CN111748310A - Double-component polyurethane adhesive and preparation method thereof - Google Patents
Double-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN111748310A CN111748310A CN202010577421.6A CN202010577421A CN111748310A CN 111748310 A CN111748310 A CN 111748310A CN 202010577421 A CN202010577421 A CN 202010577421A CN 111748310 A CN111748310 A CN 111748310A
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/4808—Mixtures of two or more polyetherdiols
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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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more 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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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a double-component polyurethane adhesive and a preparation method thereof, wherein the double-component polyurethane adhesive comprises a component A and a component B; the component A consists of the following raw materials in parts by weight: 45 to 56.2 portions of polyether polyol, 40 to 50.4 portions of filler A and 0.4 to 0.6 portion of catalyst; the component B comprises the following raw materials in parts by weight: 30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B; the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer. The invention has the beneficial effects that: the double-component polyurethane adhesive provided by the invention has good thixotropy and rapid strength increase performance; the use ratio of the double-component polyurethane adhesive provided by the invention is 1:1, and the assembly line operation of the automobile windshield can be met.
Description
Technical Field
The invention belongs to the field of polyurethane adhesives, and particularly relates to a two-component polyurethane adhesive and a preparation method thereof.
Background
The main material of the single-component moisture-curing polyurethane sealant contains isocyanate-terminated groups, and can react with moisture in the air at room temperature to form a high-strength elastomer. The sealant has good mechanical and physical properties, chemical corrosion resistance, water resistance, low temperature resistance, vibration and impact resistance and other properties, so that the sealant is widely applied to bonding of automobile windshield glass. However, the curing process of the single-component product is long, the strength needs a certain time to rise, and the single-component product is greatly influenced by temperature and humidity, so that the curing process is one of important bottlenecks in accelerating the production speed of a modern industrialized production line.
Although the bi-component polyurethane adhesive product can avoid the influence of the curing process of the mono-component product, the bi-component polyurethane adhesive product is suitable for the defects of insufficient elasticity and poor thixotropy existing in structural bonding; the product suitable for encapsulation and sealing has poor mechanical property and can not meet the standard requirement of the automobile windshield glass bonding industry. In recent years, the developed two-component polyurethane windshield glass adhesive is mainly a catalytic curing system, wherein the component A is common one-component polyurethane, and the component B is a substance containing active hydrogen or free water molecules, and the use ratio of the two-component polyurethane windshield glass adhesive is 10: 1-50: 1. Although the bonding requirement of the windshield glass can be met, due to the fact that the proportion of the AB component is greatly different, the high requirement is placed on sizing equipment, and the phenomenon that the curing speed of a product is different due to the fact that the proportion is out of control can occur.
Therefore, the two-component polyurethane adhesive is urgently needed to be developed to avoid the performance defects, meet the industrial standard and meet the requirements of an automobile windshield glass assembly line.
Disclosure of Invention
The invention provides a two-component polyurethane adhesive and a preparation method thereof, aiming at solving the technical problem that A, B components are too large in usage amount when the two-component polyurethane adhesive for windshield glass in the prior art is used and cannot meet the requirements of an automobile windshield glass assembly line.
The specific technical scheme is as follows:
a double-component polyurethane adhesive is characterized by comprising a component A and a component B;
the component A consists of the following raw materials in parts by weight:
45 to 56.2 portions of polyether polyol, 40 to 50.4 portions of filler A and 0.4 to 0.6 portion of catalyst;
the component B comprises the following raw materials in parts by weight:
30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B;
the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer.
Further, the polyether polyol comprises:
polyether glycol: 8-23 parts of polyether triol: 26-47 parts;
the relative molecular mass of the polyether glycol is 400-2000, and the hydroxyl value is 50-300 mgKOH/g;
the relative molecular mass of the polyether triol is 1000-6000, and the hydroxyl value is 28-168 mgKOH/g.
Further, the filler A is one or more of nano calcium carbonate, calcined kaolin, calcium carbonate or talcum powder; the filler B is one or more of carbon black, calcined kaolin, calcium carbonate or talcum powder.
Further, the catalyst is one or more of dibutyltin dilaurate, dioctyltin dilaurate, dimorpholinodiethyl ether or bismuth isooctanoate; the synthetic catalyst is stannous octoate.
Further, the prepolymer polyisocyanate is 4, 4' -diphenylmethane diisocyanate.
Further, the prepolymerization polyether polyol is selected from polyether polyols with the average molecular weight of 4800-6000 and three functionality degrees.
Further, the plasticizer is selected from one or more of dioctyl phthalate, diisodecyl phthalate or diisononyl phthalate.
Further, the polyisocyanate includes one or more selected from diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, or toluene diisocyanate.
Further, the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from 70-80 parts by weight of prepolymer polyether polyol, 10-15 parts by weight of prepolymer polyisocyanate, 0.05-0.1 part by weight of synthetic catalyst and 5-15 parts by weight of plasticizer, and the polyurethane prepolymer accounts for 29-38% of the component B by weight.
The preparation method of the double-component polyurethane adhesive is characterized by comprising the following steps:
preparing a component A:
adding polyether polyol and a filler A into a reactor, heating, dehydrating, cooling, adding a catalyst, and stirring to obtain a component A;
preparing a component B:
preparing a polyurethane prepolymer;
and adding the polyurethane prepolymer, polyisocyanate and the filler B into a reactor, and stirring for 1-3 hours in vacuum to prepare a component B.
Compared with the prior art, the invention has the beneficial effects that:
(1) the double-component polyurethane adhesive provided by the invention has good thixotropy and rapid strength increase performance;
(2) the volume ratio of the two-component polyurethane adhesive provided by the invention is 1 (0.95-1.05), and the assembly line operation of the automobile windshield can be met.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
A two-component polyurethane adhesive is characterized in that the two-component polyurethane comprises a component A and a component B;
the component A consists of the following raw materials in parts by weight:
45 to 56.2 portions of polyether polyol, 40 to 50.4 portions of filler A and 0.4 to 0.6 portion of catalyst;
the component B comprises the following raw materials in parts by weight:
30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B;
the polyurethane prepolymer is a compound containing terminal isocyanate, which is prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer;
the polyurethane prepolymer accounts for 29-38% of the component B by mass.
In the term of the two-component polyurethane, the polyurethane is generally divided into two parts, one group of reaction substances is polyurethane prepolymer, and the other group is polyol, and when the two-component polyurethane is used, the polyurethane prepolymer and the polyol react to carry out crosslinking and curing;
the term "polyurethane prepolymer" refers to a high molecular polymer terminated with polyisocyanate, which is obtained by reacting polyether polyol with polyisocyanate at a certain temperature under the action of a suitable synthesis catalyst, and is in a stable state at a certain temperature, and is subjected to a polymerization reaction with activated hydrogen under the action of a catalyst.
The prepolymer polyisocyanate is 4, 4' -diphenylmethane diisocyanate, and the prepolymer polyether polyol is selected from 4800-6000 average molecular weight and trifunctional polyether polyol, and is selected from one of EP3600, GEP-330 353135 and WanolF 3128;
further optimized, the NCO content of the synthesized polyurethane prepolymer is 1.0-3.0%, and the rotational viscosity is 7000 mPa.s-60000 mPa.s.
Specifically, the polyurethane prepolymer is a compound containing terminal isocyanate group, which is prepared from 70-80 parts by weight of prepolymer polyether polyol, 10-15 parts by weight of prepolymer polyisocyanate, 0.05-0.1 part by weight of synthetic catalyst and 5-15 parts by weight of plasticizer.
The 'synthetic catalyst' in the invention refers to a catalyst for the reaction of polyisocyanate and polyether polyol, and the synthetic catalyst is stannous octoate;
in the invention, the component B is polyisocyanate and polyurethane prepolymer, and when the polyurethane prepolymer and the polyisocyanate are used, the polyurethane prepolymer and polyether polyol react simultaneously.
In the present invention, the plasticizer is selected from one or more of dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) or diisononyl phthalate (DINP).
In the invention, the component A polyether polyol is used for extracting partial activated hydrogen for reacting with the component B polyurethane prepolymer and polyisocyanate, and the polyether polyol in the component A comprises:
polyether glycol: 8-23 parts of polyether triol: 26-47 parts;
the relative molecular mass of the polyether glycol is 400-2000, and the hydroxyl value is 50-300 mgKOH/g;
the relative molecular mass of the polyether triol is 1000-6000, and the hydroxyl value is 28-168 mgKOH/g.
Further, the polyether polyol in the component A is selected from polyether diol (DL-2000), polyether diol (DL-400) and polyether triol (T700);
or
Polyether diol (DL-400), polyether triol (WanolF3135), polyether triol (T700); the performance is more excellent, especially in the surface dry time.
In the invention, the term "filler" is used for ensuring the mechanical strength, increasing the thixotropy and reducing the cost, and the filler A is one or more of nano calcium carbonate, calcined kaolin, coarse whiting or talcum powder; the filler B is one or more of carbon black, calcined kaolin, heavy calcium or talcum powder.
The catalyst is used for catalyzing and promoting the crosslinking reaction of the polyurethane sealant prepolymer and activated hydrogen, and is one or more of dibutyltin dilaurate, dioctyltin dilaurate, dimorpholinyl diethyl ether or bismuth isooctanoate;
further, the polyisocyanate includes one or more selected from diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, or toluene diisocyanate.
The preparation method of the double-component polyurethane adhesive is characterized by comprising the following steps:
preparing a component A:
adding polyether polyol and a filler A into a reactor, heating to 100-120 ℃, carrying out vacuum stirring dehydration for 1-3 hours, then cooling to 55-65 ℃, adding a catalyst, and carrying out vacuum stirring for 0.5 hour to obtain a component A;
preparing a component B:
preparation of polyurethane prepolymer: the polyurethane prepolymer is prepared by reacting prepolymer polyisocyanate, prepolymer polyether polyol and plasticizer at 80 +/-5 ℃ under the action of a synthetic catalyst for 2-5 h, cooling and discharging, and filling the mixture into a closed container for later use.
And adding the polyurethane prepolymer, polyisocyanate and the filler B into a reactor, and stirring for 1-3 hours in vacuum to prepare a component B.
Example 1
The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF3128) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding 0.35 part of bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows: adding DOP and polyether triol EP-3600 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4, 4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer I.
Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer I, carbon black, calcined kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 1 example 1A Components raw materials and parts by weight
Raw materials | Parts by weight |
DL-400 (polyether glycol) | 10.0 |
WanolF3128 (polyether triol) | 46.2 |
Nano calcium carbonate (Filler A) | 43.35 |
Bismuth isooctanoate (catalyst) | 0.45 |
TABLE 2 polyurethane prepolymer I raw materials and parts by weight
TABLE 3 example 1B Components raw materials and parts by weight
Raw materials | Parts by weight |
Wanhua chemical MDI-50 (polyisocyanate) | 7.8 |
Polyurethane prepolymers I | 37 |
Carbon black (Filler B) | 15 |
Kaolin (Filler B) | 29.5 |
DINP (plasticizer) | 10.7 |
Example 2
The preparation steps of the component A are as follows: adding polyether diol (DL-2000), polyether triol (T700), nano calcium carbonate and talcum powder into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is-0.9 MPa, then cooling to 60 ℃, adding dibutyltin dilaurate, stirring for 30 minutes under the condition that the vacuum degree is-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows: adding a plasticizer and polyether triol Walol F3135 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4, 4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain a polyurethane prepolymer II.
Adding Wanhua chemical MDI-50 into a planetary stirrer, adding polyurethane prepolymer II, carbon black and calcium carbonate, stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain the component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 4 example 2A Components raw materials and parts by weight
Raw materials | Parts by weight |
DL-2000 (polyether glycol) | 23 |
T700 (polyether triol) | 26 |
Nano calcium carbonate (Filler A) | 35.5 |
Talcum powder (Filler A) | 14.9 |
Dibutyltin dilaurate (catalyst) | 0.6 |
TABLE 5 polyurethane prepolymer II raw materials and parts by weight
TABLE 6 example 2B Components raw materials and parts by weight
Raw materials | Parts by weight |
Wanhua chemical MDI-50 (polyisocyanate) | 21.5 |
Polyurethane prepolymers II | 37.0 |
Carbon black (Filler B) | 20.2 |
Calcium carbonate (Filler B) | 21.3 |
Example 3
The preparation steps of the component A are as follows: adding polyether diol (DL-2000), polyether diol (DL-400), polyether triol (T700) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring dynamic mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition that the vacuum degree is-0.9 MPa, then cooling to 60 ℃, adding bismuth isooctanoate, stirring for 30 minutes under the condition that the vacuum degree is-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows: adding DOP and polyether triol EP-3600 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4, 4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer III.
Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer III, carbon black, kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.
TABLE 7 example 3A Components raw materials and parts by weight
Raw materials | Parts by weight |
DL-2000 (polyether glycol) | 15.0 |
DL-400 (polyether glycol) | 8.0 |
T700 (polyether triol) | 26.0 |
Nano calcium carbonate (Filler A) | 41.55 |
Bismuth isooctanoate (catalyst) | 0.45 |
TABLE 8 polyurethane prepolymer III raw materials and parts by weight
TABLE 9 example 3B Components raw materials and parts by weight
Example 4
The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF3135), polyether triol (T700), talcum powder and nano calcium carbonate into a three-neck flask, adding into a planetary stirring dynamic mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding dibutyltin dilaurate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows: adding a plasticizer and polyether triol Walol F3135 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4, 4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain a polyurethane prepolymer IV.
Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer IV, carbon black, kaolin and plasticizer, stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain the component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 10 example 4A Components raw materials and parts by weight
TABLE 11 polyurethane prepolymer IV raw materials and parts by weight
TABLE 12 example 4B Components raw materials and parts by weight
Raw materials | Parts by weight |
Wanhua chemical MDI-50 (polyisocyanate) | 11.0 |
Polyurethane prepolymer IV | 32.0 |
Carbon black (Filler B) | 21.0 |
Kaolin (Filler B) | 23.0 |
DINP (plasticizer) | 13.0 |
Example 5
The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF3128) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding 0.35 part of bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows: adding Wanhua chemical MDI-50 into a planetary stirrer, adding polyurethane prepolymer I, carbon black and calcined kaolin, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 13 example 5A Components raw materials and parts by weight
Raw materials | Parts by weight |
DL-400 (polyether glycol) | 16.2 |
WanolF3128 (polyether triol) | 38.8 |
Nano calcium carbonate (Filler A) | 40 |
Bismuth isooctanoate (catalyst) | 0.4 |
TABLE 14 example 5B Components raw materials and parts by weight
Raw materials | Parts by weight |
Wanhua chemical MDI-50 (polyisocyanate) | 10 |
Polyurethane prepolymers I | 30.0 |
Carbon black (Filler B) | 22 |
Kaolin (Filler B) | 8.0 |
DINP (plasticizer) | 10 |
Comparative example 1
The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF3128), nano calcium carbonate, 1, 4-butadiene (chain extender) and triethanolamine (chain extender) into a three-neck flask, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows:
adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer I, carbon black, kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 15 comparative example 1A Components raw materials and parts by weight
Raw materials | Parts by weight |
DL-400 (polyether glycol) | 10.0 |
WanolF3128 (polyether triol) | 46.2 |
1, 4-butadiene (chain extender) | 3 |
Triethanolamine (chain extender) | 1.0 |
Nano calcium carbonate (Filler A) | 39.35 |
Bismuth isooctanoate (catalyst) | 0.45 |
TABLE 16 raw materials and weight parts of comparative example 1B component
Raw materials | Parts by weight |
Wanhua chemical MDI-50 (polyisocyanate) | 7.8 |
Polyurethane prepolymers I | 37 |
Carbon black (Filler) | 15 |
Kaolin (Filler) | 29.5 |
DINP (plasticizer) | 10.7 |
Comparative example 2
The preparation steps of the component A are as follows: adding polyether diol (DL-400), polyether triol (WanolF3128) and nano calcium carbonate into a three-neck flask, adding into a planetary stirring mixer, stirring and heating to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of-0.9 MPa, then cooling to 60 ℃, adding 0.35 part of bismuth isooctanoate, stirring for 30 minutes under the condition of vacuum degree of-0.9 MPa, and discharging to obtain the component A.
The preparation steps of the component B are as follows: adding DOP and polyether triol EP-3600 into a dry three-neck flask, vacuumizing and dehydrating for 0.5-1 h at 120 ℃, cooling to about 60 ℃, adding metered 4, 4' -diphenylmethane diisocyanate and stannous octoate, slowly heating to 80 ℃, carrying out heat preservation reaction for 3h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer I.
Adding Wanhua chemical MDI-50 into a planetary mixer, adding polyurethane prepolymer I, carbon black, calcined kaolin and a plasticizer, stirring and stirring for 30min under the condition that the vacuum degree is-0.9 MPa, introducing cooling water to control the temperature to be below 60 ℃, and discharging to obtain a component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 17 COMPARATIVE EXAMPLE 2A COMPONENT MATERIAL AND ITS WEIGHT PARTS
Raw materials | Parts by weight |
DL-400 (polyether glycol) | 10.0 |
WanolF3128 (polyether triol) | 46.2 |
Nano calcium carbonate (Filler A) | 43.35 |
Bismuth isooctanoate (catalyst) | 0.45 |
TABLE 18 polyurethane prepolymer I raw materials and parts by weight
Raw materials | Parts by weight |
DOP (plasticizer) | 10 |
EP-3600 (polyether polyol) | 76.45 |
4, 4' -diphenylmethane diisocyanate | 13.5 |
Stannous octoate (synthetic catalyst) | 0.05 |
TABLE 19 raw materials and weight parts of comparative example 2B component
Raw materials | Parts by weight |
Wanhua chemical MDI-50 (polyisocyanate) | 6 |
Polyurethane prepolymers I | 42 |
Carbon black (Filler) | 15 |
Kaolin (Filler) | 29.5 |
DINP (plasticizer) | 7.5 |
Comparative example 3
The preparation steps of the component A are as follows: adding dioctyl phthalate, 2000 molecular weight polyether diol and 5000 molecular weight polyether triol into a dry three-neck flask, vacuumizing and dehydrating for 4h at 120 ℃, cooling to about 85 ℃, adding metered diphenylmethane diisocyanate, carrying out heat preservation reaction for 2h under the protection of dry nitrogen, cooling and discharging to obtain the polyurethane prepolymer V.
Adding a polyurethane prepolymer V and polymethylene polyphenyl polyisocyanate into a planetary stirrer, stirring for 30min at the temperature of 45 ℃ in vacuum, adding dried carbon black, active calcium carbonate and heavy calcium carbonate, mixing and stirring for 2h, adding bismuth isooctanoate, N-phenyl-gamma-aminopropyltrimethoxysilane and oxazolidine water removal agents, stirring and stirring for 1h at the temperature of 45 ℃, and discharging to obtain the component A.
The preparation steps of the component B are as follows:
adding 5000 molecular weight polyether triol, castor oil polyalcohol, polyester dihydric alcohol, carbon black, activated calcium carbonate, dioctyl phthalate and 1, 4-butanediol into a planetary mixer, stirring and stirring for 4 hours under the conditions that the vacuum degree is-0.9 Mpa and the temperature is 95 ℃, introducing cooling water to control the temperature to be below 45 ℃, adding bismuth isooctanoate and N-phenyl-gamma-aminopropyltrimethoxysilane, stirring for 1.5 hours under the protection of nitrogen, and discharging to obtain a component B.
According to the formula A: b is 1:1 (volume ratio) and can be used after being fully mixed.
TABLE 20 polyurethane prepolymer V raw materials and parts by weight
Raw materials | Parts by weight |
2000 molecular weight polyether diols | 18.87 |
5000 molecular weight polyether triol | 49.06 |
Dioctyl phthalate | 18.86 |
Diphenylmethane diisocyanate | 13.21 |
TABLE 21 comparative example 3A Components raw materials and parts by weight
TABLE 22 COMPARATIVE EXAMPLE 3B COMPONENT MATERIAL AND ITS WEIGHT PARTS
Raw materials | Parts by weight |
5000 molecular weight polyether triol | 33.81 |
Castor oil polyols | 9.22 |
Polyester diol | 8.20 |
Carbon black | 15.37 |
Activated calcium carbonate | 8.20 |
Dioctyl phthalate | 21.51 |
1, 4-butanediol | 3.07 |
Bismuth Isooctanoate | 0.31 |
N-phenyl-gamma-aminopropyltrimethoxysilane | 0.31 |
Example 6
And (3) performance testing: the test was carried out according to "HG/T4363-2012 Single-component polyurethane adhesive for automotive glazings".
The results are shown in tables 23 and 24:
table 23 shows the results of the performance tests of examples
1 refers to the density of the mixed two-component polyurethane
The Tn 2 two-component polyurethane is different from the standard description of the curing depth of the one-component polyurethane, and the thickness of a glue layer can be completely cured within 24 hours.
Table 24 shows the results of the test of comparative examples
1 refers to the density of the mixed two-component polyurethane
The Tn 2 two-component polyurethane is different from the standard description of the curing depth of the one-component polyurethane, and the thickness of a glue layer can be completely cured within 24 hours.
As can be seen from the test results, the examples have significant advantages over the comparative examples in terms of elastic properties such as hardness and elongation at break, and the adhesive for automotive windshields is effective in joining windshields to vehicle bodies, and not only requires good adhesion and aging resistance, but also has elastomeric characteristics, effectively avoiding vibration fatigue during vehicle travel and avoiding stress concentration due to the shape of windshields and vehicle bodies. In the embodiment, the mechanical property is ensured, the hardness control and the elongation at break are considered, and the elasticity of the windshield glass cement is ensured.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A double-component polyurethane adhesive is characterized by comprising a component A and a component B;
the component A consists of the following raw materials in parts by weight:
45 to 56.2 portions of polyether polyol, 40 to 50.4 portions of filler A and 0.4 to 0.6 portion of catalyst;
the component B comprises the following raw materials in parts by weight:
30-37 parts of polyurethane prepolymer, 7.8-22 parts of polyisocyanate, 0-13 parts of plasticizer and 30-44 parts of filler B;
the polyurethane prepolymer is a compound containing terminal isocyanate group and prepared from prepolymer polyether polyol, prepolymer polyisocyanate, a synthetic catalyst and a plasticizer.
2. The two-component polyurethane adhesive of claim 1, wherein the polyether polyol comprises:
polyether glycol: 8-23 parts of polyether triol: 26-47 parts;
the relative molecular mass of the polyether glycol is 400-2000, and the hydroxyl value is 50-300 mgKOH/g;
the relative molecular mass of the polyether triol is 1000-6000, and the hydroxyl value is 28-168 mgKOH/g.
3. The two-component polyurethane adhesive of claim 1, wherein the filler A is one or more of nano calcium carbonate, calcined kaolin, calcium carbonate or talc; the filler B is one or more of carbon black, calcined kaolin, calcium carbonate or talcum powder.
4. The two-component polyurethane adhesive of claim 1, wherein the catalyst is one or more of dibutyltin dilaurate, dioctyltin dilaurate, dimorpholinodiethylether, or bismuth isooctanoate; the synthetic catalyst is stannous octoate.
5. The two-component polyurethane adhesive of claim 1, wherein the prepolymer polyisocyanate is 4, 4' -diphenylmethane diisocyanate.
6. The two-component polyurethane adhesive of claim 1, wherein the pre-polymerized polyether polyol is selected from the group consisting of 4800-6000 average molecular weight, trifunctional polyether polyols.
7. The two-component polyurethane adhesive of claim 1, wherein the plasticizer is selected from one or more of dioctyl phthalate, diisodecyl phthalate, or diisononyl phthalate.
8. The two-component polyurethane adhesive of claim 1, wherein the polyisocyanate comprises one or more selected from the group consisting of diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, and toluene diisocyanate.
9. The two-component polyurethane adhesive according to claim 1, wherein the polyurethane prepolymer is a compound containing terminal isocyanate group and is prepared from 70-80 parts by weight of prepolymer polyether polyol, 10-15 parts by weight of prepolymer polyisocyanate, 0.05-0.1 part by weight of synthetic catalyst and 5-15 parts by weight of plasticizer, and the mass ratio of the polyurethane prepolymer to the component B is 29-38%.
10. The preparation method of the two-component polyurethane adhesive of any one of claims 1 to 9, characterized by comprising the following steps:
preparing a component A:
adding polyether polyol and a filler A into a reactor, heating, dehydrating, cooling, adding a catalyst, and stirring to obtain a component A;
preparing a component B:
preparing a polyurethane prepolymer;
and adding the polyurethane prepolymer, polyisocyanate and the filler B into a reactor, and stirring for 1-3 hours in vacuum to prepare a component B.
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