CN111234761A - Single-component solvent-free polyurethane adhesive and preparation method thereof - Google Patents
Single-component solvent-free polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN111234761A CN111234761A CN202010184983.4A CN202010184983A CN111234761A CN 111234761 A CN111234761 A CN 111234761A CN 202010184983 A CN202010184983 A CN 202010184983A CN 111234761 A CN111234761 A CN 111234761A
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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
- C08G18/28—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
- C08G18/4054—Mixtures of compounds of group C08G18/60 with other macromolecular compounds
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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
- C08G18/4244—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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- 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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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Abstract
A single-component solvent-free polyurethane adhesive and a preparation method thereof belong to the technical field of adhesives. The adhesive consists of modified isocyanate-terminated polyurethane prepolymer, polyisocyanate and additive. The modified isocyanate-terminated polyurethane prepolymer is a diisocyanate-terminated polyester polyol, which is then modified with an amino acid. And (2) carrying out alcoholysis on the PET product and polyol under the catalysis of the composite catalyst, filtering impurities to obtain an alcoholysis product, then carrying out ester exchange and esterification with polybasic acid and a phosphite ester triphenyl ester stabilizer to obtain polyester polyol, and simultaneously selecting an amino acid modifier to carry out modification treatment on the prepared prepolymer, so that the strength and the high temperature resistance of the polyurethane can be further improved. The polyurethane adhesive disclosed by the invention is low in viscosity, reduces the production energy consumption, and has higher adhesive strength and high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of adhesives. More particularly, relates to a single-component solvent-free polyurethane adhesive and a preparation method thereof.
Background
Because the polyurethane adhesive has the characteristics of good comprehensive performances such as tear resistance, abrasion resistance, high strength and the like, the polyurethane adhesive is widely applied to the fields of soft packaging, industrial packaging, automobile interior decoration and the like. The polyurethane molecular chain segment contains soft segments with structures such as ether bonds or ester bonds and the like with the glass transition temperature lower than the normal temperature, and also contains hard segments with structures such as carbamate (-NHCOO-) and isocyanate (-NCO) with the glass transition temperature higher than the normal temperature. The isocyanate group (-NCO) has extremely strong polarity, is easy to react with active hydrogen in the material, and can prepare the polyurethane adhesive which can meet the wide adhesive property of plastics, rubber, foam, wood, glass, ceramics, metal and the like by controlling the proportion of a soft segment and a hard segment in a molecular chain through the adjustment of a formula and a base material.
In recent years, the solvent-free polyurethane adhesive does not contain an organic solvent, has no solvent residue and no migration, and has better environmental protection performance such as no environmental pollution and the like, so people gradually pay attention to the solvent-free polyurethane adhesive. Meanwhile, in the application process, the procedure step of heating and drying the solvent is omitted, so that the application equipment is simple, time-saving and economical. However, the existing solvent-free polyurethane adhesive has certain defects in the aspects of high viscosity at normal temperature, strength, high temperature resistance and the like.
Disclosure of Invention
It is a first object of the present invention to provide a one-component solvent-free polyurethane adhesive.
The second purpose of the invention is to provide a preparation method of the single-component solvent-free polyurethane adhesive.
The third purpose of the invention is to provide the application of the single-component solvent-free polyurethane adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
the single-component solvent-free polyurethane adhesive consists of modified isocyanate-terminated polyurethane prepolymer, polyisocyanate and additive.
Preferably, in the one-component solvent-free polyurethane adhesive, the modified isocyanate-terminated polyurethane prepolymer is a diisocyanate-terminated polyester polyol, which is then modified with an amino acid.
Preferably, the additive is at least one of a catalyst, an inhibitor and a coupling agent; wherein the catalyst is preferably one or more of 2, 2-dimorpholinyl diethyl ether, dibutyltin dilaurate and stannous octoate, the addition amount is 0.01-0.5 percent of the total mass, and the preferred is dibutyltin dilaurate; the inhibitor is preferably one or more of methyl p-toluenesulfonate, phosphoric acid and tributyl borate, the addition amount of the inhibitor is 0.001-0.5 percent of the total mass, and the inhibitor is further preferably phosphoric acid; the coupling agent is preferably one or more of gamma-aminopropyltriethoxysilane, gamma-isocyanate propyltriethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-glycidoxypropyltrimethoxysilane, and the addition amount of the coupling agent is 0.02-2% of the total mass.
The preparation method of the single-component solvent-free polyurethane adhesive comprises the following steps:
step 1) preparation of isocyanate terminated polyurethane prepolymer
a preparation method of polyester polyol: adding alcoholysis agent polyol into waste PET under the catalysis of composite catalysts of zinc acetate and monobutyl tin oxide, controlling the temperature of the polyol at 220-240 ℃ for alcoholysis, and filtering impurities after alcoholysis; then adding polybasic acid to carry out ester exchange reaction and esterification reaction at the temperature of 220-240 ℃ in the presence of triphenyl phosphite serving as a stabilizer; measuring an acid value, tracking the reaction process, and controlling the acid value to be 5-8mgKOH/g after the reaction is finished; then, controlling the temperature in the reaction kettle to be 220-240 ℃ and the pressure to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, finishing the reduced pressure reaction until the acid value is less than 2.0mgKOH/g, and finally controlling the hydroxyl value to be 56.1-112.2 mgKOH/g, namely controlling the molecular weight of the polyester polyol to be 1000-2000;
b preparation of isocyanate-terminated polyurethane prepolymers: firstly adding diisocyanate, then adding the polyester polyol obtained in the step a, mixing and reacting for 4-8 h at 60-100 ℃, then cooling to below 60 ℃ to obtain isocyanate-terminated polyurethane prepolymer, and carrying out the preparation of the step 2).
The PET adopts recycled PET waste (the PET material waste comprises different types of shapes and performances and is used after being crushed to the particle size of 2-3 mm).
Preferably, the polyol is selected from: one or more of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, methyl propylene glycol, pentanediol and butanediol.
Preferably, the polyacid is selected from: one or more of isophthalic acid, terephthalic acid, phthalic acid, oxalic acid and maleic acid.
Preferably, the alcoholysis reaction temperature is 220-230 ℃; the temperature of the ester exchange and esterification reaction is preferably 230 to 240 ℃, and the pressure of the reduced pressure polycondensation reaction kettle is preferably 0.09 to 0.095MPa, and more preferably 0.094 MPa.
Preferably, the addition amount of the polyol accounts for 15-35% of the mass of the PET; the adding amount of the zinc acetate accounts for 0.04-0.14% of the mass of the PET; the mass of the monobutyl tin oxide accounts for 0.08-0.18% of that of the PET; the polybasic acid accounts for 15-48% of the weight of the PET; the phosphite ester triphenyl ester accounts for 0.04-0.22% of the mass of the PET.
Preferably, the diisocyanate used for blocking is at least one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate (HMDI).
Preferably, the diisocyanate is reacted with the polyester polyol at an NCO/OH equivalent ratio of 1.5:1 to 2.5: 1. In general, the higher the equivalence ratio, the smaller the molecules of the product, and the lower the viscosity. A further preferred NCO/OH equivalent ratio is 2.0:1, i.e.one OH group reacts with one diisocyanate molecule, minimizing the amount of unreacted diisocyanate monomer in the product, reducing the degree of crosslinking in the prepolymer and reducing the viscosity.
Step 2) preparation of single-component solvent-free polyurethane adhesive
a. Adding an amino acid modifier into the isocyanate-terminated polyurethane prepolymer, mixing, and carrying out modification treatment at 50-60 ℃; then, freeze thawing treatment is carried out on the modified prepolymer, and the method comprises the following specific steps:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) then heating the prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating steps (a) - (b) for 2-3 times; obtaining a modified isocyanate-terminated polyurethane prepolymer;
b. and (b) mixing the modified isocyanate-terminated polyurethane prepolymer obtained in the step (a) with polyisocyanate, uniformly stirring, and finally adding an additive (which may not be added) to obtain the single-component solvent-free polyurethane adhesive.
Preferably, the mass ratio of the modified isocyanate-terminated polyurethane prepolymer, the polyisocyanate and the additive is 100: (10-70): (0-3).
Preferably, the amino acid modifier is polyglutamic acid and/or polylysine, the mass of which is 7% to 12% of the total mass of the polyester polyol, and more preferably, the mass ratio of the polyglutamic acid to the polylysine is 1: 1.
Preferably, the polyisocyanate is at least one of polymethylene polyphenyl polyisocyanate (PAPI), Hexamethylene Diisocyanate (HDI) trimer, IPDI trimer, HMDI trimer and a mixture of high boiling diisocyanates. Wherein the high-boiling point diisocyanate is at least one of MDI, HMDI and IPDI.
The invention adopts waste and old recovered PET as raw material to obtain polyester polyol, thereby reducing production cost. In addition, the soft ether bond or ester bond structure in the structure has better affinity with the plastic film; diisocyanate is used for sealing the polyester polyol, and a strong-polarity urethane bond is introduced into the structure, so that the toughness of the main chain structure is increased; the isocyanic acid radical of the terminal hydroxyl group can be combined with the hydroxyl group on the surface of the material to generate a chemical bond, and simultaneously reacts with the moisture on the surface of the material to generate carbamido (-NH-CO-NH-) which has high bonding strength to the base material; the diisocyanate-terminated prepolymer and the later added multifunctional NCO groups of the polyisocyanate react with active hydrogen to generate a network structure with higher crosslinking density, so that the cohesive strength of the adhesive is greatly enhanced.
The percentage content of NCO in the product is higher and can reach 8-20%, the content of effective functional groups is high, the chemical bonding with an adherend is fully realized, and the bonding force with a base material is enhanced.
The invention has the following beneficial effects:
according to the single-component solvent-free polyurethane adhesive provided by the invention, polyester polyol is obtained after alcoholysis, ester exchange and esterification reactions based on the recycled PET material waste, so that recycling of waste PET is realized, and compared with the traditional process, the production cost is reduced by about 10%.
The invention selects the amino acid modifier to modify the diisocyanate prepolymer, and can improve the strength of the polyurethane adhesive. In addition, the mechanical strength can be further improved by carrying out repeated freeze-thaw treatment on the diisocyanate prepolymer.
The single-component solvent-free polyurethane adhesive provided by the invention has good adhesive property, no VOC emission and no pollution.
The product of the invention has low viscosity, is easy to be uniformly coated, and can effectively save the cost; in addition, the content of NCO% is high and reaches 8-20%, and the utilization rate of effective NCO functional groups is high.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The test method comprises the following steps:
t-type peel strength, namely, placing the composite film at 45 ℃ and keeping the ambient humidity at 70%, carrying out T-type peel test on the flexible material according to GB/T2791-1995 flexible material to flexible material by adhesive T peel strength test method after 48 hours, and measuring the peel strength.
Example 1
Step 1:
adding 100 parts of crushed PET waste with the particle size of 2-4 mm into a reaction kettle, then respectively adding 12.5 parts of methyl propylene glycol (MPO) and 16.8 parts of diethylene glycol (DEG), and finally respectively adding 0.14 part of monobutyl tin oxide (MBTO) and 0.1 part of zinc acetate (Zn (CH)3COO)2) As a catalyst, the temperature is controlled to be 220-240 ℃ for alcoholysis reaction. And after alcoholysis is finished, filtering to remove impurities. Then 13 parts of isophthalic acid (IPA) and 13 Parts of Terephthalic Acid (PTA) are respectively added, then 0.07 part of triphenyl phosphite (TPP) as a stabilizer is added, ester exchange reaction and esterification reaction are carried out at the temperature of 230-240 ℃, and after the color of polyester becomes clear and the acid value is reduced to 5-8mgKOH/g, the ester exchange reaction and the esterification reaction are proved to be finished. Controlling the temperature of the reaction kettle to be 220-240 ℃ and the pressure in the kettle to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, sampling and testing, and finishing the vacuum polycondensation reaction when the measured acid value is less than 2.0mgKOH/g and the hydroxyl value is controlled to be 54.7 mgKOH/g-57.5 mgKOH/g, namely the molecular weight of the polyester polyol is about 2000.
Step 2:
① adding 30 parts of MDI into a reaction kettle, adding 100 parts of the polyester polyol under stirring, slowly heating to 60 ℃ from room temperature (about 1h), keeping the temperature at 60 ℃, reacting for 2h, finally keeping the temperature at 75-80 ℃, reacting for 2h, measuring the percentage content of NCO, tracking the reaction, and finishing the reaction after the percentage content of NCO tends to be stable to obtain the isocyanate-terminated polyurethane prepolymer.
②, cooling the materials to 60 ℃, adding 8 parts of polyglutamic acid modifier, mixing, carrying out modification treatment at 55 ℃, and then carrying out freeze thawing treatment on the modified prepolymer, wherein the steps are as follows:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) then heating the prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating the steps (a) - (b) for 2-3 times.
Maintaining the temperature in the reaction kettle at about 60 ℃, adding 59 parts of PAPI, uniformly stirring, adding 0.03 part of phosphoric acid inhibitor, adding 0.6 part of gamma-isocyanate propyl triethoxysilane, uniformly stirring, and discharging to obtain the single-component solvent-free polyurethane adhesive with the NCO content of 12.0%. The viscosity was about 1000 MPa.s (25 ℃ C.).
And (3) detecting the performance of the obtained product: the paint film impacter impacts, and the positive impact is 50KG without cracks; the recoil 45KG was crack free.
The adhesive is uniformly coated between two layers of base materials of PVC/RB and PVC/PVC, and after the composite base material is placed at room temperature for 2 days, the T peel strength of the PVC/RB is 3.50N/mm, and the T peel strength of the PVC/PVC is 2.75N/mm.
Example 2
Step 1:
adding 100 parts of crushed PET waste with the particle size of 2-4 mm into a reaction kettle, then adding 17 parts of diethylene glycol (DEG), and finally adding 0.1 part of zinc acetate (Zn (CH)3COO)2) As a catalyst, the temperature is controlled to be 220-240 ℃ for alcoholysis reaction. And after alcoholysis is finished, filtering to remove impurities. 13 Parts of Terephthalic Acid (PTA) is added, then 0.10 part of triphenyl phosphite (TPP) as a stabilizer is added, ester exchange reaction and esterification reaction are carried out at the temperature of 230-240 ℃, and after the color of the polyester becomes clear and the acid value is reduced to 5-8mgKOH/g, the ester exchange reaction and the esterification reaction are proved to be finished. Controlling the temperature of the reaction kettle to be 220-240 ℃ and the pressure in the kettle to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, sampling and testing, and finishing the vacuum polycondensation reaction when the measured acid value is less than 2.0mgKOH/g and the hydroxyl value is controlled to be 54.7 mgKOH/g-57.5 mgKOH/g, namely the molecular weight of the polyester polyol is about 2000.
Step 2:
① adding 23.3 parts of IPDI into a reaction kettle, adding 100 parts of the polyester polyol under stirring, slowly heating to 60 ℃ from room temperature (about 1h), keeping the temperature at 60 ℃, reacting for 1h, keeping the temperature at 70-80 ℃, reacting for 1h, keeping the temperature at 85-90 ℃ for reacting for 1h, adding 0.5 part of dibutyltin dilaurate, continuing to react for 1h, measuring the percentage content of NCO, tracking the reaction, and finishing the reaction after the percentage content of NCO tends to be stable to obtain the isocyanate-terminated polyurethane prepolymer.
②, cooling the material to 60 ℃, adding 4 parts of polyglutamic acid and 4 parts of polylysine modifier, mixing, modifying at 55 ℃, and then performing freeze thawing treatment on the modified prepolymer, wherein the steps are as follows:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) heating the modified prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating the steps (a) - (b) for 2-3 times.
Maintaining the temperature in the reaction kettle to be about 60 ℃, adding 114.5 parts of PAPI, stirring uniformly, adding 0.7 part of gamma-isocyanate propyl trimethoxy silane, stirring uniformly, and discharging to obtain the single-component solvent-free polyurethane adhesive with the NCO content of 15.8%. The viscosity was about 1200MPa · s (25 ℃).
And (3) detecting the performance of the obtained product: the paint film impacter impacts, and the positive impact is 50KG without cracks; the recoil 45KG was crack free.
The adhesive is uniformly coated between two layers of base materials of PVC/RB and PVC/PVC, and after the composite base material is placed at room temperature for 2 days, the T peel strength of the PVC/RB is 3.38N/mm, and the T peel strength of the PVC/PVC is 2.82N/mm.
Example 3
Step 1:
adding 100 parts of crushed PET waste with the particle size of 2-4 mm into a reaction kettle, then respectively adding 12.9 parts of Ethylene Glycol (EG) and 17 neopentyl glycol (NPG), finally adding 0.14 part of monobutyl tin oxide (MBTO) as a catalyst, and controlling the temperature to be 220-240 ℃ to carry out alcoholysis reaction. And after alcoholysis is finished, filtering to remove impurities. Then 18 Parts of Terephthalic Acid (PTA) is added, then 0.11 part of triphenyl phosphite (TPP) as a stabilizer is added, ester exchange reaction and esterification reaction are carried out at the temperature of 230-240 ℃, and after the color of the polyester becomes clear and the acid value is reduced to 5-8mgKOH/g, the ester exchange reaction and the esterification reaction are proved to be finished. Controlling the temperature of the reaction kettle to be 220-240 ℃ and the pressure in the kettle to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, sampling and testing, and finishing the vacuum polycondensation reaction when the measured acid value is less than 2.0mgKOH/g and the hydroxyl value is controlled to be 54.7 mgKOH/g-57.5 mgKOH/g, namely the molecular weight of the polyester polyol is about 2000.
Step 2:
① adding 23.3 parts of IPDI into a reaction kettle, adding 100 parts of the polyester polyol under stirring, slowly heating to 60 ℃ from room temperature (about 1h), keeping the temperature at 60 ℃, reacting for 1h, keeping the temperature at 70-80 ℃, reacting for 1h, keeping the temperature at 85-90 ℃ for 1h, adding 0.5 part of stannous octoate, continuing to react for 1h, measuring the percentage content of NCO, tracking the reaction, and finishing the reaction after the percentage content of NCO tends to be stable to obtain the isocyanate-terminated polyurethane prepolymer.
② cooling the materials to 60 ℃, adding 8 parts of polylysine modifier, mixing, carrying out modification treatment at 55 ℃, and then carrying out freeze thawing treatment on the modified prepolymer, wherein the steps are as follows:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) heating the modified prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating the steps (a) - (b) for 2-3 times.
And maintaining the temperature in the reaction kettle at about 60 ℃, adding 73.6 parts of PAPI, uniformly stirring and discharging to obtain the single-component solvent-free polyurethane adhesive with the NCO content of 13.0%. The viscosity was about 1400 MPa.s (25 ℃ C.).
And (3) detecting the performance of the obtained product: the paint film impacter impacts, and the positive impact is 50KG without cracks; the recoil 45KG was crack free.
The adhesive is uniformly coated between two layers of base materials of PVC/RB and PVC/PVC, and after the composite base material is placed at room temperature for 2 days, the T peel strength of the PVC/RB is 3.44N/mm, and the T peel strength of the PVC/PVC is 2.78N/mm.
Example 4
Step 1:
adding 100 parts of crushed PET waste with the particle size of 2-4 mm into a reaction kettle, then respectively adding 12.9 parts of Propylene Glycol (PG) and 17 parts of pentanediol (NPG), and finally adding 0.10 part of zinc acetate (Zn (CH)3COO)2) As a catalyst, the temperature is controlled to be 220-240 ℃ for alcoholysis reaction. After the alcoholysis is finished, the alcohol is removed,the impurities are removed by filtration. 27 Parts of Terephthalic Acid (PTA) is added, then 0.07 part of triphenyl phosphite (TPP) as a stabilizer is added, ester exchange reaction and esterification reaction are carried out at the temperature of 230-240 ℃, and after the color of the polyester becomes clear and the acid value is reduced to 5-8mgKOH/g, the ester exchange reaction and the esterification reaction are proved to be finished. Controlling the temperature of the reaction kettle to be 220-240 ℃ and the pressure in the kettle to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, sampling and testing, and finishing the vacuum polycondensation reaction when the measured acid value is less than 2.0mgKOH/g and the hydroxyl value is controlled to be 54.7 mgKOH/g-57.5 mgKOH/g, namely the molecular weight of the polyester polyol is about 2000.
Step 2:
① adding 27.5 parts of HMDI into a reaction kettle, adding 100 parts of the polyester polyol under stirring, slowly heating from room temperature to 60 ℃ (about 1h), keeping the temperature at 60 ℃, reacting for 0.5h, keeping the temperature at 70-80 ℃, reacting for 0.5h, keeping the temperature at 85-90 ℃ for 1h, adding 0.5 part of dibutyl tin dilaurate, continuing to react for 2h at 95-100 ℃, measuring NCO percentage content tracking reaction, and finishing the reaction after the NCO percentage content tends to be stable, thus obtaining the isocyanate-terminated polyurethane prepolymer.
② cooling ① to 60 ℃, adding 8 parts of polylysine modifier, mixing, modifying at 55 ℃, and then freezing and thawing the modified prepolymer, wherein the steps are as follows:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) heating the modified prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating the steps (a) - (b) for 2-3 times.
Maintaining the temperature in the reaction kettle at about 60 ℃, adding 83.9 parts of PAPI, uniformly stirring, adding 0.6 part of gamma-isocyanate propyl trimethoxy silane, uniformly stirring, and discharging to obtain the single-component solvent-free polyurethane adhesive with the NCO content of 13.5%. The viscosity was about 1300MPa · s (25 ℃).
And (3) detecting the performance of the obtained product: the paint film impacter impacts, and the positive impact is 50KG without cracks; the recoil 45KG was crack free.
The adhesive is uniformly coated between two layers of base materials of PVC/RB and PVC/PVC, and after the composite base material is placed at room temperature for 2 days, the T peel strength of the PVC/RB is 3.63N/mm, and the T peel strength of the PVC/PVC is 3.03N/mm.
Example 5
Step 1:
adding 100 parts of crushed PET waste with the particle size of 2-4 mm into a reaction kettle, then respectively adding 12.9 parts of Ethylene Glycol (EG) and 17 parts of pentanediol (NPG), and finally respectively adding 0.14 part of monobutyl tin oxide (MBTO) and 0.10 part of zinc acetate (Zn (CH)3COO)2) As a catalyst, the temperature is controlled to be 220-240 ℃ for alcoholysis reaction. And after alcoholysis is finished, filtering to remove impurities. Then 18 Parts of Terephthalic Acid (PTA) is added, then 0.10 part of triphenyl phosphite (TPP) as a stabilizer is added, ester exchange reaction and esterification reaction are carried out at the temperature of 230-240 ℃, and after the color of the polyester becomes clear and the acid value is reduced to 5-8mgKOH/g, the ester exchange reaction and the esterification reaction are proved to be finished. Controlling the temperature of the reaction kettle to be 220-240 ℃ and the pressure in the kettle to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, sampling and testing, and finishing the vacuum polycondensation reaction when the measured acid value is less than 2.0mgKOH/g and the hydroxyl value is controlled to be 54.7 mgKOH/g-57.5 mgKOH/g, namely the molecular weight of the polyester polyol is about 2000.
Step 2:
① adding 23.3 parts of IPDI into a reaction kettle, adding 100 parts of the polyester polyol under stirring, slowly heating to 60 ℃ from room temperature (about 1h), keeping the temperature at 60 ℃, reacting for 0.5h, keeping the temperature at 70-80 ℃, reacting for 0.5h, keeping the temperature at 85-90 ℃ for 1h, adding 0.5 part of dibutyl tin dilaurate, continuing to react for 2h, measuring NCO percentage content tracking reaction, and finishing the reaction after the NCO percentage content tends to be stable to obtain the isocyanate-terminated polyurethane prepolymer.
② cooling ① to 60 deg.C, adding 8 parts of polyglutamic acid modifier, mixing, modifying at 55 deg.C, and freeze thawing the modified prepolymer, which comprises the following steps:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) heating the modified prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating the steps (a) - (b) for 2-3 times.
And maintaining the temperature in the reaction kettle at about 60 ℃, adding 94.2 parts of PAPI, uniformly stirring, adding 0.7 part of gamma-isocyanate propyl triethoxysilane, uniformly stirring, and discharging to obtain the single-component solvent-free polyurethane adhesive with the NCO content of 14.5%. The viscosity was about 1500 MPa.s (25 ℃ C.).
And (3) detecting the performance of the obtained product: the paint film impacter impacts, and the positive impact is 50KG without cracks; the recoil 45KG was crack free.
The adhesive is uniformly coated between two layers of base materials of PVC/RB and PVC/PVC, and after the composite base material is placed at 45 ℃ for 2 days, the T peel strength of the PVC/RB is 3.66N/mm, and the T peel strength of the PVC/PVC is 2.95N/mm.
Claims (9)
1. A single-component solvent-free polyurethane adhesive is characterized in that the adhesive is composed of a modified isocyanate-terminated polyurethane prepolymer, polyisocyanate and an additive; the modified isocyanate-terminated polyurethane prepolymer is diisocyanate-terminated polyester polyol and is modified by amino acid; the mass ratio of the modified isocyanate-terminated polyurethane prepolymer, the polyisocyanate and the additive is 100: (10-70): (0-3).
2. The one-component solvent-free polyurethane adhesive of claim 1, wherein the additive is at least one of a catalyst, an inhibitor, and a coupling agent; wherein the catalyst is preferably one or more of 2, 2-dimorpholinyl diethyl ether, dibutyltin dilaurate and stannous octoate, the addition amount is 0.01-0.5 percent of the total mass, and the preferred is dibutyltin dilaurate; the inhibitor is preferably one or more of methyl p-toluenesulfonate, phosphoric acid and tributyl borate, the addition amount of the inhibitor is 0.001-0.5 percent of the total mass, and the inhibitor is further preferably phosphoric acid; the coupling agent is preferably one or more of gamma-aminopropyltriethoxysilane, gamma-isocyanate propyltriethoxysilane, gamma-isocyanate propyltrimethoxysilane and gamma-glycidoxypropyltrimethoxysilane, and the addition amount of the coupling agent is 0.02-2% of the total mass.
3. A process for preparing a one-component solvent-free polyurethane adhesive as claimed in claim 1 or 2, comprising the steps of:
step 1) preparation of isocyanate terminated polyurethane prepolymer
a preparation method of polyester polyol: adding alcoholysis agent polyol into waste PET under the catalysis of composite catalysts of zinc acetate and monobutyl tin oxide, controlling the temperature of the polyol at 220-240 ℃ for alcoholysis, and filtering impurities after alcoholysis; then adding polybasic acid to carry out ester exchange reaction and esterification reaction at the temperature of 220-240 ℃ in the presence of triphenyl phosphite serving as a stabilizer; measuring an acid value, tracking the reaction process, and controlling the acid value to be 5-8mgKOH/g after the reaction is finished; then, controlling the temperature in the reaction kettle to be 220-240 ℃ and the pressure to be less than or equal to 0.095MPa to carry out reduced pressure polycondensation reaction, finishing the reduced pressure reaction until the acid value is less than 2.0mgKOH/g, and finally controlling the hydroxyl value to be 56.1-112.2 mgKOH/g, namely controlling the molecular weight of the polyester polyol to be 1000-2000;
b preparation of isocyanate-terminated polyurethane prepolymers: firstly adding diisocyanate, then adding the polyester polyol obtained in the step a, mixing and reacting for 4-8 h at 60-100 ℃, then cooling to below 60 ℃ to obtain isocyanate-terminated polyurethane prepolymer, and carrying out the preparation in the step 2);
step 2) preparation of single-component solvent-free polyurethane adhesive
a. Adding an amino acid modifier into the isocyanate-terminated polyurethane prepolymer, mixing, and carrying out modification treatment at 50-60 ℃; then, freeze thawing treatment is carried out on the modified prepolymer, and the method comprises the following specific steps:
(a) cooling the modified prepolymer to 0-4 ℃, and preserving heat for 10-15 min;
(b) then heating the prepolymer to 50-60 ℃, and preserving heat for 10-15 min;
(c) repeating steps (a) - (b) for 2-3 times; obtaining a modified isocyanate-terminated polyurethane prepolymer;
b. and c, mixing the modified isocyanate-terminated polyurethane prepolymer obtained in the step a with polyisocyanate, uniformly stirring, and finally adding the additive.
4. The method according to claim 3, wherein the PET in the step 1) is used after recycled PET waste is crushed to a particle size of 2-3 mm; the polyol in step 1) is selected from: one or more of ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, methyl propylene glycol, pentanediol and butanediol;
the polybasic acid is selected from: one or more of isophthalic acid, terephthalic acid, phthalic acid, oxalic acid and maleic acid.
5. The method according to claim 3, wherein the alcoholysis reaction temperature in step 1) is 220-230 ℃; the temperature of the ester exchange and esterification reaction is 230-240 ℃, and the pressure of the reduced pressure polycondensation reaction kettle is preferably 0.09-0.095 MPa, and more preferably 0.094 MPa.
6. The method according to claim 3, wherein the polyol is added in the step 1) in an amount of 15-35% by mass of the PET; the adding amount of the zinc acetate accounts for 0.04-0.14% of the mass of the PET; the mass of the monobutyl tin oxide accounts for 0.08-0.18% of that of the PET; the polybasic acid accounts for 15-48% of the weight of the PET; the triphenyl phosphite accounts for 0.04-0.22% of the mass of the PET;
the diisocyanate used for blocking is at least one of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and 4, 4' -dicyclohexylmethane diisocyanate (HMDI);
the diisocyanate is reacted with the polyester polyol at an NCO/OH equivalent ratio of 1.5:1 to 2.5:1, more preferably 2.0: 1.
7. The method according to claim 3, wherein the amino acid modifier of step 2) is polyglutamic acid and/or polylysine, and the mass thereof is 7 to 12% of the total mass of the polyester polyol.
8. The method of claim 7, wherein the amino acid modifier is polyglutamic acid and polylysine at a mass ratio of 1: 1.
9. The method of claim 3, wherein the polyisocyanate is at least one of polymethylene polyphenyl polyisocyanate (PAPI), Hexamethylene Diisocyanate (HDI) trimer, IPDI trimer, HMDI trimer and high boiling diisocyanate; wherein the high-boiling point diisocyanate is at least one of MDI, HMDI and IPDI.
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