CN113698909B - High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof - Google Patents
High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN113698909B CN113698909B CN202111079787.1A CN202111079787A CN113698909B CN 113698909 B CN113698909 B CN 113698909B CN 202111079787 A CN202111079787 A CN 202111079787A CN 113698909 B CN113698909 B CN 113698909B
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention provides a high-temperature-resistant polyurethane hot melt adhesive which is prepared from the following raw materials: 50-100 parts by weight of polyester polyol; 10-30 parts by weight of polyether polyol; 5-25 parts by weight of dimer acid modified polyol; 8-30 parts by weight of isocyanate; 25-60 parts of tackifying resin; 0.1-1.5 parts by weight of an antioxidant; 0.1-5 parts by weight of carbon black; 0.1-3 parts by weight of a bonding promoter; 0.1-2 parts by weight of a damp-heat resistant agent; 0.05-0.5 part by weight of a catalyst; the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol; the weight ratio of the liquid polyester polyol in the polyester polyol is less than 40 percent. Compared with the prior art, the high-temperature resistant polyurethane hot melt adhesive provided by the invention adopts specific content components, realizes better overall interaction, has the characteristic of high-temperature bonding strength, and can be used for vehicle lamp assembly.
Description
Technical Field
The invention relates to the technical field of polyurethane sealants, in particular to a high-temperature-resistant polyurethane hot melt adhesive and a preparation method thereof.
Background
The bonding and sealing of the lamp is an important part of the manufacturing process of the automobile lamp. The bonding of car light should be able to guarantee that the car light does not appear when using under various adverse circumstances and receives the problem such as the atress is come unstuck, infiltration oil impregnate and is oozed and discolour and haze. In conventional vehicular lamp bonding applications, ordinary hot melt adhesives and two-component silicone adhesives are commonly used; the traditional hot melt adhesive has the advantages of fast curing and good initial adhesion, and is mainly used for bonding the traditional vehicle lamp. However, the main component of the hot melt adhesive is thermoplastic polyolefin, which is very sensitive to temperature change, is easy to flow when heated, and is also very sensitive to the permeation of water and gasoline, so that the weight problems of water leakage, fogging and the like of the car lamp are caused in use, and even the whole car lamp is scrapped; on the other hand, the adhesive force between the polyolefin hot melt adhesive and the polycarbonate material of one of the car lamp structures is insufficient, and particularly, the polycarbonate is easy to open after surface hardening and wear-resistant treatment, so that the requirement of a user on the adhesive strength of the car lamp is difficult to meet. Although the two-component silicone adhesive has improved high and low temperature performance, the initial adhesion is poor, and the devices are often not movable after being placed for hours, occupying space and prolonging delivery time. Therefore, the development of the polyurethane hot melt adhesive for the vehicle lamp with high initial adhesion and high temperature resistance is always a research and development hotspot.
The reactive polyurethane hot melt adhesive (PUR adhesive for short) is prepared by matching single-component solvent-free isocyanate-terminated prepolymer with corresponding auxiliary agent; the main component of the adhesive is an isocyanate-terminated prepolymer synthesized by polyester polyol and diisocyanate, and the adhesive can be quickly cured after being melted and sized and has better initial adhesive strength; in the post-curing process, moisture diffuses into the adhesive and reacts with isocyanate at the end group of the prepolymer to form urea, biuret and allophanate, so that linear prepolymer low molecules form a cross-linked macromolecular structure, and the hot melt adhesive has better high temperature resistance, solvent resistance and water resistance than the traditional hot melt adhesive. PUR is selected as the adhesive for the car lamp, and has the advantages of hot melt adhesive and single-component silica gel: similar to common hot melt adhesives, when the PUR adhesive is used, the PUR adhesive is heated, melted and coated on the automobile lamp through an adhesive melting machine, and is rapidly cooled and solidified to achieve higher initial bonding strength, and a bonded piece can be moved, assembled and the like; then, during the storage or transportation process of the product, the PUR adhesive can continuously react with moisture in the air, the curing degree is further increased, and the PUR adhesive becomes a colloid with high strength, temperature resistance and solvent corrosion resistance. The polyurethane car lamp adhesive has the advantages of the traditional hot melt adhesive and the double-component silicone adhesive, and can perfectly solve the contradiction between quick positioning and high-strength bonding in car lamp bonding, so that the polyurethane car lamp adhesive is an ideal substitute for the car lamp bonding adhesive.
At present, performance reports about reactive polyurethane hot melt adhesives in a plurality of patents of reactive polyurethane hot melt adhesives for vehicle lamps mainly focus on the aspects of high initial adhesion strength and strength after complete curing; for example, chinese patent publication No. CN103740316A discloses a moisture-curable polyurethane hot melt adhesive for vehicle lamps and a preparation method thereof, wherein the moisture-curable polyurethane hot melt adhesive comprises the following components in parts by weight: 60-85 parts of polyester polyol, 15-20 parts of polyisocyanate, 1-10 parts of carbon black and 0.0001-0.001 part of catalyst; the method has no tackifying resin, and the prepared polyurethane hot melt adhesive has relatively poor high-temperature adhesion to the base material of the car lamp.
Because the temperature of the hot melt adhesive part is high in the using process of the automobile lamp, the requirement on the high-temperature adhesive force of the automobile lamp adhesive is high (generally 85 ℃, the PP/PC adhesive force of the automobile lamp substrate is more than 400N); in the conventional formula of the polyurethane hot melt adhesive, the content of tackifying resin is low, so that the high-temperature adhesive property of the hot melt adhesive is poor, and no effective method for improving the high-temperature adhesive property of the polyurethane hot melt adhesive to a vehicle lamp substrate exists at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a high temperature resistant polyurethane hot melt adhesive and a preparation method thereof, and the high temperature resistant polyurethane hot melt adhesive provided by the present invention has the characteristic of high temperature bonding strength, and can be used for vehicle lamp assembly.
The invention provides a high-temperature-resistant polyurethane hot melt adhesive which is prepared from the following raw materials:
50-100 parts by weight of polyester polyol;
10-30 parts by weight of polyether polyol;
5-25 parts by weight of dimer acid modified polyol;
8-30 parts by weight of isocyanate;
25-60 parts of tackifying resin;
0.1-1.5 parts by weight of an antioxidant;
0.1-5 parts by weight of carbon black;
0.1-3 parts by weight of a bonding promoter;
0.1-2 parts by weight of a damp-heat resistant agent;
0.05-0.5 part by weight of a catalyst;
the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol; the weight ratio of the liquid polyester polyol in the polyester polyol is less than 40 percent.
Preferably, the hydroxyl value of the solid polyester polyol is 10-50 KOH/mg; the solid polyester polyol is prepared by polycondensation of one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, phthalic anhydride and 1, 4-cyclohexanedicarboxylic acid with one or more of 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, neopentyl glycol, diethylene glycol, 1, 2-propanediol and 2-methylpropanediol; the softening point of the solid polyester polyol is more than 75 ℃.
Preferably, the hydroxyl value of the liquid polyester polyol is 18-80 KOH/mg.
Preferably, the hydroxyl value of the polyether polyol is 25-160 KOH/mg; the polyether polyol is selected from one or more of polyoxypropylene diol, polyoxypropylene triol and polytetrahydrofuran ether diol.
Preferably, the hydroxyl value of the dimer acid modified polyol is 35-80 KOH/mg.
Preferably, the isocyanate is selected from toluene diisocyanate and/or diphenylmethane diisocyanate; the ratio of isocyanate to hydroxyl of polyol is 1.4-2.0.
Preferably, the tackifying resin is selected from one or more of acrylic resin, hydroxy acrylic resin and polyester resin; the molecular weight of the tackifying resin is 20000-100000, the hydroxyl value is 0-10 KOH/mg, and the softening point is more than 90 ℃.
Preferably, the adhesion promoter is selected from one or more of bis- (gamma-trimethoxysilylpropyl) amine, gamma-mercaptopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-isocyanatopropyltrimethoxysilane and N-phenyl-gamma-aminopropyltrimethoxysilane.
Preferably, the catalyst is selected from one or more of dibutyltin dilaurate, triethylenediamine and dimorpholinodiethyl ether.
The invention also provides a preparation method of the high-temperature-resistant polyurethane hot melt adhesive, which comprises the following steps:
mixing polyester polyol, polyether polyol, dimer acid modified polyol and tackifying resin, then dehydrating in vacuum at 110-130 ℃ for 1-3 h until the water content is less than or equal to 500ppm, then cooling to 80-90 ℃, adding isocyanate, reacting at 80-100 ℃ for 1-3 h, then adding a damp-heat resistant agent and carbon black, and continuing stirring for 0.5-1 h; and finally, adding an antioxidant, a bonding promoter and a catalyst, and reacting for 20-60 min at 90-120 ℃ under a vacuum condition to obtain the high-temperature-resistant polyurethane hot melt adhesive.
The invention provides a high-temperature-resistant polyurethane hot melt adhesive which is prepared from the following raw materials: 50-100 parts by weight of polyester polyol; 10-30 parts by weight of polyether polyol; 5-25 parts by weight of dimer acid modified polyol; 8-30 parts by weight of isocyanate; 25-60 parts of tackifying resin; 0.1-1.5 parts by weight of an antioxidant; 0.1-5 parts by weight of carbon black; 0.1-3 parts by weight of a bonding promoter; 0.1-2 parts by weight of a damp-heat resistant agent; 0.05-0.5 part by weight of a catalyst; the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol; the weight ratio of the liquid polyester polyol in the polyester polyol is less than 40 percent. Compared with the prior art, the high-temperature resistant polyurethane hot melt adhesive provided by the invention adopts specific content components, realizes better overall interaction, has the characteristic of high-temperature bonding strength, and can be used for vehicle lamp assembly. The experimental result shows that the conventional adhesiveness of the high-temperature-resistant polyurethane hot melt adhesive is 1679-1710N, the adhesiveness at 85 ℃ is 860-1056N, the high-temperature-resistant polyurethane hot melt adhesive has the characteristic of high-temperature adhesive strength after complete curing, and the high-temperature-resistant polyurethane hot melt adhesive can be used as a hot melt adhesive for vehicle lamps.
In addition, the preparation method provided by the invention has the advantages of easily available raw materials, simple operation, mild conditions and excellent industrial application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high-temperature-resistant polyurethane hot melt adhesive which is prepared from the following raw materials:
50-100 parts by weight of polyester polyol;
10-30 parts by weight of polyether polyol;
5-25 parts by weight of dimer acid modified polyol;
8-30 parts by weight of isocyanate;
25-60 parts of tackifying resin;
0.1-1.5 parts by weight of an antioxidant;
0.1-5 parts by weight of carbon black;
0.1-3 parts by weight of a bonding promoter;
0.1-2 parts by weight of a damp-heat resistant agent;
0.05-0.5 part by weight of a catalyst;
the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol; the weight ratio of the liquid polyester polyol in the polyester polyol is less than 40 percent.
In the invention, the high-temperature-resistant polyurethane hot melt adhesive is prepared from the following raw materials:
50-100 parts by weight of polyester polyol;
10-30 parts by weight of polyether polyol;
5-25 parts by weight of dimer acid modified polyol;
8-30 parts by weight of isocyanate;
25-60 parts of tackifying resin;
0.1-1.5 parts by weight of an antioxidant;
0.1-5 parts by weight of carbon black;
0.1-3 parts by weight of a bonding promoter;
0.1-2 parts by weight of a damp-heat resistant agent;
0.05-0.5 part by weight of a catalyst;
the compound is preferably prepared from the following raw materials:
55-80 parts by weight of polyester polyol;
15-25 parts by weight of polyether polyol;
6-20 parts by weight of dimer acid modified polyol;
11-22 parts by weight of isocyanate;
40-50 parts of tackifying resin;
0.2 part by weight of antioxidant;
1-1.5 parts by weight of carbon black;
1-2 parts of a bonding promoter;
0.2-0.6 part by weight of a damp-heat resistant agent;
0.1 to 0.2 part by weight of a catalyst.
In the present invention, the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol, preferably solid polyester polyol or a mixture of solid polyester polyol and liquid polyester polyol (wherein the weight ratio of the liquid polyester polyol in the polyester polyol is < 40%, preferably the weight ratio of the liquid polyester polyol in the polyester polyol is 1/3).
In the invention, the hydroxyl value of the solid polyester polyol is preferably 10-50 KOH/mg; the solid polyester polyol is preferably solid polyester polyol formed by polycondensation of one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, phthalic anhydride and 1, 4-cyclohexanedicarboxylic acid with one or more of 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, neopentyl glycol, diethylene glycol, 1, 2-propanediol and 2-methylpropanediol; the softening point of the solid polyester polyols is preferably > 75 ℃. The source of the solid polyester polyol is not particularly limited in the present invention, and commercially available products known to those skilled in the art can be used, and the solid polyester polyol is selected from but not limited to Dynacoll7380, Dynacoll 7330, Dynacoll7130, Dynacoll7131, Dynacoll 7140, Dynacoll 7150, Dynacoll 7320, Dynacoll7340, Dynacoll 7331, Dynacoll7390, Dynacoll 7321; hooke F-3000, F-7530, F-3230, F-24230, F-7931, F-88933, F-39030, F-39031, F-37070 and F-37033, and is preferably one or two of Dynacoll7340, Dynacoll7130, Dynacoll7390 and Dynacoll 7331.
In the invention, the hydroxyl value of the liquid polyester polyol is preferably 18-80 KOH/mg. The source of the liquid polyester polyol is not particularly limited, and the liquid polyester polyol can be obtained from commercially available commodities known to a person skilled in the art, and the commercially available commodities are selected from but not limited to Yongchuang Dynacoll7210, Dynacoll7250, Dynacoll7230, Dynacoll 7255 and Dynacoll 7231; hooke F-37040, F-4910, F-37030, F-37031, F-37032, FJ-20030, preferably Dynacoll 7231.
In the invention, the hydroxyl value of the polyether polyol is preferably 25-160 KOH/mg; the polyether polyol is preferably selected from one or more of polyoxypropylene diol, polyoxypropylene triol and polytetrahydrofuran ether diol. The source of the polyether polyol is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used, wherein the polyoxypropylene glycol is selected from, but not limited to, DL2000, DL1000, DL4000, Vanhua chemical
C2010D，
C2020，
C2030，
C2040D, VORANOL 2110TB of Dow chemical, VORANOL 2120, VORANOL 3000LM, VORANOL 4240, VORANOL 222-; the polypropylene oxideAlkene triol is selected from one or more of, but not limited to, Voranol 1000LM, Voranol 3003N, Voranol 4701, Voranol CP6001, Voratec SD301, Voranol 230-42N, Voranol WT5000, Voranol 2471, Voranol4000LM, Wanhua chemical WANOL F3056D, WANOL F3128, WANOL F3135, WANOL F3156; the polytetrahydrofuran ether diol is selected from one or more of, but not limited to, mitsubishi chemical PTMG type diol PTMG-1000, PTMG-2000, PTMG-3000, PTMG-4000, dawn PTMEG-1000, PTMEG-2000, PTMEG-3000 diols, preferably VORANOL 1000LM polyether polyol, VORANOL 3003N polyether polyol, PTMG-2000 polyether polyol, or VORANOL4000LM polyether polyol.
In the invention, the hydroxyl value of the dimer acid modified polyol is preferably 35-80 KOH/mg. The source of the dimer acid-modified polyol is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used, and the dimer acid-modified polyol is selected from, but not limited to, procollasts 3190, 3191, 3192, 3190, and/or primlasts 3190, and preferably is dimer acid primlasts 3190.
In the present invention, the isocyanate is preferably selected from toluene diisocyanate and/or diphenylmethane diisocyanate, more preferably toluene diisocyanate or diphenylmethane diisocyanate. The source of the isocyanate is not particularly limited in the present invention, and commercially available ones well known to those skilled in the art may be used. In the present invention, the ratio (R value) of the isocyanate to the hydroxyl group of the polyol is preferably 1.4 to 2.0.
In the present invention, the tackifying resin is preferably one or more selected from acrylic resins, hydroxyacrylic resins, and polyester resins, and more preferably acrylic resins. The source of the tackifying resin is not particularly limited, and commercially available products known to those skilled in the art can be adopted, and the tackifying resin is selected from but not limited to AC1420, AC1520, AC1620, AC1630, AC1631, AC1920, AC4830, AC2740, mitsubishi BR106, BR116, BR113, celluloid Elvacite 2013, Elvacite 2016, Elvacite5013, Elvacite4014, toyobo GK255, VYLON822, VYLON290, VYLON296, GK885, GK880, GK888, GM900, GM913, GM920, GM990, GM6400, GM420-K01, 30P, and is preferably one or more of the group consisting of the acrylic resins AC1631, AC1620, AC1920 and AC 4830.
In the invention, the molecular weight of the tackifying resin is preferably 20000-100000, the hydroxyl value is preferably 0-10 KOH/mg, and the softening point is preferably more than 90 ℃.
In the present invention, the antioxidant preferably comprises, more preferably consists of, a primary antioxidant and a secondary antioxidant; the primary antioxidant is preferably selected from one or more of RIANOX1010, RIANOX1076 and RIANOX1790, more preferably RIANOX 1010; the auxiliary antioxidant is preferably selected from one or more of RIANOX168, RIANOX 626, RIANOXDSTP and RIANOX DLTP, more preferably RIANOX 168. The source of the antioxidant is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the adhesion promoter is preferably selected from one or more of bis- (gamma-trimethoxysilylpropyl) amine, gamma-mercaptopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-isocyanatopropyltrimethoxysilane, and N-phenyl-gamma-aminopropyltrimethoxysilane; in the preferred embodiment of the invention, the adhesion promoter is KH560,
1124. SILQUEST Y9669 or SILQUEST a-189; commercially available products known to those skilled in the art may be used.
In the present invention, the anti-moist heat agent is preferably selected from stabaxolol i and/or stabaxolol p200, more preferably stabaxolol i or stabaxolol p 200; commercially available products known to those skilled in the art may be used.
In the present invention, the catalyst is preferably one or more selected from the group consisting of dibutyltin dilaurate, triethylenediamine and dimorpholinodiethyl ether, and more preferably dibutyltin dilaurate and/or dimorpholinodiethyl ether. The source of the catalyst in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
The high-temperature-resistant polyurethane hot melt adhesive provided by the invention adopts specific content components, realizes better overall interaction, has the characteristic of high-temperature bonding strength, and can be used for vehicle lamp assembly.
The invention also provides a preparation method of the high-temperature-resistant polyurethane hot melt adhesive, which comprises the following steps:
mixing polyester polyol, polyether polyol, dimer acid modified polyol and tackifying resin, then dehydrating in vacuum at 110-130 ℃ for 1-3 h until the water content is less than or equal to 500ppm, then cooling to 80-90 ℃, adding isocyanate, reacting at 80-100 ℃ for 1-3 h, then adding a damp-heat resistant agent and carbon black, and continuing stirring for 0.5-1 h; finally, adding an antioxidant, a bonding promoter and a catalyst, and reacting for 20-60 min at 90-120 ℃ under a vacuum condition to obtain a high-temperature-resistant polyurethane hot melt adhesive;
preferably:
mixing polyester polyol, polyether polyol, dimer acid modified polyol and tackifying resin, then dehydrating in vacuum at 115-120 ℃ for 2h until the water content is less than or equal to 500ppm, then cooling to 80-90 ℃, adding isocyanate, reacting at 95-100 ℃ for 1h, then adding a damp-heat resistant agent and carbon black, and continuing stirring for 0.5-1 h; and finally, adding an antioxidant, a bonding promoter and a catalyst, and reacting for 1h at 90-110 ℃ under a vacuum condition to obtain the high-temperature-resistant polyurethane hot melt adhesive.
The preparation method provided by the invention has the advantages of easily available raw materials, simple operation, mild conditions and excellent industrial application prospect.
The invention provides a high-temperature-resistant polyurethane hot melt adhesive which is prepared from the following raw materials: 50-100 parts by weight of polyester polyol; 10-30 parts by weight of polyether polyol; 5-25 parts by weight of dimer acid modified polyol; 8-30 parts by weight of isocyanate; 25-60 parts of tackifying resin; 0.1-1.5 parts by weight of an antioxidant; 0.1-5 parts by weight of carbon black; 0.1-3 parts by weight of a bonding promoter; 0.1-2 parts by weight of a damp-heat resistant agent; 0.05-0.5 part by weight of a catalyst; the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol; the weight ratio of the liquid polyester polyol in the polyester polyol is less than 30 percent. Compared with the prior art, the high-temperature resistant polyurethane hot melt adhesive provided by the invention adopts specific content components, realizes better overall interaction, has the characteristic of high-temperature bonding strength, and can be used for vehicle lamp assembly. The experimental result shows that the conventional adhesiveness of the high-temperature-resistant polyurethane hot melt adhesive is 1679-1710N, the adhesiveness at 85 ℃ is 860-1056N, the high-temperature-resistant polyurethane hot melt adhesive has the characteristic of high-temperature adhesive strength after complete curing, and the high-temperature-resistant polyurethane hot melt adhesive can be used as a hot melt adhesive for vehicle lamps.
In addition, the preparation method provided by the invention has the advantages of easily available raw materials, simple operation, mild conditions and excellent industrial application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available products; the invention adopts the following mode to measure the performance of the polyurethane hot melt adhesive:
the adhesive force testing method comprises the following steps: the test was carried out according to GB/T7124. The base material adopts PC/PP-T40, the size of the base material is 100mm multiplied by 25mm multiplied by 2.5mm, and the PP base material needs plasma flame treatment; the bonding area is 25mm multiplied by 0.8mm, and the testing speed is 12.7 mm/min.
Conventional adhesion test methods: the module is maintained for 14 days under standard conditions, and the adhesive force is tested.
85 ℃ adhesion test method: after curing the module at 85 ℃ for 30min, the adhesion was tested at 85 ℃.
Example 1
Adding VORANOL 1000LM polyether polyol, Yingchuang polyester polyols Dynacoll7130 and 7340, Yingchuang acrylic resin AC1631 and dimer acid PRIPLLAST 3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 of the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and continuously stirring for 0.5-1 hour; finally, adding a primary antioxidant, a secondary antioxidant, a bonding promoter KH560 and a catalyst in a formula ratio, and stirring and dispersing for reaction for 1h at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in table 1.
Table 1 data table of raw material formulations of example 1
| Raw materials | Parts by weight |
| VORANOL 1000LM | 25 |
| Dynacoll 7340 | 40 |
| Dynacoll 7130 | 40 |
| PRIPLAST 3190 | 20 |
| AC1631 | 40 |
| MDI | 22 |
| Anti-damp-heat agent stabaxol I | 0.6 |
| Primary antioxidant RIANOX1010 | 0.1 |
| Secondary antioxidant RIANOX168 | 0.1 |
| Carbon black | 1 |
| KH560 | 2 |
| Dimorpholinyl diethyl ether as catalyst | 0.2 |
Example 2
Adding VORANOL 3003N polyether polyol, Yingchuang polyester polyols Dynacoll7390 and 7231, Yingchuang acrylic resin AC1620 and dimer acid PRIPLLAST 3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 with the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and continuously stirring for 0.5-1 hour; finally, adding a main antioxidant, an auxiliary antioxidant, a binder silquest a-189 and a catalyst in a formula ratio, and stirring and dispersing for reaction for 1 hour at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in Table 2.
Table 2 data table of raw material recipe of example 2
Example 3
Adding PTMG-2000 polyether polyol, Yingchuang polyester polyols Dynacoll7390 and 7331, Yingchuang acrylic resin AC1920 and dimer acid PRIPLAST3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 of the formula amount, heating to 95 ℃ for reaction1h, adding the anti-damp and heat agent and the carbon black, and continuously stirring for 0.5-1 h; finally, adding the primary antioxidant, the secondary antioxidant and the adhesion promoter in the formula amount
1124. Stirring and dispersing the catalyst for reaction for 1h at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in Table 3.
Table 3 data table of raw material recipe in example 3
Example 4
Adding VORANOL4000LM polyether polyol, Yingchuang polyester polyols Dynacoll 7331 and 7340, Yingchuang acrylic resin AC4830 and dimer acid PRIPLLAST 3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 90 ℃, adding MDI-50 of the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and continuously stirring for 0.5-1 hour; finally, adding a main antioxidant, an auxiliary antioxidant, a tackifier SILQUEST Y9669 and a catalyst in a formula amount, stirring and dispersing for reaction for 1 hour at 100-110 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formula amounts of the raw materials used in this example are shown in Table 4.
Table 4 data table of raw material recipe of example 4
| Raw materials | Parts by weight |
| VORANOL 4000LM | 15 |
| Dynacoll 7340 | 50 |
| Dynacoll 7331 | 30 |
| PRIPLAST 3190 | 15 |
| AC4830 | 40 |
| MDI | 14 |
| Anti-damp-heat agent stabaxol I | 0.3 |
| Primary antioxidant RIANOX1010 | 0.1 |
| Secondary antioxidant RIANOX168 | 0.1 |
| Carbon black | 1.5 |
| SILQUEST Y9669 | 2 |
| Catalyst dimorpholinodiethylether: dibutyl tin dilaurate ═ 1: 1 | 0.2 |
Comparative example 1
Adding VORANOL 1000LM polyether polyol, Yingchuang polyester polyol Dynacoll7360, Yingchuang acrylic resin AC1631 and dimer acid PRIPLAST3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 according to the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and continuously stirring for 0.5-1 hour; finally, adding a primary antioxidant, a secondary antioxidant, a bonding promoter KH560 and a catalyst in a formula ratio, and stirring and dispersing for reaction for 1h at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in table 5.
Table 5 data table for raw material formulation of comparative example 1
| Raw materials | Parts by weight |
| VORANOL 1000LM | 25 |
| Dynacoll 7360 | 80 |
| PRIPLAST 3190 | 20 |
| AC1631 | 40 |
| MDI | 22 |
| Anti-damp-heat agent stabaxol I | 0.6 |
| Primary antioxidant RIANOX1010 | 0.1 |
| Secondary antioxidant RIANOX168 | 0.1 |
| Carbon black | 1 |
| KH560 | 2 |
| Dimorpholinyl diethyl ether as catalyst | 0.2 |
Comparative example 2
Adding VORANOL 1000LM polyether polyol, Yingchuang polyester polyol Dynacoll7130 and 7340, adding dimer acid PRIPLLAST 3190 into a reaction kettle according to the formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 according to the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp and heat resistant agent and carbon black, and continuing stirring for 0.5-1 hour; finally, adding a primary antioxidant, a secondary antioxidant, a bonding promoter KH560 and a catalyst in a formula ratio, and stirring and dispersing for reaction for 1h at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in table 6.
Table 6 data table for the raw material formulation of comparative example 2
Comparative example 3
Adding VORANOL 3003N polyether polyol, Yingchuang polyester polyols Dynacoll7250 and 7231, Yingchuang acrylic resin AC1620 and dimer acid PRIPLLAST 3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 with the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and continuously stirring for 0.5-1 hour; finally, adding a main antioxidant, an auxiliary antioxidant, a binder silquest a-189 and a catalyst in a formula ratio, and stirring and dispersing for reaction for 1 hour at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in table 7.
Table 7 data table for the formulation of the comparative example 3 feedstock
| Raw materials | Parts by weight |
| VORANOL 3003N | 25 |
| Dynacoll 7250 | 40 |
| Dynacoll 7231 | 20 |
| PRIPLAST 3190 | 6 |
| AC1620 | 50 |
| MDI | 10 |
| Anti-damp-heat agent Stabaxol P200 | 0.6 |
| Primary antioxidant RIANOX1010 | 0.1 |
| Secondary antioxidant RIANOX168 | 0.1 |
| Carbon black | 1 |
| silquest a-189 | 2 |
| Catalyst dibutyltin dilaurate | 0.2 |
Comparative example 4
Adding VORANOL 3003N polyether polyol, Yingchuang polyester polyol Dynacoll7390, Yingchuang acrylic resin AC1620 and dimer acid PRIPLLAST 3190 into a reaction kettle according to a formula amount, heating to 115-120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa until the water content is less than or equal to 500ppm, then cooling to 80 ℃, adding MDI-50 according to the formula amount, heating to 95 ℃ for reaction for 1 hour, then adding a damp-heat resistant agent and carbon black, and continuously stirring for 0.5-1 hour; finally, adding a main antioxidant, an auxiliary antioxidant, a binder silquest a-189 and a catalyst in a formula ratio, and stirring and dispersing for reaction for 1 hour at 90-95 ℃ under vacuum; and (3) uniformly dispersing to obtain the reactive polyurethane hot melt adhesive. The formulation amounts of the raw materials used in this comparative example are shown in Table 8.
Table 8 data table for the raw material formulation of comparative example 4
| Raw materials | Parts by weight |
| VORANOL 3003N | 25 |
| Dynacoll 7390 | 10 |
| PRIPLAST 3190 | 6 |
| AC1620 | 50 |
| MDI | 11 |
| Anti-damp-heat agent Stabaxol P200 | 0.6 |
| Primary antioxidant RIANOX1010 | 0.1 |
| Secondary antioxidant RIANOX168 | 0.1 |
| Carbon black | 1 |
| silquest a-189 | 2 |
| Catalyst dibutyltin dilaurate | 0.2 |
The properties of the polyurethane hot melt adhesives prepared in the above examples 1 to 4 and comparative examples 1 to 4 were tested, and the test results are shown in table 9.
TABLE 9 data of various properties of the polyurethane hot melt adhesives prepared in examples 1-4 and comparative examples 1-4
According to the embodiments, the high-temperature-resistant polyurethane hot melt adhesive provided by the invention has the characteristic of high-temperature bonding strength after complete curing, and can be used as a hot melt adhesive for vehicle lamps.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A high-temperature-resistant polyurethane hot melt adhesive is prepared from the following raw materials:
55-80 parts by weight of polyester polyol;
15-25 parts by weight of polyether polyol;
6-20 parts by weight of dimer acid modified polyol;
11-22 parts by weight of isocyanate;
40-50 parts of tackifying resin;
0.2 part by weight of antioxidant;
1-1.5 parts by weight of carbon black;
1-2 parts of a bonding promoter;
0.2-0.6 part by weight of a damp-heat resistant agent;
0.1-0.2 parts by weight of a catalyst;
the polyester polyol is selected from one or more of solid polyester polyol and liquid polyester polyol; the weight ratio of the liquid polyester polyol in the polyester polyol is less than 40 percent;
the hydroxyl value of the dimer acid modified polyol is 35-80 mgKOH/g;
the tackifying resin is selected from one or more of acrylic resin, hydroxy acrylic resin and polyester resin; the molecular weight of the tackifying resin is 20000-100000, the hydroxyl value is 0-10 mgKOH/g, and the softening point is more than 90 ℃.
2. The high-temperature-resistant polyurethane hot melt adhesive as claimed in claim 1, wherein the hydroxyl value of the solid polyester polyol is 10 to 50 mgKOH/g; the solid polyester polyol is prepared by polycondensation of one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, phthalic anhydride and 1, 4-cyclohexanedicarboxylic acid with one or more of 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, neopentyl glycol, diethylene glycol, 1, 2-propanediol and 2-methylpropanediol; the softening point of the solid polyester polyol is more than 75 ℃.
3. The high-temperature-resistant polyurethane hot melt adhesive as claimed in claim 1, wherein the hydroxyl value of the liquid polyester polyol is 18 to 80 mgKOH/g.
4. The high-temperature-resistant polyurethane hot melt adhesive as claimed in claim 1, wherein the hydroxyl value of the polyether polyol is 25-160 mgKOH/g; the polyether polyol is selected from one or more of polyoxypropylene diol, polyoxypropylene triol and polytetrahydrofuran ether diol.
5. The high-temperature resistant polyurethane hot melt adhesive according to claim 1, wherein the isocyanate is selected from toluene diisocyanate and/or diphenylmethane diisocyanate; the ratio of isocyanate to hydroxyl of polyol is 1.4-2.0.
6. The high-temperature resistant polyurethane hot melt adhesive according to claim 1, wherein the adhesion promoter is one or more selected from the group consisting of bis- (gamma-trimethoxysilylpropyl) amine, gamma-mercaptopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-isocyanatopropyltrimethoxysilane, and N-phenyl-gamma-aminopropyltrimethoxysilane.
7. The high temperature resistant polyurethane hot melt adhesive of claim 1, wherein the catalyst is selected from one or more of dibutyltin dilaurate, triethylenediamine, and dimorpholinodiethyl ether.
8. The preparation method of the high-temperature-resistant polyurethane hot melt adhesive as claimed in any one of claims 1 to 7, comprising the following steps:
mixing polyester polyol, polyether polyol, dimer acid modified polyol and tackifying resin, then dehydrating in vacuum at 110-130 ℃ for 1-3 h until the water content is less than or equal to 500ppm, then cooling to 80-90 ℃, adding isocyanate, reacting at 80-100 ℃ for 1-3 h, then adding a damp-heat resistant agent and carbon black, and continuing stirring for 0.5-1 h; and finally, adding an antioxidant, a bonding promoter and a catalyst, and reacting for 20-60 min at 90-120 ℃ under a vacuum condition to obtain the high-temperature-resistant polyurethane hot melt adhesive.
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