CN111808569A - Damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant and preparation method thereof - Google Patents
Damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant and preparation method thereof Download PDFInfo
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- CN111808569A CN111808569A CN202010727799.XA CN202010727799A CN111808569A CN 111808569 A CN111808569 A CN 111808569A CN 202010727799 A CN202010727799 A CN 202010727799A CN 111808569 A CN111808569 A CN 111808569A
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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
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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
- C09J11/04—Non-macromolecular additives inorganic
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a damp and heat resistant and high-strength one-component polyurethane primer-free bonding sealant and a preparation method thereof, and belongs to the technical field of polyurethane sealants, the one-component polyurethane primer-free bonding sealant disclosed by the invention contains a self-made white carbon black modified polyurethane prepolymer, and the integral damp and heat resistant performance of a product can be enhanced after the white carbon black modified polyurethane prepolymer is added into a polyurethane sealant, so that compared with the one-component polyurethane primer-free bonding sealant which is not added with the white carbon black modified polyurethane prepolymer, the one-component polyurethane primer-free bonding sealant disclosed by the invention can obviously improve the colloid bonding stability after damp and heat aging; the obtained single-component polyurethane primer-free adhesive sealant has high mechanical property after being cured for 7 days under standard conditions, wherein the shear strength reaches more than 7.5MPa, the tensile strength reaches more than 12.5MPa, and the tear strength reaches more than 25N/mm, so that the physical and mechanical property requirements of the polyurethane adhesive sealant during the assembly of windshields by different traffic vehicles can be met.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesive sealants, in particular to a damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant and a preparation method thereof.
Background
The single-component polyurethane adhesive sealant is a polyurethane adhesive prepared by fully and uniformly mixing NCO-terminated polyurethane prepolymer with a filler, a plasticizer, a curing agent, an auxiliary agent and the like, and the adhesive principle is that isocyanate groups in colloid react with water molecules in air to gradually start to be cured from outside to inside to form a cross-linked network, and simultaneously the colloid reacts with active groups on the surface of an adhered substrate to form firm adhesion; the single-component polyurethane adhesive sealant has good mechanical property, weather resistance, oil resistance and excellent elasticity, is widely applied to the adhesion and sealing of windshield rubber of vehicles, ships, high-speed rails and other transportation vehicles, and has wide application prospect.
However, the single-component polyurethane adhesive sealant used in the market at present is mostly matched with a primer, is inconvenient to use and not environment-friendly, and is more and more popular with customers from the aspects of smell, environmental friendliness, construction convenience and production efficiency, and for the primer-free products, an auxiliary agent is often added to enhance adhesion in the process of designing a formula, although 100% CF damage can occur to a substrate, the mechanical property of the products is often reduced due to the addition of the auxiliary agent, the tensile shear strength is generally between 3 and 5MPa, and the requirements of automobile host factories, glass manufacturing factories or other customers with higher index requirements cannot be met; in addition, after the primer-free polyurethane adhesive on the market is aged in a high-temperature and high-humidity environment, the adhesive force with the base material is reduced, and 100% CF damage with the base material cannot be guaranteed.
The surface of the white carbon black has a large amount of active hydroxyl groups which can be combined with isocyanate groups under certain conditions, so that the heat resistance, moisture resistance and ageing resistance of the polyurethane sealant can be improved to a certain extent by introducing the white carbon black into a polyurethane sealant system. Under the general condition, the white carbon black is directly added into a product together with other fillers to be mixed and stirred, but the white carbon black is directly added into a polyurethane sealant system, so that the reaction of silicon hydroxyl and NCO groups can be caused to form hydrogen bonds, the thickening and viscosity of the sealant are gradually increased, and the problem that the product is difficult to extrude is caused at all times.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a single-component polyurethane primer-free adhesive sealant with humidity and heat resistance and high strength and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the single-component polyurethane primer-free adhesive sealant with the characteristics of humidity resistance, heat resistance and high strength comprises the following raw materials in parts by weight: 8-15 parts of hydroxyl-terminated polyether polyol, 3-10 parts of first polyester polyol, 4-5 parts of first isocyanate, 12-22 parts of first plasticizer, 15-35 parts of white carbon black modified polyurethane prepolymer, 0.5-1 part of water removing agent, 18-25 parts of inorganic filler, 1-3 parts of resin filler, 1-2 parts of auxiliary agent and 0.01-0.4 part of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxypropylene ether or polyoxyethylene ether with the molecular weight of 3000-6000;
the first polyester polyol is difunctional polyester polyol with the molecular weight of 500-3000;
the first isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate;
the first plasticizer is one or a mixture of two of epoxidized soybean oil, dipropylene glycol dibenzoate, diisodecyl phthalate, diisononyl phthalate, dioctyl phthalate, butyl benzyl phthalate or alkyl phenyl sulfonate;
the water removing agent is p-tolyl sulfonyl isocyanate or/and calcium oxide;
the inorganic filler is one, two or three of acetylene black, light calcium carbonate, heavy calcium carbonate, nano calcium carbonate, diatomite, talcum powder, zinc oxide, silicon micropowder or organic bentonite;
the resin filler is one, two or three of polyphenol glycidyl ether epoxy resin, terpene resin, tall oil rosin, esterified rosin, styrene series resin or alkyl phenolic resin;
the auxiliary agent is one, two or three of calcium oxide, calcium hydroxide or aniline methyl trimethoxy silane;
the first catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials in parts by weight:
0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst at the temperature of 60-85 ℃ for 3-4 hours;
the second plasticizer is one or two of diisodecyl phthalate, diisononyl phthalate and alkyl sulfonate;
the second catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the second isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate.
Preferably, the first polyester polyol is a polycaprolactone polyol or/and a polycarbonate polyol.
Preferably, in the preparation process of the white carbon black modified polyurethane prepolymer, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, specifically: uniformly dispersing 0.05-1.25 parts by weight of white carbon black in 20-25 parts by weight of a second plasticizer to obtain a suspension, and then carrying out ultrasonic treatment; during each ultrasonic treatment, the frequency of the ultrasonic wave is more than 15kHz, the time of each ultrasonic treatment is 5-15 minutes, and the treatment times are 4-8; and after each ultrasonic treatment, the suspension is stirred to be cooled, and when the temperature of the suspension is reduced to be below 30 ℃, the next ultrasonic treatment can be carried out.
Preferably, after the ultrasonic treatment is carried out for 4 times, the suspension after the temperature reduction needs to adopt a particle size analyzer to measure the median particle diameter D50 of the white carbon black in the suspension, when the D50 value of the white carbon black is below 5 μm, the ultrasonic treatment is ended, otherwise, the ultrasonic treatment is continued until the measured D50 value meets the requirement, and the design can ensure that the agglomerated white carbon black is relatively uniformly dispersed in the second plasticizer.
Preferably, the first isocyanate is diphenylmethane diisocyanate or/and toluene diisocyanate.
Preferably, the inorganic filler is acetylene black and/or nano calcium carbonate.
Preferably, the resin filler is a polyphenol type glycidyl ether epoxy resin.
Preferably, the second isocyanate is hexamethylene diisocyanate.
Preferably, the second plasticizer is diisodecyl phthalate and diisononyl phthalate in a mass ratio of 1: 1.
Preferably, the first catalyst is dibutyltin dilaurate; the second catalyst is stannous octoate.
The invention also discloses a preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant, which comprises the following steps:
preparation of prepolymer: adding 8-15 parts by weight of hydroxyl-terminated polyether polyol and 3-10 parts by weight of first polyester polyol into a reaction kettle, heating to 120 ℃, carrying out vacuum dehydration for 0.5-1 hour under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 55-65 ℃, adding 4-5 parts by weight of first isocyanate and 1-3 parts by weight of resin filler, heating to 80-90 ℃, reacting for 4-5 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
the hydroxyl-terminated polyether polyol is trifunctional polyoxypropylene ether or polyoxyethylene ether with the molecular weight of 3000-6000;
the first polyester polyol is difunctional polyester polyol with the molecular weight of 500-3000;
the first isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate;
the resin filler is one, two or three of polyphenol glycidyl ether epoxy resin, terpene resin, tall oil rosin, esterified rosin, styrene series resin or alkyl phenolic resin;
secondly, adding the prepolymer obtained in the step one into a stirrer, sequentially adding 15-35 parts of white carbon black modified polyurethane prepolymer, 12-22 parts of first plasticizer, 0.5-1 part of water removing agent and 18-25 parts of inorganic filler, heating to 48-52 ℃, stirring for 30-40 minutes under the conditions that the shearing speed is not lower than 10m/s and the vacuum degree is not lower than 0.092MPa, cooling to 28-32 ℃, continuing stirring for 15-20 minutes, adding 1-2 parts of auxiliary agent and 0.01-0.4 part of first catalyst, and stirring and uniformly mixing under the condition that the vacuum degree is not lower than 0.092MPa to obtain the humidity-heat-resistant high-strength single-component polyurethane primer-free bonding sealant;
the first plasticizer is one or a mixture of two of epoxidized soybean oil, dipropylene glycol dibenzoate, diisodecyl phthalate, diisononyl phthalate, dioctyl phthalate, butyl benzyl phthalate or alkyl phenyl sulfonate;
the water removing agent is p-tolyl sulfonyl isocyanate or/and calcium oxide;
the inorganic filler is one, two or three of acetylene black, light calcium carbonate, heavy calcium carbonate, nano calcium carbonate, diatomite, talcum powder, zinc oxide, silicon micropowder or organic bentonite;
the auxiliary agent is one, two or three of calcium oxide, calcium hydroxide or aniline methyl trimethoxy silane;
the first catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials in parts by weight:
0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst at the temperature of 60-85 ℃ for 3-4 hours;
the second plasticizer is one or two of diisodecyl phthalate, diisononyl phthalate and alkyl sulfonate;
the second catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the second isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate.
Compared with the prior art, the invention has the following advantages:
the one-component polyurethane primer-free bonding sealant contains a self-made white carbon black modified polyurethane prepolymer, hydroxyl on the surface of white carbon black is utilized to react with NCO groups in a small amount of isocyanate under a specific condition to form a certain space grid structure, and the moisture and heat resistance of the whole product can be enhanced after the polyurethane sealant is added, so that the colloidal bonding stability of the one-component polyurethane primer-free bonding sealant after the moisture and heat aging can be obviously improved compared with the sealant without adding the white carbon black modified polyurethane prepolymer;
the single-component polyurethane primer-free adhesive sealant disclosed by the invention has higher mechanical properties after being cured for 7 days under standard conditions, wherein the shear strength reaches more than 7.5MPa, the tensile strength reaches more than 12.5MPa, and the tear strength reaches more than 25N/mm, so that the physical and mechanical property requirements of the polyurethane adhesive sealant during the assembly of different traffic vehicles on windshields can be met;
the single-component polyurethane primer-free adhesive sealant can achieve 100% CF of cohesive failure with glazed glass and a metal paint plate, and after the sealant is subjected to damp-heat aging for 300 hours, the cohesive failure rate with the glazed glass can reach more than 95%, and the cohesive failure rate with the paint plate can reach 100%;
according to the preparation method of the preferable white carbon black modified polyurethane prepolymer, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, so that the white carbon black is dispersed in the second plasticizer more uniformly, and the modified polyurethane prepolymer obtained after the white carbon black modification forms a spatial network structure with an inserted-Si-O-Si chain segment in the subsequent reaction process, so that the moving range of a polyurethane chain is limited, and the physical and mechanical properties of the modified polyurethane prepolymer are enhanced to a certain extent. In addition, Si-O bonds with higher energy than C-O bonds are introduced into the polyurethane chain segments, so that the thermal stability and hydrolysis resistance of the modified cross-linked network are higher, and the cohesive failure rate of the modified cross-linked network with glazed glass and a painted metal plate reaches 100% after the modified cross-linked network is subjected to damp-heat aging for 300 hours;
the preparation method of the single-component polyurethane primer-free adhesive sealant has the advantages of few process steps, easiness in operation, capability of being completed by using conventional equipment, capability of achieving a good adhesive effect without coating a primer when in use, safety, environmental friendliness, convenience in construction and capability of improving the construction efficiency of the sealant.
Detailed Description
The invention is further described with reference to specific examples.
The resin filler of the invention can be selected from the following manufacturers or models, and can also be selected from other products on the market.
A polyphenol type glycidyl ether epoxy resin DOW DER 732;
terpene resin T-100, Hiden New Material science and technology, Inc.;
tall oil rosin, Suzhou Gis chemical Co., Ltd;
esterified rosin zibo haobo chemical limited;
styrene series resin poly-alpha-methylstyrene resin;
alkylphenol formaldehyde resin saint lacott R7522E;
example 1
A damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant comprises the following raw materials: 8kg of hydroxyl-terminated polyether polyol, 3kg of first polyester polyol, 4kg of first isocyanate, 12kg of first plasticizer, 15kg of white carbon black modified polyurethane prepolymer, 0.5kg of water removing agent, 18kg of inorganic filler, 1kg of resin filler, 1kg of auxiliary agent and 0.01kg of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxypropylene ether with the average molecular weight of 3000;
the first polyester polyol is a difunctional polyester polyol with an average molecular weight of 500;
the first isocyanate is diphenylmethane diisocyanate;
the first plasticizer is epoxidized soybean oil;
the water removing agent is p-tolyl sulfonyl isocyanate;
the inorganic filler is acetylene black;
the resin filler is polyphenol type glycidyl ether epoxy resin;
the auxiliary agent is calcium oxide, and can absorb carbon dioxide and water in the reaction process of the polyurethane sealant, so that bubbles of a product in the curing process and the reduction of the stability of the product in the storage process are avoided;
the first catalyst is dibutyltin dilaurate;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials:
0.05kg of white carbon black, 15kg of second isocyanate, 40kg of second polyester polyol with the average molecular weight of 400, 20kg of second plasticizer and 0.01kg of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 0.05kg of white carbon black, 15kg of second isocyanate, 40kg of second polyester polyol with the average molecular weight of 400, 20kg of second plasticizer and 0.01kg of second catalyst for 3 hours at the temperature of 60 ℃;
the second plasticizer is diisodecyl phthalate;
the second catalyst is dibutyltin dilaurate;
the second isocyanate is diphenylmethane diisocyanate.
Example 2
A damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant comprises the following raw materials: 15kg of hydroxyl-terminated polyether polyol, 10kg of first polyester polyol, 5kg of first isocyanate, 22kg of first plasticizer, 35kg of white carbon black modified polyurethane prepolymer, 1kg of water removing agent, 25kg of inorganic filler, 3kg of resin filler, 2kg of auxiliary agent and 0.4kg of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxyethylene ether with the molecular weight of 6000;
the first polyester polyol is a difunctional polyester polyol with the molecular weight of 3000;
the first isocyanate is toluene diisocyanate;
the first plasticizer is dipropylene glycol dibenzoate;
the water removing agent is calcium oxide;
the inorganic filler is light calcium carbonate;
the resin filler is terpene resin;
the auxiliary agent is calcium hydroxide;
the first catalyst is dibutyltin dichloride;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials:
1.25kg of white carbon black, 25kg of second isocyanate, 55kg of second polyester polyol with the average molecular weight of 1000, 25kg of second plasticizer and 0.2kg of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 1.25kg of white carbon black, 25kg of second isocyanate, 55kg of second polyester polyol with the molecular weight of 1000, 25kg of second plasticizer and 0.2kg of second catalyst at 85 ℃ for 4 hours;
the second plasticizer is diisononyl phthalate;
the second catalyst is dibutyltin dichloride;
the second isocyanate is toluene diisocyanate.
Example 3
A damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant comprises the following raw materials: 10kg of hydroxyl-terminated polyether polyol, 5kg of first polyester polyol, 4.2kg of first isocyanate, 18kg of first plasticizer, 20kg of white carbon black modified polyurethane prepolymer, 0.6kg of water removing agent, 20kg of inorganic filler, 1.5kg of resin filler, 1.2kg of auxiliary agent and 0.1kg of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxypropylene ether with the molecular weight of 4000;
the first polyester polyol is a difunctional polyester polyol with the molecular weight of 1000;
the first isocyanate is composed of isophorone diisocyanate and hexamethylene diisocyanate according to the mass ratio of 1: 1;
the first plasticizer is composed of diisodecyl phthalate and diisononyl phthalate according to the mass ratio of 1: 2;
the water removing agent is composed of p-tolyl sulfonyl isocyanate and calcium oxide according to the mass ratio of 1: 2;
the inorganic filler is composed of nano calcium carbonate and diatomite according to the mass ratio of 1: 1;
the resin filler is composed of tall oil rosin and esterified rosin according to the mass ratio of 1: 2;
the auxiliary agent consists of calcium hydroxide and aniline methyl trimethoxy silane according to the mass ratio of 1: 2;
the first catalyst is dibutyltin diacetate;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials:
0.5kg of white carbon black, 18kg of second isocyanate, 45kg of second polyester polyol with the average molecular weight of 500, 22kg of second plasticizer and 0.1kg of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 0.5kg of white carbon black, 18kg of second isocyanate, 45kg of second polyester polyol with the average molecular weight of 500, 22kg of second plasticizer and 0.1kg of second catalyst at 70 ℃ for 3.5 hours;
the second plasticizer is composed of diisodecyl phthalate and alkyl sulfonate according to the mass ratio of 5: 6;
the second catalyst is dimorpholinodiethyl ether;
the second isocyanate is composed of isophorone diisocyanate and hexamethylene diisocyanate according to the mass ratio of 1: 3.
Example 4
A damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant comprises the following raw materials: 12kg of hydroxyl-terminated polyether polyol, 8kg of first polyester polyol, 4.2kg of first isocyanate, 15kg of first plasticizer, 30kg of white carbon black modified polyurethane prepolymer, 0.8kg of water removing agent, 22kg of inorganic filler, 2.5kg of resin filler, 1.4kg of auxiliary agent and 0.2kg of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxyethylene ether with the molecular weight of 5000;
the first polyester polyol is a difunctional polycaprolactone polyol with a molecular weight of 2000;
the first isocyanate is composed of 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate according to the mass ratio of 3: 4;
the first plasticizer is composed of dioctyl phthalate and butyl benzyl phthalate according to the mass ratio of 2: 3;
the water removing agent is p-tolyl sulfonyl isocyanate;
the inorganic filler is composed of talcum powder and zinc oxide according to the mass ratio of 1: 1;
the resin filler is composed of styrene series resin and alkyl phenolic resin according to the mass ratio of 3: 2;
the auxiliary agent is composed of calcium oxide, calcium hydroxide and aniline methyl trimethoxy silane according to the mass ratio of 3: 2;
the first catalyst is composed of dibutyltin dilaurate and triethylamine according to the mass ratio of 1: 1;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials:
1kg of white carbon black, 22kg of second isocyanate, 50kg of second polyester polyol with the average molecular weight of 600, 24kg of second plasticizer and 0.15kg of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 1kg of white carbon black, 22kg of second isocyanate, 50kg of second polyester polyol with the average molecular weight of 600, 24kg of second plasticizer and 0.15kg of second catalyst at 80 ℃ for 3.2 hours;
the second plasticizer is composed of diisodecyl phthalate and alkyl sulfonate according to the mass ratio of 3: 2;
the second catalyst is stannous octoate;
the second isocyanate is composed of 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate according to the mass ratio of 5: 6.
Example 5
A damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant comprises the following raw materials: 14kg of hydroxyl-terminated polyether polyol, 6kg of first polyester polyol, 4.5kg of first isocyanate, 20kg of first plasticizer, 25kg of white carbon black modified polyurethane prepolymer, 0.6kg of water removing agent, 24kg of inorganic filler, 2kg of resin filler, 1.8kg of auxiliary agent and 0.3kg of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxyethylene ether with the molecular weight of 5000;
the first polyester polyol is a difunctional polycarbonate polyol with a molecular weight of 2500;
the first isocyanate is composed of diphenylmethane diisocyanate and toluene diisocyanate according to the mass ratio of 1: 1;
the first plasticizer is composed of epoxidized soybean oil and alkyl phenyl sulfonate according to the mass ratio of 1: 1;
the water removing agent is p-tolyl sulfonyl isocyanate;
the inorganic filler is composed of acetylene black, acetylene black and nano calcium carbonate according to the mass ratio of 1: 2;
the resin filler is composed of polyphenol type glycidyl ether epoxy resin, terpene resin and esterified rosin according to the mass ratio of 2: 1;
the auxiliary agent consists of calcium oxide and aniline methyl trimethoxy silane according to the mass ratio of 1: 1;
the first catalyst is dibutyltin dilaurate;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials:
1.20kg of white carbon black, 16kg of second isocyanate, 42kg of second polyester polyol with the average molecular weight of 800, 23kg of second plasticizer and 0.05kg of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 1.20kg of white carbon black, 16kg of second isocyanate, 42kg of second polyester polyol with the molecular weight of 800, 23kg of second plasticizer and 0.05kg of second catalyst at 80 ℃ for 4 hours;
the second plasticizer is composed of diisodecyl phthalate and diisononyl phthalate according to the mass ratio of 1: 1;
the second catalyst is stannous octoate;
the second isocyanate is hexamethylene diisocyanate.
Example 6
Except the white carbon black modified polyurethane prepolymer, the other components are the same as the components of the damp-heat resistant and high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 1, and the preparation process of the white carbon black modified polyurethane prepolymer in the embodiment comprises the following steps:
firstly, carrying out ultrasonic treatment on the white carbon black and a second plasticizer, specifically: uniformly dispersing 0.05kg of white carbon black in 20kg of second plasticizer, and then carrying out ultrasonic treatment; during each ultrasonic treatment, the frequency of the ultrasonic wave is more than 15kHz, the time of each ultrasonic treatment is 5 minutes, and the times of the ultrasonic treatment are 4 times;
then adding 15kg of second isocyanate, 40kg of second polyester polyol with the average molecular weight of 400 and 0.01kg of second catalyst into the mixture to react for 3 hours at the temperature of 60 ℃ to obtain the white carbon black modified polyurethane prepolymer.
Example 7
Except for the white carbon black modified polyurethane prepolymer, the other components are the same as the components of the damp-heat resistant and high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 2, in the preparation process of the white carbon black modified polyurethane prepolymer in the embodiment, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, specifically: uniformly dispersing 1.25kg of white carbon black in 25kg of second plasticizer, and then carrying out ultrasonic treatment; during each ultrasonic treatment, the frequency of the ultrasonic waves is more than 15kHz, the time of each ultrasonic treatment is 15 minutes, and the frequency of the ultrasonic waves is 8;
then adding 25kg of second isocyanate, 55kg of second polyester polyol with the molecular weight of 1000 and 0.2kg of second catalyst into the mixture, and reacting for 4 hours at 85 ℃ to obtain the white carbon black modified polyurethane prepolymer.
Example 8
Except for the white carbon black modified polyurethane prepolymer, the other components are the same as the components of the damp-heat resistant and high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 3, in the preparation process of the white carbon black modified polyurethane prepolymer in the embodiment, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, specifically: uniformly dispersing 0.5kg of white carbon black in 22kg of second plasticizer, and then carrying out ultrasonic treatment; the frequency of the ultrasonic wave is more than 15kHz in each ultrasonic treatment, the time of each ultrasonic treatment is 6 minutes, and the number of ultrasonic treatment is 5.
Then 18kg of second isocyanate, 45kg of second polyester polyol with the molecular weight of 500 and 0.1kg of second catalyst are added to the mixture to react for 3.5 hours at 70 ℃ to obtain the white carbon black modified polyurethane prepolymer.
Example 9
Except for the white carbon black modified polyurethane prepolymer, the other components are the same as the components of the damp-heat resistant and high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 4, in the preparation process of the white carbon black modified polyurethane prepolymer in the embodiment, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, specifically: uniformly dispersing 1kg of white carbon black in 24kg of second plasticizer, and then carrying out ultrasonic treatment; the frequency of the ultrasonic wave is more than 15kHz in each ultrasonic treatment, the time of each ultrasonic treatment is 10 minutes, and the times of the ultrasonic treatment are 6 times.
Then 22kg of second isocyanate, 50kg of second polyester polyol with the average molecular weight of 600 and 0.15kg of second catalyst are added to the mixture to react for 3.2 hours at 80 ℃ to obtain the white carbon black modified polyurethane prepolymer.
Example 10
Except for the white carbon black modified polyurethane prepolymer, the other components are the same as the components of the damp-heat resistant and high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 5, in the preparation process of the white carbon black modified polyurethane prepolymer in the embodiment, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, specifically: uniformly dispersing 1.20kg of white carbon black in 23kg of second plasticizer, and then carrying out ultrasonic treatment; the frequency of the ultrasonic wave is more than 15kHz during each ultrasonic treatment, the time of each ultrasonic treatment is 8 minutes, and the times of the ultrasonic treatment are 5 times;
then 16kg of second isocyanate, 42kg of second polyester polyol with the molecular weight of 800 and 0.05kg of second catalyst are added to the mixture to react for 4 hours at 80 ℃ to obtain the white carbon black modified polyurethane prepolymer.
Example 11
The preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 1 comprises the following steps:
preparation of prepolymer: adding 8kg of hydroxyl-terminated polyether polyol and 3kg of first polyester polyol into a reaction kettle, heating to 120 ℃, carrying out vacuum dehydration for 0.5 hour under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 55 ℃, adding 4kg of first isocyanate and 1kg of resin filler, heating to 80 ℃, reacting for 4 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
secondly, adding the prepolymer obtained in the step I into a stirrer, sequentially adding 12kg of a first plasticizer, 15kg of white carbon black modified polyurethane prepolymer, 0.5kg of a water removing agent and 18kg of an inorganic filler, heating to 48 ℃, stirring for 30 minutes under the conditions that the shearing speed is not less than 10m/s and the vacuum degree is not less than 0.092MPa, cooling to 28 ℃, continuing stirring for 15 minutes, adding 1kg of an auxiliary agent and 0.01kg of a first catalyst, and stirring and uniformly mixing under the conditions that the vacuum degree is not less than 0.092MPa to obtain the humidity-heat-resistant high-strength one-component polyurethane primer-free adhesive sealant.
Example 12
The preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 2 comprises the following steps:
preparation of prepolymer: adding 15kg of hydroxyl-terminated polyether polyol and 10kg of first polyester polyol into a reaction kettle, heating to 120 ℃, dehydrating for 1 hour under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 65 ℃, adding 5kg of first isocyanate and 3kg of resin filler, heating to 90 ℃, reacting for 5 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
secondly, adding the prepolymer obtained in the step one into a stirrer, sequentially adding 22kg of first plasticizer, 35kg of white carbon black modified polyurethane prepolymer, 1kg of water removing agent and 25kg of inorganic filler, heating to 48-52 ℃, stirring for 40 minutes under the conditions that the shearing speed is not lower than 10m/s and the vacuum degree is not lower than 0.092MPa, cooling to 32 ℃, continuing stirring for 20 minutes, adding 2kg of auxiliary agent and 0.4kg of first catalyst, and stirring and uniformly mixing under the conditions that the vacuum degree is not lower than 0.092MPa to obtain the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant.
Example 13
The preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 3 comprises the following steps:
preparation of prepolymer: adding 10kg of hydroxyl-terminated polyether polyol and 5kg of first polyester polyol into a reaction kettle, heating to 120 ℃, carrying out vacuum dehydration for 40 minutes under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 58 ℃, adding 4.2kg of first isocyanate and 1.5kg of resin filler, heating to 82 ℃, reacting for 4.2 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
and secondly, adding the prepolymer obtained in the step I into a stirrer, sequentially adding 18kg of first plasticizer, 20kg of white carbon black modified polyurethane prepolymer, 0.6kg of water removing agent and 20kg of inorganic filler, heating to 50 ℃, stirring for 35 minutes under the conditions that the shearing speed is not less than 10m/s and the vacuum degree is not less than 0.092MPa, cooling to 30 ℃, continuing stirring for 18 minutes, adding 1.2kg of auxiliary agent and 0.1kg of first catalyst, and uniformly stirring under the conditions that the vacuum degree is not less than 0.092MPa to obtain the damp-heat resistant high-strength one-component polyurethane primer-free adhesive sealant.
Example 14
The preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 4 comprises the following steps:
preparation of prepolymer: adding 12kg of hydroxyl-terminated polyether polyol and 8kg of first polyester polyol into a reaction kettle, heating to 120 ℃, carrying out vacuum dehydration for 45 minutes under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 60 ℃, adding 4.2kg of first isocyanate and 2.5kg of resin filler, heating to 85 ℃, reacting for 4.5 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
secondly, adding the prepolymer obtained in the step I into a stirrer, sequentially adding 15kg of first plasticizer, 30kg of white carbon black modified polyurethane prepolymer, 0.8kg of water removing agent and 22kg of inorganic filler, heating to 51 ℃, stirring for 38 minutes under the conditions that the shearing speed is not lower than 10m/s and the vacuum degree is not lower than 0.092MPa, cooling to 30 ℃, continuing stirring for 20 minutes, adding 1.4kg of auxiliary agent and 0.2kg of first catalyst, and stirring and uniformly mixing under the conditions that the vacuum degree is not lower than 0.092MPa to obtain the damp-heat resistant high-strength one-component polyurethane primer-free adhesive sealant.
Example 15
The preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant in the embodiment 5 comprises the following steps:
preparation of prepolymer: adding 14kg of hydroxyl-terminated polyether polyol and 6kg of first polyester polyol into a reaction kettle, heating to 120 ℃, carrying out vacuum dehydration for 50 minutes under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 62 ℃, adding 4.5kg of first isocyanate and 2kg of resin filler, heating to 86 ℃, reacting for 4.5 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
and secondly, adding the prepolymer obtained in the step I into a stirrer, sequentially adding 20kg of a first plasticizer, 25kg of white carbon black modified polyurethane prepolymer, 0.6kg of a water removing agent and 24kg of an inorganic filler, heating to 50 ℃, stirring for 34 minutes under the conditions that the shearing speed is not less than 10m/s and the vacuum degree is not less than 0.092MPa, cooling to 30 ℃, continuously stirring for 18 minutes, adding 1.8kg of an auxiliary agent and 0.3kg of a first catalyst, and uniformly stirring under the conditions that the vacuum degree is not less than 0.092MPa to obtain the damp-heat-resistant high-strength one-component polyurethane primer-free adhesive sealant.
Example 16
The process for preparing the humidity and heat resistant, high strength, one-component polyurethane primer-free adhesive sealant of example 6 is the same as example 11.
Example 17
The process for preparing the humidity and heat resistant, high strength, one-component polyurethane primer-free adhesive sealant of example 7 is the same as that of example 12.
Example 18
The process for preparing the humidity and heat resistant, high strength, one-component polyurethane primer-free adhesive sealant of example 8 is the same as example 13.
Example 19
The process for preparing the humidity and heat resistant, high strength, one-component polyurethane primer-free adhesive sealant of example 9 is the same as example 14.
Example 20
The process for preparing the humidity and heat resistant, high strength, one-component polyurethane primer-free adhesive sealant of example 10 is the same as example 15.
Comparative example 1
Replacing 20kg of the white carbon black modified polyurethane prepolymer in the embodiment 3 with 0.5kg of white carbon black, and keeping the rest components unchanged; and obtaining the single-component polyurethane primer-free adhesive sealant.
Comparative example 2
1kg of white carbon black is used for replacing 30kg of the white carbon black modified polyurethane prepolymer in the embodiment 4, and the rest components are unchanged; and obtaining the single-component polyurethane primer-free adhesive sealant.
Comparative example 3
Replacing 25kg of the white carbon black modified polyurethane prepolymer in the embodiment 5 with 1.2kg of white carbon black, and keeping the rest components unchanged; and obtaining the single-component polyurethane primer-free adhesive sealant.
The results of the mechanical property and humidity and heat resistance test on the humidity and heat resistance and high strength one-component polyurethane primer-free adhesive sealant obtained in examples 11 to 15 and the one-component polyurethane primer-free adhesive sealant obtained in comparative examples 1 to 3 are shown in table 1. The results of the mechanical property and humidity and heat resistance test on the humidity and heat resistance and high strength one-component polyurethane primer-free adhesive sealant obtained in examples 11 to 15 are shown in table 2.
Gluing the sample at a standard laboratory temperature to prepare a test piece with the thickness of 2 mm, wherein the laboratory condition is performed according to GB/T2941-2006, and the test piece is placed for 7 days for testing.
Tensile strength and elongation at break were performed in accordance with GB/T528-2009.
The shear strength was performed according to GB/T7124-2008, the test piece being a rigid metal piece which had been previously treated with a primer.
The tear strength is performed in accordance with GB/T529-.
The damp and heat resistance experiment is carried out according to the experiment test standard of a certain automobile host factory, the temperature of the bonded sample piece curing environment is 70 ℃, the humidity is 90%, and the curing time is 300 hours.
The extrudability was performed according to GB/T13477.3-2017, the test temperature was (23. + -. 0.5) ℃ C., the sample volume was 400mL, the extrusion pore size was 4mm, the gas source pressure was 700kPa or more, and the extrusion pressure was (600. + -. 2.5) kPa.
The Shore A hardness is executed according to GB/T531.1-2008, the thickness of the three-layer test sample which is flatly overlapped is not less than 6.0mm, and the test is carried out by a Shore A hardness tester.
Table 1 shows the mechanical properties and the results of the damp-heat resistant test experiment of the damp-heat resistant, high-strength single-component polyurethane primer-free adhesive sealant obtained in examples 11 to 15
Table 2 mechanical properties and test results of damp and heat resistant experiment of the damp and heat resistant, high strength, single component polyurethane primer-free adhesive sealant obtained in examples 16 to 20
As can be seen from the data in tables 1 and 2, the moisture-heat-resistant and high-strength one-component polyurethane primer-free adhesive sealant disclosed by the application can not only increase the tensile strength, shear strength and elongation at break, but also improve the extrudability of the sealant due to the addition of the white carbon black-modified polyurethane prepolymer, so that the sealant has moderate hardness and is easier to operate in construction; particularly, the single-component polyurethane primer-free adhesive sealant has the advantages that cohesive failure of the single-component polyurethane primer-free adhesive sealant with glazed glass and a painted metal plate can reach 100% CF (CF), after the single-component polyurethane primer-free adhesive sealant is subjected to damp-heat aging for 300 hours, the cohesive failure rate with the glazed glass reaches over 95%, and the cohesive failure rate with the painted metal plate reaches 100%;
according to the preferable technical scheme, the white carbon black and the second plasticizer are subjected to ultrasonic treatment, so that the white carbon black is dispersed in the second plasticizer more uniformly, a space grid structure obtained subsequently is more uniform, the tensile strength, the shear strength and the elongation at break of the white carbon black are enhanced to a certain degree, and after the white carbon black and the second plasticizer are subjected to damp-heat aging for 300 hours, the cohesive failure rate of the white carbon black, glazed glass and a painted metal plate reaches 100%; in the preferred scheme, the influence of directly adding the white carbon black on the product is reduced by introducing the fumed silica into the prepolymer, the indexes such as strength and the like are improved, and the extrudability is not influenced;
the white carbon black in the comparative example only plays a role of filler, so the effect on the adhesive failure condition of the contact surface is not obvious, and after the wet heat aging, the cohesive failure rate with the glazed glass is only 30 percent, and the cohesive failure rate with the painted metal plate is only 50 percent.
Claims (10)
1. A damp and heat resistant high-strength single-component polyurethane primer-free adhesive sealant is characterized in that: the composite material comprises the following raw materials in parts by weight: 8-15 parts of hydroxyl-terminated polyether polyol, 3-10 parts of first polyester polyol, 4-5 parts of first isocyanate, 12-22 parts of first plasticizer, 15-35 parts of white carbon black modified polyurethane prepolymer, 0.5-1 part of water removing agent, 18-25 parts of inorganic filler, 1-3 parts of resin filler, 1-2 parts of auxiliary agent and 0.01-0.4 part of first catalyst;
the hydroxyl-terminated polyether polyol is trifunctional polyoxypropylene ether or polyoxyethylene ether with the molecular weight of 3000-6000;
the first polyester polyol is difunctional polyester polyol with the molecular weight of 500-3000;
the first isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate;
the first plasticizer is one or a mixture of two of epoxidized soybean oil, dipropylene glycol dibenzoate, diisodecyl phthalate, diisononyl phthalate, dioctyl phthalate, butyl benzyl phthalate or alkyl phenyl sulfonate;
the water removing agent is p-tolyl sulfonyl isocyanate or/and calcium oxide;
the inorganic filler is one, two or three of acetylene black, light calcium carbonate, heavy calcium carbonate, nano calcium carbonate, diatomite, talcum powder, zinc oxide, silicon micropowder or organic bentonite;
the resin filler is one, two or three of polyphenol glycidyl ether epoxy resin, terpene resin, tall oil rosin, esterified rosin, styrene series resin or alkyl phenolic resin;
the auxiliary agent is one, two or three of calcium oxide, calcium hydroxide or aniline methyl trimethoxy silane;
the first catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials in parts by weight:
0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst at the temperature of 60-85 ℃ for 3-4 hours;
the second plasticizer is one or two of diisodecyl phthalate, diisononyl phthalate and alkyl sulfonate;
the second catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the second isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate.
2. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the first polyester polyol is polycaprolactone polyol or/and polycarbonate polyol.
3. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: in the preparation process of the white carbon black modified polyurethane prepolymer, firstly carrying out ultrasonic treatment on white carbon black and a second plasticizer, specifically: uniformly dispersing 0.05-1.25 parts by weight of white carbon black in 20-25 parts by weight of a second plasticizer to obtain a suspension, and then carrying out ultrasonic treatment; during each ultrasonic treatment, the frequency of the ultrasonic wave is more than 15kHz, the time of each ultrasonic treatment is 5-15 minutes, and the treatment times are 4-8; and (3) cooling the suspension by stirring after each ultrasonic treatment, and carrying out the next ultrasonic treatment when the temperature of the suspension is reduced to be below 30 ℃.
4. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the first isocyanate is diphenylmethane diisocyanate or/and toluene diisocyanate.
5. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the inorganic filler is acetylene black and/or nano calcium carbonate.
6. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the resin filler is polyphenol type glycidyl ether epoxy resin.
7. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the second isocyanate is hexamethylene diisocyanate.
8. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the second plasticizer is composed of diisodecyl phthalate and diisononyl phthalate according to the mass ratio of 1: 1.
9. The damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the first catalyst is dibutyltin dilaurate; the second catalyst is stannous octoate.
10. The preparation method of the damp-heat resistant high-strength single-component polyurethane primer-free adhesive sealant as claimed in claim 1, is characterized in that: the method comprises the following steps:
preparation of prepolymer: adding 8-15 parts by weight of hydroxyl-terminated polyether polyol and 3-10 parts by weight of first polyester polyol into a reaction kettle, heating to 120 ℃, carrying out vacuum dehydration for 0.5-1 hour under the condition that the vacuum degree is not lower than 0.092MPa, cooling to 55-65 ℃, adding 4-5 parts by weight of first isocyanate and 1-3 parts by weight of resin filler, heating to 80-90 ℃, reacting for 4-5 hours under the protection of nitrogen, cooling and discharging to obtain a prepolymer;
the hydroxyl-terminated polyether polyol is trifunctional polyoxypropylene ether or polyoxyethylene ether with the molecular weight of 3000-6000;
the first polyester polyol is difunctional polyester polyol with the molecular weight of 500-3000;
the first isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate;
the resin filler is one, two or three of polyphenol glycidyl ether epoxy resin, terpene resin, tall oil rosin, esterified rosin, styrene series resin or alkyl phenolic resin;
secondly, adding the prepolymer obtained in the step one into a stirrer, sequentially adding 15-35 parts of white carbon black modified polyurethane prepolymer, 12-22 parts of first plasticizer, 0.5-1 part of water removing agent and 18-25 parts of inorganic filler, heating to 48-52 ℃, stirring for 30-40 minutes under the conditions that the shearing speed is not lower than 10m/s and the vacuum degree is not lower than 0.092MPa, cooling to 28-32 ℃, continuing stirring for 15-20 minutes, adding 1-2 parts of auxiliary agent and 0.01-0.4 part of first catalyst, and stirring and uniformly mixing under the condition that the vacuum degree is not lower than 0.092MPa to obtain the humidity-heat-resistant high-strength single-component polyurethane primer-free bonding sealant;
the first plasticizer is one or a mixture of two of epoxidized soybean oil, dipropylene glycol dibenzoate, diisodecyl phthalate, diisononyl phthalate, dioctyl phthalate, butyl benzyl phthalate or alkyl phenyl sulfonate;
the water removing agent is p-tolyl sulfonyl isocyanate or/and calcium oxide;
the inorganic filler is one, two or three of acetylene black, light calcium carbonate, heavy calcium carbonate, nano calcium carbonate, diatomite, talcum powder, zinc oxide, silicon micropowder or organic bentonite;
the auxiliary agent is one, two or three of calcium oxide, calcium hydroxide or aniline methyl trimethoxy silane;
the first catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the white carbon black modified polyurethane prepolymer is prepared from the following raw materials in parts by weight:
0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst;
the white carbon black modified polyurethane prepolymer is prepared by reacting 0.05-1.25 parts of white carbon black, 15-25 parts of second isocyanate, 40-55 parts of second polyester polyol with the molecular weight of 400-1000, 20-25 parts of second plasticizer and 0.01-0.2 part of second catalyst at the temperature of 60-85 ℃ for 3-4 hours;
the second plasticizer is one or two of diisodecyl phthalate, diisononyl phthalate and alkyl sulfonate;
the second catalyst is one or a mixture of two of dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dimorpholinyl diethyl ether and triethylamine;
the second isocyanate is one or a mixture of two of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025256A (en) * | 2021-03-10 | 2021-06-25 | 浙江亚厦装饰股份有限公司 | Adhesive for waterproof bottom box of assembly type toilet ground and preparation method of adhesive |
| CN114181362A (en) * | 2021-12-02 | 2022-03-15 | 山东北方现代化学工业有限公司 | Special surface treating agent applied to bonding of PUR and Kevlar fiber and preparation method thereof |
| CN115160537A (en) * | 2022-08-03 | 2022-10-11 | 广东粤港澳大湾区国家纳米科技创新研究院 | High-heat-conduction material with bonding and sealing performances and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897652A (en) * | 2014-04-16 | 2014-07-02 | 山东北方现代化学工业有限公司 | Environment-friendly high-strength polyurethane adhesive sealant and preparation method thereof |
| CN107880234A (en) * | 2017-11-27 | 2018-04-06 | 烟台德邦科技有限公司 | A kind of preparation method of resistant to elevated temperatures polyurethane hot melt |
| CN109337636A (en) * | 2018-09-19 | 2019-02-15 | 山东北方现代化学工业有限公司 | A kind of one-component polyurethane sealant of rapid link and preparation method thereof |
| CN109554152A (en) * | 2018-10-30 | 2019-04-02 | 山东北方现代化学工业有限公司 | A kind of heat-resisting one-component polyurethane sealant and preparation method thereof |
| CN111073584A (en) * | 2019-12-20 | 2020-04-28 | 山东北方现代化学工业有限公司 | Single-component polyurethane sealant and low-temperature and rapid preparation method thereof |
-
2020
- 2020-07-24 CN CN202010727799.XA patent/CN111808569B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897652A (en) * | 2014-04-16 | 2014-07-02 | 山东北方现代化学工业有限公司 | Environment-friendly high-strength polyurethane adhesive sealant and preparation method thereof |
| CN107880234A (en) * | 2017-11-27 | 2018-04-06 | 烟台德邦科技有限公司 | A kind of preparation method of resistant to elevated temperatures polyurethane hot melt |
| CN109337636A (en) * | 2018-09-19 | 2019-02-15 | 山东北方现代化学工业有限公司 | A kind of one-component polyurethane sealant of rapid link and preparation method thereof |
| CN109554152A (en) * | 2018-10-30 | 2019-04-02 | 山东北方现代化学工业有限公司 | A kind of heat-resisting one-component polyurethane sealant and preparation method thereof |
| CN111073584A (en) * | 2019-12-20 | 2020-04-28 | 山东北方现代化学工业有限公司 | Single-component polyurethane sealant and low-temperature and rapid preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025256A (en) * | 2021-03-10 | 2021-06-25 | 浙江亚厦装饰股份有限公司 | Adhesive for waterproof bottom box of assembly type toilet ground and preparation method of adhesive |
| CN114181362A (en) * | 2021-12-02 | 2022-03-15 | 山东北方现代化学工业有限公司 | Special surface treating agent applied to bonding of PUR and Kevlar fiber and preparation method thereof |
| CN114181362B (en) * | 2021-12-02 | 2024-02-27 | 山东北方现代化学工业有限公司 | Special surface treatment agent applied to adhesion of PUR and Kevlar fibers and preparation method thereof |
| CN115160537A (en) * | 2022-08-03 | 2022-10-11 | 广东粤港澳大湾区国家纳米科技创新研究院 | High-heat-conduction material with bonding and sealing performances and preparation method thereof |
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