CN110734733A - one-component polyurethane sealant suitable for metal bonding and preparation method thereof - Google Patents
one-component polyurethane sealant suitable for metal bonding and preparation method thereof Download PDFInfo
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- CN110734733A CN110734733A CN201911179378.1A CN201911179378A CN110734733A CN 110734733 A CN110734733 A CN 110734733A CN 201911179378 A CN201911179378 A CN 201911179378A CN 110734733 A CN110734733 A CN 110734733A
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of sealants, in particular to single-component polyurethane sealants suitable for metal bonding and a preparation method thereof, wherein the preparation raw materials of the single-component polyurethane sealants comprise 35-50 parts by weight of polyurethane prepolymer, 5-40 parts by weight of plasticizer, 0.5-6 parts by weight of water absorbent, 1-1.5 parts by weight of adhesion promoter and 0.01-1 part by weight of catalyst.
Description
Technical Field
The invention relates to the field of sealants, in particular to single-component polyurethane sealant suitable for metal bonding and a preparation method thereof.
Background
The sealant is materials used for filling the configured gap to achieve sealing effect, and can deform along with the shape of the sealing surface and is not easy to flow.
At present, polyurethane sealant is mainly divided into a single component and a double component, wherein the single component is a moisture curing type, and the double component is a reaction curing type. The double components have the characteristics of quick curing and good performance, but need to be prepared when in use, and have complex process. The single-component sealant has the characteristics of convenience in construction, no need of blending and easiness in extrusion, and is suitable for automatic pipelining, so that development and utilization of the single-component sealant are concerned.
However, the single-component sealant has poor thermal stability, the conventional product can only bear transient high temperature of 120 ℃, bubbles and cracks can be generated in a high-temperature thermal environment, the aging resistance is poor, the bonding property to metal is poor, and the requirement cannot be met, so that the application of the single-component sealant in step is limited.
Disclosure of Invention
Aiming at problems in the prior art, in the aspect of the invention, single-component polyurethane sealant is provided, and the preparation raw materials comprise, by weight, 35-50 parts of polyurethane prepolymer, 5-40 parts of plasticizer, 0.5-6 parts of water absorbent, 1-1.5 parts of adhesion promoter and 0.01-1 part of catalyst, wherein the preparation raw materials of the adhesion promoter comprise isocyanate and silane coupling agent, and the molar ratio of the isocyanate to the silane coupling agent is 1 (1.5-2).
As preferable embodiments of the present invention, the isocyanate includes at least of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.
As preferred embodiments of the present invention, the isocyanates include isophorone diisocyanate and hexamethylene diisocyanate.
According to preferable technical schemes, the molar ratio of the isophorone diisocyanate to the hexamethylene diisocyanate is 1 (1-2).
According to preferable technical schemes, the silane coupling agent comprises a silane coupling agent D, and the preparation method of the silane coupling agent D comprises the steps of adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-neck flask, opening a condensing device and a stirring device, introducing nitrogen, heating to 75-85 ℃, dropwise adding dimethylaminopropylacrylamide and eugenol glycidyl ether, completing dropwise adding within 2-3 h, heating to 110-130 ℃, and reacting for 1h to obtain the silane coupling agent D.
As preferable technical schemes, the silane coupling agent also comprises diethylenetriaminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane.
According to preferable technical schemes, the molar ratio of the diethylenetriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1 (2-3).
According to preferable technical schemes, the preparation raw materials of the single-component polyurethane sealant further comprise, by weight, 20-40 parts of calcium carbonate, 2-10 parts of carbon black and 0.5-5 parts of fumed silica.
As preferred technical schemes of the invention, the calcium carbonate comprises at least of heavy calcium carbonate, light calcium carbonate and nano calcium carbonate.
In a second aspect of the invention, of the one-part polyurethane sealant is provided for bonding metals.
Compared with the prior art, the invention has the following beneficial effects:
the adhesion promoter prepared by using isophorone diisocyanate and hexamethylene diisocyanate as isocyanates and using diethylenetriaminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and a silane coupling agent D as silane coupling agents is used in the single-component polyurethane sealant, so that the sealant has good fluidity, avoids the formation of a weak water vapor boundary layer, can maintain -determined tensile strength, can resist aging, high temperature and low temperature, can bear extreme application environment, is stable in storage, and has an application range of .
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
According to the aspect of the invention, single-component polyurethane sealant is provided, and the preparation raw materials comprise, by weight, 35-50 parts of polyurethane prepolymer, 5-40 parts of plasticizer, 0.5-6 parts of water absorbent, 1-1.5 parts of adhesion promoter and 0.01-1 part of catalyst.
In embodiments, the raw materials for preparing the one-component polyurethane sealant further include, by weight, 20-40 parts of calcium carbonate, 2-10 parts of carbon black, and 0.5-5 parts of fumed silica.
In preferred embodiments, the preparation raw materials of the one-component polyurethane sealant comprise 40 parts of polyurethane prepolymer, 20 parts of plasticizer, 4 parts of water absorbent, 1.2 parts of adhesion promoter, 0.2 part of catalyst, 30 parts of calcium carbonate, 6 parts of carbon black and 3 parts of fumed silica by weight.
Polyurethane prepolymer
The polyurethane is a high molecular polymer formed by the reaction of polyisocyanate and polyether or polyester polyol under conditions, the prepolymer of the polyurethane is simply a reactive semi-finished product obtained by controlling proportion of the polyisocyanate and the polyol to react, and the reaction ratio is different due to the various types of the polyisocyanate and the polyol.
The polyurethane prepolymer disclosed by the invention is purchased from Wuhanshi Quanxing new material science and technology Co., Ltd, and has the model of SG-AC 50.
Plasticizer
Plasticizer is a polymer material additive which is widely used by in industrial production and is also called plasticizer, all substances which are added into polymer materials and can increase the plasticity of the polymers are called plasticizer, the plasticizer can improve the performance of the polymer materials, reduce the production cost and improve the production benefit, the plasticizer is important chemical product additives and is generally applied to materials such as plastic products, concrete, mud ash, cement, gypsum, cosmetics, cleaning agents and the like as the additive, particularly, phthalate is required to be added into the polyvinyl chloride plastic products in order to increase the plasticity of the plastics and improve the strength of the plastics, and the content of the phthalate can reach 50% of the product sometimes, the plasticizer mainly has the functions of weakening the secondary bond between resin molecules, increasing the mobility of the bond between the resin molecules, reducing the crystallinity of the resin molecules, increasing the plasticity of the resin molecules, enhancing the flexibility of the resin molecules, being easy to process and being legally used for industrial application, widely exists in food packaging, cosmetics, medical devices, environmental water bodies, such as preservative films, food packaging, toys and the like.
In embodiments, the plasticizer is a phthalate and/or an aliphatic diacid ester.
Examples of the phthalate ester include dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate and di (2-propylheptyl) phthalate.
Examples of the aliphatic diacid esters include dimethyl adipate, dibutyl adipate, dioctyl adipate, and diethyl sebacate.
Preferably, the plasticizer is dioctyl phthalate.
Water absorbent
In embodiments, the water absorbing agent includes at least of p-toluenesulfonyl isocyanate, triethyl orthoformate, and calcium oxide.
Preferably, the water absorbent is p-methyl benzenesulfonyl isocyanate.
Adhesion promoter
In embodiments, the preparation raw material of the adhesion promoter comprises isocyanate and a silane coupling agent, and the molar ratio of the isocyanate to the silane coupling agent is 1 (1.5-2).
Preferably, the molar ratio of the isocyanate to the silane coupling agent is 1: 1.8.
in embodiments, the isocyanate includes at least of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.
Preferably, the isocyanates include isophorone diisocyanate and hexamethylene diisocyanate.
Preferably, the mole ratio of isophorone diisocyanate to hexamethylene diisocyanate is 1: (1-2); more preferably, the molar ratio of isophorone diisocyanate to hexamethylene diisocyanate is 1: 1.5.
in embodiments, the silane coupling agent comprises a silane coupling agent D, and the preparation method of the silane coupling agent D comprises the steps of adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-neck flask, opening a condensing device and a stirring device, introducing nitrogen, heating to 75-85 ℃, dropwise adding dimethylaminopropylacrylamide and eugenol glycidyl ether, completing dropwise adding within 2-3 h, heating to 110-130 ℃, and reacting for 1h to obtain the silane coupling agent D.
Preferably, the weight ratio of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and dimethylaminopropylacrylamide to toluene is 1: (1-2); more preferably, the weight ratio of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and dimethylaminopropylacrylamide to toluene is 1: 1.5.
preferably, the molar ratio of the gamma-glycidylpropylmethyldimethoxysilane to the dimethylaminopropylacrylamide is (1-1.5): 1; more preferably, the molar ratio of gamma-glycidylpropylmethyldimethoxysilane to dimethylaminopropylacrylamide is 1.2: 1.
preferably, the weight of the chloroplatinic acid-isopropanol is 50 x 10 of the total weight of gamma-glycidylpropylmethyldimethoxysilane and dimethylaminopropylacrylamide-6。
Preferably, the molar ratio of the eugenol glycidyl ether to the dimethylaminopropyl acrylamide is (0.3-0.6): 1; more preferably, the molar ratio of eugenol glycidyl ether to dimethylaminopropyl acrylamide is 0.5: 1.
the structural formula of the eugenol glycidyl ether is shown in the specification
In preferable embodiments, the preparation method of the silane coupling agent D comprises the steps of adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-neck flask, opening a condensing device and a stirring device, introducing nitrogen for 5min, heating to 80 ℃, dropwise adding dimethylaminopropylacrylamide and eugenol glycidyl ether, completing dropwise addition within 2.5h, heating to 120 ℃, and reacting for 1h to obtain the silane coupling agent D.
In embodiments, the silane coupling agent further includes divinyltriaminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane.
Preferably, the mol ratio of the diethylenetriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1: (2-3); more preferably, the mole ratio of the diethylenetriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1: 2.5.
preferably, the molar ratio of the silane coupling agent D to the 3-anilinopropyltrimethoxysilane is (1-2): 1; more preferably, the silane coupling agent D and the 3-anilinopropyltrimethoxysilane are present in a molar ratio of 1.5: 1.
catalyst and process for preparing same
In embodiments, the catalyst is an organotin-based catalyst and/or a tertiary amine-based catalyst.
Examples of the organotin catalyst include di-n-butyltin dilaurate, dibutyltin bis (acetylacetonate), stannous octoate, dibutyltin diacetate and the like.
Examples of the tertiary amine catalyst include triethylenediamine, cyclohexylmethyl tertiary amine, and dimorpholinyldiethyl ether.
Preferably, the catalyst is di-n-butyltin dilaurate.
Calcium carbonate
In , the calcium carbonate comprises at least of heavy calcium carbonate, light calcium carbonate and nano calcium carbonate.
Preferably, the calcium carbonate comprises nano calcium carbonate, and further , the particle size of the nano calcium carbonate is preferably 40-80 nm.
The nano calcium carbonate is purchased from Shandong Hongxiang zinc industry Co., Ltd, and has a particle size of 40-80 nm.
Carbon black
In embodiments, the carbon black is a rubber carbon black.
The rubber carbon black of the invention is purchased from XianRehui International trade company, No. , and has the model number N330.
Fumed silica
In embodiments, the fumed silica has a particle size of 20 to 40 nm.
Preferably, the fumed silica has a particle size of 30 nm.
The fumed silica is purchased from Shanghai ink high-tech materials, Inc., and has a particle size of 30 nm.
In embodiments, the method of making the one-part polyurethane sealant includes the steps of:
(1) drying the calcium carbonate, the carbon black and the fumed silica at 120 ℃ for 5-24 h;
(2) adding the plasticizer, the polyurethane prepolymer and the water absorbent into a stirring reaction kettle, vacuumizing, and stirring and defoaming for 0.5 h;
(3) stopping stirring, adding the dried calcium carbonate, carbon black and fumed silica, stirring and vacuumizing for 1-2 h;
(4) adding an adhesion promoter into the mixture obtained in the step (3);
(5) adding a catalyst under the protection of nitrogen;
(6) vacuumizing, continuously stirring for 10-20 min, and uniformly mixing;
(7) charging nitrogen to relieve vacuum to normal pressure, discharging and packaging.
In preferred embodiments, the method of making the one-part polyurethane sealant includes the steps of:
(1) drying calcium carbonate, carbon black and fumed silica at 120 ℃ for 15 h;
(2) adding the plasticizer, the polyurethane prepolymer and the water absorbent into a stirring reaction kettle, vacuumizing, and stirring and defoaming for 0.5 h;
(3) stopping stirring, adding the dried calcium carbonate, carbon black and fumed silica, stirring and vacuumizing for 1.5 h;
(4) adding an adhesion promoter into the mixture obtained in the step (3);
(5) adding a catalyst under the protection of nitrogen;
(6) vacuumizing, continuously stirring for 15min, and uniformly mixing;
(7) charging nitrogen to relieve vacuum to normal pressure, discharging and packaging.
In a second aspect of the invention, of the one-part polyurethane sealant is provided for bonding metals.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
The embodiment 1 of the invention provides single-component polyurethane sealant for bonding metal, which is prepared from 35 parts of polyurethane prepolymer, 5 parts of plasticizer, 0.5 part of water absorbent, 1 part of adhesion promoter, 0.01 part of catalyst, 20 parts of calcium carbonate, 2 parts of carbon black and 0.5 part of fumed silica in parts by weight.
The polyurethane prepolymer is purchased from Wuhanshi Quanxing new material science and technology Co., Ltd and has the model of SG-AC50, the plasticizer is dioctyl phthalate, the water absorbent is p-methyl benzenesulfonyl isocyanate, the catalyst is di-N-butyltin dilaurate, the nano calcium carbonate is purchased from Shandong Hongxiang zinc industry Co., Ltd, the rubber carbon black is purchased from XianHui International trade Co., Ltd, in , has the model of N330, and the fumed silica is purchased from Shanghai ink high-new material science and technology Co., Ltd and has the particle size of 30 nm.
The preparation raw materials of the adhesion promoter comprise isocyanate and a silane coupling agent; the molar ratio of the isocyanate to the silane coupling agent is 1: 1.5; the isocyanate comprises isophorone diisocyanate and hexamethylene diisocyanate, and the molar ratio of the isophorone diisocyanate to the hexamethylene diisocyanate is 1: 1; the silane coupling agent comprises diethylenetriaminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and a silane coupling agent D, wherein the molar ratio of the diethylenetriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1: 2; the molar ratio of the silane coupling agent D to the 3-anilinopropyltrimethoxysilane is 1: 1.
the preparation method of the silane coupling agent D comprises the following steps: adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-mouth flask, opening a condensing device and a stirring device, introducing nitrogen for 5min, heating to 80 ℃, dropwise adding dimethylaminopropylacrylamide, completing dropwise adding within 2.5h, heating to 120 ℃, and reacting for 1h to obtain the product.
The weight ratio of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and the dimethylaminopropylacrylamide to the toluene is 1: 1; the mol ratio of the gamma-glycidylpropylmethyldimethoxysilane to the dimethylaminopropylacrylamide is 1: 1; the weight of the chloroplatinic acid-isopropanol is 50 x 10 of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and the dimethylaminopropylacrylamide-6(ii) a The mol ratio of the eugenol glycidyl ether to the dimethylaminopropyl acrylamide is 0.5: 1.
the preparation method of the adhesion promoter comprises the following steps: adding isocyanate into a beaker, heating to 50 ℃, slowly dropwise adding a silane coupling agent, and reacting for 3 hours at 60 ℃ to obtain the isocyanate.
The preparation method of the one-component polyurethane sealant comprises the following steps:
(1) drying calcium carbonate, carbon black and fumed silica at 120 ℃ for 15 h;
(2) adding the plasticizer, the polyurethane prepolymer and the water absorbent into a stirring reaction kettle, vacuumizing, and stirring and defoaming for 0.5 h;
(3) stopping stirring, adding the dried calcium carbonate, carbon black and fumed silica, stirring and vacuumizing for 1.5 h;
(4) adding an adhesion promoter into the mixture obtained in the step (3);
(5) adding a catalyst under the protection of nitrogen;
(6) vacuumizing, continuously stirring for 15min, and uniformly mixing;
(7) charging nitrogen to relieve vacuum to normal pressure, discharging and packaging.
Example 2
The embodiment 2 of the invention provides single-component polyurethane sealant for bonding metal, which is prepared from the following raw materials, by weight, 50 parts of polyurethane prepolymer, 40 parts of plasticizer, 6 parts of water absorbent, 1.5 parts of adhesion promoter, 1 part of catalyst, 40 parts of calcium carbonate, 10 parts of carbon black and 5 parts of fumed silica.
The polyurethane prepolymer is purchased from Wuhanshi Quanxing new material science and technology Co., Ltd and has the model of SG-AC50, the plasticizer is dioctyl phthalate, the water absorbent is p-methyl benzenesulfonyl isocyanate, the catalyst is di-N-butyltin dilaurate, the nano calcium carbonate is purchased from Shandong Hongxiang zinc industry Co., Ltd, the rubber carbon black is purchased from XianHui International trade Co., Ltd, in , has the model of N330, and the fumed silica is purchased from Shanghai ink high-new material science and technology Co., Ltd and has the particle size of 30 nm.
The preparation raw materials of the adhesion promoter comprise isocyanate and a silane coupling agent; the molar ratio of the isocyanate to the silane coupling agent is 1: 2; the isocyanate comprises isophorone diisocyanate and hexamethylene diisocyanate, and the molar ratio of the isophorone diisocyanate to the hexamethylene diisocyanate is 1: 2; the silane coupling agent comprises diethylenetriaminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and a silane coupling agent D, wherein the molar ratio of the diethylenetriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1: 3; the molar ratio of the silane coupling agent D to the 3-anilinopropyltrimethoxysilane is 2: 1.
the preparation method of the silane coupling agent D comprises the following steps: adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-mouth flask, opening a condensing device and a stirring device, introducing nitrogen for 5min, heating to 80 ℃, dropwise adding dimethylaminopropylacrylamide, completing dropwise adding within 2.5h, heating to 120 ℃, and reacting for 1h to obtain the product.
The weight ratio of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and the dimethylaminopropylacrylamide to the toluene is 1: 2; the mol ratio of the gamma-glycidylpropylmethyldimethoxysilane to the dimethylaminopropylacrylamide is 1.5: 1; the weight of the chloroplatinic acid-isopropanol is 50 x 10 of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and the dimethylaminopropylacrylamide-6(ii) a The mol ratio of the eugenol glycidyl ether to the dimethylaminopropyl acrylamide is 0.5: 1.
the preparation method of the adhesion promoter comprises the following steps: adding isocyanate into a beaker, heating to 50 ℃, slowly dropwise adding a silane coupling agent, and reacting for 3 hours at 60 ℃ to obtain the isocyanate.
The preparation method of the one-component polyurethane sealant comprises the following steps:
(1) drying calcium carbonate, carbon black and fumed silica at 120 ℃ for 15 h;
(2) adding the plasticizer, the polyurethane prepolymer and the water absorbent into a stirring reaction kettle, vacuumizing, and stirring and defoaming for 0.5 h;
(3) stopping stirring, adding the dried calcium carbonate, carbon black and fumed silica, stirring and vacuumizing for 1.5 h;
(4) adding an adhesion promoter into the mixture obtained in the step (3);
(5) adding a catalyst under the protection of nitrogen;
(6) vacuumizing, continuously stirring for 15min, and uniformly mixing;
(7) charging nitrogen to relieve vacuum to normal pressure, discharging and packaging.
Example 3
The embodiment 3 of the invention provides single-component polyurethane sealant for bonding metal, which is prepared from the following raw materials, by weight, 40 parts of polyurethane prepolymer, 20 parts of plasticizer, 4 parts of water absorbent, 1.2 parts of adhesion promoter, 0.2 part of catalyst, 30 parts of calcium carbonate, 6 parts of carbon black and 3 parts of fumed silica.
The polyurethane prepolymer is purchased from Wuhanshi Quanxing new material science and technology Co., Ltd and has the model of SG-AC50, the plasticizer is dioctyl phthalate, the water absorbent is p-methyl benzenesulfonyl isocyanate, the catalyst is di-N-butyltin dilaurate, the nano calcium carbonate is purchased from Shandong Hongxiang zinc industry Co., Ltd, the rubber carbon black is purchased from XianHui International trade Co., Ltd, in , has the model of N330, and the fumed silica is purchased from Shanghai ink high-new material science and technology Co., Ltd and has the particle size of 30 nm.
The preparation raw materials of the adhesion promoter comprise isocyanate and a silane coupling agent; the molar ratio of the isocyanate to the silane coupling agent is 1: 1.8; the isocyanate comprises isophorone diisocyanate and hexamethylene diisocyanate, and the molar ratio of the isophorone diisocyanate to the hexamethylene diisocyanate is 1: 1.5; the silane coupling agent comprises diethylenetriaminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane and a silane coupling agent D, wherein the molar ratio of the diethylenetriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1: 2.5; the molar ratio of the silane coupling agent D to the 3-anilinopropyltrimethoxysilane is 1.5: 1.
the preparation method of the silane coupling agent D comprises the following steps: adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-mouth flask, opening a condensing device and a stirring device, introducing nitrogen for 5min, heating to 80 ℃, dropwise adding dimethylaminopropylacrylamide, completing dropwise adding within 2.5h, heating to 120 ℃, and reacting for 1h to obtain the product.
The weight ratio of the total weight of the gamma-glycidylpropylmethyldimethoxysilane and the dimethylaminopropylacrylamide to the toluene is 1: 1.5; the mol ratio of the gamma-glycidylpropylmethyldimethoxysilane to the dimethylaminopropylacrylamide is 1.2: 1; the weight of the chloroplatinic acid-isopropanol is gamma-glycidylpropanol50 x 10 of the total weight of the dimethylmethyldimethoxysilane and the dimethylaminopropylacrylamide-6(ii) a The mol ratio of the eugenol glycidyl ether to the dimethylaminopropyl acrylamide is 0.5: 1.
the preparation method of the adhesion promoter comprises the following steps: adding isocyanate into a beaker, heating to 50 ℃, slowly dropwise adding a silane coupling agent, and reacting for 3 hours at 60 ℃ to obtain the isocyanate.
The preparation method of the one-component polyurethane sealant comprises the following steps:
(1) drying calcium carbonate, carbon black and fumed silica at 120 ℃ for 15 h;
(2) adding the plasticizer, the polyurethane prepolymer and the water absorbent into a stirring reaction kettle, vacuumizing, and stirring and defoaming for 0.5 h;
(3) stopping stirring, adding the dried calcium carbonate, carbon black and fumed silica, stirring and vacuumizing for 1.5 h;
(4) adding an adhesion promoter into the mixture obtained in the step (3);
(5) adding a catalyst under the protection of nitrogen;
(6) vacuumizing, continuously stirring for 15min, and uniformly mixing;
(7) charging nitrogen to relieve vacuum to normal pressure, discharging and packaging.
Example 4
Example 4 of the present invention provides one-part polyurethane sealants for bonding metals, the specific embodiment of which is the same as example 3 except that the isocyanate is isophorone diisocyanate.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Example 5
Example 5 of the present invention provides one-part polyurethane sealants for bonding metals, the specific embodiment of which is the same as example 3, except that the isocyanate is hexamethylene diisocyanate.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Example 6
The embodiment 6 of the invention provides single-component polyurethane sealants for bonding metals, which is similar to the embodiment 3 in the specific implementation mode, and is characterized in that the silane coupling agent is diethylenetriaminopropyltrimethoxysilane.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Example 7
Example 7 of the present invention provides one-part polyurethane sealants for bonding metals, which is similar to example 3 except that the silane coupling agent is 3-anilinopropyltrimethoxysilane.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Example 8
The embodiment 8 of the invention provides single-component polyurethane sealants for bonding metals, which is similar to the embodiment 3 in the specific implementation mode, and is characterized in that the silane coupling agents are diethylenetriaminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Example 9
Example 9 of the present invention provides one-component polyurethane sealants for bonding metals, which is similar to example 3 except that the silane coupling agent is silane coupling agent D.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Example 10
The embodiment 10 of the invention provides single-component polyurethane sealants for bonding metals, which are the same as the embodiment 3 in the specific implementation mode, and the differences are that the silane coupling agents are gamma-aminopropyl methyl diethoxy silane, diethylenetriaminopropyl trimethoxy silane and a silane coupling agent D, and the molar ratio of the diethylenetriaminopropyl trimethoxy silane to the gamma-aminopropyl methyl diethoxy silane is 1: 2.5.
The preparation method of the single-component sealant has the same specific implementation mode as that of the example 3.
Performance evaluation
1. Tensile strength: the tensile strength of the single-component polyurethane sealant obtained in the embodiment 1-10 is tested according to the GB/T16777-2008 standard, and the test condition is 23 ℃, and the ultraviolet aging is 720 hours.
2. High temperature resistance: the one-component polyurethane sealant obtained in examples 1 to 10 was placed on a 60 ℃ slant surface, and the slant surface was placed in an oven and heat-treated at 300 ℃ for 2 hours to observe whether or not softening occurred.
3. And the low temperature resistance is that the single-component polyurethane sealant obtained in the embodiment 1-10 is coated on a metal round bar with the diameter of 25mm, the coating thickness is 1mm, then the metal round bar is placed in an environment of 100 ℃ below zero for months, and then the metal round bar is taken out to observe whether cracking occurs.
4. Bonding strength: the one-component polyurethane sealant obtained in example 3 was tested for adhesion strength to steel plates in accordance with GB/T13477.8-2002.
TABLE 1
From the test results in table 1, it can be seen that the one-component polyurethane sealant provided by the present invention has excellent adhesive properties, is stable in storage, can endure extreme environments, and is sealant using pan.
The foregoing examples are illustrative only and serve to explain features of the method of the invention the appended claims are intended to claim as much as possible, and the examples presented herein are illustrative of selected embodiments based on a combination of all possible examples.
Claims (10)
- The single-component polyurethane sealant is characterized by comprising, by weight, 35-50 parts of polyurethane prepolymer, 5-40 parts of plasticizer, 0.5-6 parts of water absorbent, 1-1.5 parts of adhesion promoter and 0.01-1 part of catalyst, wherein the adhesion promoter comprises isocyanate and silane coupling agent, and the molar ratio of the isocyanate to the silane coupling agent is 1 (1.5-2).
- 2. The one-part polyurethane sealant according to claim 1, wherein the isocyanate comprises at least of diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 4' -dicyclohexylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, 1, 5-naphthalene diisocyanate, and xylylene diisocyanate.
- 3. The one-part polyurethane sealant according to claim 2, wherein the isocyanate comprises isophorone diisocyanate and hexamethylene diisocyanate.
- 4. The one-part polyurethane sealant according to claim 3, wherein the molar ratio of isophorone diisocyanate to hexamethylene diisocyanate is 1: (1-2).
- 5. The one-part polyurethane sealant according to claim 1, wherein the silane coupling agent comprises a silane coupling agent D, and the preparation method of the silane coupling agent D comprises: adding gamma-glycidylpropylmethyldimethoxysilane, toluene and chloroplatinic acid-isopropanol into a four-mouth flask, opening a condensing device and a stirring device, introducing nitrogen, heating to 75-85 ℃, dropwise adding dimethylaminopropylacrylamide and eugenol glycidyl ether within 2-3 h, heating to 110-130 ℃, and reacting for 1h to obtain the product.
- 6. The one-part polyurethane sealant according to claim 5, wherein the silane coupling agent further comprises divinyltriaminopropyltrimethoxysilane and 3-anilinopropyltrimethoxysilane.
- 7. The one-part polyurethane sealant according to claim 6, wherein the mole ratio of the divinyltriaminopropyltrimethoxysilane to the 3-anilinopropyltrimethoxysilane is 1: (2-3).
- 8. The one-component polyurethane sealant according to any one of the claims 1 to 7 and , wherein the one-component polyurethane sealant further comprises 20 to 40 parts by weight of calcium carbonate, 2 to 10 parts by weight of carbon black, and 0.5 to 5 parts by weight of fumed silica.
- 9. The one-part polyurethane sealant according to claim 8, wherein the calcium carbonate comprises at least of heavy calcium carbonate, light calcium carbonate and nano calcium carbonate.
- 10, one-component polyurethane sealant according to any one of claims 1-9 to for bonding metals.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911179378.1A CN110734733A (en) | 2019-11-27 | 2019-11-27 | one-component polyurethane sealant suitable for metal bonding and preparation method thereof |
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| CN201911179378.1A CN110734733A (en) | 2019-11-27 | 2019-11-27 | one-component polyurethane sealant suitable for metal bonding and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112265330A (en) * | 2020-11-05 | 2021-01-26 | 杭州盛得新材料有限公司 | Fabric laminate with recycled modified PVB and preparation method thereof |
| CN114634787A (en) * | 2021-04-25 | 2022-06-17 | 上海蒂姆新材料科技有限公司 | PU adhesive and preparation method thereof |
-
2019
- 2019-11-27 CN CN201911179378.1A patent/CN110734733A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112265330A (en) * | 2020-11-05 | 2021-01-26 | 杭州盛得新材料有限公司 | Fabric laminate with recycled modified PVB and preparation method thereof |
| CN112265330B (en) * | 2020-11-05 | 2021-06-25 | 杭州盛得新材料有限公司 | Fabric laminate with recycled modified PVB and preparation method thereof |
| CN114634787A (en) * | 2021-04-25 | 2022-06-17 | 上海蒂姆新材料科技有限公司 | PU adhesive and preparation method thereof |
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