CN110964475B - Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof - Google Patents
Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN110964475B CN110964475B CN201911327622.4A CN201911327622A CN110964475B CN 110964475 B CN110964475 B CN 110964475B CN 201911327622 A CN201911327622 A CN 201911327622A CN 110964475 B CN110964475 B CN 110964475B
- Authority
- CN
- China
- Prior art keywords
- hot melt
- moisture
- melt adhesive
- polyurethane hot
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- 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
-
- 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
-
- 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
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
Abstract
The invention provides a moisture-curing polyurethane hot melt adhesive and a preparation method and application thereof, wherein the preparation raw materials of the moisture-curing polyurethane hot melt adhesive comprise the following components in parts by weight: 500-800 parts of polyether polyol, 30-200 parts of chain extender, 200-300 parts of polyisocyanate, 3-8 parts of monofunctional group end-capping reagent and 0.1-0.6 part of catalyst; the monofunctional end-capping reagent can seal a part of NCO groups in the system, so that the hot melt adhesive still keeps certain viscosity after being cured and converted into a solid state, can be stably bonded with nylon yarns, avoids the problem that the polyurethane system is not firmly bonded due to volume change in the curing process, and obviously improves the bonding strength and the bonding stability. The moisture-curing polyurethane hot melt adhesive has appropriate viscosity and initial bonding strength, stronger final bonding strength and bonding stability, and can fully meet the requirement for compounding nylon yarn fabrics.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a moisture-curable polyurethane hot melt adhesive and a preparation method and application thereof.
Background
The adhesive serves as one of the most widely used raw materials in the textile industry, and plays an irreplaceable role in the production, processing and application processes of textiles. In terms of its chemical composition, the textile adhesives include high molecular weight polymers such as polyurethane, acrylic polymers, polyethylene, and polyvinyl alcohol. In the production process of nylon fabric (nylon yarn), the traditional solvent-based adhesive has a remarkable effect on nylon yarn compounding, but the solvent-based adhesive causes resource waste and brings non-negligible environmental pollution because a large amount of organic volatile gas is discharged in the using process. With the high importance of the country on the environmental protection problem in recent years, the solvent-based adhesive is gradually replaced by the solvent-free adhesive, and the hot melt adhesive has a very wide application prospect as an important solvent-free adhesive.
The polyurethane hot melt adhesive is prepared by taking polyurethane resin or prepolymer as a main material and adding a catalyst, an antioxidant, a tackifier, a filler and other auxiliaries. The polyurethane hot melt adhesive can be divided into two types, one is a thermoplastic polyurethane elastomer hot melt adhesive, the other is a reactive polyurethane hot melt adhesive, and the reactive polyurethane hot melt adhesives can be divided into a moisture curing type and a closed type according to different reaction mechanisms. The moisture-curing type polyurethane hot melt adhesive is an NCO-terminated adhesive generated by the reaction of polyester or polyether polyol and isocyanate, and gradually becomes high-viscosity state or solid state after melting and gluing, so that certain initial bonding strength is provided, and NCO groups in a system can gradually react with moisture in the air to form a cross-linked network structure, so that the bonding strength and the solvent resistance of the moisture-curing type polyurethane hot melt adhesive are greatly improved. Compared with the traditional thermoplastic hot melt adhesive, the moisture-curing type polyurethane hot melt adhesive has better cold resistance, heat resistance, solvent resistance, aging resistance and stronger final bonding strength, so that the moisture-curing type polyurethane hot melt adhesive is widely applied to the industries of textile, electronics, automobiles, woodworking, construction, shoe industry, book binding and the like.
The main component of nylon yarn is polyamide, the polyamide has regular chemical structure and high crystallinity, and the traditional hot melt adhesive, such as ethylene-vinyl acetate copolymer (EVA), has extremely poor wettability and unsatisfactory bonding strength; in contrast, polyurethane adhesives can better meet the bonding requirements of nylon yarns. CN109609074A discloses a preparation method of a single-component moisture-curing polyurethane hot melt adhesive, which comprises the following specific steps: mixing polyether polyol, polyester polyol, a tackifier and an antioxidant, performing vacuum dehydration, adding isocyanate and a catalyst for reaction, sequentially adding a chain extender and a filler, and reacting to obtain a hot melt adhesive; the tackifier is copolyamide hot melt adhesive resin, and a traditional single-component moisture-curing polyurethane hot melt adhesive system can be specially modified, so that the adhesion of the hot melt adhesive to nylon fabrics is more pertinent; however, the copolyamide has a high melting point and poor compatibility with polyurethane, a uniform and stable system is difficult to obtain, the viscosity of the obtained hot melt adhesive is 5000-6500 mPa.s/120 ℃, the viscosity of the hot melt adhesive for compounding the general fabric and the polymer film is 1000-3000 mPa.s/120 ℃, and the viscosity of the hot melt adhesive is too high, so that the application range of the hot melt adhesive is limited to a certain extent. CN1261519C discloses a polyurethane adhesive for nylon film compounding, which is prepared from a main agent and a curing agent in a mass ratio of 100 (10-20); the main agent comprises a polyurethane prepolymer, polyamide and an organic solvent, and the curing agent is an addition product of polyisocyanate and polyol; the polyurethane adhesive can improve the peel strength and the flexibility of a nylon composite film, but is a solvent-type adhesive essentially and cannot meet the development requirements of the existing textile industry.
Therefore, it is a research focus in the field to develop a solvent-free polyurethane adhesive with high bonding strength and good bonding stability to better meet the bonding requirements in the textile industry, especially nylon fabrics.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a moisture-curing type polyurethane hot melt adhesive and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a moisture-curable polyurethane hot melt adhesive, which comprises the following raw materials in parts by weight:
the moisture-curing type polyurethane hot melt adhesive provided by the invention comprises the preparation raw materials of polyether polyol, a chain extender, polyisocyanate, a monofunctional group end-capping reagent and a catalyst, wherein the adhesive contains NCO groups, and the NCO groups are gradually changed into a high-viscosity state or even a solid state after melting and gluing so as to provide certain initial bonding strength; and then NCO groups in the system can gradually react with moisture in the air to form a stable cross-linked network structure, so that the bonding strength and the bonding stability of the adhesive are greatly improved. The traditional moisture-curing type polyurethane hot melt adhesive can be accompanied with certain volume change in the curing process, so that the traditional moisture-curing type polyurethane hot melt adhesive is dislocated with an adhered object (such as nylon yarn) to cause poor adhesion, and the adhesive force and the adhesion stability of the adhesive to the nylon yarn are reduced. Aiming at the problem, a monofunctional end-capping reagent is introduced into the preparation raw materials of the moisture-curing polyurethane hot melt adhesive, so that a part of NCO groups in the system can be sealed, a certain viscosity of the moisture-curing polyurethane hot melt adhesive is still maintained after the moisture-curing polyurethane hot melt adhesive is cured and converted into a solid state, the moisture-curing polyurethane hot melt adhesive can be stably bonded with nylon yarns, the phenomenon that the polyurethane system is dislocated with an adherend and is not firmly bonded due to volume change in the curing process is effectively avoided, and the bonding strength and the bonding stability between the adhesive and the adherend are remarkably improved.
In the present invention, the polyether polyol may be used in an amount of 510 parts by weight, 520 parts by weight, 540 parts by weight, 560 parts by weight, 580 parts by weight, 600 parts by weight, 620 parts by weight, 640 parts by weight, 660 parts by weight, 680 parts by weight, 700 parts by weight, 720 parts by weight, 740 parts by weight, 760 parts by weight, 780 parts by weight or 790 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and conciseness, and specific points included in the range are not exhaustive.
The chain extender may be used in an amount of 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight or 190 parts by weight, and specific points therebetween are not exhaustive, and the present invention is not limited to specific points included in the range for brevity and conciseness.
The polyisocyanate may be used in an amount of 210 parts by weight, 220 parts by weight, 230 parts by weight, 240 parts by weight, 250 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight, or 290 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The monofunctional blocking agent may be used in an amount of 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, 5 parts by weight, 5.2 parts by weight, 5.5 parts by weight, 5.8 parts by weight, 6 parts by weight, 6.2 parts by weight, 6.5 parts by weight, 6.8 parts by weight, 7 parts by weight, 7.2 parts by weight, 7.5 parts by weight, 7.7 parts by weight, or 7.9 parts by weight, and specific point values therebetween, which are not intended to be limited by space and included in the range for the sake of brevity, are not exhaustive.
The catalyst may be used in an amount of 0.13 parts by weight, 0.15 parts by weight, 0.18 parts by weight, 0.2 parts by weight, 0.22 parts by weight, 0.25 parts by weight, 0.28 parts by weight, 0.3 parts by weight, 0.33 parts by weight, 0.35 parts by weight, 0.38 parts by weight, 0.4 parts by weight, 0.42 parts by weight, 0.45 parts by weight, 0.48 parts by weight, 0.5 parts by weight, 0.52 parts by weight, 0.55 parts by weight, 0.57 parts by weight, or 0.59 parts by weight, and specific values therebetween, are not limited to space and specific values included in the range are not exhaustive in the present invention for the sake of brevity.
In the invention, when the amount of the preparation raw materials is within the range, the obtained moisture-curable polyurethane hot melt adhesive has proper viscosity, bonding force and bonding stability. If the amount of the monofunctional end-capping agent is too small, the phenomenon of poor adhesion of the polyurethane system due to volume change in the curing process cannot be avoided; if the amount of the monofunctional end-capping reagent is too much, the end-capping part does not participate in the curing reaction, so that the whole system has sticky hand feeling after curing, and the monofunctional end-capping reagent is not suitable for the textile compounding field.
Preferably, the polyether polyol has a hydroxyl value of 28-112 mg KOH/g, such as 29mg KOH/g, 30mg KOH/g, 32mg KOH/g, 34mg KOH/g, 36mg KOH/g, 38mg KOH/g, 40mg KOH/g, 45mg KOH/g, 50mg KOH/g, 55mg KOH/g, 60mg KOH/g, 65mg KOH/g, 70mg KOH/g, 75mg KOH/g, 80mg KOH/g, 85mg KOH/g, 90mg KOH/g, 95mg KOH/g, 100mg KOH/g, 105mg KOH/g, 110mg KOH/g, or 111mg KOH/g, and the specific values therebetween are limited in breadth and for the sake of brevity, and the present invention is not exhaustive, more preferably 28 to 37mg KOH/g.
Preferably, the polyether polyol has a number average molecular weight of 3000 to 4000g/mol, such as 3100g/mol, 3200g/mol, 3300g/mol, 3400g/mol, 3500g/mol, 3600g/mol, 3700g/mol, 00g/mol, 3900g/mol or 3950g/mol, and specific values therebetween, which are not intended to be exhaustive for reasons of brevity and brevity.
Preferably, the polyether polyol is a polyoxypropylene diol.
Preferably, the moisture-curable polyurethane hot melt adhesive further comprises 1-200 parts by weight of polyester polyol, wherein the polyester polyol can be contained in an amount of 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 40 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 110 parts by weight, 130 parts by weight, 150 parts by weight, 170 parts by weight or 190 parts by weight, and specific points between the above points are limited by space and for brevity, and the invention is not exhaustive.
As a preferable technical scheme, the preparation raw materials of the moisture-curing type polyurethane hot melt adhesive also comprise polyester polyol, and the polyester polyol and the polyether polyol are matched with each other, so that the moisture-curing type polyurethane hot melt adhesive can be endowed with appropriate toughness and hardness.
Preferably, the number average molecular weight of the polyester polyol is 500 to 1500g/mol, such as 600g/mol, 700g/mol, 800g/mol, 900g/mol, 1000g/mol, 1100g/mol, 1200g/mol, 1300g/mol, 1400g/mol or 1450g/mol, and the specific values therebetween are limited in space and for the sake of brevity and are not exhaustive of the specific values included in the ranges.
Preferably, the polyester polyol is selected from any one of or a combination of at least two of neopentyl glycol polyphthalate, polyethylene phthalate anhydride or neopentyl glycol polyterephthalate.
Preferably, the chain extender is a diol and/or a polyether having a number average molecular weight of 200 to 600g/mol (e.g., 250g/mol, 300g/mol, 350g/mol, 400g/mol, 450g/mol, 500g/mol, 550g/mol, etc.).
Preferably, the diol is dipropylene glycol and/or diethylene glycol.
Preferably, the polyether with the number average molecular weight of 200-600 g/mol is polyoxypropylene glycol with the number average molecular weight of 200-600 g/mol.
Preferably, the polyisocyanate is an aromatic polyisocyanate.
Preferably, the aromatic polyisocyanate is 4,4' -diphenylmethane diisocyanate.
Preferably, the catalyst is an aliphatic amine catalyst.
Preferably, the aliphatic amine catalyst is dimorpholinyldiethylether.
Preferably, the monofunctional capping agent is a monoalcohol and/or morpholine.
Preferably, the monohydric alcohol is selected from any one of isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol or tert-butanol or a combination of at least two thereof.
Preferably, the raw materials for preparing the moisture-curable polyurethane hot melt adhesive also comprise 0.1 to 0.3 part by weight (for example, 0.12 part by weight, 0.14 part by weight, 0.16 part by weight, 0.18 part by weight, 0.2 part by weight, 0.22 part by weight, 0.24 part by weight, 0.26 part by weight, 0.28 part by weight or 0.29 part by weight) of antioxidant.
Preferably, the antioxidant is triethylene glycol bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylic acid ], illustratively including but not limited to YS 245.
Preferably, the raw materials for preparing the moisture-curable polyurethane hot melt adhesive further comprise 0.01 to 0.06 part by weight (for example, 0.02 part by weight, 0.03 part by weight, 0.04 part by weight or 0.05 part by weight) of a stabilizer.
Preferably, the stabilizer is phosphoric acid.
Preferably, the preparation raw materials of the moisture-curable polyurethane hot melt adhesive comprise the following components in parts by weight:
in another aspect, the present invention provides a preparation method of the moisture-curable polyurethane hot melt adhesive, comprising the following steps:
(1) adding polyether glycol into a reaction container for dehydration, and adding 25-75% (such as 27%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 73% of the formula) of polyisocyanate for reaction;
(2) adding the polyisocyanate with the residual formula amount into the material reacted in the step (1), uniformly mixing, and adding a chain extender for reaction;
(3) adding a monofunctional end-capping reagent into the material reacted in the step (2) for reaction;
(4) and (4) adding a catalyst into the material reacted in the step (3) for reaction to obtain the moisture-curing type polyurethane hot melt adhesive.
In the preparation process of the moisture-curing type polyurethane hot melt adhesive, polyisocyanate is added into a reaction system in batches, namely, firstly, polyisocyanate with the formula amount of 25-75% reacts with polyol, and then, polyisocyanate with the rest formula amount is added. Wherein, the polyisocyanate with the formula amount of 25-75% added in the first step is mainly used for obtaining polyurethane with longer molecular chain, and the molecular chain composed of high molecular weight polyether provides viscosity for the moisture-curing polyurethane hot melt adhesive; the second step adds the remaining amount of the polyisocyanate formulated primarily for strength. If all the polyisocyanates in the formula are added at one time, molecular chains meeting the requirements of chain length and rigidity cannot be obtained, so that the viscosity of the hot melt adhesive is insufficient.
Preferably, the reaction temperature in step (1) is 70-100 ℃, such as 72 ℃, 75 ℃, 77 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 97 ℃ or 99 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction time in step (1) is 3-4 h, such as 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h or 3.9h, and the specific values therebetween are not exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the reaction in step (1) is divided into 2 stages, the reaction temperature in the first stage is 70-80 ℃ (such as 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 79 ℃ and the like), and the reaction time is 2.5-3 h (such as 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3h and the like); the reaction temperature in the second stage is 90-100 deg.C (e.g. 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C or 99 deg.C), and the reaction time is 0.5-1 h (e.g. 0.6h, 0.7h, 0.8h, 0.9h or 1 h).
Preferably, the reaction temperature in step (2) is 90-100 ℃, such as 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃ or 99 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time in step (2) is 0.5-2 h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h or 1.9h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive list of the specific values included in the range.
Preferably, the monofunctional blocking agent of step (3) is added at a temperature of 70-80 ℃, for example 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 79 ℃, and specific values therebetween, are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction temperature in step (3) and step (4) is 70-80 ℃, such as 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 79 ℃, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the reaction time in step (3) and step (4) is 0.5-1 h, such as 0.6h, 0.7h, 0.8h, 0.9h or 1h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the preparation method specifically comprises the following steps:
(1) adding polyether polyol, polyester polyol, a stabilizer and an antioxidant into a reaction container for dehydration, then adding 25-75% of polyisocyanate according to the formula amount, reacting for 2.5-3 h at 70-80 ℃, and then heating to 90-100 ℃ for reacting for 0.5-1 h;
(2) adding the polyisocyanate with the residual formula amount into the material reacted in the step (1), uniformly mixing, adding a chain extender, and reacting for 0.5-2 h at 90-100 ℃;
(3) cooling the material reacted in the step (2) to 70-80 ℃, adding a monofunctional end-capping agent, and reacting for 0.5-1 h at 70-80 ℃;
(4) and (3) adding a catalyst into the material reacted in the step (3), and reacting for 0.5-1 h at 70-80 ℃ to obtain the moisture-curing type polyurethane hot melt adhesive.
In another aspect, the present invention provides a use of the moisture-curable polyurethane hot melt adhesive as described above in textile, electronics, machinery, construction, wood or book binding.
Preferably, the woven material is a nylon fabric.
Compared with the prior art, the invention has the following beneficial effects:
in the moisture-curing polyurethane hot melt adhesive provided by the invention, through screening and compounding of polymerized monomers, the moisture-curing polyurethane hot melt adhesive has proper viscosity and initial bonding strength and strong bonding strengthThe final bonding strength and the bonding stability of the nylon yarn have obvious bonding effect on the nylon yarn compounding. The monofunctional end-capping reagent is introduced into the raw materials for preparing the moisture-curing polyurethane hot melt adhesive, and a part of NCO groups in the system can be sealed, so that the hot melt adhesive still keeps certain viscosity after being cured and converted into a solid state, can be stably bonded with nylon yarns, effectively avoids the phenomenon that the polyurethane system is dislocated with an adherend and is not firmly bonded due to volume change in the curing process, and remarkably improves the bonding strength and the bonding stability. The moisture-curable polyurethane hot melt adhesive provided by the invention has proper viscosity and initial bonding strength, the viscosity is 2750-3500 mPa & s/100 ℃, the opening time is 120-210 min, the final bonding strength and bonding stability are high, and the water pressure resistance can reach 8000-10000 mm H2And O, the requirement for compounding the nylon yarn fabric can be fully met.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The experimental materials used in the examples and comparative examples of the present invention were as follows:
(1) polyether polyol: polyoxypropylene diol, trade name TED-28, number average molecular weight 4000g/mol, hydroxyl value 28mg KOH/g.
(2) Polyester polyol: the number is HDPOL-310P, and the number average molecular weight is 1000 g/mol.
(3) Chain extender: polyoxypropylene diol, trade name PPG 400, number average molecular weight 400 g/mol; dipropylene glycol.
(4) Catalyst: dimorpholinodiethyl ether; a stabilizer: phosphoric acid; antioxidant: under the trade name YS245, triethylene glycol bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylic acid ].
(5) Monofunctional end-capping agent: isopropyl alcohol; morpholine.
(6) Polyisocyanate: 4,4' -diphenylmethane diisocyanate (MDI).
Example 1
The embodiment provides a moisture-curable polyurethane hot melt adhesive, which comprises the following preparation raw materials:
the preparation method comprises the following specific steps:
(1) adding 650 parts by weight of polyoxypropylene glycol (4000), 150 parts by weight of polyester polyol, 0.22 part by weight of antioxidant YS245 and 0.05 part by weight of phosphoric acid into a reaction vessel, mixing and dehydrating until the water content is less than or equal to 500ppm, then adding 117 parts by weight of MDI, reacting for 3 hours at 75 ℃, and then heating to 95 ℃ for 1 hour;
(2) adding 126 parts by weight of MDI (diphenyl-methane-diisocyanate) into the material reacted in the step (1), stirring for 0.5h, uniformly mixing, adding 67.87 parts by weight of chain extender polyoxypropylene glycol (400), and reacting for 2h at 95 ℃;
(3) cooling the material reacted in the step (2) to 75 ℃, adding 3.17 parts by weight of isopropanol, and reacting for 0.5h at 75 ℃;
(4) and (3) adding 0.55 part by weight of dimorpholinyl diethyl ether into the material reacted in the step (3), and reacting for 0.5h at 75 ℃ to obtain the moisture-curing type polyurethane hot melt adhesive.
Example 2
The embodiment provides a moisture-curable polyurethane hot melt adhesive, which comprises the following preparation raw materials:
the preparation method comprises the following specific steps:
(1) adding 700 parts by weight of polyoxypropylene glycol (4000), 100 parts by weight of polyester polyol, 0.21 part by weight of antioxidant YS245 and 0.05 part by weight of phosphoric acid into a reaction vessel, mixing and dehydrating until the water content is less than or equal to 500ppm, then adding 103.12 parts by weight of MDI, reacting for 3 hours at 70 ℃, and then heating to 90 ℃ for reacting for 1 hour;
(2) adding 146.58 parts by weight of MDI into the material reacted in the step (1), stirring for 0.5h, uniformly mixing, adding 38 parts by weight of chain extender dipropylene glycol, and reacting for 1h at 90 ℃;
(3) cooling the material reacted in the step (2) to 70 ℃, adding 3.02 parts by weight of isopropanol, and reacting for 0.5h at 70 ℃;
(4) and (3) adding 0.52 part by weight of dimorpholinyl diethyl ether into the material reacted in the step (3), and reacting at 70 ℃ for 0.5h to obtain the moisture-curing type polyurethane hot melt adhesive.
Example 3
The embodiment provides a moisture-curable polyurethane hot melt adhesive, which comprises the following preparation raw materials:
the preparation method comprises the following specific steps:
(1) adding 800 parts by weight of polyoxypropylene glycol (4000), 0.25 part by weight of antioxidant YS245 and 0.06 part by weight of phosphoric acid into a reaction vessel, mixing and dehydrating until the water content is less than or equal to 500ppm, then adding 75 parts by weight of MDI, reacting at 80 ℃ for 3 hours, and heating to 100 ℃ for 1 hour;
(2) adding 217.5 parts by weight of MDI (diphenyl-methane-diisocyanate) into the material reacted in the step (1), stirring for 0.5h, uniformly mixing, adding 181.8 parts by weight of chain extender polyoxypropylene glycol (400), and reacting for 2h at 100 ℃;
(3) cooling the material reacted in the step (2) to 80 ℃, then adding 5.27 parts by weight of morpholine, and reacting for 0.5h at 80 ℃;
(4) and (3) adding 0.6 part by weight of dimorpholinyl diethyl ether into the material reacted in the step (3), and reacting for 0.5h at 80 ℃ to obtain the moisture-curing type polyurethane hot melt adhesive.
Example 4
The embodiment provides a moisture-curable polyurethane hot melt adhesive, which comprises the following preparation raw materials:
the preparation method comprises the following specific steps:
(1) adding 800 parts by weight of polyoxypropylene glycol (4000), 0.22 part by weight of antioxidant YS245 and 0.05 part by weight of phosphoric acid into a reaction vessel, mixing and dehydrating until the water content is less than or equal to 500ppm, then adding 75 parts by weight of MDI, reacting for 3 hours at 80 ℃, and heating to 95 ℃ for 1 hour;
(2) adding 191 parts by weight of MDI (diphenyl-methane-diisocyanate) into the material reacted in the step (1), stirring for 0.5h, uniformly mixing, adding 55 parts by weight of chain extender dipropylene glycol, and reacting for 1h at 95 ℃;
(3) cooling the material reacted in the step (2) to 75 ℃, then adding 4.64 parts by weight of morpholine, and reacting for 0.5h at 75 ℃;
(4) and (3) adding 0.56 part by weight of dimorpholinyl diethyl ether into the material reacted in the step (3), and reacting for 0.5h at 75 ℃ to obtain the moisture-curing type polyurethane hot melt adhesive.
Example 5
This example is different from example 1 in that the monofunctional end-capping agent isopropanol was used in an amount of 8 parts by weight as a preparation raw material, and the rest of the preparation raw material and the preparation steps were the same as those of example 1.
Comparative example 1
This comparative example differs from example 1 in that the starting materials were prepared without the monofunctional blocking agent isopropanol, and the remaining starting materials and preparation steps were the same as in example 1.
Comparative example 2
This comparative example is different from example 1 in that the monofunctional group terminator isopropanol was used in an amount of 2 parts by weight in the preparation starting materials, and the remaining preparation starting materials and preparation steps were the same as those of example 1.
Comparative example 3
This comparative example is different from example 1 in that the monofunctional group terminator isopropanol was used in an amount of 9 parts by weight in the preparation starting materials, and the remaining preparation starting materials and preparation steps were the same as those of example 1.
Comparative example 4
This comparative example is different from example 1 in that the monofunctional blocking agent isopropanol in the preparation starting material was replaced with an equal part by weight of silane blocking agent (N-phenyl-3-aminopropyltrimethoxysilane, trade name Y9669), and the remaining preparation starting materials and preparation steps were the same as in example 1.
Comparative example 5
This comparative example was the same as the preparation raw material of example 1 except for the preparation procedure.
The preparation method comprises the following specific steps:
(1) adding 650 parts by weight of polyoxypropylene glycol (4000), 150 parts by weight of polyester polyol, 0.22 part by weight of antioxidant YS245 and 0.05 part by weight of phosphoric acid into a reaction vessel, mixing and dehydrating until the water content is less than or equal to 500ppm, then adding 243 parts by weight of MDI, reacting for 3 hours at 75 ℃, and then heating to 95 ℃ for 1 hour;
(2) adding 67.87 parts by weight of chain extender polyoxypropylene glycol (400) into the material reacted in the step (1), and reacting for 2 hours at 95 ℃;
(3) cooling the material reacted in the step (2) to 75 ℃, adding 3.17 parts by weight of isopropanol, and reacting for 0.5h at 75 ℃;
(4) and (3) adding 0.55 part by weight of dimorpholinyl diethyl ether into the material reacted in the step (3), and reacting for 0.5h at 75 ℃ to obtain the moisture-curing type polyurethane hot melt adhesive.
And (3) performance testing:
(1) viscosity: the units are mPas/100 ℃, and the test is carried out according to the method specified in the standard GB/T2794-2013.
(2) Opening time: in min, according to the method specified in the standard ASTM D4497-1994 (2004).
(3) Water pressure resistance: unit is mm H2O, the test method comprises the following steps: coating the moisture-curing polyurethane hot melt adhesive on a TPU film to be compounded with nylon yarns, wherein the average coating weight is 11g/m2The water pressure resistance test was carried out after curing at 23 ℃ and 65% relative humidity for 24 h.
The viscosity, the open time and the water pressure resistance of the moisture-curable polyurethane hot melt adhesives provided in examples 1 to 5 and comparative examples 1 to 5 of the present invention were measured according to the methods described above, and the specific data are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the moisture-curable polyurethane hot melt adhesives provided in the embodiments 1 to 5 of the present invention have suitable viscosity and initial adhesive strength, the viscosity of the moisture-curable polyurethane hot melt adhesives is 2750 to 3500mPa · s/100 ℃, the open time of the moisture-curable polyurethane hot melt adhesives is 120 to 210min, the final adhesive strength and the adhesive stability are high, and the water pressure resistance can reach 8000 to 10000mm H2And O, the requirement for compounding the nylon yarn fabric can be fully met.
If the raw materials for preparing the moisture-curing type polyurethane hot melt adhesive do not contain the monofunctional end-capping reagent (comparative example 1) or the amount of the monofunctional end-capping reagent is too small (comparative example 2), the final adhesive force of the moisture-curing type polyurethane hot melt adhesive is reduced, and the water pressure resistance is lower; and the use amount of the monofunctional end-capping agent in the raw materials for preparation is too much (comparative example 3), so that the capped chain segments are more, the capped chain segments do not participate in the curing reaction, the modulus of the final system is low, even if the water pressure resistance is higher, the cured chain segments still stick to the hand, and the method cannot be applied to the compounding of nylon fabrics and polymer films (TPU films).
If the monofunctional end-capping agent in the preparation raw material is replaced by the silane end-capping agent N-phenyl-3-aminopropyltrimethoxysilane (comparative example 4), the obtained moisture-curable polyurethane hot melt adhesive still has the problem of low adhesive property. The principle of improving the bonding effect of the silane end capping agent is that the siloxy reacts with water to release silanol, and the silanol and the small molecular alcohol are mutually condensed or form a hydrogen bond with the hydroxyl of the substrate, so that the bonding property is improved; however, the advantages of nylon yarns cannot be realized on the premise that nylon yarns are not subjected to surface treatment, so that the silane end-capping agent cannot achieve the effect of improving the bonding performance in the nylon yarn composite system.
In the preparation process of the moisture-curing type polyurethane hot melt adhesive, polyisocyanate is added into a reaction system for reaction twice, so that the obtained product has proper viscosity and higher bonding strength; if the polyisocyanate is added into the reaction system (comparative example 5) all at once, the final bonding strength of the hot melt adhesive is reduced, and the hand feeling is hard, so that the later application of the nylon yarn composite material is influenced.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it is not meant to be construed as being limited thereto. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (32)
1. The moisture-curing polyurethane hot melt adhesive is characterized in that the preparation raw materials of the moisture-curing polyurethane hot melt adhesive comprise the following components in parts by weight:
the monofunctional end-capping reagent is monohydric alcohol and/or morpholine, and the monohydric alcohol is selected from any one or combination of at least two of isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol or tert-butanol;
the moisture-curable polyurethane hot melt adhesive is prepared by adopting the following method, and the method comprises the following steps:
(1) adding polyether polyol into a reaction container for dehydration, and adding polyisocyanate with the formula amount of 25-75% for reaction;
(2) adding the polyisocyanate with the residual formula amount into the material reacted in the step (1), uniformly mixing, and adding a chain extender for reaction;
(3) adding a monofunctional end-capping reagent into the material reacted in the step (2) for reaction;
(4) and (4) adding a catalyst into the material reacted in the step (3) for reaction to obtain the moisture-curing type polyurethane hot melt adhesive.
2. The moisture-curing polyurethane hot melt adhesive according to claim 1, wherein the polyether polyol has a hydroxyl value of 28-112 mg KOH/g.
3. The moisture-curing polyurethane hot melt adhesive according to claim 1, wherein the hydroxyl value of the polyether polyol is 28-37 mg KOH/g.
4. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the polyether polyol has a number average molecular weight of 3000 to 4000 g/mol.
5. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the polyether polyol is a polyoxypropylene glycol.
6. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the raw materials for preparing the moisture-curable polyurethane hot melt adhesive further comprise 1-200 parts by weight of polyester polyol.
7. The moisture-curable polyurethane hot melt adhesive according to claim 6, wherein the polyester polyol has a number average molecular weight of 500 to 1500 g/mol.
8. The moisture-curable polyurethane hot melt adhesive according to claim 6, wherein the polyester polyol is selected from any one of or a combination of at least two of neopentyl glycol polyphthalate, polyethylene phthalate, or neopentyl glycol terephthalate.
9. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the chain extender is a diol and/or a polyether having a number average molecular weight of 200-600 g/mol.
10. The moisture-curable polyurethane hot melt adhesive according to claim 9, wherein the glycol is dipropylene glycol and/or diethylene glycol.
11. The moisture-curable polyurethane hot melt adhesive according to claim 9, wherein the polyether is a polyoxypropylene glycol.
12. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the polyisocyanate is an aromatic polyisocyanate.
13. The moisture-curable polyurethane hot melt adhesive according to claim 12, wherein the aromatic polyisocyanate is 4,4' -diphenylmethane diisocyanate.
14. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the catalyst is an aliphatic amine catalyst.
15. The moisture-curable polyurethane hot melt adhesive according to claim 14, wherein the aliphatic amine catalyst is dimorpholinyldiethylether.
16. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the raw materials for preparing the moisture-curable polyurethane hot melt adhesive further comprise 0.1-0.3 part by weight of an antioxidant.
17. The moisture-curable polyurethane hot melt adhesive according to claim 16, wherein the antioxidant is triethylene glycol bis- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylic acid ].
18. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the raw materials for preparing the moisture-curable polyurethane hot melt adhesive further comprise 0.01-0.06 part by weight of a stabilizer.
19. The moisture-curable polyurethane hot melt adhesive according to claim 18, wherein the stabilizer is phosphoric acid.
20. The moisture-curable polyurethane hot melt adhesive according to claim 1, which is characterized in that the preparation raw materials of the moisture-curable polyurethane hot melt adhesive comprise the following components in parts by weight:
21. the preparation method of the moisture-curing polyurethane hot melt adhesive as claimed in any one of claims 1 to 20, wherein the preparation method comprises the following steps:
(1) adding polyether polyol into a reaction container for dehydration, and adding polyisocyanate with the formula amount of 25-75% for reaction;
(2) adding the polyisocyanate with the residual formula amount into the material reacted in the step (1), uniformly mixing, and adding a chain extender for reaction;
(3) adding a monofunctional end-capping reagent into the material reacted in the step (2) for reaction;
(4) and (4) adding a catalyst into the material reacted in the step (3) for reaction to obtain the moisture-curing type polyurethane hot melt adhesive.
22. The method according to claim 21, wherein the temperature of the reaction in the step (1) is 70 to 100 ℃.
23. The preparation method of claim 21, wherein the reaction time in the step (1) is 3-4 h.
24. The preparation method according to claim 21, wherein the reaction in the step (1) is divided into 2 stages, the reaction temperature in the first stage is 70-80 ℃, and the reaction time is 2.5-3 h; the reaction temperature of the second stage is 90-100 ℃, and the reaction time is 0.5-1 h.
25. The method according to claim 21, wherein the temperature of the reaction in the step (2) is 90 to 100 ℃.
26. The preparation method of claim 21, wherein the reaction time in the step (2) is 0.5-2 h.
27. The method according to claim 21, wherein the monofunctional blocking agent used in step (3) is added at a temperature of 70 to 80 ℃.
28. The method according to claim 21, wherein the reaction temperature in the steps (3) and (4) is 70 to 80 ℃ independently of each other.
29. The method according to claim 21, wherein the reaction time in the steps (3) and (4) is 0.5 to 1 hour.
30. The method according to claim 21, comprising the steps of:
(1) adding polyether polyol, polyester polyol, a stabilizer and an antioxidant into a reaction container for dehydration, then adding 25-75% of polyisocyanate according to the formula amount, reacting for 2.5-3 h at 70-80 ℃, and then heating to 90-100 ℃ for reacting for 0.5-1 h;
(2) adding the polyisocyanate with the residual formula amount into the material reacted in the step (1), uniformly mixing, adding a chain extender, and reacting for 0.5-2 h at 90-100 ℃;
(3) cooling the material reacted in the step (2) to 70-80 ℃, adding a monofunctional end-capping agent, and reacting for 0.5-1 h at 70-80 ℃;
(4) and (3) adding a catalyst into the material reacted in the step (3), and reacting for 0.5-1 h at 70-80 ℃ to obtain the moisture-curing type polyurethane hot melt adhesive.
31. Use of the moisture-curable polyurethane hot melt adhesive according to any one of claims 1 to 20 in textile, electronics, machinery, construction, wood or book binding.
32. Use according to claim 31, wherein the woven material is a nylon fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911327622.4A CN110964475B (en) | 2019-12-20 | 2019-12-20 | Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911327622.4A CN110964475B (en) | 2019-12-20 | 2019-12-20 | Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110964475A CN110964475A (en) | 2020-04-07 |
| CN110964475B true CN110964475B (en) | 2022-02-22 |
Family
ID=70035718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911327622.4A Active CN110964475B (en) | 2019-12-20 | 2019-12-20 | Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110964475B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423837B (en) * | 2020-04-08 | 2022-04-05 | 上海抚佳精细化工有限公司 | TPU hot melt adhesive and preparation method thereof |
| CN113025258A (en) * | 2021-04-07 | 2021-06-25 | 无锡莱恩科技有限公司 | Moisture-curing hot melt adhesive for compounding flexible printed circuit board and preparation method thereof |
| CN114806486B (en) * | 2022-05-31 | 2023-05-30 | 韦尔通科技股份有限公司 | Preparation method of heat-conducting filler and high-heat-conducting reactive polyurethane hot melt adhesive composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752169A (en) * | 2005-09-28 | 2006-03-29 | 东北林业大学 | Wet solidified polyurethane thermosol and preparing process thereof |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
| CN105367736A (en) * | 2015-12-01 | 2016-03-02 | 烟台德邦科技有限公司 | Preparation method for polyurethane hot melt adhesive with good reworking performance |
| CN107857867A (en) * | 2017-11-28 | 2018-03-30 | 四川正大新材料科技有限公司 | A kind of formula of polyurethane sealing package material and the encapsulating material containing the formula |
| CN109609074A (en) * | 2018-12-03 | 2019-04-12 | 南通天洋新材料有限公司 | A kind of preparation method of wet-solidifying single-component polyurethane hot melt adhesive |
| CN110382649A (en) * | 2017-03-09 | 2019-10-25 | H.B.富乐公司 | Reactive hot-melt with low monomeric diisocyanate content melts polyurethane binder |
-
2019
- 2019-12-20 CN CN201911327622.4A patent/CN110964475B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752169A (en) * | 2005-09-28 | 2006-03-29 | 东北林业大学 | Wet solidified polyurethane thermosol and preparing process thereof |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
| CN105367736A (en) * | 2015-12-01 | 2016-03-02 | 烟台德邦科技有限公司 | Preparation method for polyurethane hot melt adhesive with good reworking performance |
| CN110382649A (en) * | 2017-03-09 | 2019-10-25 | H.B.富乐公司 | Reactive hot-melt with low monomeric diisocyanate content melts polyurethane binder |
| CN107857867A (en) * | 2017-11-28 | 2018-03-30 | 四川正大新材料科技有限公司 | A kind of formula of polyurethane sealing package material and the encapsulating material containing the formula |
| CN109609074A (en) * | 2018-12-03 | 2019-04-12 | 南通天洋新材料有限公司 | A kind of preparation method of wet-solidifying single-component polyurethane hot melt adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110964475A (en) | 2020-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110964475B (en) | Moisture-curing polyurethane hot melt adhesive and preparation method and application thereof | |
| US20180016385A1 (en) | Polyurethane, and its preparation method and use | |
| EP2547744B1 (en) | Silane moisture curable hot melts | |
| CN110229645B (en) | High initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN110114380B (en) | Two-component polyurethane adhesive | |
| KR101875173B1 (en) | Mdi based linings and membranes from prepolymers with very low free monomeric isocyanates | |
| CN107459959B (en) | Boiling-resistant solvent-free adhesive for flexible package and preparation method thereof | |
| US11629277B2 (en) | Moisture curable polyurethane adhesive composition | |
| WO2008067967A2 (en) | Unsaturated polymers | |
| CN111303819B (en) | Low-odor high-initial-adhesion single-component moisture curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN108048020B (en) | Single-component moisture-curing reaction type polyurethane hot melt adhesive and preparation method thereof | |
| CN114450323A (en) | Low free polyurethane prepolymer compositions | |
| US20120172524A1 (en) | Reactive hot-melt adhesive agent composition | |
| CN112552859B (en) | High-initial-adhesion low-shrinkage high-strength polyurethane hot melt adhesive and preparation method thereof | |
| KR20170066338A (en) | A reactive polyurethane hot melt adhesive and the use thereof | |
| US20170158929A1 (en) | Reactive Hot-Melt Adhesive Composition | |
| CN111909348A (en) | Reactive polyurethane hot melt adhesive composition and preparation and application thereof | |
| CN113861852A (en) | Single-component moisture curing reaction type polyurethane hot melt adhesive for electronic products and preparation method thereof | |
| CN109355061B (en) | Epoxy soybean oil adhesive with function of modifying polyurethane by amine curing agent and preparation method thereof | |
| CN116162434A (en) | Epoxy modified low-VOC (volatile organic compound) double-component polyurethane adhesive and preparation method thereof | |
| CN113214772B (en) | Reactive polyurethane hot melt adhesive and preparation method and application thereof | |
| CN109852323A (en) | Organic-silicon-modified one-component reaction type polyurethane hot-melt adhesive and preparation method thereof | |
| CN110885660A (en) | Polyurethane hot melt adhesive for low surface energy material and preparation method thereof | |
| CN114262597A (en) | Single-component thermosetting polyurethane modified epoxy structural adhesive and preparation method thereof | |
| CN110003423B (en) | Modified isocyanate prepolymer, polyurethane composite material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |