CN112724913A - Double-component polyurethane adhesive and preparation method thereof - Google Patents
Double-component polyurethane adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN112724913A CN112724913A CN202011477436.1A CN202011477436A CN112724913A CN 112724913 A CN112724913 A CN 112724913A CN 202011477436 A CN202011477436 A CN 202011477436A CN 112724913 A CN112724913 A CN 112724913A
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- polyol
- polyurethane adhesive
- component polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
-
- 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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- 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
- C08G18/6576—Compounds of group C08G18/69
- C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6588—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
- C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides a double-component polyurethane adhesive and a preparation method thereof, wherein the double-component polyurethane adhesive consists of a component A and a component B; the component A is prepared from the following raw materials in parts by weight: 65-85 parts of vegetable oil polyol, 5-20 parts of polymer polyol, 5-12 parts of micromolecule polyol, 0.3-1.3 parts of defoaming agent, 0.01-0.5 part of wetting agent, 0.3-3 parts of water removing agent and 0.1-1.5 parts of rheological additive; the component B comprises polyurethane prepolymer, and the structure of the polyurethane prepolymer has a rigid benzene ring and a side group protection structure. Compared with the prior art, the corrosion-resistant and corrosion-resistant paint has good acid and alkali resistance and hydrolysis resistance, and provides a foundation for use under a strong corrosion condition; the mixing viscosity is low, so that the material has good fluidity and wettability, and is convenient for subsequent use; the strength and the toughness are considered, so that the alloy has good post-processing performance; the adhesive has high shearing strength with ABS and PVC, and has good adhesive property.
Description
Technical Field
The invention belongs to the field of adhesive manufacturing, and particularly relates to a two-component polyurethane adhesive and a preparation method thereof.
Background
The hollow fiber membrane module is an assembly configuration with the highest packing density, and is generally 16000-30000 m2/m3And the water yield is high. The method has wide application in the fields of sewage treatment (such as municipal domestic sewage treatment, electronic industry wastewater, food industry wastewater, chemical industry wastewater and landfill leachate), pretreatment of reverse osmosis and nanofiltration (such as seawater desalination and ultrapure water preparation), circulating water treatment (such as boilers, swimming pools and landscaping water), dairy products, electrophoretic coating, biochemical technology and the like.
The hollow fiber membrane materials mainly used in the market at present comprise polysulfone, polyethersulfone, polyvinylidene fluoride, polycarbonate, polypropylene, polyvinyl chloride, porous ceramic and the like. Membrane modules require potting of membrane filaments with adhesive while bonding of assembly materials (end caps or skirts). The end cover and skirt are made of ABS resin or PVC resin. Therefore, the adhesive must have good adhesion to ABS or PVC to prevent debonding.
The polyurethane adhesive has good flexibility and adhesion when ABS resin or PVC resin is used as a bonding base material, the curing heat release temperature is low, and the problem of yarn burning cannot occur, but the bonding product of the polyurethane adhesive is often subjected to corrosive environments such as strong acid, strong alkali and the like in the environmental protection field, but the current bi-component polyurethane product cannot be used in the environmental protection field due to the fact that acid and alkali resistance, low viscosity, high strength and high toughness cannot be taken into consideration. For example, in patent CN107083229A, a two-component polyurethane adhesive with fast curing speed, moderate hardness, high shear strength, and good resistance to wet heat aging is prepared, and is suitable for bonding and potting water treatment membranes. However, the conventional polyurethane adhesive has poor adhesion with an end cap or a skirt of ABS or PVC, and the problem of poor adhesion is easy to occur. The patent US2016/0298009 prepares a two-component polyurethane adhesive suitable for roll type reverse osmosis membrane, which has good bonding and sealing effects, good acid and alkali resistance, no occurrence of permeability foaming, but too high viscosity after mixing, and is not suitable for potting and bonding of hollow fiber membranes. The patent CN105153982A prepares a flexible epoxy adhesive by adopting polyurethane modified epoxy resin, is applied to the end capping of membrane filaments, reduces the hardness of the cured epoxy resin, has good boiling resistance and acid and alkali resistance, and can replace the combination of epoxy hard glue and polyurethane soft glue for use. However, the viscosity of the glue solution is high, and the wettability of the hollow fiber membrane yarn is deficient. The patent CN104726050B prepares a stable and flexible isocyanate prepolymer by adding a stabilizer, an antioxidant, a toughening agent and the like, is applied to the end capping of a water treatment membrane component, and has excellent water resistance and aging resistance, but because an organic ester toughening agent such as phthalic acid ester such as DOP, DBP and the like is added, the toughness is improved, and the bonding performance of polyurethane is also reduced. At present, there are also various techniques for using a combination of adhesives to achieve the packaging quality, for example, patent CN106178958A mentions that the first layer of glue is epoxy resin or polyurethane, the second layer of glue is hard epoxy resin or hard polyurethane, and the third layer of glue is soft epoxy resin, silica gel or polyurethane. The process of multiple pouring is complex and time-consuming, and the production efficiency is seriously reduced.
Therefore, a two-component polyurethane adhesive which can keep good flexibility and has good acid-base resistance and bonding strength under one-time filling and sealing is necessary.
Disclosure of Invention
In order to solve the technical problems, the invention provides a two-component polyurethane adhesive and a preparation method thereof.
The specific technical scheme is as follows:
a double-component polyurethane adhesive is characterized in that the double-component polyurethane adhesive consists of a component A and a component B;
the component A is prepared from the following raw materials in parts by weight:
65-85 parts of vegetable oil polyol, 5-20 parts of polymer polyol, 5-12 parts of micromolecule polyol, 0.3-1.3 parts of defoaming agent, 0.01-0.5 part of wetting agent, 0.3-3 parts of water removing agent and 0.1-1.5 parts of rheological additive;
the component B comprises a polyurethane prepolymer, and the polyurethane prepolymer is prepared from the following raw materials in parts by weight:
15 to 35 portions of dimer acid polyester polyol, 5 to 15 portions of aromatic polyether polyol and 60 to 75 portions of isocyanate; when the adhesive is used, the mass ratio of the component A to the component B is (0.6-1): 1.
Further, when used, the weight ratio of the component A to the component B is (0.8-1.0): 1.
Further, the vegetable oil polyol is selected from one or more of castor oil and castor oil modified polyol; wherein the castor oil modified polyol is prepared from castor oil by a hydroformylation reduction method, an epoxidation ring-opening method or an ester exchange method.
Preferably, the vegetable oil polyol is selected from those produced by Vertellus corporation
D-140、
D-290、
T-400、
D-2000、
320A 30 Castor oil modified polyol, A21 Castor oil modified polyol, available from Shanghai Jing Rib, BASF
819、
750、
805, respectively.
Further, the polymer polyol is polyether polyol and/or polyolefin polyol with the functionality of 1.5-2.5; preferably, the polyolefin polyol is one or a mixture of more of hydroxyl-terminated butadiene styrene liquid rubber, hydroxyl-terminated polybutadiene polyol, hydroxyl-terminated polybutadiene-acrylonitrile polyol and hydrogenated hydroxyl-terminated polybutadiene polyol.
Further, the polymer polyol is at least one of a linear hydroxyl-terminated polybutadiene polyol or a hydrogenated hydroxyl-terminated polybutadiene polyol having a hydroxyl functionality of 1.5 to 2.5 and a molecular weight of 2000 to 4000, more preferably one or more of Poly bd R45V, LBH-2000, LBH-3000 manufactured by Cray Valley, or LBH-P2000, LBH-P3000, LHBH-P3000 manufactured by Sartomer.
Further, the defoaming agent is one or more of non-silicon type, organic silicon type and polyether modified organic silicon type, preferably one or more of BYK1790, BYK067A and BYK085 of BYK company, Defom 6800 of Germany modest company and MOK6621 defoaming agent of Merck company.
Further, the wetting agent is selected from one or more of polysiloxane and polyether modified polysiloxane, preferably one or more of BYK307 and BYK310 of BYK company, TEGO-4100 and TEGO-Wet265 of Digao company, and DOW Corning500W and DOW Corning501W of Dow Corning company.
Further, the water removal agent is crystallized synthetic zeolite, preferably one or more of a 3A molecular sieve, a 4A molecular sieve or a 5A molecular sieve.
Further, the rheological additive is hydrophobic fumed silica, and the specific surface area is 80-300 m2(ii) in terms of/g. Preferably Cabot corporation
TS710、
TS-610、
TS-720, AEROSIL R972, AEROSIL R974, AEROSIL R812S from Degussa, HDKH13L, HDK H15, HDK H18 from Wacker.
Further, the isocyanate is selected from one or more of a mixture of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied MDI, and carbodiimide-modified 4, 4-diphenylmethane diisocyanate.
Further, the dimer acid polyester polyol is prepared by esterification of dimer acid and dihydric alcohol, wherein the dimer acid comprises but is not limited to:
the dimer acid polyester polyol prepared by selecting the dimer acid as the raw material has strong side group protection and hydrolysis resistance stability, and can be normally used in a strong hydrolysis environment.
Preferred dimer acid polyester polyols are: such as BY3026 and BY3022 in Beijing Baiyuan chemical industry, DA2110, DA20 and DA21 in Shanghai Jingri, and one or more of the chemical industry SP-3190 in Heda.
Further, the aromatic polyether polyol is bisphenol A type polyether polyol, preferably one or more of Agodiol P3, Dianol320, Dianol240, manufactured by SEPPIC, France, BA-P3, BA-P4U, manufactured by Japanese emulsifier corporation, Koremul-BSA30F, and Koremul-BSA20F, manufactured by HanNong, Korea.
The preparation method of the two-component polyurethane adhesive comprises the following steps:
preparing a component A: removing water in the vegetable oil polyol, the polymer polyol and the micromolecule polyol, uniformly mixing, adding the defoaming agent, the wetting agent, the water removing agent and the rheological additive, and uniformly mixing;
preparing a component B: and adding the isocyanate into a reactor, dropwise adding the aromatic polyether polyol for reaction, dropwise adding the dimer acid polyester polyol, and reacting under a protective gas to prepare the polyester polyol.
Further, when the component B is prepared, adding the isocyanate into a reactor, stirring and heating to 70-80 ℃, dropwise adding the aromatic polyether polyol, and introducing nitrogen at 80 +/-2 ℃ for reacting for 1-3 hours after the end of adding; and then dropwise adding the dimer acid polyester polyol, and introducing nitrogen at the temperature of 80 +/-2 ℃ to react for 1-3 hours to prepare the dimer acid polyester polyol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention is prepared from a component A which takes vegetable oil polyalcohol, polymer polyalcohol and micromolecular polyalcohol as main components and is supplemented with a defoaming agent, a wetting agent, a water removing agent and a rheological additive; the bi-component polyurethane adhesive prepared by introducing the isocyanate-terminated polyurethane block prepolymer with a rigid benzene ring structure and a side group protection structure into the prepolymer as a component B has good acid and alkali resistance and hydrolysis resistance, and provides a foundation for use under the strong corrosion condition;
(2) the mixing viscosity is low, so that the material has good fluidity and wettability, and is convenient for subsequent use;
(3) the strength and the toughness are considered, so that the alloy has good post-processing performance;
(4) the adhesive has high shearing strength with ABS and PVC, and has good adhesive property.
Detailed Description
The following description is given in conjunction with the examples, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: adding 72 parts by weight of first-grade refined castor oil (hydroxyl value is 164mgKOH/g) and 10 parts by weight of first-grade refined castor oil into a reactor
T-400, 6 parts of hydroxyl-terminated polybutadiene Polybd R45V, 11 parts of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then 0.59 part of defoaming agent BYK6880, 0.01 part of wetting agent BYK307, 0.3 part of 3A molecular sieve and 0.1 part of fumed silica HDK H15 are stirred for 1 hour in a vacuum state and discharged to prepare a component A.
Preparing a component B: adding 67.5 parts of isocyanate CDMDI100L and 6.7 parts of isocyanate Suprasec 1004 into a reactor, continuously introducing nitrogen, dropwise adding 5.8 parts of bisphenol A type polyether polyol BSA-30F, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 20 parts of dimer acid polyester polyol DA21, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Example 2
The embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: according to the parts by weight, 61.5 parts of first-class refined castor oil (hydroxyl value is 164mgKOH/g), 10 parts of A30 castor oil modified polyol and 15 parts of hydrogenated hydroxyl-terminated polybutadiene polyol Cray are added into a reactor
HLBH-P2000, 10 parts of 1, 4-butanediol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then 0.5 part of defoaming agent BYK067A, 0.2 part of wetting agent TEGO-4100, 1.5 parts of 4A molecular sieve and 0.3 part of fumed silica AEROSIL R972 are respectively stirred for 1 hour in a vacuum state and discharged to prepare a component A.
Preparing a component B: respectively adding 63 parts of isocyanate MDI and 7 parts of isocyanate MDI-50 into a reactor, continuously introducing nitrogen, dropwise adding 5 parts of bisphenol A type polyether polyol BSA-30F, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 25 parts of dimer acid polyester polyol BY3022, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Example 3
The embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: according to the weight portion, 75 portions of first-grade refined castor oil (hydroxyl value is 164mgKOH/g) and 5 portions are added into a reactor
T-400 (hydroxyl value 450mgKOH/g) and 9.5 parts of hydroxyl-terminated polybutadiene polyol Cray
LBH-P2000, 7 parts of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and 1 part of defoamer MOK6621, 0.2 part of wetting agent TEGO-Wet265, 1.8 parts of 3A molecular sieve and 0.5 part of fumed silica are respectively added
TS-720, stirring for 1 hour under vacuum state, discharging to obtain component A.
Preparing a component B: respectively adding 54 parts of isocyanate CDMDI100L and 6 parts of isocyanate MDI-50 into a reactor, continuously introducing nitrogen, dropwise adding 10 parts of bisphenol A type polyether polyol BSA-30F, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 30 parts of dimer acid polyester polyol SP-3190, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Example 4:
the embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: adding 72 parts by weight of first-grade refined castor oil (hydroxyl value is 164mgKOH/g) and 5 parts by weight of first-grade refined castor oil into a reactor
T-400, 10 parts of hydroxyl-terminated polybutadiene Polybd R45V, 5.3 parts of 2-ethane-1, 3-hexanediol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then stirred for 1 hour in a vacuum state for discharging 1.3 parts of defoaming agent BYK1790, 0.4 part of wetting agent DOW Corning501W, 3 parts of 5A molecular sieve and 1 part of fumed silica HDK H18 respectively to prepare a component A.
Preparing a component B: respectively adding 50 parts of isocyanate MDI and 15 parts of isocyanate Isonate 50 into a reactor, continuously introducing nitrogen, dropwise adding 10 parts of bisphenol A type polyether polyol BA-P4U, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 25 parts of dimer acid polyester polyol BY3026, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Example 5
The embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A:according to the parts by weight, 50 parts of first-grade refined castor oil (hydroxyl value is 164mgKOH/g), 18 parts of castor oil modified polyol A30 and 20 parts of hydrogenated hydroxyl-terminated polybutadiene polyol Cray are added into a reactor
HLBH-P2000, 8.3 portions of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then 0.8 portion of defoamer BYK6880, 0.4 portion of wetting agent TEGO-4100, 2 portions of 3A molecular sieve and 0.5 portion of fumed silica AEROSIL R812S are stirred for 1 hour in a vacuum state and discharged to prepare a component A.
Preparing a component B: respectively adding 54 parts of isocyanate MDI and 6 parts of isocyanate Lupranate MI into a reactor, continuously introducing nitrogen, dropwise adding 15 parts of bisphenol A type polyether polyol Agodiol P3, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 25 parts of dimer acid polyester polyol DA21, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Example 6
The embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: according to the weight portion, 70 portions of first-grade refined castor oil (hydroxyl value is 164mgKOH/g) and 15 portions of first-grade refined castor oil are added into a reactor
T-400, 5 parts of hydroxyl-terminated polybutadiene RV-45 and 7 parts of 2-ethane-1, 3-hexanediol, heating to 120 ℃, stirring and dehydrating for 2 hours in a vacuum state, then cooling to 60 ℃, and respectively adding 0.6 part of defoaming agent BYK6880, 0.5 part of wetting agent DOW Corning500W, 1.5 parts of 4A molecular sieve and 0.4 part of fumed silica
TS-710, stirring for 1 hour under vacuum state, discharging to obtain component A.
Preparing a component B: respectively adding 68 parts of isocyanate CDMDI100L and 5 parts of isocyanate MDI-50 into a reactor, continuously introducing nitrogen, dropwise adding 12 parts of bisphenol A type polyether polyol BSA-30F, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 15 parts of dimer acid polyester polyol SP-3190, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Example 7
The embodiment provides a preparation method of a two-component polyurethane adhesive, which comprises the following steps:
preparing a component A: according to parts by weight, 70 parts of first-grade refined castor oil (hydroxyl value is 164mgKOH/g), 15 parts of castor oil modified polyol A30, 5.5 parts of hydroxyl-terminated polybutadiene polyol LBH-P3000 and 5 parts of 1, 4-butanediol are added into a reactor, heated to 120 ℃, stirred and dehydrated for 2 hours under a vacuum state, then cooled to 60 ℃, and respectively stirred for 1 hour under a vacuum state for 1 hour to obtain a component A, wherein 1.2 parts of defoaming agent BYK085, 0.2 part of wetting agent TEGO-Wet265, 2.5 parts of 3A molecular sieve and 0.6 part of fumed silica HDKH 13L.
Preparing a component B: respectively adding 55 parts of isocyanate CDMDI100L and 5 parts of isocyanate Cosmonate MX-200 into a reactor, continuously introducing nitrogen, dropwise adding 5 parts of bisphenol A type polyether polyol Agodiol P3, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 35 parts of dimer acid polyester polyol BY3026, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 0.9: 1.
The parts by weight of the components A in each example are summarized as follows:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Vegetable oil polyols | 82 | 71.5 | 80 | 79 | 68 | 85 | 85 |
| Polymer polyols | 6 | 15 | 9.5 | 10 | 20 | 5 | 5.5 |
| Small molecule polyol | 11 | 11 | 7 | 5.3 | 8.3 | 7 | 5 |
| Defoaming agent | 0.59 | 0.5 | 1 | 1.3 | 0.8 | 0.6 | 1.2 |
| Wetting agent | 0.01 | 0.2 | 0.2 | 0.4 | 0.4 | 0.5 | 0.2 |
| Water removing agent | 0.3 | 1.5 | 1.8 | 3 | 2 | 1.5 | 2.5 |
| Rheology aid | 0.1 | 0.3 | 0.5 | 1 | 0.5 | 0.4 | 0.6 |
| Total up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
The parts by weight of the components in the embodiment B are summarized as follows:
comparative example 1
The comparative example provides a preparation method of a two-component polyurethane adhesive, comprising the following steps:
preparing a component A: according to the weight portion, 75 portions (hydroxyl value is 164mgKOH/g) and 10 portions of first-grade refined castor oil are added into a reactor
T-400 and 10.4 parts of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then 0.8 part of defoaming agent BYK6880, 0.3 part of wetting agent TEGO-4100, 2 parts of 3A molecular sieve and 0.5 part of fumed silica AEROSIL R812S are stirred for 1 hour in a vacuum state and discharged to prepare a component A.
Preparing a component B: respectively adding 60 parts of isocyanate MDI and 6 parts of isocyanate MDI-50 into a reactor, continuously introducing nitrogen, dropwise adding 34 parts of dimer acid polyester polyol DA21, reacting for 2 hours at 80 +/-2 ℃, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Comparative example 2
The comparative example provides a preparation method of a two-component polyurethane adhesive, comprising the following steps:
preparing a component A: according to parts by weight, 70 parts of first-grade refined castor oil (hydroxyl value is 164mgKOH/g), 9 parts of castor oil modified polyol A30 and 8 parts of hydroxyl-terminated polybutadiene RV-45 are added into a reactor, 10 parts of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then 0.55 part of defoaming agent MOK6621, 0.25 part of wetting agent TEGO-Wet265, 2 parts of 3A molecular sieve and 0.2 part of fumed silica are respectively added
TS-720, stirring for 1 hour under vacuum state, discharging to obtain component A.
Preparing a component B: respectively adding 55 parts of isocyanate CDMDI100L into a reactor, continuously introducing nitrogen, then adding 38 parts of dimer acid polyester polyol BY3022, reacting for 2 hours at 80 +/-2 ℃, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Comparative example 3
The comparative example provides a preparation method of a two-component polyurethane adhesive, comprising the following steps:
preparing a component A: according to the weight portion, 80 portions (hydroxyl value is 164mgKOH/g) and 10 portions of first-grade refined castor oil are added into a reactor
T-400 and 6.25 parts of 1, 4-butanediol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and then 0.55 part of defoaming agent BYK085, 0.2 part of wetting agent TEGO-Wet265, 2.4 parts of 3A molecular sieve and 0.6 part of fumed silica are respectively added
TS-710, stirring for 1 hour under vacuum state, discharging to obtain component A.
Preparing a component B: respectively adding 55 parts of isocyanate MDI and 6 parts of isocyanate Cosmonate MX-200 into a reactor, continuously introducing nitrogen, dropwise adding 9 parts of bisphenol A type polyether polyol Agodiol P3, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 30 parts of dimer acid polyester polyol BY3026, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 0.9: 1.
Comparative example 4
The comparative example provides a preparation method of a two-component polyurethane adhesive, comprising the following steps:
preparing a component A: according to the parts by weight, 70 parts of first-grade refined castor oil (hydroxyl value is 164mgKOH/g), 7 parts of castor oil modified polyol A30 and 15 parts of hydrogenated hydroxyl-terminated polybutadiene polyol Cray are added into a reactor
HLBH-P2000, 7.5 parts of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, 0.5 part of defoamer BYK6880 is added, stirred for 1 hour in a vacuum state and discharged to prepare a component A.
Preparing a component B: adding 56 parts of isocyanate MDI and 6.5 parts of isocyanate MDI-50 into a reactor, continuously introducing nitrogen, dropwise adding 18.75 parts of bisphenol A polyether polyol BSA-30F, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 18.75 parts of dimer acid polyester polyol SP-3190, continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B. When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
Comparative example 5
The comparative example provides a preparation method of a two-component polyurethane adhesive, comprising the following steps:
preparing a component A: according to the weight portion, 75 portions of first-grade refined castor oil (hydroxyl value is 164mgKOH/g) and 5 portions are added into a reactor
T-400 and 9.5 parts of Cray
LBH-P2000, 7 parts of dipropylene glycol are heated to 120 ℃, stirred and dehydrated for 2 hours in a vacuum state, then cooled to 60 ℃, and 1 part of defoamer MOK6621, 0.2 part of wetting agent TEGO-Wet265, 1.8 parts of 3A molecular sieve and 0.5 part of fumed silica are respectively added
TS-720, stirring for 1 hour under vacuum state, discharging to obtain component A.
Preparing a component B: respectively adding 54 parts of isocyanate CDMDI100L and 6 parts of isocyanate MDI-50 into a reactor, continuously introducing nitrogen, dropwise adding 10 parts of bisphenol A type polyether polyol BSA-30F, reacting at 80 +/-2 ℃ for 1 hour after the addition is finished, then adding 30 parts of polyether polyol DL-2000D (hydroxyl value 56mgKOH/g), continuously reacting at 80 +/-2 ℃ for 1 hour, cooling to 60 ℃, and discharging to obtain the component B.
When in use, the component A and the component B are uniformly mixed according to the mass ratio of 1: 1.
The following performance tests were carried out in the preparation of the two-component polyurethane adhesives of the examples, comparative examples and the current market:
tensile strength and elongation at break were tested according to GB/T528;
testing the mixed viscosity refers to a GB/T2794 viscosity testing method;
the hardness test refers to a GB/T2411 hardness test method;
the shear strength is tested according to the test method of GB/T7124 tensile shear strength;
the acid and alkali resistance test is to observe the appearance of the colloid after the solidified colloid is immersed in 10 percent hydrochloric acid solution and 10 percent sodium hydroxide solution for 30 days; the above test is carried out in an environment with a temperature of 23 + -2 deg.C and a humidity of 50 + -5%.
Table 1 example test results
Table 2 comparative example test results
As can be seen from the above table, the two-component polyurethane adhesive of the present invention has comprehensive excellent properties: specifically, the tensile strength of the body is more than or equal to 18MPa, the elongation at break is more than or equal to 200%, the Shore A hardness is 80-95, the mixed viscosity is less than 5000MPa & gts, the acid and alkali resistance is excellent, the adhesive has no stickiness and no discoloration after being soaked in 10 wt% acid-base solution for 30 days, the adhesive property with ABS and PVC is excellent, the ABS shear strength is more than 12MPa, the PVC shear strength is more than 6MPa, and the adhesive does not fall off after being subjected to a water hammer test for 4 ten thousand times under the pressure of 5Kg, and the properties are that the adhesive is applied to ABS and PVC, the early-stage product is easy to process, and the product is stable in the subsequent high-humidity, acid-base and high-impact environments.
Compared with comparative examples 1 and 2, the component B in examples 1 to 7 is a polymer which is obtained by block copolymerization of dimer acid polyester polyol, aromatic polyether polyol and isocyanate and has a rigid benzene ring and a side group protection structure, has higher tensile strength and elongation at break, excellent acid and alkali resistance, does not fall off after 4 ten thousand water hammer tests, and has excellent bonding performance with ABS and PVC.
Compared with comparative example 3, the component A of examples 1 to 7 contains polyolefin polyol, so that the system has good flexibility, does not fall off after 4 ten thousand water hammer tests under the pressure of 5Kg, has excellent bonding performance with ABS and PVC, and has excellent fracture productivity.
Compared with comparative example 4, examples 1 to 7 have a low mixing viscosity, good workability, and toughness while ensuring strength.
Compared with a comparative example 5, the dimer acid polyester polyol is adopted in the block copolymer synthesized in the component B in the embodiment 3, and due to the protection of bulky side chains of the dimer acid polyester polyol, compared with other polyether polyols, the system has better bonding performance on PVC and ABS with low surface energy, and simultaneously has good flexibility and hydrolysis resistance. And is obviously superior to the two-component polyurethane adhesive for the hollow fiber membrane sold in the market.
Moreover, the component proportion is further optimized by the inventor team aiming at the performance, and the component A is prepared from the following raw materials in parts by weight:
70-72 parts of vegetable oil polyalcohol, 5-15 parts of polymer polyalcohol, 10-12 parts of micromolecular polyalcohol, 0.3-0.8 part of defoaming agent, 0.01-0.2 part of wetting agent, 0.3-1.5 parts of water removing agent and 0.1-0.3 part of rheological additive;
the component B is prepared from the following raw materials in parts by weight:
20 to 25 portions of dimer acid polyester polyol, 5 to 7 portions of aromatic polyether polyol and 70 to 75 portions of isocyanate; the viscosity can be reduced to be below 1500mpa × s within the range, the fluidity is better, and the subsequent construction is convenient.
When the weight portion of the dimer acid polyester polyol is controlled to be 30-35 portions, the breaking elongation of the two-component polyurethane adhesive can be increased to more than 300%, but the shear strength of PVC is still kept to be 6.8MPa and the shear strength of ABS is still kept to be more than 13.5 MPa.
When the component A and the component B are controlled to be in the following parts by weight, the toughness index, the strength index and the bonding property are optimal, and the component A is prepared from the following raw materials in parts by weight:
80 parts of vegetable oil polyol, 9.5 parts of polymer polyol, 7 parts of small molecular weight polyol, 1 part of defoaming agent, 0.2 part of wetting agent, 1.8 parts of water removing agent and 0.5 part of rheological additive;
the component B is prepared from the following raw materials in parts by weight:
30 parts of dimer acid polyester polyol, 10 parts of aromatic polyether polyol and 60 parts of isocyanate.
Secondly, the component A vegetable oil polyol is selected from
When one of T-400 and A30 is mixed with the first-grade refined castor oil for use, the strength is increased, when the polymer polyol in the component A is one or two of Poly bd R45V and LBH-P2000, the flexibility of a molecular system is more excellent, and the elongation at break can be improved to more than 220%. The hydrophobic fumed silica is used as a rheological additive to be matched with the impregnating compound, so that the rheological property of the product can be well improved, and the construction is more convenient. The molecular sieve is used as a water removal agent, so that trace water on the surface of the hollow fiber membrane can be effectively absorbed, the glue is not foamed when being cured, and the appearance and the reliability of the product are improved.
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 is prepared from the following raw materials in parts by weight:
65-85 parts of vegetable oil polyol, 5-20 parts of polymer polyol, 5-12 parts of micromolecule polyol, 0.3-1.3 parts of defoaming agent, 0.01-0.5 part of wetting agent, 0.3-3 parts of water removing agent and 0.1-1.5 parts of rheological additive;
the component B comprises a polyurethane prepolymer, and the polyurethane prepolymer is prepared from the following raw materials in parts by weight:
15 to 35 portions of dimer acid polyester polyol, 5 to 15 portions of aromatic polyether polyol and 60 to 75 portions of isocyanate;
when the adhesive is used, the mass ratio of the component A to the component B is (0.6-1): 1.
2. The two-component polyurethane adhesive according to claim 1, wherein the component A is prepared from the following raw materials in parts by weight:
70-82 parts of vegetable oil polyalcohol, 5-15 parts of polymer polyalcohol, 10-12 parts of micromolecular polyalcohol, 0.3-0.8 part of defoaming agent, 0.01-0.2 part of wetting agent, 0.3-1.5 parts of water removing agent and 0.1-0.3 part of rheological additive;
the component B is prepared from the following raw materials in parts by weight:
20 to 25 portions of dimer acid polyester polyol, 5 to 7 portions of aromatic polyether polyol and 70 to 75 portions of isocyanate.
3. The two-component polyurethane adhesive of claim 1, wherein the vegetable oil polyol is selected from one or more of castor oil, castor oil modified polyol; wherein the castor oil modified polyol is prepared from castor oil by an epoxidation ring-opening method, a hydroformylation reduction method or an ester exchange method.
4. The two-component polyurethane adhesive of claim 1, wherein the polymer polyol is a polyether polyol and/or a polyolefin polyol.
5. The two-component polyurethane adhesive according to claim 1, wherein the small molecular polyol is selected from small molecular diols, and the molecular mass is 50-250.
6. The two-component polyurethane adhesive of claim 1, wherein the defoamer is one or more of non-silicon type, organic silicon type and polyether modified organic silicon type; the wetting agent is selected from one or more of polysiloxane and polyether modified polysiloxane; the water removing agent is crystallized synthetic zeolite; the rheological additive is fumed silica.
7. The two-component polyurethane adhesive of claim 1, wherein the isocyanate is selected from one or more of 2, 4-diphenylmethane diisocyanate and 4, 4-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, liquefied MDI, and carbodiimide-modified 4, 4-diphenylmethane diisocyanate.
8. The two-component polyurethane adhesive of claim 1, wherein the dimer acid polyester polyol is prepared by esterification of a dimer acid and a diol.
9. The two-component polyurethane adhesive of claim 1, wherein the aromatic polyether polyol is a bisphenol a type polyether polyol.
10. The preparation method of the two-component polyurethane adhesive of any one of claims 1 to 9, comprising the following steps:
preparing a component A: removing water in the vegetable oil polyol, the polymer polyol and the micromolecule polyol, uniformly mixing, adding the defoaming agent, the wetting agent, the water removing agent and the rheological additive, and uniformly mixing;
preparing a component B: and adding the isocyanate into a reactor, dropwise adding the aromatic polyether polyol for reaction, dropwise adding the dimer acid polyester polyol, and reacting under a protective gas to prepare the polyester polyol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011477436.1A CN112724913B (en) | 2020-12-15 | 2020-12-15 | Double-component polyurethane adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011477436.1A CN112724913B (en) | 2020-12-15 | 2020-12-15 | Double-component polyurethane adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112724913A true CN112724913A (en) | 2021-04-30 |
| CN112724913B CN112724913B (en) | 2022-10-11 |
Family
ID=75602354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011477436.1A Active CN112724913B (en) | 2020-12-15 | 2020-12-15 | Double-component polyurethane adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724913B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717677A (en) * | 2021-08-24 | 2021-11-30 | 湖北南北车新材料有限公司 | Double-component polyurethane adhesive and preparation method thereof |
| CN114058318A (en) * | 2021-11-19 | 2022-02-18 | 康达新材料(集团)股份有限公司 | Two-component polyurethane pouring sealant with fluidity and uniform curing and preparation method thereof |
| CN114149558A (en) * | 2021-11-26 | 2022-03-08 | 湖北南北车新材料有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof |
| CN114316206A (en) * | 2021-12-14 | 2022-04-12 | 福建汇得新材料有限公司 | Wet-process polyurethane resin and preparation method and application thereof |
| CN114456703A (en) * | 2022-01-17 | 2022-05-10 | 东来涂料技术（上海）股份有限公司 | High-performance transparent matte varnish and preparation method thereof |
| CN115385609A (en) * | 2022-07-11 | 2022-11-25 | 广州市北二环交通科技有限公司 | Construction method for treating new and old concrete joint surface |
| CN115820191A (en) * | 2022-09-28 | 2023-03-21 | 上海安彼太新材料有限公司 | Two-component polyurethane structural adhesive for high-elasticity bonding of power battery |
| CN117264596A (en) * | 2023-10-10 | 2023-12-22 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
| CN117264596B (en) * | 2023-10-10 | 2024-05-10 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694068A (en) * | 2013-12-04 | 2015-06-10 | 湖北回天新材料股份有限公司 | Halogen-free flame-retardant two-component polyurethane adhesive for railway vehicle and preparation method thereof |
| CN105255436A (en) * | 2015-11-17 | 2016-01-20 | 湖北回天新材料股份有限公司 | High-strength two-component polyurethane corner glue and preparation method thereof |
| CN110305614A (en) * | 2019-06-13 | 2019-10-08 | 南京威邦新材料有限公司 | A kind of rock wool board bi-component solvent-free polyurethane adhesive and preparation method thereof |
| CN110467900A (en) * | 2019-07-25 | 2019-11-19 | 温州大学新材料与产业技术研究院 | A kind of dedicated no-solvent polyurethane adhesive of nylon nib |
| CN110790890A (en) * | 2019-11-22 | 2020-02-14 | 大连理工大学 | Polyurethane elastomer for metal composite sandwich plate core material and use method thereof |
| US20200140729A1 (en) * | 2017-05-30 | 2020-05-07 | Dow Global Technologies Llc | Two-component solventless adhesive compositions |
| CN111808570A (en) * | 2020-08-27 | 2020-10-23 | 格丽泰新材料科技（苏州）有限公司 | Double-component polyurethane adhesive and application thereof |
| CN112029393A (en) * | 2020-07-27 | 2020-12-04 | 湖北南北车新材料有限公司 | Double-component polyurethane coating and preparation method thereof |
| CN112048278A (en) * | 2020-09-15 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Boiling-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof |
-
2020
- 2020-12-15 CN CN202011477436.1A patent/CN112724913B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104694068A (en) * | 2013-12-04 | 2015-06-10 | 湖北回天新材料股份有限公司 | Halogen-free flame-retardant two-component polyurethane adhesive for railway vehicle and preparation method thereof |
| CN105255436A (en) * | 2015-11-17 | 2016-01-20 | 湖北回天新材料股份有限公司 | High-strength two-component polyurethane corner glue and preparation method thereof |
| US20200140729A1 (en) * | 2017-05-30 | 2020-05-07 | Dow Global Technologies Llc | Two-component solventless adhesive compositions |
| CN110305614A (en) * | 2019-06-13 | 2019-10-08 | 南京威邦新材料有限公司 | A kind of rock wool board bi-component solvent-free polyurethane adhesive and preparation method thereof |
| CN110467900A (en) * | 2019-07-25 | 2019-11-19 | 温州大学新材料与产业技术研究院 | A kind of dedicated no-solvent polyurethane adhesive of nylon nib |
| CN110790890A (en) * | 2019-11-22 | 2020-02-14 | 大连理工大学 | Polyurethane elastomer for metal composite sandwich plate core material and use method thereof |
| CN112029393A (en) * | 2020-07-27 | 2020-12-04 | 湖北南北车新材料有限公司 | Double-component polyurethane coating and preparation method thereof |
| CN111808570A (en) * | 2020-08-27 | 2020-10-23 | 格丽泰新材料科技（苏州）有限公司 | Double-component polyurethane adhesive and application thereof |
| CN112048278A (en) * | 2020-09-15 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Boiling-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717677A (en) * | 2021-08-24 | 2021-11-30 | 湖北南北车新材料有限公司 | Double-component polyurethane adhesive and preparation method thereof |
| CN114058318A (en) * | 2021-11-19 | 2022-02-18 | 康达新材料(集团)股份有限公司 | Two-component polyurethane pouring sealant with fluidity and uniform curing and preparation method thereof |
| CN114149558A (en) * | 2021-11-26 | 2022-03-08 | 湖北南北车新材料有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof |
| CN114149558B (en) * | 2021-11-26 | 2023-07-18 | 湖北南北车新材料有限公司 | Aqueous polyurethane dispersion, preparation method and application thereof |
| CN114316206A (en) * | 2021-12-14 | 2022-04-12 | 福建汇得新材料有限公司 | Wet-process polyurethane resin and preparation method and application thereof |
| CN114316206B (en) * | 2021-12-14 | 2023-10-24 | 福建汇得新材料有限公司 | Wet polyurethane resin and preparation method and application thereof |
| CN114456703A (en) * | 2022-01-17 | 2022-05-10 | 东来涂料技术（上海）股份有限公司 | High-performance transparent matte varnish and preparation method thereof |
| CN115385609A (en) * | 2022-07-11 | 2022-11-25 | 广州市北二环交通科技有限公司 | Construction method for treating new and old concrete joint surface |
| CN115820191A (en) * | 2022-09-28 | 2023-03-21 | 上海安彼太新材料有限公司 | Two-component polyurethane structural adhesive for high-elasticity bonding of power battery |
| CN117264596A (en) * | 2023-10-10 | 2023-12-22 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
| CN117264596B (en) * | 2023-10-10 | 2024-05-10 | 佛山市极威新材料有限公司 | Honeycomb glue with good water resistance and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112724913B (en) | 2022-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112724913B (en) | Double-component polyurethane adhesive and preparation method thereof | |
| CN101967222B (en) | Preparation method of epoxidized castor oil modified water-borne polyurethane | |
| KR102339480B1 (en) | Polyurethane adhesives for reverse osmosis modules | |
| EP3153535A1 (en) | Polyurethane-modified epoxy resin, method for producing same, epoxy resin composition and cured product | |
| CN106928809B (en) | Epoxy resin coating and preparation method thereof | |
| CN111349417B (en) | Polyurethane adhesive composition and polyurethane adhesive | |
| CN107083229A (en) | A kind of preparation method of membrane for water treatment bi-component polyurethane pouring sealant | |
| CN112724363B (en) | Polyurethane pouring sealant for submarine cable pouring and sealing and preparation method thereof | |
| CN105419714A (en) | Epoxy resin two-component polyurethane adhesive and preparation method thereof | |
| CN111073587B (en) | Ultralow temperature-resistant environment-friendly double-component polyurethane adhesive and preparation and application thereof | |
| KR101649759B1 (en) | Manufacturing method of waterborne polyurethane using epoxy resin | |
| CN102977316B (en) | Slow gel flexible polyurethane foam composition | |
| KR20220044207A (en) | One-component polyurethane prepolymer composition | |
| CN112341983B (en) | Waterborne polyurethane adhesive and preparation method thereof | |
| AU2014267466A1 (en) | Isocyanate-Epoxide hybrid resins | |
| CA2942481C (en) | Polyurethane adhesives for reverse osmosis modules | |
| KR102101723B1 (en) | Modified castor oil-containg-polyurethane resin composition for potting agent for hollow fiber separator membrane and method for preparing the same | |
| KR101476405B1 (en) | No-solvent polyurethane adhesion composition having high adhesive strength at low temperature | |
| CN111732850B (en) | Formula of waterborne polyurethane ink binder for food flexible packaging and preparation method thereof | |
| CN113831830A (en) | High-barrier polyurethane self-repairing composition and preparation method thereof | |
| CN114133908A (en) | High-strength fast-curing polyurethane adhesive and preparation method thereof | |
| WO2006002811A1 (en) | Method for producing amino-functional polyurethane prepolymers | |
| CN114574089A (en) | Single-component polyurethane waterproof coating capable of being formed by one-step construction and application thereof | |
| CN106995521A (en) | A kind of waterborne polyurethane resin | |
| EP3070127A1 (en) | Polyurethane resin composition for hollow fiber membrane potting agent and hollow fiber membrane module |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |