CN111057513A - High-low temperature universal bi-component polyurethane adhesive - Google Patents
High-low temperature universal bi-component polyurethane adhesive Download PDFInfo
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- CN111057513A CN111057513A CN201911271663.6A CN201911271663A CN111057513A CN 111057513 A CN111057513 A CN 111057513A CN 201911271663 A CN201911271663 A CN 201911271663A CN 111057513 A CN111057513 A CN 111057513A
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- component
- polyurethane adhesive
- component polyurethane
- parts
- low temperature
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Classifications
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention discloses a high-low temperature universal bi-component polyurethane adhesive, which consists of a main agent A component and a curing agent B component, and comprises the following components in parts by mass: (1) the main agent A component is an active hydrogen component and comprises: 5-10 parts of polytetrahydrofuran polyol, 4.3-5.5 parts of hydroxyethylated bisphenol A, 6-15 parts of filler, 3-12 parts of iron oxide red, 60.5-74.5 parts of solvent, 0.01-0.015 part of catalyst, 0.12-0.25 part of coupling agent and 0.1-0.2 part of fumed silica, wherein (2) the component B of curing agent is a diluent with polyisocyanate NCO percent of 13 percent; the mass ratio of the component A to the component B is 100: 40-75. The adhesive is used for bonding a polyurethane casting material and a steel base material, has a wide construction temperature range, has high tensile bonding strength when being bonded at the temperature of 10-100 ℃, and has the characteristics of excellent salt water aging resistance and heat aging resistance, and low cost.
Description
Technical Field
The invention belongs to the technical field of adhesives, relates to a high-low temperature universal bi-component polyurethane adhesive, and particularly relates to an adhesive suitable for bonding a steel substrate and a polyurethane casting material.
Background
The polyurethane elastomer has the characteristics of good elasticity, excellent mechanical property, excellent wear resistance, oil resistance, low temperature resistance, tearing resistance, corrosion resistance, vibration absorption capacity and the like, and is widely applied to the fields of metallurgy, automobile, chemical industry, textile, building materials, rail transit and the like. In practical application, the application fields of the polyurethane elastomer casting material and the metal base material are very wide, such as wheels for high-bearing vehicles of rail transit and industrial machinery, bridge expansion joints and the like, and the bonding effect has great influence on the application of the polyurethane casting material and the service life of products.
In the field of engineering construction, the ground temperature is very high in summer in some areas, and the temperature is very low in winter in some areas, but in the prior art, the adhesive for bonding the metal base material and the polyurethane casting material can be bonded by low-temperature vulcanization and high-temperature heat vulcanization, and the variety of the general-purpose adhesive with high and low temperature is very few. Although Thixon403/404 is suitable for room temperature and 120 deg.C vulcanization bonding, this type of adhesive is expensive. The universal two-component polyurethane adhesive developed by Lupeng (Lupeng. development of universal two-component polyurethane adhesive [ J ]. Xinjiang chemical industry, 2004, 3: 1-4) is a two-component polyurethane adhesive prepared by taking a polyurethane prepolymer as a main component (component A) and taking a trimethylolpropane-TDI adduct as a curing agent (component B), and the adhesive has a good high-temperature bonding effect but a poor low-temperature bonding effect, and meanwhile, the hydrolysis resistance of the adhesive is poor because a soft segment in the main agent is polyester polyol. In practical application, the adhesive is required to have wide temperature range construction adaptability and excellent weather resistance, and in order to meet the operability of outdoor construction, the bi-component adhesive is required to have certain proportion tolerance.
Disclosure of Invention
In order to overcome the defects that the high-temperature vulcanization bonding and the low-temperature vulcanization bonding of the adhesive in the prior art cannot be compatible, the invention provides a high-low temperature universal bi-component polyurethane adhesive. The adhesive is used for bonding a polyurethane casting material and a steel base material, has a wide construction temperature range, has high tensile bonding strength when being bonded at the temperature of 10-100 ℃, and has the characteristics of excellent salt water aging resistance and heat aging resistance, and low cost.
In order to solve the technical problems, the technical scheme of the invention is as follows: a high-low temperature universal bi-component polyurethane adhesive is composed of a main agent A component and a curing agent B component, and comprises the following components in parts by mass:
(1) the main agent A component is an active hydrogen component and comprises:
(2) the component B of the curing agent is a diluent of polyisocyanate diluted by a solvent until NCO percent is 13 percent, and the solvent for dilution is ethyl acetate, butyl acetate or acetone and the like.
The mass ratio of the component A to the component B is 100: 40-75.
The molecular weight of the polytetrahydrofuran Polyol (PTMG) is preferably 500-1000, and the hydroxyl value of the hydroxyethylated bisphenol A is preferably 324-340 mgKOH/g. The filler can be talcum powder, light calcium carbonate, titanium dioxide and the like and a mixture thereof; the solvent can be ethyl acetate, butyl acetate or dichloromethane and the like and a mixture thereof; the catalyst is a common tin catalyst; the coupling agent may be gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), 3-methacryloxypropyltrimethoxysilane (KH570), gamma-mercaptopropyltriethoxysilane (KH580), gamma-mercaptopropyltrimethoxysilane (KH590), or the like, preferably KH 570. Other raw materials are all the common varieties and specifications in the field.
The polyisocyanate is polymethylene polyphenyl polyisocyanate, HDI dimer, HDI trimer, HDI biuret or TDI-TMP or HDI-TMP addition product.
According to the adhesive provided by the invention, through designing the structure of the adhesive, the adhesive has a good bonding effect when constructed under the environment condition of 10-100 ℃, the construction temperature latitude is large, the defect that the requirement of the adhesive construction on the environment is strict is overcome, and a technical support is provided for producing various structural bonding products by high-temperature hot vulcanization bonding or low-temperature vulcanization bonding of polyurethane. Meanwhile, the proportion of the active hydrogen A component and the curing agent B component of the adhesive is changed in a wider proportion range, the defect that the proportion of the two components of the traditional double-component adhesive is strict is overcome, and the cost is lower.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Uniformly mixing the adhesives according to the mass ratio, brushing the mixture on a base material, pouring a polyurethane material 1h after the adhesives are coated to prepare a tensile bonding sample, and testing the tensile bonding strength according to the GB/T13477.8-2002 method.
The 100 ℃ bonding sample is a polyurethane material poured for 1h after gluing, then cured for 16h at 100 ℃ and tested for tensile bonding strength.
The normal temperature bonding sample is a polyurethane material poured for 1 hour after gluing, and is placed for 168 hours at normal temperature to carry out tensile bonding strength test, and the samples under the environment temperature conditions of 10 ℃ and 25 ℃ are respectively prepared.
The saline aging resistant sample is a polyurethane material poured for 1 hour after gluing, placed for 168 hours at 25 ℃, then aged for 168 hours at 40 ℃ in 4% NaCl saline, and subjected to a tensile bonding strength test.
The 100 ℃ heat aging resistant bonding sample is a polyurethane material poured for 1h after gluing, cured for 16h at 100 ℃, subjected to heat aging for 168h at 100 ℃ and subjected to tensile bonding strength test.
Example 1
Preparation of component A: 8.1g of PTMG650, 4.3g of hydroxyethylated bisphenol A (hydroxyl value is 340mgKOH/g), 3g of titanium dioxide, 6g of talcum powder, 12g of iron oxide red, 66.6g of ethyl acetate, 0.15g of KH560, 0.01g of stannous octoate catalyst and 0.1g of white carbon black are accurately weighed according to the mass ratio, and the dried raw materials are sequentially added into a three-mouth bottle to be uniformly stirred and then discharged to obtain the component A.
The component B is a diluted TDI-TMP adduct, and the NCO percent is 13 percent.
The adhesive is prepared by the A/B according to the mass ratio of 100/50.
Example 2
Preparation of component A: 5g of PTMG500, 5.5g of hydroxyethylated bisphenol A (hydroxyl value is 324mgKOH/g), 6g of light calcium carbonate, 9g of iron oxide red, a mixed solvent of 74.5g of butyl acetate and dichloromethane in a mass ratio of 1: 1, 0.15g of KH570, 0.015g of dibutyltin dilaurate catalyst and 0.15g of white carbon black are accurately weighed according to a mass ratio, and the dried raw materials are sequentially added into a three-mouth bottle to be uniformly stirred and then discharged to obtain the component A.
The component B is a diluted solution of HDI-TMP addition product, and NCO percent is 13 percent.
The adhesive is prepared by the A/B according to the mass ratio of 100/40.
Example 3
Preparation of component A: 10g of PTMG1000, 5.1g of hydroxyethylated bisphenol A (hydroxyl value is 340mgKOH/g), 6g of talcum powder, 6g of light calcium carbonate, 12g of iron oxide red, 60.5g of mixed solvent formed by mixing dichloromethane and ethyl acetate according to the mass ratio of 1: 1, 0.25gKH580, 0.015g of dibutyltin dilaurate catalyst and 0.2g of white carbon black are accurately weighed according to the mass ratio, and the dried raw materials are sequentially added into a three-mouth bottle to be uniformly stirred and then discharged to obtain the component A.
The component B is a diluted TDI-TMP adduct, and the NCO percent is 13 percent.
The adhesive is prepared by the A/B according to the mass ratio of 100/75.
Example 4
Preparation of component A: 6.5g of PTMG650, 5.5g of hydroxyethylated bisphenol A (hydroxyl value is 324mgKOH/g), 15g of talcum powder, 3g of iron oxide red, 70g of mixed solvent of butyl acetate and ethyl acetate in a ratio of 1: 1, 0.15g of KH570, 0.01g of dibutyltin dilaurate catalyst and 0.2g of white carbon black are accurately weighed according to the mass ratio, and the dried raw materials are sequentially added into a three-mouth bottle to be uniformly stirred and then discharged to obtain the component A.
The component B is a diluted solution of HDI trimer (HT-100, Wanhua chemical group Co., Ltd.) and NCO% ═ 13%.
The adhesive is prepared by the A/B according to the mass ratio of 100/50.
Comparative example 1
Preparation of component A: 15.2g of PTMG650, 6g of talcum powder, 6g of light calcium carbonate, 12g of iron oxide red, 60.5g of mixed solvent of dichloromethane and ethyl acetate in a mass ratio of 1: 1, 0.15g of KH580, 0.015g of dibutyltin dilaurate catalyst and 0.2g of white carbon black are accurately weighed according to the mass ratio, and the dried raw materials are sequentially added into a three-mouth bottle to be uniformly stirred and then discharged to obtain the component A.
The component B is a diluted TDI-TMP adduct, and the NCO percent is 13 percent.
The adhesive is prepared by the A/B according to the mass ratio of 100/50.
TABLE 1 tensile bond Strength of examples and comparative examples under different experimental conditions
Claims (8)
1. A high-low temperature universal bi-component polyurethane adhesive is composed of a main agent A component and a curing agent B component, and comprises the following components in parts by mass:
(1) the main agent A component is an active hydrogen component and comprises:
(2) the component B of the curing agent is a diluent with 13 percent of polyisocyanate NCO;
the mass ratio of the component A to the component B is 100: 40-75.
2. The two-component polyurethane adhesive as claimed in claim 1, wherein the molecular weight of the polytetrahydrofuran Polyol (PTMG) is 500-1000, and the hydroxyl value of the hydroxyethylated bisphenol A is 324-340 mgKOH/g.
3. The two-component polyurethane adhesive of claim 1, wherein the filler is talc, light calcium carbonate, titanium dioxide, or a mixture thereof.
4. The two-component polyurethane adhesive of claim 1, wherein the solvent is ethyl acetate, butyl acetate or dichloromethane, or a mixture thereof.
5. The high and low temperature universal two-component polyurethane adhesive of claim 1, wherein the catalyst is a tin catalyst.
6. The high and low temperature universal two-component polyurethane adhesive according to claim 1, wherein the coupling agent is gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), 3-methacryloxypropyltrimethoxysilane (KH570), gamma-mercaptopropyltriethoxysilane (KH580), or gamma-mercaptopropyltrimethoxysilane (KH 590).
7. The high and low temperature universal two-component polyurethane adhesive of claim 1, wherein the polyisocyanate is polymethylene polyphenyl polyisocyanate, HDI dimer, HDI trimer, HDI biuret or TDI-TMP, HDI-TMP adduct.
8. The two-component polyurethane adhesive of claim 1, wherein the polyisocyanate is diluted with ethyl acetate, butyl acetate, or acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911271663.6A CN111057513B (en) | 2019-11-29 | 2019-11-29 | High-low temperature universal bi-component polyurethane adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911271663.6A CN111057513B (en) | 2019-11-29 | 2019-11-29 | High-low temperature universal bi-component polyurethane adhesive |
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| Publication Number | Publication Date |
|---|---|
| CN111057513A true CN111057513A (en) | 2020-04-24 |
| CN111057513B CN111057513B (en) | 2022-08-30 |
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| CN201911271663.6A Active CN111057513B (en) | 2019-11-29 | 2019-11-29 | High-low temperature universal bi-component polyurethane adhesive |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181620A (en) * | 2018-08-22 | 2019-01-11 | 黎明化工研究设计院有限责任公司 | One kind can be bonded time long room temperature curing weatherable polyurethane adhesive |
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2019
- 2019-11-29 CN CN201911271663.6A patent/CN111057513B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181620A (en) * | 2018-08-22 | 2019-01-11 | 黎明化工研究设计院有限责任公司 | One kind can be bonded time long room temperature curing weatherable polyurethane adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 王霞等: "《现代建筑涂料—树脂合成与配方设计》", 30 September 2005, 上海交通大学出版社 * |
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| CN111057513B (en) | 2022-08-30 |
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