CN112552859A - High-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive and preparation method thereof - Google Patents
High-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive and preparation method 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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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention creates synthesis and preparation of a high initial viscosity low shrinkage high strength polyurethane hot melt adhesive, which is prepared from the following raw materials in parts by weight: 10-30 parts of crystalline polyester polyol, 20-40 parts of non-crystalline polyester polyol, 5-15 parts of polyol of a self-made flexible polyether polyurethane chain segment containing a rigid group, 13-18 parts of isocyanate, 0.1-0.5 part of catalyst, 0.1-0.5 part of silane coupling agent and 0.1-0.3 part of flatting agent. The polyurethane hot melt adhesive prepared from the self-made flexible polyether polyurethane side chain polyol containing the rigid group can achieve higher initial adhesion strength without adding tackifying resin, avoids the problems of high compatibility of the tackifying resin and a system, high melting temperature and the like, increases the flexibility of the product, reduces shrinkage by virtue of the flexible side group, ensures the product performance, reduces the pressure maintaining time of the product, and is suitable for application of narrow-frame electronic products.
Description
Technical Field
The invention relates to the field of adhesives, and particularly relates to a high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive and a preparation method thereof.
Background
The moisture-curing PUR hot melt adhesive has the characteristics of a hot melt adhesive and a reactive adhesive, namely the application temperature is lower than that of the traditional hot melt adhesive, the bonding strength is high after curing, and the moisture-curing PUR hot melt adhesive is heat-resistant and chemical-resistant, and can show excellent bonding performance on substrates containing active hydrogen such as wood, ceramics and fabrics and smooth substrates such as metal, glass, plastics and rubber. The PUR hot melt adhesive is widely applied to various industries, and particularly develops rapidly in the electronic industry. However, with the rapid development of modernization, the demand of various electronic products increases, and the electronic products require thinner, narrower, large-screen and more efficient, and put forward higher requirements on the process and performance of the products. The initial strength is high, the use of a pressing tool is reduced, automatic operation is formed, and the excellent final strength and toughness become new demand points of the polyurethane hot melt adhesive.
In the traditional scheme, crystalline polyol is matched with tackifying resin in order to realize the method for accelerating the initial adhesion strength, but most of the crystalline polyol has poor compatibility with the tackifying resin, so that the selection of raw materials is limited.
Disclosure of Invention
The invention discloses a high initial adhesion low shrinkage high strength polyurethane hot melt adhesive and a preparation method thereof, which synthesizes the polyurethane hot melt adhesive by providing self-made flexible polyether polyurethane side chain polyhydric alcohol containing rigid groups, and realizes the effect of high initial adhesion strength. Meanwhile, the problems of compatibility and stability of products caused by different polarities of polyester polyol and polyether polyol are solved, the flexible polyether chain segment has strong adjustability, and the dual advantages of polyester type and polyether type polyurethane hot melt adhesives are integrated.
In order to realize the technical effect, the application discloses a high just glue low shrink high strength polyurethane hot melt adhesive, including the raw materials of following parts by weight:
5-15 parts of self-made flexible polyether polyurethane chain segment polyol containing rigid groups,
10-30 parts of crystalline polyester polyol;
20-40 parts of non-crystalline polyester polyol;
13-18 parts of MDI;
0.1-0.5 part of catalyst;
0.1-0.5 of silane coupling agent;
0.1-0.3 of leveling agent;
the self-made flexible polyether polyurethane chain segment polyol containing the rigid group is obtained by reacting isocyanate, polyether polyol and monofunctional small molecular alcohol and then reacting with trifunctional small molecular alcohol with the same molar weight as the residual NCO.
Further, isocyanate used by the self-made flexible polyether polyurethane chain segment polyol containing the rigid group is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate; the polyether glycol is at least one of polytetrahydrofuran ether glycol, polyoxypropylene glycol and tetrahydrofuran-propylene oxide copolymerized glycol; the used monofunctional small molecular alcohol is n-butyl alcohol; the trifunctional small-molecular alcohol used is trimethylolpropane.
Further, the self-made flexible polyether polyurethane chain segment polyol containing the rigid group has a structure shown in a formula (I).
Formula (I).
Further, the self-made flexible polyether polyurethane chain segment polyol containing the rigid group is prepared by the following steps:
(1) vacuumizing and dehydrating the quantitative polyether polyol at the temperature of 120-125 ℃ for 2 h;
(2) reducing the temperature to 60-65 ℃, adding weighed isocyanate, slowly heating, controlling the reaction temperature to 80-85 ℃, and maintaining the reaction for 2 hours;
(3) then reducing the temperature to 60-65 ℃, adding accurately weighed monofunctional small molecular alcohol, metering to enable OH/NCO to be 1:2, keeping the temperature at 80-85 ℃ along with the reaction, and maintaining the reaction for 2 hours;
(4) and then cooling to 60-65 ℃, adding accurately weighed trifunctional micromolecule polyol to ensure that the mole number of the added trifunctional micromolecule polyol is equal to that of the residual NCO, keeping the temperature at 80-85 ℃, maintaining the reaction for 2 hours, and continuously vacuumizing for 1 hour to obtain the self-made flexible polyether polyurethane chain segment polyol containing the rigid group.
Further, the crystalline polyester polyol is selected from one or more than two of poly (hexamethylene adipate), poly (hexamethylene terephthalate), poly (hexamethylene dodecanedioate), poly (butylene adipate-terephthalate), poly (diethylene adipate) and polycaprolactone diol.
Further, the non-crystalline polyester polyol is selected from one or more of poly (adipic acid-hexanediol-neopentyl glycol ester) diol, poly (2-methyl-1, 3-propylene glycol terephthalate) diol and poly (adipic acid-3-methyl-1, 5-pentanediol diol).
Further, the catalyst is selected from at least one of 2, 2-dimorpholinoethyl ether, N-methylmorpholine, N-ethylmorpholine, N-dimethylbenzylamine, bis (methylaminoethyl) ether and triethylenediamine.
Further, the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and glycidoxypropyltrimethoxysilane.
Further, the leveling agent is EKFA FL 3740.
The invention also discloses a preparation method of the high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive, which comprises the following steps:
(1) 10-30 parts of crystalline polyester polyol, 20-40 parts of non-crystalline polyester polyol and 5-15 parts of self-made dihydric alcohol with flexible side groups, uniformly mixing, vacuumizing and dehydrating at the temperature of 120-125 ℃ for 2h, and ensuring the vacuum degree to be less than or equal to-0.098 MPa until the measured water content is less than or equal to 250 ppm;
(2) cooling the mixed polyol to 80-85 ℃, adding 13-18 parts of isocyanate, naturally heating for 15min, keeping at 110-;
(3) keeping at 110-;
(4) discharging under the protection of nitrogen to a special pipe for hot melt adhesive, filling into an aluminum foil bag, adding a drying agent, and vacuumizing for storage.
The beneficial effects of the invention include:
(1) the invention adopts the self-made carbamate-based macroside-group dihydric alcohol with the flexible polyether chain segment, effectively improves the initial adhesion strength of the product, reduces the pressure maintaining time of a mould, increases the production line efficiency and is beneficial to automatic operation.
(2) The main chain soft satin adopts polyester polyol, so that the bonding strength of the product is increased, the side chain is polyurethane group with flexible polyether chain segment, the compatibility problem between polyester and polyether is effectively solved, and the side chain polyether soft satin has strong molecule adjustability, good flexibility and small shrinkage, and is suitable for narrow-frame high-strength electronic products.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a self-made flexible polyether polyurethane side chain polyol (hereinafter referred to as self-made dihydric alcohol) containing a rigid group, which is prepared according to the following steps:
(1) and (3) vacuumizing and dehydrating the quantified polytetrahydrofuran ether glycol at 120 ℃ for 2 h.
(2) The temperature is reduced to 65 ℃, weighed toluene diisocyanate is added, the temperature is slowly increased, the reaction temperature is controlled to be 85 ℃, and the reaction is maintained for 2 hours.
(3) Then the temperature is reduced to 65 ℃, accurately weighed n-butanol is added, the amount is measured to ensure that the OH/NCO is 1:2, the temperature is kept at 85 ℃ along with the reaction, and the reaction is maintained for 2 hours.
(4) And then cooling to 65 ℃, adding accurately weighed trimethylolpropane to ensure that the mole number of the added trimethylolpropane is equal to that of the residual NCO, keeping the temperature at 85 ℃, maintaining the reaction for 2 hours, continuously vacuumizing for 1 hour to obtain the graft chain polyol, and sealing and storing for later use.
The self-made diols used in examples 1-5 below were all prepared by the above procedure.
Example 1:
a high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive comprises the following raw materials:
in this example, the preparation method is as follows:
(1) 23.5 parts of polyhexamethylene adipate, 16.5 parts of polyhexamethylene terephthalate, 34 parts of polyhexamethylene adipate-neopentyl glycol ester diol and 7 parts of self-made dihydric alcohol are uniformly mixed, and the mixture is vacuumized and dehydrated for 2 hours at the temperature of 125 ℃ with the vacuum degree of less than or equal to-0.098 MPa and the measured water content of less than or equal to 250ppm for the next operation.
(2) And cooling the mixed polyol to 80-85 ℃, adding 18 parts of diphenylmethane diisocyanate, naturally heating for 15min, keeping at 110-115 ℃, and reacting for 80min under the protection of nitrogen.
(3) 0.35 part of 2, 2-dimorpholinoethyl ether, 0.4 part of S-196 and 0.25 part of EKFA FL 3740 are added while keeping at 110 ℃ and 115 ℃ and stirred for 30min under vacuum.
(4) Discharging under the protection of nitrogen to a special hot melt adhesive pipe, filling the special hot melt adhesive pipe into an aluminum foil bag, adding a drying agent, vacuumizing and storing.
Example 2:
a high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive comprises the following raw materials:
in this example, the preparation method is as follows:
(1) 28.5 parts of polyhexamethylene adipate, 12.5 parts of polyhexamethylene terephthalate, 32 parts of polyhexamethylene adipate-neopentyl glycol ester diol and 10 parts of self-made dihydric alcohol are uniformly mixed, and the mixture is vacuumized and dehydrated for 2 hours at the temperature of 125 ℃ with the vacuum degree of less than or equal to-0.098 MPa and the measured water content of less than or equal to 250ppm for the next operation.
(2) And cooling the mixed polyol to 80-85 ℃, adding 16 parts of diphenylmethane diisocyanate, naturally heating for 15min, keeping at 110-115 ℃, and reacting for 80min under the protection of nitrogen.
(3) 0.35 part of 2, 2-dimorpholinoethyl ether, 0.4 part of S-196 and 0.25 part of EKFA FL 3740 are added while keeping at 110 ℃ and 115 ℃ and stirred for 30min under vacuum.
(4) Discharging under the protection of nitrogen to a special hot melt adhesive pipe, filling the special hot melt adhesive pipe into an aluminum foil bag, adding a drying agent, vacuumizing and storing.
Example 3:
a high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive comprises the following raw materials:
in this example, the preparation method is as follows:
(1) 23.5 parts of polyhexamethylene adipate, 13.5 parts of polyhexamethylene terephthalate, 26 parts of polyhexamethylene adipate-neopentyl glycol ester diol, 10 parts of poly-2-methyl-1, 3-propylene glycol terephthalate and 10 parts of self-made dihydric alcohol, uniformly mixing, vacuumizing and dehydrating at the temperature of 120 ℃ and 125 ℃ for 2 hours, ensuring the vacuum degree to be less than or equal to-0.098 MPa, and carrying out next step operation when the water content is measured to be less than or equal to 250 ppm.
(2) And cooling the mixed polyol to 80-85 ℃, adding 16 parts of diphenylmethane diisocyanate, naturally heating for 15min, keeping at 110-115 ℃, and reacting for 90min under the protection of nitrogen.
(3) 0.35 part of 2, 2-dimorpholinoethyl ether, 0.4 part of S-196 and 0.25 part of EKFA FL 3740 are added while keeping at 110 ℃ and 115 ℃ and stirred for 40min under vacuum.
(4) Discharging under the protection of nitrogen to a special hot melt adhesive pipe, filling the special hot melt adhesive pipe into an aluminum foil bag, adding a drying agent, vacuumizing and storing.
Example 4:
a high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive comprises the following raw materials:
in this example, the preparation method is as follows:
(1) 23.5 parts of polyhexamethylene adipate, 10.5 parts of polyhexamethylene terephthalate, 26 parts of polyhexamethylene adipate-neopentyl glycol ester diol, 10 parts of poly-2-methyl-1, 3-propylene glycol terephthalate and 13 parts of self-made dihydric alcohol, uniformly mixing, vacuumizing and dehydrating at the temperature of 120 ℃ and 125 ℃ for 2 hours, ensuring the vacuum degree to be less than or equal to-0.098 MPa and measuring the water content to be less than or equal to 250ppm for next step operation.
(2) And cooling the mixed polyol to 80-85 ℃, adding 15.5 parts of diphenylmethane diisocyanate, naturally heating for 15min, keeping at 110-115 ℃, and reacting for 90min under the protection of nitrogen.
(3) 0.35 part of 2, 2-dimorpholinoethyl ether, 0.4 part of S-196 and 0.25 part of EKFA FL 3740 are added while keeping at 110 ℃ and 115 ℃ and stirred for 40min under vacuum.
(4) Discharging under the protection of nitrogen to a special hot melt adhesive pipe, filling the special hot melt adhesive pipe into an aluminum foil bag, adding a drying agent, vacuumizing and storing.
Comparative example
In this comparative example, the preparation method is as follows:
(1) 15 parts of poly (hexamethylene adipate), 200021 parts of PPG (polyether glycol) polyether, 26 parts of poly (hexamethylene adipate-neopentyl glycol) ester diol and 26 parts of BR-11621 parts of acrylic resin, uniformly mixing, vacuumizing and dehydrating at the temperature of 130-135 ℃ for 2h, ensuring the vacuum degree to be less than or equal to-0.098 MPa, and measuring the water content to be less than or equal to 250ppm for the next operation.
(2) And cooling the mixed polyol to 100-105 ℃, adding 16 parts of diphenylmethane diisocyanate, naturally heating for 15min, keeping at 115-120 ℃, and reacting for 90min under the protection of nitrogen.
(3) 0.35 part of 2, 2-dimorpholinoethyl ether, 0.4 part of S-196 and 0.25 part of EKFA FL 3740 are added while maintaining the temperature at 115 ℃ and 120 ℃, and the mixture is stirred for 40min under vacuum.
(4) Discharging under the protection of nitrogen to a special hot melt adhesive pipe, filling the special hot melt adhesive pipe into an aluminum foil bag, adding a drying agent, vacuumizing and storing.
The hot melt adhesive samples prepared in examples 1 to 4 were compared with the samples prepared in the comparative example for performance tests, and the test items included: color state, viscosity, open time, initial adhesive strength, final adhesive strength. The testing temperature is 22 plus or minus 3 ℃ and the humidity is 42 plus or minus 5 percent
The specific test method is as follows:
(1) and (3) viscosity detection:
referring to GB/T21059-2007 test methods, the samples tested were heated to 110 ℃ and tested for viscosity at 10rpm on spindle # 27 with a Brookfield DV viscometer.
(2) Opening time:
according to the HG/T3716-2003 test method, glue solution with the thickness of 0.15-0.2mm is coated on release paper, paper strips are pressed into a melt at a specific time, and when the fibers of the paper strips are not torn any more, the opening time is obtained.
(3) Initial adhesion strength test:
referring to a GB/T7124-2008 test method, a PC standard sample is used; heating a No. 26 needle to 130 ℃, heating a rubber tube to 100 ℃, discharging the rubber under the pressure of 0.4Mpa, and dispensing for 3S; after the glue is dispensed, the test piece is naturally buckled, then a 200g gland is used for pressing for 10min, and the shearing strength is measured.
(4) Shear strength:
referring to a GB/T7124-2008 test method, a PC standard sample is used; heating a No. 26 needle to 130 ℃, heating a rubber tube to 100 ℃, discharging the rubber under the pressure of 0.4Mpa, and dispensing for 3S; after the glue is dispensed, the test piece is naturally buckled, then a gland with the weight of 200g is used for pressing for 10min, and then the test piece is naturally placed and cured for 24 hours, and then the shearing strength is measured.
As can be seen from the performance test data of the examples and the comparative examples in the table, the self-made carbamate-based macroside group diol with the flexible polyether chain segment is adopted, so that higher initial adhesion strength can be achieved within 10min, the initial adhesion strength of the product is effectively improved, the pressure maintaining time of a tool is reduced, the production line efficiency is increased, and the automatic operation is facilitated.
The main chain soft satin adopts polyester polyol, so that the bonding strength of the product is increased, the side chain is polyurethane group with flexible polyether chain segment, the compatibility problem between polyester and polyether is effectively solved, and the side chain polyether soft satin has strong molecule adjustability, good flexibility and small shrinkage, and is suitable for narrow-frame high-strength electronic products.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Claims (10)
1. The high-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive is characterized by comprising the following raw materials in parts by weight:
5-15 parts of self-made flexible polyether polyurethane chain segment polyol containing rigid groups,
10-30 parts of crystalline polyester polyol;
20-40 parts of non-crystalline polyester polyol;
13-18 parts of MDI;
0.1-0.5 part of catalyst;
0.1-0.5 of silane coupling agent;
0.1-0.3 of leveling agent;
the self-made flexible polyether polyurethane chain segment polyol containing the rigid group is obtained by reacting isocyanate, polyether polyol and monofunctional small molecular alcohol and then reacting with trifunctional small molecular alcohol with the same molar weight as the residual NCO.
2. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 1, characterized in that: the isocyanate used for the self-made flexible polyether polyurethane chain segment polyol containing the rigid group is at least one of toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate; the polyether glycol is at least one of polytetrahydrofuran ether glycol, polyoxypropylene glycol and tetrahydrofuran-propylene oxide copolymerized glycol; the used monofunctional small molecular alcohol is n-butyl alcohol; the trifunctional small-molecular alcohol used is trimethylolpropane.
3. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 2, characterized in that: the above-mentioned
The self-made flexible polyether polyurethane chain segment polyol containing the rigid group has a structure as shown in a formula (I):
formula (I).
4. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 3, characterized in that the self-made rigid group-containing flexible polyether polyurethane segment polyol is prepared by the following steps:
(1) vacuumizing and dehydrating the quantitative polyether polyol at the temperature of 120-125 ℃ for 2 h;
(2) reducing the temperature to 60-65 ℃, adding weighed isocyanate, slowly heating, controlling the reaction temperature to 80-85 ℃, and maintaining the reaction for 2 hours;
(3) then reducing the temperature to 60-65 ℃, adding accurately weighed monofunctional small molecular alcohol, metering to enable OH/NCO to be 1:2, keeping the temperature at 80-85 ℃ along with the reaction, and maintaining the reaction for 2 hours;
(4) and then cooling to 60-65 ℃, adding accurately weighed trifunctional micromolecule polyol to ensure that the mole number of the added trifunctional micromolecule polyol is equal to that of the residual NCO, keeping the temperature at 80-85 ℃, maintaining the reaction for 2 hours, and continuously vacuumizing for 1 hour to obtain the self-made flexible polyether polyurethane chain segment polyol containing the rigid group.
5. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 1, characterized in that: the crystalline polyester polyol is selected from one or more than two of poly (hexamethylene adipate), poly (hexamethylene terephthalate), poly (hexamethylene dodecanedioate), poly (butylene adipate-terephthalate), poly (diethylene adipate) and polycaprolactone diol.
6. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 1, characterized in that: the non-crystalline polyester polyol is selected from one or more than two of poly adipic acid-hexanediol-neopentyl glycol ester diol, poly terephthalic acid-2-methyl-1, 3-propylene glycol ester diol and poly adipic acid-3-methyl-1, 5-pentanediol diol.
7. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 1, characterized in that: the catalyst is at least one selected from 2, 2-dimorpholinoethyl ether, N-methylmorpholine, N-ethylmorpholine, N-dimethylbenzylamine, di (methylaminoethyl) ether and triethylenediamine.
8. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 1, characterized in that: the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane and glycidoxypropyltrimethoxysilane.
9. The high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to claim 1, characterized in that: the leveling agent is EKFA FL 3740.
10. A method for preparing the high initial adhesion low shrinkage high strength polyurethane hot melt adhesive according to any one of claims 1 to 9, which is characterized by comprising the following steps:
(1) 10-30 parts of crystalline polyester polyol, 20-40 parts of non-crystalline polyester polyol and 5-15 parts of self-made dihydric alcohol with flexible side groups, uniformly mixing, vacuumizing and dehydrating at the temperature of 120-125 ℃ for 2h, and ensuring the vacuum degree to be less than or equal to-0.098 MPa until the measured water content is less than or equal to 250 ppm;
(2) cooling the mixed polyol to 80-85 ℃, adding 13-18 parts of isocyanate, naturally heating for 15min, keeping at 110-;
(3) keeping at 110-;
(4) discharging under the protection of nitrogen to a special pipe for hot melt adhesive, filling into an aluminum foil bag, adding a drying agent, and vacuumizing for storage.
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| CN113736417A (en) * | 2021-09-29 | 2021-12-03 | 韦尔通(厦门)科技股份有限公司 | Polyether ester type polyurethane hot melt adhesive with good heat resistance and preparation method thereof |
| CN114395349A (en) * | 2022-01-13 | 2022-04-26 | 佛山南宝高盛高新材料有限公司 | Biodegradable paper bag hot melt adhesive for low temperature and preparation method thereof |
| CN114774066A (en) * | 2022-05-17 | 2022-07-22 | 烟台信友新材料有限公司 | Fast-positioning low-shrinkage UV (ultraviolet) moisture dual-curing polyurethane hot melt adhesive and preparation method thereof |
| CN115651597A (en) * | 2022-12-29 | 2023-01-31 | 烟台泰盛精化科技有限公司 | High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof |
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| CN114774066A (en) * | 2022-05-17 | 2022-07-22 | 烟台信友新材料有限公司 | Fast-positioning low-shrinkage UV (ultraviolet) moisture dual-curing polyurethane hot melt adhesive and preparation method thereof |
| CN115651597A (en) * | 2022-12-29 | 2023-01-31 | 烟台泰盛精化科技有限公司 | High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof |
| CN115651597B (en) * | 2022-12-29 | 2023-03-03 | 烟台泰盛精化科技有限公司 | High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof |
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