CN111303819B - Low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof - Google Patents
Low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- 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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- 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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- 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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- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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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
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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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Abstract
The invention discloses a low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive and a preparation method thereof, wherein the polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight: 10-30 parts of isocyanate, 20-50 parts of polyether diol, 10-50 parts of poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol, 10-40 parts of poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol, 5-30 parts of poly adipic acid-1, 6 hexanediol glycol, 0.05-0.5 part of antioxidant, 0.01-0.1 part of stabilizer and 0.01-0.5 part of catalyst; the NCO% content of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive is 1.5% -3.0%. The invention does not use tackifying resin, and has extremely low smell, better initial adhesion effect and higher later-period adhesion strength.
Description
Technical Field
The invention relates to the field of polyurethane hot melt adhesives, in particular to a low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and a preparation method thereof.
Background
A reactive polyurethane reactive adhesive (PUR), which is one of polyurethane Hot melts and can be melted by heating, and has good fluidity and coatability after being melted; the molecular chain contains carbamate (-NHCOO-), and partial prepolymer is blocked by NCO, can react with moisture in the air or active hydrogen substances on a bonding surface (metal, ceramic, wood, plastic, paper, leather and the like) to form a chemical bond, and has excellent physical and chemical properties.
Since the PUR is solvent-free and has excellent physicochemical properties, the PUR is widely applied to the industries of textile compounding, woodworking home decoration coating, flat pasting, electronics and the like. In the prior art, the synthesis of the PUR is a process combining physical blending and chemical reaction, tackifying resins (including rosin, terpene resins, petroleum resins, phenolic resins, EVA, TPU, acrylic resins, etc.) are used in the synthesis, and the use of the tackifying resins can cause the PUR to generate pungent odor in the production and gluing processes, and can affect the wettability of the PUR to a bonding surface, thereby affecting the later bonding strength.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and the preparation method thereof, which do not use tackifying resin, and have extremely low odor, better initial adhesion effect and higher later-stage adhesion strength.
The purpose of the invention is realized by the following technical scheme:
a low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight:
the NCO% content of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive is 1.5% -3.0%.
Preferably, the hydroxyl values of the poly adipic acid-neopentyl glycol-1, 6-hexanediol glycol, the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol and the poly adipic acid-1, 6-hexanediol glycol are both 20-220 mgKOH/g, and the acid values are both 0.1-3 mgKOH/g.
Preferably, the number average molecular weight of the poly adipic acid-neopentyl glycol-1, 6-hexanediol glycol, the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol and the poly adipic acid-1, 6-hexanediol glycol is 500-6000.
Preferably, the molar ratio of neopentyl glycol to 1,6 hexanediol in the poly adipic acid-neopentyl glycol-1, 6 hexanediol diol is 1: 1-5: 1.
Preferably, the molar ratio of adipic acid to aromatic acid in the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol ester is 1: 4-1: 1, and the molar ratio of diethylene glycol to ethylene glycol is 1: 1-1: 5; the aromatic acid in the poly adipic acid-aromatic acid-diethylene glycol-glycol is at least one of terephthalic acid, isophthalic acid, phthalic acid and phthalic anhydride.
Preferably, the polyether diol mainly contains propylene oxide, the mass content of ethylene oxide is 0%, and the hydroxyl value is 20-280 mgKOH/g.
Preferably, the isocyanate is at least one of diphenylmethane-4, 4-diisocyanate, 1, 5-naphthalene diisocyanate, and 4, 4-dicyclohexylmethane diisocyanate.
Preferably, the catalyst is at least one of N-methylmorpholine, methyl ethyl ether, dibutyltin dilaurate and triethylene diamine.
Preferably, the stabilizer is a compound formed by mixing phosphoric acid and polyphosphoric acid according to the mass ratio of 1-10: 1.
A preparation method of a low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive comprises the following steps:
step 1, weighing isocyanate, polyol, an antioxidant, a stabilizer and a catalyst according to the proportion of the raw materials of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive, wherein the polyol is polyether diol, poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol diol, poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol diol and poly adipic acid-1, 6 hexanediol glycol diol.
And 2, adding 5-40% of the total amount of the polyol and an antioxidant into a reaction kettle, heating to 110-140 ℃, dehydrating at the vacuum degree of-0.05-0.095 MPa for 1 hour, cooling to below 110 ℃, adding isocyanate, controlling the mole number of isocyanate groups/mole number of hydroxyl groups to be 1.15-2.5, reacting at 100-110 ℃ for 1-1.5 hours, then adding the rest polyol and a stabilizer, dehydrating at the vacuum degree of 100-140 ℃ and 0.05-0.095 MPa for 1 hour, cooling to 90-100 ℃, adding the rest isocyanate, reacting at the temperature of 100-120 ℃ for 1 hour, adding a catalyst, heating to 110-130 ℃, stirring for 0.5 hour, defoaming in vacuum for 15-40 minutes, and discharging to obtain the low-odor high-tack single-component moisture curing reaction hot melt adhesive polyurethane.
According to the technical scheme provided by the invention, the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive provided by the invention takes isocyanate, polyether diol, poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol, poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol, poly adipic acid-1, 6 hexanediol glycol, an antioxidant, a stabilizer and a catalyst in a specific ratio as raw materials, does not use tackifying resin, has no bad odor in the production and use processes, does not generate peculiar smell in long-term use, has the advantages of high initial adhesion, high final adhesion strength, zero VOC, wide applicable base materials and the like, and can be used for adhesion in industries such as woodworking, metal, glass, plastics, textile and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the 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 of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive and the preparation method thereof provided by the invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
A low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive is prepared from the following raw materials in parts by weight:
the NCO% content of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive is 1.5% -3.0%.
Wherein, the low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive can comprise the following embodiments:
(1) the isocyanate is at least one of diphenylmethane-4, 4-diisocyanate, 1, 5-naphthalene diisocyanate and 4, 4-dicyclohexylmethane diisocyanate.
(2) The polyether glycol mainly contains propylene oxide, the mass content of ethylene oxide is 0%, and the hydroxyl value is 20-280 mgKOH/g.
(3) The poly adipic acid-neopentyl glycol-1, 6 hexanediol diol, the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol diol and the poly adipic acid-1, 6 hexanediol diol are esterification and polycondensation products of micromolecular dibasic acid and micromolecular dibasic alcohol, the hydroxyl value is 20-220 mgKOH/g, and the acid value is 0.1-3 mgKOH/g.
(4) The number average molecular weight of the poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol, the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol and the poly adipic acid-1, 6 hexanediol glycol is 500-6000.
(5) The molar ratio of neopentyl glycol to 1,6 hexanediol ester in the poly adipic acid-neopentyl glycol-1, 6 hexanediol ester diol is 1: 1-5: 1.
(6) The molar ratio of adipic acid to aromatic acid in the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol ester glycol is 1: 4-1: 1, and the molar ratio of diethylene glycol to ethylene glycol is 1: 1-1: 5. The aromatic acid in the poly adipic acid-aromatic acid-diethylene glycol-glycol is at least one of terephthalic acid, isophthalic acid, phthalic acid and phthalic anhydride.
(7) The stabilizer is a compound formed by mixing phosphoric acid and polyphosphoric acid according to the mass ratio of 1-10: 1.
(8) The catalyst is at least one of N-methylmorpholine, methyl ethyl ether, dibutyltin dilaurate and triethylene diamine.
Specifically, the preparation method of the low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive provided by the invention comprises the following steps:
step 1, weighing isocyanate, polyol, an antioxidant, a stabilizer and a catalyst according to the proportion of the raw materials of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive, wherein the polyol is polyether diol, poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol diol, poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol diol and poly adipic acid-1, 6 hexanediol glycol diol.
And 2, adding 5-40% of the total amount of the polyol and an antioxidant into a reaction kettle, heating to 110-140 ℃, dehydrating at the vacuum degree of-0.05-0.095 MPa for 1 hour, cooling to below 110 ℃, adding isocyanate, controlling the mole number of isocyanate groups/mole number of hydroxyl groups to be 1.15-2.5, reacting at 100-110 ℃ for 1-1.5 hours, then adding the rest polyol and a stabilizer, dehydrating at the vacuum degree of 100-140 ℃ and 0.05-0.095 MPa for 1 hour, cooling to 90-100 ℃, adding the rest isocyanate, reacting at the temperature of 100-120 ℃ for 1 hour, adding a catalyst, heating to 110-130 ℃, stirring for 0.5 hour, defoaming in vacuum for 15-40 minutes, discharging, and packaging under the protection of nitrogen or in a vacuum sealing manner to obtain the low-odor high-viscosity single-component moisture curing reaction polyurethane.
Compared with the prior art, the low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive and the preparation method thereof provided by the invention have the following advantages:
(1) the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive provided by the invention uses a prepolymer method to polymerize and adjust the molecular weight distribution of the synthesized PU resin, so that the initial adhesion of the polyurethane hot melt adhesive and the wettability of an adhesive surface can be greatly improved.
(2) The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive provided by the invention has the advantages that NCO end capping can enable the polyurethane hot melt adhesive and an adhesive surface to generate chemical reaction, and the later-stage adhesive force is improved.
(3) The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive provided by the invention does not use tackifying resin, achieves the effect of high initial adhesion (initial adhesion), greatly reduces the odor of PUR in the high-temperature melting process, and does not release pungent odor in the long-term use process.
(4) The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive provided by the invention does not use tackifying resin, has no bad odor in the production and use processes, does not generate peculiar smell in long-term use, and has the characteristics of high initial adhesion, high final adhesion strength, zero VOC, wide applicable base materials and the like.
(5) The low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive provided by the invention belongs to a solvent-free environment-friendly adhesive, and can be used for bonding in industries such as woodworking, automobiles, household appliances, book binding, textile and the like.
In conclusion, the embodiment of the invention does not use tackifying resin, and has extremely low smell, better initial adhesion effect and higher later-period adhesion strength.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the following detailed description of the low-odor high-initial-adhesion one-component moisture-curing reactive polyurethane hot melt adhesive and the preparation method provided by the embodiment of the present invention are provided by specific examples.
The following raw material numbers are used for illustration of the examples:
DP 1000: polyether glycol (neat PO, number average molecular weight 1000);
DP 2000: polyether glycol (neat PO, number average molecular weight 2000);
PDE-5000S: poly adipic acid-phthalic acid-diethylene glycol-ethylene glycol (one of poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol, number average molecular weight 5500, adipic acid to phthalic acid molar ratio of 1:1, diethylene glycol to ethylene glycol molar ratio of 1: 2);
PNH-3000: poly (adipate-neopentyl glycol ester diol) -1,6 hexanediol diol (number average molecular weight 3000, neopentyl glycol to 1,6 hexanediol molar ratio 3: 1);
pH-4000: poly (1, 6 hexanediol adipate) diol (number average molecular weight 4500);
MDI-100: diphenylmethane-4, 4-diisocyanate.
Example 1
A low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive comprises the following steps: 100.0kg of DP1000, 55.0kg of DP2000, 200.0kg of PDE-5000S and 0.5kg of antioxidant 1010 are put into a reaction kettle, stirred uniformly, heated to 110 ℃, dehydrating at vacuum degree of-0.09 MPa for 1h, cooling to below 100 deg.C, adding 45kg MDI-100, heating to 105 deg.C, reacting for 1.5 hr, then adding 150.0kg DP2000, 145kg PNH-3000, 200.0kg PH-4000 and 0.1kg stabilizer, heating to 105-110 ℃, dehydrating under-0.09 MPa for 1 hour, cooling to 100 ℃, adding 100kg of MDI-100, heating to 115 ℃ for reaction for 1 hour, adding 0.5kg of N-methylmorpholine, fully stirring for 30 minutes at 120 ℃ and under the pressure of-0.09 MPa, closing the stirring, performing vacuum defoamation for 20 minutes, discharging, packaging and storing under vacuum or nitrogen protection, thus preparing 1000kg of low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive.
Example 2
A low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive comprises the following steps: 100.0kg of DP1000, 55.0kg of PNH-3000, 200.0kg of PDE-5000S and 0.5kg of antioxidant 1010 are put into a reaction kettle, stirred uniformly, heated to 110 ℃, dehydrating at vacuum degree of-0.09 MPa for 1h, cooling to below 100 deg.C, adding 45kg MDI-100, heating to 105 deg.C, reacting for 1.5 hr, then adding 210.0kg of DP2000, 90kg of PNH-3000, 200.0kg of PH-4000 and 0.1kg of stabilizer, heating to 105-110 ℃, dehydrating for 1 hour under the vacuum degree of-0.09 MPa, cooling to 100 ℃, adding 100kg of MDI-100, heating to 115 ℃ for reaction for 1 hour, adding 0.5kg of N-methylmorpholine, fully stirring for 30 minutes at 120 ℃ and under the pressure of-0.09 MPa, closing the stirring, performing vacuum defoamation for 20 minutes, discharging, packaging and storing under vacuum or nitrogen protection, thus preparing 1000kg of low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive.
Example 3
A low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive comprises the following steps: 100.0kg of DP1000, 100.0kg of PNH-3000, 150.0kg of PDE-5000S and 0.5kg of antioxidant 1010 are put into a reaction kettle, stirred uniformly, heated to 110 ℃, dehydrating at vacuum degree of-0.09 MPa for 1h, cooling to below 100 deg.C, adding 50kg MDI-100, heating to 105 deg.C, reacting for 1.5 hr, then adding 210.0kg of DP2000, 45kg of PNH-3000, 50kg of PDE-5000S, 200.0kg of PH-4000 and 0.1kg of stabilizer, heating to 105-110 ℃, dehydrating for 1 hour under the vacuum degree of-0.09 MPa, cooling to 100 ℃, adding 95kg of MDI-100, heating to 115 ℃ for reaction for 1 hour, adding 0.5kg of N-methylmorpholine, fully stirring for 30 minutes at 120 ℃ and under the pressure of-0.09 MPa, closing the stirring, performing vacuum defoamation for 20 minutes, discharging, packaging and storing under vacuum or nitrogen protection, thus preparing 1000kg of low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive.
Comparative example 1
A preparation method of the reactive polyurethane hot melt adhesive comprises the following steps: 100.0kg of DP1000, 200.0kg of DP2000, 145kg of PNH-3000, 200.0kg of PDE-5000S, 200.0kg of PH-4000, 0.5kg of antioxidant 1010 and 0.1kg of stabilizer are put into a reaction kettle, uniformly stirred, heated to 110 ℃, dehydrated for 1 hour under the vacuum degree of-0.09 MPa, cooled to below 100 ℃, added with 145kg of MDI-100, heated to 115 ℃ for reaction for 1 hour, added with 0.5kg of dimorpholinoethyl ether, fully stirred for 30 minutes under the conditions of 120 ℃ and-0.09 MPa, closed stirring, vacuum defoamed for 20 minutes, discharged, packaged and stored under vacuum or nitrogen protection, thus obtaining the reactive polyurethane hot melt adhesive.
Comparative example 2
A preparation method of the reactive polyurethane hot melt adhesive comprises the following steps: 70.0kg of DP1000, 147.0kg of DP2000, 101.5kg of PNH-3000, 140.0kg of PDE-5000S, 140.0kg of PH-4000, 300kg of acrylic resin 106, 0.5kg of antioxidant 1010 and 0.1kg of stabilizer are put into a reaction kettle, uniformly stirred, heated to 110 ℃, dehydrated under the vacuum degree of-0.09 MPa for 1h, cooled to below 100 ℃, added with 101.5kg of MDI-100, heated to 115 ℃ for reaction for 1 hour, added with 0.5kg of dimorpholinoethyl ether, fully stirred for 30 minutes under the conditions of 120 ℃ and-0.09 MPa, closed to stir for vacuum defoaming for 20 minutes, discharged, packaged and stored under vacuum or nitrogen protection, thus obtaining the reactive polyurethane hot melt adhesive.
Comparative example 3
A preparation method of the reactive polyurethane hot melt adhesive comprises the following steps: 70.0kg of DP1000, 147.0kg of DP2000, 101.5kg of PNH-3000, 140.0kg of PDE-5000S, 140.0kg of PH-4000, 300kg of thermoplastic polyurethane resin TPU, 0.5kg of antioxidant 1010 and 0.1kg of stabilizer are put into a reaction kettle, uniformly stirred, heated to 110 ℃, dehydrated under the vacuum degree of-0.09 MPa for 1h, cooled to below 100 ℃, added with 101.5kg of MDI-100, heated to 115 ℃ for reaction for 1h, added with 0.5kg of dimorpholinoethyl ether, fully stirred for 30 minutes under the conditions of 120 ℃ and-0.09 MPa, closed stirring and vacuum defoamed for 20 minutes, discharged, packaged and stored under vacuum or nitrogen protection, thus obtaining the reactive hot melt adhesive polyurethane.
Performance detection
(1) Detection of initial adhesion and 24-hour peel strength: the initial adhesion test and the 24-hour peel strength test were performed on inventive examples 1 to 3 and comparative examples 1 to 3 in an environment having a temperature of 25 ℃ and a humidity of 45% using a PVC foam sheet as a test substrate and a PVC film having a dyne value of 32 to 34 and a thickness of 420 μm as a film material, and the results are shown in the following table 1:
the testing method comprises heating the reactive polyurethane hot melt adhesive to 120-130 deg.C, melting into fluid, and mixing at a ratio of 50g/m2The sizing amount is rolled on a test base material by a roller, a prepared film material is attached, and the veneering is pressed by the same pressure; on the facing, a 1-in wide PVC film was cut, and the initial tack strength at 3 minutes and the peel strength after 24 hours curing were measured at 90 ° and 180 °, respectively.
TABLE 1
(2) And (3) odor detection:
standard methods of odor detection: the reactive polyurethane hot melt adhesives of examples 1 to 3 and comparative examples 1 to 3 of the present invention were heated to 130 ℃ in an NDJ-1C rotational viscometer, and were rotated at a rotation speed of 20rpm for 15 minutes, and then immediately measured, 5 testers evaluated the odor, and the final average value was the test result, as shown in table 2 below:
judging the grade: 1 is odorless; 2-slightly odorous; 3-tasted but not irritating; 4, pungent smell; 5 ═ strong pungent odor; 6 ═ intolerable taste;
TABLE 2
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Odor grade | 2 | 2 | 2.5 | 3 | 3.5 | 3 |
As can be seen from tables 1 and 2: the low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive prepared in the embodiments 1 to 3 of the invention uses new raw materials and a synthesis process under the condition that tackifying resins such as acrylic resin, TPU, EVA, petroleum resin and the like are not used, so that the odor of the single-component moisture curing polyurethane hot melt adhesive is reduced, and the initial adhesion and the later adhesion are improved to a great extent.
In conclusion, the embodiment of the invention does not use tackifying resin, and has extremely low smell, better initial adhesion effect and higher later-period adhesion strength.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive is characterized by being prepared from the following raw materials in parts by weight:
10-30 parts of isocyanate,
20-50 parts of polyether glycol,
10-50 parts of poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol,
10-40 parts of poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol ester glycol,
5-30 parts of poly adipic acid-1, 6 hexanediol glycol,
0.05 to 0.5 portion of antioxidant,
0.01 to 0.1 part of a stabilizer,
0.01-0.5 part of catalyst;
the NCO percent content of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive is 1.5 to 3.0 percent;
the preparation method of the low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive comprises the following steps:
step 1, weighing isocyanate, polyol, an antioxidant, a stabilizer and a catalyst according to the proportion of the raw materials of the low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive, wherein the polyol is polyether diol, poly adipic acid-neopentyl glycol-1, 6 hexanediol glycol diol, poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol diol and poly adipic acid-1, 6 hexanediol glycol diol;
and 2, adding 5-40% of the total amount of the polyol and an antioxidant into a reaction kettle, heating to 110-140 ℃, dehydrating at a vacuum degree of 0.05-0.095 MPa for 1 hour, cooling to below 110 ℃, adding isocyanate, controlling the mole number of isocyanate groups/mole number of hydroxyl groups to be 1.15-2.5, reacting at 100-110 ℃ for 1-1.5 hours, then adding the rest polyol and a stabilizer, dehydrating at a vacuum degree of 0.05-0.095 MPa for 1 hour at 100-140 ℃, cooling to 90-100 ℃, adding the rest isocyanate, reacting at a temperature of 100-120 ℃ for 1 hour, adding a catalyst, heating to 110-130 ℃, stirring for 0.5 hour, defoaming in vacuum for 15-40 minutes, and discharging to obtain the low-odor high-viscosity single-component moisture curing reaction type polyurethane hot melt adhesive.
2. The low-odor high-initial-adhesion single-component moisture-curing reactive polyurethane hot melt adhesive as claimed in claim 1, wherein the hydroxyl values of the poly (adipic acid-neopentyl glycol-1, 6-hexanediol glycol), the poly (adipic acid-aromatic acid-diethylene glycol-ethylene glycol) and the poly (adipic acid-1, 6-hexanediol) are respectively 20-220 mgKOH/g, and the acid values are respectively 0.1-3 mgKOH/g.
3. The low-odor high-initial-viscosity single-component moisture-curing reactive polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the number average molecular weight of the poly (neopentyl glycol) -1, 6-hexanediol adipate diol, the poly (adipic acid-aromatic acid-diethylene glycol-ethylene glycol diol), and the poly (adipic acid-1, 6-hexanediol adipate diol is 500-6000.
4. The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the molar ratio of neopentyl glycol to 1,6 hexanediol in the poly (neopentyl glycol adipate-1, 6 hexanediol) glycol is 1:1 to 5: 1.
5. The low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the molar ratio of adipic acid to aromatic acid in the poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol is 1:4 to 1:1, and the molar ratio of diethylene glycol to ethylene glycol is 1:1 to 1: 5;
the aromatic acid in the poly adipic acid-aromatic acid-diethylene glycol-glycol is at least one of terephthalic acid, isophthalic acid, phthalic acid and phthalic anhydride.
6. The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the polyether diol mainly comprises propylene oxide, the mass content of ethylene oxide is 0%, and the hydroxyl value is 20-280 mgKOH/g.
7. The low-odor high-tack one-component moisture-curable polyurethane hot melt adhesive according to claim 1 or 2, wherein the isocyanate is at least one of diphenylmethane-4, 4 '-diisocyanate, 1, 5-naphthalene diisocyanate, and 4, 4' -dicyclohexylmethane diisocyanate.
8. The low odor high initial viscosity one-component moisture curing reactive polyurethane hot melt adhesive of claim 1 or 2, wherein the catalyst is at least one of N-methylmorpholine, methylaminoethyl ether, dibutyltin dilaurate, and triethylenediamine.
9. The low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive as claimed in claim 1 or 2, wherein the stabilizer is a compound formed by mixing phosphoric acid and polyphosphoric acid according to a mass ratio of 1-10: 1.
10. A preparation method of a low-odor high-initial-adhesion single-component moisture curing reactive polyurethane hot melt adhesive is characterized by comprising the following steps:
step 1, weighing isocyanate, polyol, antioxidant, stabilizer and catalyst according to the raw material proportion of the low-odor high-initial-viscosity single-component moisture curing reaction type polyurethane hot melt adhesive as described in any one of the claims 1 to 9, wherein the polyol is polyether diol, poly adipic acid-neopentyl glycol-1, 6 hexanediol diol, poly adipic acid-aromatic acid-diethylene glycol-ethylene glycol diol and poly adipic acid-1, 6 hexanediol diol;
step 2, adding 5-40% of the total amount of the polyol and an antioxidant into a reaction kettle, heating to 110-140 ℃, dehydrating at a vacuum degree of 0.05-0.095 MPa for 1 hour, cooling to below 110 ℃, adding isocyanate, controlling the value of the mole number of isocyanate groups/the mole number of hydroxyl groups to be 1.15-2.5, reacting at 100-110 ℃ for 1-1.5 hours, then adding the rest polyol and a stabilizer, dehydrating at a vacuum degree of 0.05-0.095 MPa of 100-140 ℃ for 1 hour, cooling to 90-100 ℃, adding the rest isocyanate, reacting at 100-120 ℃ for 1 hour, adding a catalyst, heating to 110-130 ℃, stirring for 0.5 hour, defoaming in vacuum for 15-40 minutes, and discharging to obtain the low-odor high-tack single-component moisture curing reaction polyurethane of any one of the claims 1-9.
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| CN111662671A (en) * | 2020-07-22 | 2020-09-15 | 北京高盟新材料股份有限公司 | Reactive polyurethane hot melt adhesive for bonding aluminum plate and wood veneer and preparation method thereof |
| CN111944474A (en) * | 2020-09-01 | 2020-11-17 | 重庆韩拓科技有限公司 | Thermally reversible polyurethane hot melt adhesive and preparation method thereof |
| CN111978909B (en) * | 2020-09-08 | 2022-06-07 | 北京高盟新材料股份有限公司 | Reactive polyurethane hot melt adhesive for low-temperature coating and preparation method thereof |
| CN112760075A (en) * | 2020-12-25 | 2021-05-07 | 烟台德邦科技股份有限公司 | High-initial-strength hot-melt type two-component polyurethane structural adhesive and preparation method thereof |
| CN115340841B (en) * | 2022-08-31 | 2023-06-30 | 北京高盟新材料股份有限公司 | Polyurethane hot melt adhesive for bonding automobile exterior trim parts and preparation method thereof |
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| DE10149142A1 (en) * | 2001-10-05 | 2003-04-24 | Henkel Kgaa | Reactive polyurethane hot-melt adhesive for laminating acrylic film, e.g. with PVC window frames, is obtained by reacting polyisocyanate with polyether-polyol and partly crystalline polyester-polyol or low molecular weight polymer |
| US20070155859A1 (en) * | 2006-01-04 | 2007-07-05 | Zhengzhe Song | Reactive polyurethane hot melt adhesive |
| CN102732203A (en) * | 2012-06-26 | 2012-10-17 | 中国科学院理化技术研究所嘉兴工程中心 | Preparation method of reaction type polyurethane hot melt adhesive for automotive lamps |
| EP3168248B1 (en) * | 2015-11-11 | 2018-10-31 | Henkel AG & Co. KGaA | Curing method for polyurethanes |
| CN108251037B (en) * | 2017-12-29 | 2021-10-01 | 浙江华峰新材料有限公司 | Single-component moisture-curing reaction type polyurethane hot melt adhesive and preparation method thereof |
| CN108822784A (en) * | 2018-05-25 | 2018-11-16 | 南通天洋新材料有限公司 | A kind of moisture-curable polyurethane hot melt adhesive and preparation method thereof |
| CN112601792B (en) * | 2018-08-23 | 2023-09-01 | 汉高股份有限及两合公司 | Moisture curable polyurethane adhesive compositions |
| CN110229645B (en) * | 2019-07-12 | 2021-10-08 | 重庆韩拓科技有限公司 | High initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof |
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