, at present, the hyperbranched polyphenylene oxide is not reported to be used for the solvent-free two-component PU adhesive.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bi-component polyurethane adhesive which can be used for interlayer bonding at low temperature, has high curing speed after bonding, obtains higher initial and final peeling strength and can effectively solve the problem that the edge warping is easily caused when an industrial belt is bonded at high temperature, and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
the adhesive is formed by mixing a component A and a component B, wherein the component A is an isocyanate-terminated polyurethane prepolymer, the component B is a catalytic component containing a hydroxyl-terminated chain extender, and the component A and the component B are mixed according to the mol ratio of NCO to OH of 0.85-2.5 to 1 of functional groups.
The component A is prepared from the following raw materials in parts by weight: 15-90 parts of polyester polyol, 1-50 parts of hyperbranched polyphenylene oxide and 25-80 parts of isocyanate.
The polyester polyol comprises one or more of polycarbonate diol, adipic acid polyester polyol, polycaprolactone polyol or phthalic anhydride polyester polyol.
The relative molecular weight of the polyester polyol is 1000-6000.
As a preferable technical scheme, the hydroxyl value of the hyperbranched polyphenylene oxide is 20-250mg KOH/g.
The isocyanate comprises one or more of diphenyl methylene diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate or isophorone diisocyanate.
The component B comprises the following components in parts by weight: 1-10 parts of a hydroxyl-terminated chain extender, 0-10 parts of tackifying resin and 0.1-5 parts of a catalyst.
The hydroxyl-terminated chain extender comprises one or more of 1, 6-hexanediol, 1, 5-pentanediol, neopentyl glycol, 1, 4-butanediol, 1, 3-propanediol, 1, 2-ethanediol or trimethylolpropane, and the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, bismuth 2-ethylhexanoate or triethylene diamine.
The tackifying resin is liquid rosin resin.
A preparation method of a bi-component polyurethane adhesive comprises the following steps:
step (1): preparing the following components in parts by weight:
15-90 parts of polyester polyol, 1-50 parts of hyperbranched polyphenylene oxide, 25-80 parts of isocyanate, 1-10 parts of a hydroxyl-terminated chain extender, 0-10 parts of tackifying resin and 0.1-5 parts of a catalyst;
step (2): vacuum dehydrating polyester polyol and hyperbranched polyphenyl ether according to parts by weight, adding isocyanate in an inert atmosphere or a vacuum-pumping dehydration state, reacting for 0.5-8 hours at 50-120 ℃, sampling and analyzing the NCO% content to reach 1.5-15%, cooling, and hermetically filling nitrogen for storage to obtain a component A;
and (3): after the hydroxyl-terminated chain extender and the tackifying resin are dehydrated in vacuum according to the weight part, adding a catalyst, and uniformly mixing to obtain a component B;
and (4): and (3) heating and melting the component A prepared in the step (2), cooling to 50-90 ℃, and mixing the component A with the component B according to the mol ratio of NCO to OH of 0.85-2.5 to 1 of the functional groups to obtain the bi-component polyurethane adhesive.
The use of a two-component polyurethane adhesive for the production of industrial belts.
Compared with the prior art, the invention has the following characteristics:
1) in the preparation of the component A, hyperbranched polyphenyl ether with a highly branched structure and low melt viscosity and a large number of active terminal hydroxyl groups on the surface is used for reacting with polyester polyol with excellent performance and isocyanate to obtain a macromolecular prepolymer with a cross-linked network structure and lower viscosity;
2) in the invention, the component A is directly mixed with the component B, the viscosity is lower, due to the cross-linked network structure and the fact that a large number of ether groups of the hyperbranched polyphenylene oxide can form hydrogen bonds with amino groups of carbamate groups to achieve physical cross-linking, the effects of higher initial adhesion and ultimate peel strength are obtained after the two-component polyurethane is coated, and the peel strength after the two-component polyurethane is placed for 3min is about 1N/mm;
3) the two-component polyurethane adhesive disclosed by the invention is simple to prepare, environment-friendly, suitable for a composite process of an industrial belt substrate structure, capable of being laminated at a low temperature, high in curing speed after bonding, good in low temperature resistance, water resistance and heat resistance, and capable of effectively solving the technical problem that the edge warping is easily caused when an industrial belt is laminated at a high temperature.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
preparation of hyperbranched polyphenylene oxide:
N22.0g of 4-bromo-4', 4 "-dihydroxytriphenylmethane, 0.75g of anhydrous K were added under an atmosphere2CO380mL of toluene and 80mL of DMSO were added to the three-port flaskIn a bottle, after heating, refluxing and dehydrating for about 3 hours, cooling the reaction system to 45 ℃, adding 0.01g of CuCl as a catalyst, then heating to 170 +/-2 ℃ and reacting for 40 hours at constant temperature. After the reaction liquid is cooled to room temperature, the reaction liquid is acidified by hydrochloric acid, stirred for a period of time, dropped into a methanol/water mixed solution (v/v ═ 4/6) for precipitation, filtered, and dried in vacuum at 60 ℃ to obtain a crude product. Dissolving the crude product in a small amount of THF, and filtering; precipitating the filtrate with cyclohexane, filtering, washing with cyclohexane, and vacuum drying at 90 deg.C to obtain brick red powdered polymer hyperbranched polyphenylene oxide shown in chemical formula I.
1H NMR(DMSO-d6)：δ5.21-5.31(t，-(Ph)3CH)，δ6.40-7.65(br，Ph-H)，δ9.82(s，-Ph-OH).
Wherein a + b is more than or equal to 3 and less than or equal to 10, and a and b are positive integers. The hydroxyl value of the hyperbranched polyphenylene oxide is measured to be 20-250mgKOH/g by a back titration method and a potassium hydroxide ethanol standard solution.
10g of ethylene glycol adipate with the relative molecular weight of 1000 and 1g of hyperbranched polyphenylene oxide are dehydrated in vacuum, 15g of diphenyl methylene diisocyanate is added to react for 8 hours at 50 ℃ under nitrogen atmosphere, after sampling and analyzing that the content of NCO% reaches a set value (8%), cooling and then sealing and filling nitrogen for storage to obtain a component A (marked as A-1) containing-NCO;
the component B is prepared by uniformly blending 0.01g of dibutyltin dilaurate after 1g of 1, 6-hexanediol and 1g of liquid rosin resin are dehydrated in vacuum, and the component B (marked as B-1) is obtained;
and (3) cooling the A-1 component to 50 ℃ after melting, and uniformly mixing the A-1 component and the B-1 component according to the molar ratio of NCO/OH (NCO/OH) of the functional groups being 0.85 to obtain the bi-component polyurethane adhesive.
Example 2:
in this example, hyperbranched polyphenylene ether was prepared as in example 1.
50g of polycaprolactone diol ester diol with the relative molecular weight of 1000 and 15g of hyperbranched polyphenylene oxide are dehydrated in vacuum, 80g of isophorone diisocyanate is added to react for 6 hours at 60 ℃ under nitrogen atmosphere, after sampling and analyzing that the content of NCO% reaches a set value (15%), cooling and then sealing and filling nitrogen for storage, and a component A (marked as A-2) containing-NCO is obtained;
the component B is prepared by adding 0.5g of 2-bismuth ethylhexanoate into 5g of 1, 3-propylene glycol and 4g of liquid rosin resin after vacuum dehydration and uniformly blending to obtain a component B (marked as component B-2);
and (3) cooling the A-2 component to 60 ℃ after melting, and uniformly mixing the A-2 component and the B-2 component according to the molar ratio of NCO/OH (NCO/OH) of the functional groups being 1.05 to obtain the bi-component polyurethane adhesive.
Example 3:
in this example, hyperbranched polyphenylene ether was prepared as in example 1.
45g of phthalic anhydride diethylene glycol with the relative molecular weight of 2000 and 15g of hyperbranched polyphenylene oxide are dehydrated in vacuum, 38g of polymethylene polyphenyl isocyanate is added to react for 5 hours at 70 ℃ under nitrogen atmosphere, after sampling and analyzing that the content of NCO% reaches a set value (8%), cooling and then sealing and filling nitrogen for storage are carried out, and a component A (marked as A-3) containing-NCO is obtained;
8g of 1, 4-butanediol and 5g of liquid rosin resin are dehydrated in vacuum, and 0.16g of dibutyltin dilaurate is added and uniformly blended to obtain a component B (marked as B-3);
and cooling the A-3 component to 70 ℃ after melting, and uniformly mixing the A-3 component and the B-3 component according to the molar ratio of NCO/OH which is 1.15 of the functional group to obtain the bi-component polyurethane adhesive.
Example 4:
in this example, hyperbranched polyphenylene ether was prepared as in example 1.
60g of polycarbonate diol with the relative molecular weight of 3000 and 40g of hyperbranched polyphenylene oxide are dehydrated in vacuum, 45g of diphenylmethylene diisocyanate is added to react for 4 hours at 80 ℃ in a vacuum-pumping dehydration state, and after the content of NCO% reaches a set value (5.1%) through sampling analysis, the temperature is reduced, and then the mixture is sealed and flushed with nitrogen for storage, so that a component A (marked as A-4) containing-NCO is obtained;
8g of 1, 5-pentanediol, 8g of liquid rosin resin, and 0.9g of stannous octoate are added after vacuum dehydration and are uniformly blended to obtain a component B (marked as component B-4);
and cooling the A-4 component to 80 ℃ after melting, and uniformly mixing the A-4 component and the B-4 component according to the molar ratio of NCO/OH which is 1.25 of the functional group to obtain the bi-component polyurethane adhesive.
Example 5:
in this example, hyperbranched polyphenylene ether was prepared as in example 1.
70g of poly butylene adipate glycol with the relative molecular weight of 3000 and 41g of hyperbranched polyphenyl ether are dehydrated in vacuum, 53g of toluene diisocyanate is added to react for 3 hours at 90 ℃ in a vacuum-pumping dehydration state, and after the NCO% content is sampled and analyzed to reach a set value (3.3%), the mixture is cooled and sealed and flushed with nitrogen for storage to obtain an A component (marked as A-5) containing-NCO;
the component B is prepared by adding 0.15g of dibutyltin dilaurate into 9g of 1, 4-butanediol and 10g of liquid rosin resin after vacuum dehydration and uniformly blending, and the component B (marked as B-5) is obtained;
and cooling the A-5 component to 55 ℃ after melting, and uniformly mixing the A-5 component and the B-5 component according to the molar ratio of NCO/OH which is 1.6 of the functional groups to obtain the bi-component polyurethane adhesive.
Example 6:
in this example, hyperbranched polyphenylene ether was prepared as in example 1.
27g of polyhexamethylene adipate glycol with the relative molecular weight of 6000, 63g of polycarbonate glycol with the molecular weight of 2000 and 50g of hyperbranched polyphenylene oxide are dehydrated in vacuum, 33 parts of diphenylmethane diisocyanate and 11 parts of toluene diisocyanate are added to react for 0.5 hour at 120 ℃ in an argon atmosphere, after sampling and analyzing that the content of NCO% reaches a set value (1.5%), cooling and then sealing and filling nitrogen for storage, thus obtaining an A component (marked as A-6) containing-NCO;
the component B is prepared by adding 5g of triethylene diamine into 10g of trimethylolpropane and 10g of liquid rosin resin after vacuum dehydration and uniformly blending to obtain a component B (marked as B-6);
and cooling the A-6 component to 90 ℃ after melting, and uniformly mixing the A-6 component and the B-6 component according to the molar ratio of NCO/OH (2.5) of the functional groups to obtain the bi-component polyurethane adhesive.
Test operation of the above embodiment: a0.8 mm double-component polyurethane adhesive of the above example was applied to an industrial belt base material (polyester fabric), and immediately laminated to a PU film, and the resultant was pressed with a 1kg roller, baked at 80 ℃ for 3 minutes, cooled at room temperature, left to stand, and after a measurement time, a 34mm wide strip-shaped measurement sample was prepared, and the peel strength was measured at a speed of 100 mm/min.
The product performance of the two-component PU adhesive prepared by the invention is shown in Table 1.
TABLE 1
As can be seen from the data in the table, the solvent-free bi-component polyurethane adhesive is suitable for industrial belt substrates, has low viscosity, short surface drying time, high curing speed and high peel strength, can still retain 80 percent of the peel strength after being boiled in water for 3 days, and is environment-friendly and safe without solvent volatilization.
Example 7:
the two-component polyurethane adhesive is prepared by mixing a component A and a component B, wherein the component A is an isocyanate-terminated polyurethane prepolymer, the component B is a catalytic component containing a hydroxyl-terminated chain extender, and the component A and the component B are mixed according to the molar ratio of NCO to OH which is 0.85 to 1.
The component A is prepared from the following raw materials in parts by weight: 15 parts of polyester polyol, 1 part of hyperbranched polyphenyl ether and 25 parts of isocyanate.
The polyester polyol is formed by mixing polycaprolactone polyol and phthalic anhydride polyester polyol according to the mass ratio of 1:1, and the relative molecular weight of the polyester polyol is 1000.
The isocyanate is formed by mixing diphenylmethane diisocyanate, toluene diisocyanate and isophorone diisocyanate according to the mass ratio of 1:1: 2.
The component B comprises the following components in parts by weight: 1 part of hydroxyl-terminated chain extender, 0.2 part of tackifying resin and 0.1 part of catalyst.
The hydroxyl-terminated chain extender is neopentyl glycol, the catalyst is dibutyltin dilaurate, and the tackifying resin is liquid rosin resin.
The preparation method of the bi-component polyurethane adhesive of the embodiment specifically comprises the following steps:
step (1): preparing the following components in parts by weight:
15 parts of polyester polyol, 1 part of hyperbranched polyphenyl ether, 25 parts of isocyanate, 1 part of a hydroxyl-terminated chain extender, 0.2 part of tackifying resin and 0.1 part of catalyst;
step (2): vacuum dehydrating polyester polyol and hyperbranched polyphenyl ether according to parts by weight, adding isocyanate in an inert atmosphere or a vacuum-pumping dehydration state, reacting for 8 hours at 50 ℃, sampling and analyzing the NCO% content to reach 1.5%, cooling, and hermetically filling nitrogen for storage to obtain a component A;
and (3): after the hydroxyl-terminated chain extender and the tackifying resin are dehydrated in vacuum according to the weight part, adding a catalyst, and uniformly mixing to obtain a component B;
and (4): and (3) heating and melting the component A prepared in the step (2), cooling to 50 ℃, and mixing the component A with the component B according to the molar ratio of NCO to OH being 0.85 to 1 of the functional groups to obtain the bi-component polyurethane adhesive.
The two-component polyurethane adhesive of this example was used in the preparation of industrial belts.
Example 8:
the two-component polyurethane adhesive is prepared by mixing a component A and a component B, wherein the component A is an isocyanate-terminated polyurethane prepolymer, the component B is a catalytic component containing a hydroxyl-terminated chain extender, and the component A and the component B are mixed according to the molar ratio of NCO to OH which is 2.5 to 1 of functional groups.
The component A is prepared from the following raw materials in parts by weight: 90 parts of polyester polyol, 50 parts of hyperbranched polyphenyl ether and 80 parts of isocyanate.
The polyester polyol is polycarbonate diol having a relative molecular weight of 6000. The isocyanate is toluene diisocyanate.
The component B comprises the following components in parts by weight: 10 parts of a hydroxyl-terminated chain extender, 10 parts of tackifying resin and 5 parts of a catalyst.
The hydroxyl-terminated chain extender is prepared by mixing 1, 6-hexanediol, 1, 4-butanediol, 1, 3-propanediol and trimethylolpropane according to the mass ratio of 1:1:1: 1. The catalyst is 2-ethyl bismuth hexanoate, and the tackifying resin is liquid rosin resin.
The preparation method of the bi-component polyurethane adhesive of the embodiment specifically comprises the following steps:
step (1): preparing the following components in parts by weight:
90 parts of polyester polyol, 50 parts of hyperbranched polyphenyl ether, 80 parts of isocyanate, 10 parts of a hydroxyl-terminated chain extender, 10 parts of tackifying resin and 5 parts of a catalyst;
step (2): vacuum dehydrating polyester polyol and hyperbranched polyphenyl ether according to parts by weight, adding isocyanate in an inert atmosphere or a vacuum-pumping dehydration state, reacting for 0.5 hour at 120 ℃, sampling and analyzing the NCO% content to reach 15%, cooling, and hermetically filling nitrogen for storage to obtain a component A;
and (3): after the hydroxyl-terminated chain extender and the tackifying resin are dehydrated in vacuum according to the weight part, adding a catalyst, and uniformly mixing to obtain a component B;
and (4): and (3) heating and melting the component A prepared in the step (2), cooling to 90 ℃, and mixing the component A with the component B according to the mol ratio of NCO to OH being 2.5 to 1 of functional groups to obtain the bi-component polyurethane adhesive.
The two-component polyurethane adhesive of this example was used in the preparation of industrial belts.
Example 9:
the two-component polyurethane adhesive is prepared by mixing a component A and a component B, wherein the component A is an isocyanate-terminated polyurethane prepolymer, the component B is a catalytic component containing a hydroxyl-terminated chain extender, and the component A and the component B are mixed according to the molar ratio of NCO to OH which is 2 to 1 of functional groups.
The component A is prepared from the following raw materials in parts by weight: 65 parts of polyester polyol, 30 parts of hyperbranched polyphenylene oxide and 42 parts of isocyanate.
The polyester polyol is adipic acid polyester polyol with the relative molecular weight of 5000. The isocyanate is isophorone diisocyanate.
The component B comprises the following components in parts by weight: 6 parts of a hydroxyl-terminated chain extender, 4 parts of tackifying resin and 1 part of catalyst.
The hydroxyl-terminated chain extender is prepared by mixing 1, 5-pentanediol, 1, 2-ethanediol and trimethylolpropane according to the mass ratio of 1:1: 2. The catalyst is triethylene diamine, and the tackifying resin is liquid rosin resin.
The preparation method of the bi-component polyurethane adhesive of the embodiment specifically comprises the following steps:
step (1): preparing the following components in parts by weight:
65 parts of polyester polyol, 30 parts of hyperbranched polyphenylene oxide, 42 parts of isocyanate, 6 parts of a hydroxyl-terminated chain extender, 4 parts of tackifying resin and 1 part of catalyst;
step (2): vacuum dehydrating polyester polyol and hyperbranched polyphenyl ether according to parts by weight, adding isocyanate in an inert atmosphere or a vacuum-pumping dehydration state, reacting for 2 hours at 90 ℃, sampling and analyzing the NCO% content to reach 5%, cooling, and hermetically filling nitrogen for storage to obtain a component A;
and (3): after the hydroxyl-terminated chain extender and the tackifying resin are dehydrated in vacuum according to the weight part, adding a catalyst, and uniformly mixing to obtain a component B;
and (4): and (3) heating and melting the component A prepared in the step (2), cooling to 75 ℃, and mixing the component A with the component B according to the mol ratio of NCO to OH being 2 to 1 of the functional groups to obtain the bi-component polyurethane adhesive.
The two-component polyurethane adhesive of this example was used in the preparation of industrial belts.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The bi-component polyurethane adhesive is characterized by being prepared by mixing a component A and a component B, wherein the component A is an isocyanate-terminated polyurethane prepolymer, the component B is a catalytic component containing a hydroxyl-terminated chain extender, and the component A and the component B are mixed according to the molar ratio of NCO to OH of 0.85-2.5 to 1 of functional groups;
the component A is prepared from the following raw materials in parts by weight: 15-90 parts of polyester polyol, 1-50 parts of hyperbranched polyphenylene oxide and 25-80 parts of isocyanate.
2. The two-component polyurethane adhesive of claim 1, wherein the polyester polyol comprises one or more of polycarbonate diol, adipic acid polyester polyol, polycaprolactone polyol, or phthalic anhydride polyester polyol.
3. The two-component polyurethane adhesive as claimed in claim 2, wherein the polyester polyol has a relative molecular weight of 1000-6000.
4. The two-component polyurethane adhesive of claim 1, wherein the isocyanate comprises one or more of diphenylmethylene diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, or isophorone diisocyanate.
5. The two-component polyurethane adhesive of claim 1, wherein the component B comprises the following components in parts by weight: 1-10 parts of a hydroxyl-terminated chain extender, 0-10 parts of tackifying resin and 0.1-5 parts of a catalyst.
6. The two-component polyurethane adhesive of claim 5, wherein the hydroxyl terminated chain extender comprises one or more of 1, 6-hexanediol, 1, 5-pentanediol, neopentyl glycol, 1, 4-butanediol, 1, 3-propanediol, 1, 2-ethanediol, or trimethylolpropane, and the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, bismuth 2-ethylhexanoate, or triethylenediamine.
7. The two-component polyurethane adhesive of claim 6, wherein the tackifying resin is a liquid rosin resin.
8. A process for preparing the two-component polyurethane adhesive of claim 1, comprising the steps of:
step (1): preparing the following components in parts by weight:
15-90 parts of polyester polyol, 1-50 parts of hyperbranched polyphenylene oxide, 25-80 parts of isocyanate, 1-10 parts of a hydroxyl-terminated chain extender, 0-10 parts of tackifying resin and 0.1-5 parts of a catalyst;
step (2): vacuum dehydrating polyester polyol and hyperbranched polyphenyl ether according to parts by weight, adding isocyanate in an inert atmosphere or a vacuum-pumping dehydration state, reacting for 0.5-8 hours at 50-120 ℃, sampling and analyzing the NCO% content to reach 1.5-15%, cooling, and hermetically filling nitrogen for storage to obtain a component A;
and (3): after the hydroxyl-terminated chain extender and the tackifying resin are dehydrated in vacuum according to the weight part, adding a catalyst, and uniformly mixing to obtain a component B;
and (4): and (3) heating and melting the component A prepared in the step (2), cooling to 50-90 ℃, and mixing the component A with the component B according to the mol ratio of NCO to OH of 0.85-2.5 to 1 of the functional groups to obtain the bi-component polyurethane adhesive.
9. Use of a two-component polyurethane adhesive as claimed in claim 1, characterized in that the polyurethane adhesive is used for the production of industrial belts.
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| CN108587118B (en) * | 2017-12-29 | 2020-12-04 | 东莞市雄林新材料科技股份有限公司 | TPU material with high dimensional stability for tool parts and preparation method thereof |
| CN109294213A (en) * | 2018-08-31 | 2019-02-01 | 苏州意诺工业皮带有限公司 | Solvent-free double-component polyurethane glue dipping base fabric prepares conveyer belt and preparation method thereof |
| CN109593507A (en) * | 2018-12-17 | 2019-04-09 | 烟台德邦科技有限公司 | Polyurethane adhesive for bonding soft package battery cell |
| CN110105519B (en) * | 2019-04-26 | 2021-07-16 | 浙江华峰热塑性聚氨酯有限公司 | Particle for hot melt adhesive film and preparation method thereof |
| CN111892899A (en) * | 2019-05-05 | 2020-11-06 | 郑州大学 | Low-temperature easily-extruded double-component polyurethane hollow glass sealant and preparation method thereof |
| CN111138839B (en) * | 2019-12-19 | 2021-11-30 | 苏州意诺工业皮带有限公司 | Graphene modified TPU conveyer belt and preparation method thereof |
| CN112457816A (en) * | 2020-12-14 | 2021-03-09 | 山东华诚高科胶粘剂有限公司 | Adhesive for yellowing-resistant adhesive stone permeable pavement and application thereof |
| CN114150507A (en) * | 2021-12-23 | 2022-03-08 | 苏州意诺工业皮带有限公司 | Belt for wrapper and preparation method thereof |
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| CN102190792A (en) * | 2011-04-10 | 2011-09-21 | 苏州大学 | Functionalized hyperbranched polyphenylene ether and method for preparing same |
| CN107118734A (en) * | 2017-06-02 | 2017-09-01 | 新纶复合材料科技（常州）有限公司 | A kind of double component solvent-free polyurethane adhesive |
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| CN1624067A (en) * | 2004-10-29 | 2005-06-08 | 东华大学 | Dry type compound polyurethane adhesive and its preparation method |
| CN102190792A (en) * | 2011-04-10 | 2011-09-21 | 苏州大学 | Functionalized hyperbranched polyphenylene ether and method for preparing same |
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