CN111892901A - Fast-curing two-component polyurethane sealant for hollow glass and preparation method thereof - Google Patents
Fast-curing two-component polyurethane sealant for hollow glass and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- 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
- 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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- 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
- C08K2201/011—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
Abstract
The invention relates to a fast curing two-component polyurethane sealant for hollow glass and a preparation method thereof. The component A comprises 15-35 parts by weight of end-capped polyurethane virgin rubber, 47-73 parts by weight of inorganic filler and 12-18 parts by weight of plasticizer; the component B comprises 15-25 parts by weight of curing agent, 15-25 parts by weight of carbon black and 50-70 parts by weight of plasticizer. The end-capped polyurethane virgin rubber is prepared by sequentially synthesizing polyether diol with the molecular weight of 600-8000 g/mol, polyether triol, diisocyanate and a sealing agent under the action of a catalyst. The R value is regulated and controlled, and the liquid polyamide resin with the viscosity (40 ℃) of 2000-40000 mPa & S is used as the curing agent, so that the two-component polyurethane sealant with excellent surface drying performance within the range of-10-35 ℃ can be prepared, and the sealant has good thixotropy and workability, high gluing efficiency, can adapt to industrial flow line production, and has wide application prospect.
Description
Technical Field
The invention relates to a fast-curing two-component polyurethane sealant for hollow glass and a preparation method thereof, belonging to the technical field of sealants.
Background
The sealant for the hollow glass needs to be dried in the air after glue application is finished, and the surface drying and curing are waited, and the time consumed in the stage influences the feasibility and the production efficiency of flow line production, so that the sealant has the capability of quick surface drying and curing when the efficient and continuous production of the hollow glass is realized. The national standard GB/T29775-2013 specifies a method and a limit value for measuring the surface drying time at 23 +/-2 ℃ and 50 +/-5 RH percent. Considering that the environment temperature of actual production is generally-10-35 ℃, the surface drying and curing of the sealant can be rapidly completed within the temperature range. The molecular structure of the polyurethane has excellent designability, the invention synthesizes the end-capped polyurethane virgin rubber from the perspective of molecular design, and a curing agent with high reaction activity is adopted for deblocking and curing, so that the adverse effect of air humidity is avoided, and the rapid surface drying and curing can be realized.
Disclosure of Invention
The invention aims to provide a fast-curing two-component polyurethane sealant for hollow glass and a preparation method thereof.
The invention relates to a fast curing two-component polyurethane sealant for hollow glass, which comprises the following components in parts by weight:
component A
15-35 parts of end-capped polyurethane virgin rubber;
47-73 parts of an inorganic filler;
12-18 parts of a plasticizer;
component B
15-25 parts of a curing agent;
15-25 parts of carbon black;
50-70 parts of a plasticizer.
Preferably, the end-capped polyurethane virgin rubber in the component A of the fast-curing two-component polyurethane sealant for hollow glass is prepared by respectively reacting polyether diol and polyether triol with diisocyanate and a sealant in sequence under the action of a catalyst.
Preferably, in the synthesis of the end-capped polyurethane virgin rubber of the component A of the fast-curing two-component polyurethane sealant for hollow glass, the polyether diol and the polyether triol are polyoxypropylene ether, polyoxyethylene ether and polytetramethylene ether with the functionality of 2 and 3, and the number average molecular weight is 600-8000 g/mol.
Preferably, in the synthesis of the blocked polyurethane raw rubber of the component A of the fast curing two-component polyurethane sealant for hollow glass, the diisocyanate is one or a mixture of Toluene Diisocyanate (TDI), diphenylmethane-4-4' -diisocyanate (MDI), isophorone diisocyanate (IPDI) and polymeric MDI.
Preferably, in the synthesis of the blocked polyurethane crude rubber of the component A of the fast curing two-component polyurethane sealant for hollow glass, the blocking agent is caprolactam, p-chlorophenol, p-bromophenol, p-nitrophenol, 2-pyridinol, 3-hydroxypyridine, 8-hydroxyquinoline, thiophenol, 2-mercaptopyridine, trifluoroethanol, trichloroethanol, 2-ethylhexanol, N-dibutylhydroxyacetamide, N-hydroxysuccinimide, N-morpholinoethanol, 2,2' -dimethyl-1, 3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxyethylpyridine, methylethylketoxime, acetanilide, N-methylacetamide, 2-methylimidazole, N-ethyl-4-methylimidazole, 3, 5-dimethylpyrazole.
Preferably, in the synthesis of the end-capped polyurethane crude rubber of the fast curing two-component polyurethane sealant A component for hollow glass, the catalyst is one or a mixture of dibutyltin dilaurate (DBTDL), tetramethylbutanediamine, triethylenediamine and stannous octoate.
Preferably, in the synthesis of the blocked polyurethane virgin rubber of the component A of the fast-curing two-component polyurethane sealant for hollow glass, the R value is defined as the molar ratio of isocyanate groups to polyether active hydrogen, and the R value is 2.0-4.0.
Preferably, the preparation method of the end-capped polyurethane virgin rubber of the component A of the fast-curing two-component polyurethane sealant for hollow glass comprises the following steps:
step (1): adding polyether diol and polyether triol into a reactor according to a set R value formula, heating to 115 ℃, controlling the vacuum degree to be not more than-0.095 MPa, and removing water for 1-2 hours under the condition;
step (2): and cooling to 75-85 ℃, adding a certain amount of diisocyanate, reacting for 0.5-1 hour under the protection of nitrogen, adding a catalyst, continuously reacting for 1-2 hours, adding a certain amount of sealant, reacting for 0.5-1 hour to obtain the end-capped polyurethane virgin rubber, and sealing for later use.
Preferably, the inorganic filler in the component A of the fast curing two-component polyurethane sealant for hollow glass is a mixture of more than two of heavy calcium carbonate, light calcium carbonate and nano calcium carbonate
Preferably, the plasticizer in the A component and the B component of the fast curing two-component polyurethane sealant for hollow glass is one or a mixture of more of dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
Preferably, the curing agent in the component B of the fast curing two-component polyurethane sealant for hollow glass is a multifunctional multi-branched active hydrogen compound, is one or a mixture of two of liquid polyamide resins, has the viscosity (40 ℃) of 2000-40000 mPa & lt/EN & gt and has the amine value of 200-450 mgKOH/g.
The preparation method of the fast curing two-component polyurethane sealant A and B for hollow glass comprises the following steps: (1) sequentially adding end-capped polyurethane virgin rubber, inorganic filler and plasticizer into a planetary power mixer, stirring for 20-40 minutes under the vacuum condition of not more than-0.095 MPa, cooling to room temperature, metering, discharging and packaging to obtain a component A; (2) and (3) sequentially adding a curing agent, carbon black and a plasticizer into a planetary power mixer, stirring for 20-40 minutes under the vacuum degree condition of not more than-0.095 MPa, cooling to room temperature, metering, discharging and packaging to obtain the component B.
The fast-curing two-component polyurethane sealant for the hollow glass comprises a component A and a component B in a mass ratio of (8-12): 1, the mixed sealant has good thixotropy and workability, excellent surface drying performance at the temperature of-10-35 ℃, high gluing efficiency, suitability for industrial flow line production and wide application prospect.
Detailed description of the preferred embodiment
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The raw materials used in the experiments in the examples and comparative examples of the present invention are as follows, but the present invention is not limited to the following raw materials, and the following raw materials are only specific examples to further specifically illustrate the effects of the puncture-proof sealing layer material for patch-type vacuum tires described in the present application:
polyether triol: shanghai Gaoqiangjingshi GEP-330N, the molecular weight is 4750g/mol, and the hydroxyl value is 35 mgKOH/g; the molecular weight of the Shandong Lanxingdao EP-3600 is 6000g/mol, and the hydroxyl value is 28 mgKOH/g.
Polyether glycol: dongdong DL2000D, molecular weight 2000g/mol, hydroxyl value 56 mgKOH/g; doxodongtong Docosa DL400, molecular weight 400g/mol, hydroxyl value 70 mgKOH/g.
Diisocyanate: MDI-100, purchased from Tantai Wanhua.
A sealing agent: caprolactam available from Sigma-Aldrich.
Inorganic filler: NC-60A heavy calcium carbonate, NAK-2108 nano calcium carbonate, purchased from Xufeng powder.
Plasticizer, DOP, available from Nanjing Rongji chemical industry.
Catalyst: dibutyl tin dilaurate, available from alatin.
Curing agent: polyamide No. 300, Versamind 125, amine number 315mgKOH/g, viscosity (40 ℃)8000 mPa.s, available from German Kenin; polyamide No. 650, with an amine value of 225mgKOH/g and a viscosity (40 ℃) of 30000mPa & s, available from Yongjiang province in Zhejiang province.
Carbon black: n330, available from cabot.
Surface drying time: the test is carried out by referring to the A method specified in GB/T13477.5-2002.
Degree of curing: the test is carried out according to the first method specified in GB/T32369-Maximum of) X 100%, where TSi is the tensile strength, TS, of the cured 24 hour sampleMaximum ofTensile strength maxima were taken for the test groups after 28 days of cure.
Example 1
Preparing end-capped polyurethane raw rubber: setting the R value to be 2.0, weighing 0.020mol of polyoxypropylene ether triol GEP-330N (95.00g containing 0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL2000D (42.33g containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, cooling the temperature to 75-80 ℃, adding 0.102mol of diisocyanate MDI-100(25.53g, containing 0.204mol of-NCO) into the mixture, and stirring the mixture for 1 hour; adding 3.167X 10-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; 0.102mol (11.54g) of caprolactam is added, after 1.5h of reaction, the obtained prepolymer is cooled to room temperature, and the blocked polyurethane virgin rubber is obtained.
Preparation of the component A and the component B: end-capped polyurethane virgin rubber (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were added in sequence to a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding liquid polyamide resin No. 300 (18.00g), carbon black (22.00g) and plasticizer (60.00g) into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed a dry time of 108 minutes (-10 ℃), 74 minutes (-0 ℃), 42 minutes (23 ℃) and 29 minutes (35 ℃).
Example 2
Preparing end-capped polyurethane raw rubber: setting the R value to be 2.5, weighing 0.020mol of polyoxypropylene ether triol GEP-330N (95.00g containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL2000D (42.33g containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, reducing the temperature to 75-80 ℃, and reducing the temperature to 1.275 multiplied by 10- 1mol diisocyanate MDI-100(31.91g, containing 0.255mol-NCO) was added thereto and stirred for 1 hour; adding 3.167X 10-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; adding 1.275X 10-1mol (14.43g) of caprolactam, reacting for 1.5h, and cooling the obtained prepolymer to room temperature to obtain the blocked polyurethane virgin rubber.
Preparation of the component A and the component B: a caprolactam-terminated polyurethane prepolymer (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were sequentially fed into a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding liquid polyamide resin No. 300 (22.00g), carbon black (22.00g) and plasticizer (56.00g) into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed a drying time of 101 minutes (-10 ℃), 72 minutes (-0 ℃), 39 minutes (23 ℃), 27 minutes (35 ℃).
Example 3
Preparing end-capped polyurethane raw rubber: setting the R value to be 3.0, weighing 0.020mol of polyoxypropylene ether triol GEP330N (95.00g, containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL2000D (42.33g, containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, reducing the temperature to 75-80 ℃, and reducing the temperature to 1.530 multiplied by 10- 1mol diisocyanate MDI-100(38.29g, containing 0.306mol-NCO)Adding the mixture and stirring the mixture for 1 hour; adding 3.167X 10-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; adding 1.530X 10-1mol (17.31g) of caprolactam, reacting for 1.5h, and cooling the obtained prepolymer to room temperature to obtain the blocked polyurethane virgin rubber.
Preparation of the component A and the component B: a caprolactam-terminated polyurethane prepolymer (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were sequentially fed into a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding liquid polyamide resin No. 300 (24.00g), carbon black (22.00g) and plasticizer (54.00g) into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed a drying time of 97 minutes (-10 ℃), 70 minutes (-0 ℃), 36 minutes (23 ℃) and 25 minutes (35 ℃).
Example 4
Preparing end-capped polyurethane raw rubber: setting the R value to be 2.0, weighing 0.020mol of polyoxypropylene ether triol GEP330N (95.00g, containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL2000D (42.33g, containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, cooling the temperature to 75-80 ℃, adding 0.102mol of diisocyanate MDI-100(25.53g, containing 0.204mol of-NCO) into the mixture, and stirring the mixture for 1 hour; adding 3.167X 10-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; 0.102mol (11.54g) of caprolactam is added, after 1.5h of reaction, the obtained prepolymer is cooled to room temperature, and the blocked polyurethane virgin rubber is obtained.
Preparation of the component A and the component B: end-capped polyurethane virgin rubber (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were added in sequence to a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding 650# (15.00g) of liquid polyamide resin, 20.00g of carbon black and 65.00g of plasticizer into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain the component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed dry times of 104 minutes (-10 ℃), 74 minutes (-0 ℃), 39 minutes (23 ℃) and 32 minutes (35 ℃).
Example 5
Preparing end-capped polyurethane raw rubber: setting the R value to be 2.5, weighing 0.020mol of polyoxypropylene ether triol GEP330N (95.00g, containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL2000D (42.33g, containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, reducing the temperature to 75-80 ℃, and reducing the temperature to 1.275 multiplied by 10- 1mol diisocyanate MDI-100(31.91g, containing 0.255mol-NCO) was added thereto and stirred for 1 hour; then 3.167X 10 are added-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; adding 1.275X 10-1mol (14.43g) of caprolactam, reacting for 1.5h, and cooling the obtained prepolymer to room temperature to obtain the blocked polyurethane virgin rubber.
Preparation of the component A and the component B: a caprolactam-terminated polyurethane prepolymer (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were sequentially fed into a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding 650# (15.00g) of liquid polyamide resin, 20.00g of carbon black and 65.00g of plasticizer into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain the component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed a drying time of 92 minutes (-10 ℃), 67 minutes (-0 ℃), 34 minutes (23 ℃) and 22 minutes (35 ℃).
Example 6
End cappingPreparing a polyurethane raw rubber: setting the R value to be 3.0, weighing 0.020mol of polyoxypropylene ether triol GEP330N (95.00g, containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL2000D (42.33g, containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, reducing the temperature to 75-80 ℃, and reducing the temperature to 1.530 multiplied by 10- 1mol diisocyanate MDI-100(38.29g, containing 0.306mol-NCO) was added thereto and stirred for 1 hour; adding 3.167X 10-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; adding 1.530X 10-1mol (17.31g) of caprolactam, reacting for 1.5h, and cooling the obtained prepolymer to room temperature to obtain the blocked polyurethane virgin rubber.
Preparation of the component A and the component B: a caprolactam-terminated polyurethane prepolymer (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were sequentially fed into a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding 650# (15.00g) of liquid polyamide resin, 20.00g of carbon black and 65.00g of plasticizer into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain the component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed a dry time of 94 minutes (-10 ℃), 64 minutes (-0 ℃), 33 minutes (23 ℃) and 20 minutes (35 ℃).
Comparative example 1
Preparing end-capped polyurethane raw rubber: setting the R value to be 2.0, weighing 0.020mol of polyoxypropylene ether triol GEP330N (95.00g, containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL400(8.40g, containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, cooling the temperature to 75-80 ℃, adding 0.102mol of diisocyanate MDI-100(25.53g, containing 0.204mol of-NCO) into the mixture, and stirring the mixture for 1 hour; adding 3.167X 10-5mol catalystDibutyltin dilaurate (0.02g), and stirring and reacting for 1 hour to obtain a polyurethane prepolymer containing terminal isocyanate groups; 0.102mol (11.54g) of caprolactam is added, after 1.5h of reaction, the obtained prepolymer is cooled to room temperature, and the blocked polyurethane virgin rubber is obtained.
Preparation of the component A and the component B: end-capped polyurethane virgin rubber (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were added in sequence to a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding liquid polyamide resin No. 300 (18.00g), carbon black (22.00g) and plasticizer (60.00g) into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests showed dry times of 308 minutes (-10 ℃), 238 minutes (-0 ℃), 157 minutes (23 ℃) and 133 minutes (35 ℃).
Comparative example 2
Preparing end-capped polyurethane raw rubber: setting the R value to be 2.0, weighing 0.020mol of polyoxypropylene ether triol GEP330N (95.00g, containing 0.0.06mol-OH), 0.021mol of polyoxypropylene ether diol DL400(8.40g, containing 0.042mol-OH) and 60.00g of plasticizer DOP into a reactor, keeping the vacuum degree of the obtained mixture at-0.098 MPa by using a vacuum pump, heating to 110 ℃, and removing water for 1-2 hours; introducing nitrogen for protection, cooling the temperature to 75-80 ℃, adding 0.102mol of diisocyanate MDI-100(25.53g, containing 0.204mol of-NCO) into the mixture, and stirring the mixture for 1 hour; adding 3.167X 10-5The mol of catalyst dibutyltin dilaurate (0.02g) is continuously stirred and reacted for 1 hour to obtain polyurethane prepolymer containing terminal isocyanate groups; 0.102mol (11.54g) of caprolactam is added, after 1.5h of reaction, the obtained prepolymer is cooled to room temperature, and the blocked polyurethane virgin rubber is obtained.
Preparation of the component A and the component B: end-capped polyurethane virgin rubber (20.00g), DOP (15.00g), ground calcium carbonate (53.00g) and nano calcium carbonate (12.00g) were added in sequence to a planetary power mixer. Stirring at high speed for 20min under nitrogen protection, cooling to room temperature, metering, discharging and packaging to obtain component A. Adding 650# (15.00g) of liquid polyamide resin, 20.00g of carbon black and 65.00g of plasticizer into a planetary power mixer, stirring at high speed for 20min under the protection of nitrogen, cooling to room temperature, metering, discharging and packaging to obtain the component B. The component A and the component B are mixed according to the mass ratio of 10: 1, the sizing tests show a drying time of 293 minutes (-10 ℃), 226 minutes (-0 ℃), 151 minutes (23 ℃) and 127 minutes (35 ℃).
The invention sets examples 7-12 and comparative examples 3-6, and the experimental steps and the method are the same as those of the examples 1-6, so that a series of fast curing two-component polyurethane sealant for hollow glass is obtained.
The end-capped polyurethane base rubber formulations of examples 7 to 12 and comparative examples 3 to 6 are shown in Table 1
The proportions of the two components and the surface drying time in the specific examples 7 to 12 and comparative examples 3 to 6 are shown in Table 2
The above description is only an example of the present invention, and is not intended to limit the present invention. The invention is susceptible to various modifications and alternative forms. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. The fast curing two-component polyurethane sealant is characterized by being prepared by mixing a component A of end-capped polyurethane virgin rubber, an inorganic filler and a plasticizer with a component B of a curing agent, carbon black and the plasticizer in a certain weight part.
2. The fast curing two-component polyurethane sealant for hollow glass according to claim 1 and the preparation method thereof are characterized in that the component A comprises the following components: 15-35 parts of end-capped polyurethane virgin rubber; 47-73 parts of an inorganic filler; 12-18 parts of a plasticizer; the component B comprises: 15-25 parts of a curing agent; 15-25 parts of carbon black; 50-70 parts of a plasticizer.
3. The fast curing two-component polyurethane sealant for hollow glass as claimed in claim 1-2 and its preparation method, wherein the end-capped polyurethane virgin rubber in component A is prepared by reacting polyether diol and polyether triol with diisocyanate, sealant and catalyst respectively.
4. The fast curing two-component polyurethane sealant for hollow glass as claimed in claims 1-3 and its preparation method, wherein in the synthesis of the end-capped polyurethane virgin rubber in component A, the polyether diol and the polyether triol are polyoxypropylene ether, polyoxyethylene ether and polytetramethylene ether with functionality of 2 and 3, and the number average molecular weight is 600-8000 g/mol.
5. The fast curing two-component polyurethane sealant for hollow glass according to claims 1-4 and the preparation method thereof, wherein in the synthesis of the blocked polyurethane raw rubber in the component A, the diisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane-4-4' -diisocyanate (MDI), isophorone diisocyanate (IPDI) and liquefied MDI.
6. The fast curing two-component polyurethane sealant for hollow glass as claimed in claims 1 to 5 and its preparation method, wherein in the synthesis of the blocked polyurethane virgin rubber in component A, the blocking agent is caprolactam, p-chlorophenol, p-bromophenol, p-nitrophenol, 2-pyridinol, 3-hydroxypyridine, 8-hydroxyquinoline, thiophenol, 2-mercaptopyridine, trifluoroethanol, trichloroethanol, 2-ethylhexanol, N-dibutylhydroxyacetamide, N-hydroxysuccinimide, N-morpholinoethanol, 2,2' -dimethyl-1, 3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxyethylpyridine, methyl ethyl ketoxime, acetanilide, N-methylacetamide, 2-methylimidazole, N-ethyl-4-methylimidazole and 3, 5-dimethylpyrazole.
7. The hollow glass fast curing two-component polyurethane sealant and the preparation method thereof as claimed in claims 1-6, wherein in the synthesis of the end-capped polyurethane virgin rubber in the component A, the catalyst is one or more of dibutyl tin dilaurate (DBTDL), tetramethyl butanediamine, triethylene diamine and stannous octoate.
8. The fast curing two-component polyurethane sealant for hollow glass as claimed in claims 1-7 and its preparation method, wherein R is defined as the molar ratio of isocyanate group to polyether active hydrogen in the synthesis of the blocked polyurethane raw rubber in component A, and R is 2.0-3.0.
9. The fast curing two-component polyurethane sealant for hollow glass as claimed in claims 1-8 and the preparation method thereof, wherein the preparation method of the end-capped polyurethane virgin rubber in the component A comprises the following steps:
step (1): adding polyether diol and polyether triol into a reactor according to a set R value formula, heating to 115 ℃, controlling the vacuum degree to be not more than-0.095 MPa, and removing water for 1-2 hours under the condition;
step (2): and cooling to 75-85 ℃, adding a certain amount of diisocyanate, reacting for 0.5-1 hour under the protection of nitrogen, adding a catalyst, continuously reacting for 1-2 hours, adding a certain amount of sealant, reacting for 0.5-1 hour to obtain the end-capped polyurethane virgin rubber, and sealing for later use.
10. The hollow glass fast curing two-component polyurethane sealant and the preparation method thereof as claimed in claims 1-9, wherein the inorganic filler in the component A is a mixture of two or more of heavy calcium carbonate, light calcium carbonate and nano calcium carbonate.
11. The fast curing two-component polyurethane sealant for hollow glass according to claims 1-10 and the preparation method thereof, wherein the plasticizer in the component A and the component B is one or more of dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP).
12. The fast curing two-component polyurethane sealant for hollow glass as claimed in claims 1-11, wherein the curing agent in component B is one or two mixtures of polyfunctional multi-branched active hydrogen compound, liquid polyamide resin, viscosity (40 ℃) is 2000-40000 mPa.S, and amine value is 200-450 mgKOH/g.
13. The fast curing two-component polyurethane sealant for hollow glass as claimed in claims 1-12 and the preparation method thereof are characterized in that the preparation method of the component A and the component B is as follows: (1) sequentially adding end-capped polyurethane virgin rubber, a filler and a plasticizer into a planetary power mixer, stirring for 20-40 minutes under the condition of a vacuum degree not greater than-0.095 MPa, cooling to room temperature, metering, discharging and packaging to obtain a component A; (2) and (3) sequentially adding a curing agent, carbon black and a plasticizer into a planetary power mixer, stirring for 20-40 minutes under the vacuum degree condition of not more than-0.095 MPa, cooling to room temperature, metering, discharging and packaging to obtain the component A.
14. A fast-curing two-component polyurethane sealant for hollow glass and a preparation method thereof are characterized in that a component A and a component B are mixed according to a mass ratio of (8-12): 1, the mixed sealant has good thixotropy and workability, and has excellent surface drying performance within the temperature range of-10 to 35 ℃.
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| CN115029097A (en) * | 2022-06-22 | 2022-09-09 | 郑州华普密封材料有限公司 | Easily-extruded double-component polyurethane hollow glass sealant and preparation method thereof |
| CN115029097B (en) * | 2022-06-22 | 2024-03-26 | 郑州华普密封材料有限公司 | Easily-extruded double-component polyurethane hollow glass sealant and preparation method thereof |
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