CN107955516A - Double-composition polyurethane waterproof paint containing non-polar polymer modified compound and preparation method thereof - Google Patents
Double-composition polyurethane waterproof paint containing non-polar polymer modified compound and preparation method thereof Download PDFInfo
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- CN107955516A CN107955516A CN201711243722.XA CN201711243722A CN107955516A CN 107955516 A CN107955516 A CN 107955516A CN 201711243722 A CN201711243722 A CN 201711243722A CN 107955516 A CN107955516 A CN 107955516A
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3814—Polyamines
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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
- C08G18/65—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
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of double-composition polyurethane waterproof paint containing non-polar polymer modified compound and preparation method thereof, which includes component A and B component；The component A is base polyurethane prepolymer for use as, and in terms of parts by weight, the base polyurethane prepolymer for use as is made of 2 40 parts of 3 15 parts of isocyanates and the first polyalcohol；In terms of parts by weight, the B component includes：Second 2 20 parts of polyalcohol, main chain contain 0.1 2 parts of 2 30 parts of epoxidation modification compound, 2 15 parts of chain extender and the catalyst of the non-polar polymer of multiple C=C double bonds.Polyurethane water-proof paint and the asphalt water-proof coiled material and polymer membranes of the present invention is respectively provided with good adhesive property, for being bonded of asphalt water-proof coiled material or polymer membranes, compound or maintenance.
Description
Technical field
The invention belongs to waterproof material technical field, contains non-polar polymer modified compound more particularly, to one kind
Double-composition polyurethane waterproof paint of thing and preparation method thereof.
Background technology
Waterproof material is used as the building enclosure of building, to prevent the infiltration of rainwater, snow-broth and underground water；Prevent air
In moisture, steam and other pernicious gases and liquid erosion；To prevent oozing for plumbing from turning over as separation structure；These are anti-
The material of infiltration, leakage and erosion is referred to as waterproof material.Waterproof material is various in style, mainly there is polyurethane water-proof paint, drip
The waterproof materials such as blue or green class waterproof roll, macromolecule coiled material.
Polyurethane water-proof paint is a kind of chemical reaction type high molecular water-proof paint of excellent performance, is nothing before construction curing
Shape liquid, therefore has the title of " liquid rubber ", construction solidify afterwards film forming, can form that one layer continuous, pliability is good, jointless whole
Body rubber waterproof membrane.The waterproof membrane has excellent in mechanical performance, wearability is prominent, chemical resistance is good, integral waterproofing effect
The advantages that good, be widely used in roofing, basement, toilet bath room, ditch pond and the moisture-proof of chemical plant ground of building, waterproof,
Antiseepage etc..
Most of asphalt water-proof coiled material is all SBS modified asphalt waterproof coiled materials, with s-B-S (SBS)
The pitch that thermoplastic elastomer (TPE) makees modifying agent invades stain and coating material, and upper surface is coated with polyethylene film, fine sand, mineral piece (grain)
The sheet waterproof material that can be crimped made by the isolated material such as material or aluminium foil, copper foil.At home and abroad in waterproof material, SBS
Modified asphalt waterproof coiled material is still most important, most widely used waterproof material.
Polymer membranes, then be the nonpolar height based on TPO waterproof rolls or HDPE self-adhesion glued membrane waterproof rolls
Molecule coiled material.TPO waterproof rolls, that is, thermoplastic polyolefin waterproof roll, are to use advanced polymerization technique by EP rubbers
Thermoplastic polyolefin (TPO) synthetic resin being combined together with polypropylene is base-material, adds antioxidant, antioxidant, softening agent
Manufactured new type waterproof coiled material；HDPE self-adhesions glued membrane waterproof roll, that is, high density polyethylene (HDPE) self-adhesion glued membrane waterproof roll, is to aim at
Underground to form firmly anti-cohesive waterproof roll with a kind of can be overlay with rear pouring concrete structure that Tunnel Engineering is developed, and three
Layer is compound, and bottom is high density polyethylene (HDPE) (HDPE) sheet material.
Since waterproof material species is various, waterproof construction design or maintenance frequently involve the compound of different types of material or
Overlap joint, especially waterproof roll and water-repellent paint compound or overlap joint, the overlap joint of above-mentioned three classes waterproof material and it is compound just particularly
It is common.But due to asphalt water-proof coiled material, polymer membranes is non-polar material, and surface energy is low, and polyurethane coating film is
Polar material, surface energy are high, both overlap or compound, and it is poor to there is bonding, or even the problem of come off.Therefore there is an urgent need to develop one
Kind can be rolled up with asphalt water-proof coiled material or the polyurethane water-proof paint of polymer membranes energy good bonding with solving asphalt waterproofing
Material or polymer membranes bad engineering roadblock Nian Jie with polyurethane water-proof paint.
The content of the invention
It is Nian Jie with polyurethane water-proof paint not present invention aim to address asphalt water-proof coiled material or polymer membranes
Good application problem, there is provided a kind of double-composition polyurethane waterproof paint containing non-polar polymer modified compound, in reality
In engineer application so that it has good cementability with asphalt water-proof coiled material or polymer membranes.
To achieve these goals, the first aspect of the present invention provides a kind of containing non-polar polymer modified compound
Double-composition polyurethane waterproof paint, the double-composition polyurethane waterproof paint include component A and B component；
The component A is base polyurethane prepolymer for use as, and in terms of parts by weight, the base polyurethane prepolymer for use as is by 3-15 parts of isocyanates
It is made for 2-40 parts with the first polyalcohol；
In terms of parts by weight, the B component includes：Second 2-20 parts of polyalcohol, main chain contain the non-of multiple C=C double bonds
0.1-2 parts of 2-30 parts of the epoxidation modification compound of polar polymer, 2-15 parts of chain extender and catalyst.
Preferably, the component A further includes：0-40 parts of plasticizer, 0-20 parts of solvent, auxiliary agent 0-2 parts by weight；The B groups
Part further includes：5-30 parts of plasticizer, 5-30 parts of solvent, 10-80 parts of pigment, 0.1-2 parts of auxiliary agent.
The second aspect of the present invention provides a kind of preparation method of above-mentioned double-composition polyurethane waterproof paint, its feature exists
In the preparation method is one of following two modes；
Mode one：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and isocyanates haptoreaction；After cooling, go out in the presence of an inert gas
Material, is made component A；
The preparation of B component：
I) non-polar polymer and organic peroxide acid that main chain is contained to multiple C=C double bonds carries out haptoreaction, and master is made
Chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii the second polyalcohol after vacuum dehydration and solid chain extender) are contained into the non-of multiple C=C double bonds with the main chain
The epoxidation modification compound of polar polymer is uniformly mixed, and obtains mixture；After cooling, the mixture is mixed with catalyst
Close uniformly, cool down again, discharge in the presence of an inert gas, B component is made.
Mode two：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and isocyanates haptoreaction；After cooling, in the presence of an inert gas go out
Material, is made component A；
The preparation of B component：
I) non-polar polymer and organic peroxide acid that main chain is contained to multiple C=C double bonds carries out haptoreaction, and master is made
Chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii) the second polyalcohol after vacuum dehydration and the main chain are contained to the non-polar polymer of multiple C=C double bonds
Epoxidation modification compound is uniformly mixed, and obtains mixture；After cooling, the mixture, catalyst and liquid chain extender are mixed
Close uniformly, cool down again, discharge in the presence of an inert gas, B component is made.
The third aspect of the present invention provides a kind of preparation method of above-mentioned double-composition polyurethane waterproof paint, the preparation method
For one of following two modes；
Mode one：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and plasticizer and isocyanates haptoreaction；After cooling, add solvent and
Auxiliary agent, cools down again, discharges in the presence of an inert gas, and component A is made；
The preparation of B component：
I) non-polar polymer that main chain contains multiple C=C double bonds, partial solvent with organic peroxide acid contact anti-
Should, obtained main chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii) the second polyalcohol, plasticizer, pigment and the solid chain extender after vacuum dehydration are contained with the main chain multiple
The epoxidation modification compound of the non-polar polymer of C=C double bonds is uniformly mixed, and obtains mixture；After cooling, by the mixing
Thing, catalyst, residual solvent and auxiliary agent are uniformly mixed, and are cooled down again, are discharged in the presence of an inert gas, and B component is made.
Mode two：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and plasticizer and isocyanates haptoreaction；After cooling, add solvent and
Auxiliary agent, cools down again, discharges in the presence of an inert gas, and component A is made；
The preparation of B component：
I) non-polar polymer that main chain contains multiple C=C double bonds, partial solvent with organic peroxide acid contact anti-
Should, obtained main chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii the second polyalcohol, plasticizer and the pigment after vacuum dehydration and the main chain) are contained into multiple C=C double bonds
The epoxidation modification compound of non-polar polymer is uniformly mixed, and obtains mixture；After cooling, by the mixture, catalyst,
Liquid chain extender, residual solvent and auxiliary agent are uniformly mixed, and are cooled down again, are discharged in the presence of an inert gas, and B component is made.
Technical scheme has the following advantages that：
The present invention can effectively solve the compound of asphalt water-proof coiled material or polymer membranes and polyurethane water-proof paint or
Bonding problem, and directly can prevent asphalt water-proof coiled material or macromolecule using polyurethane water-proof paint as bonding water-repellent paint
Water coiled material is bonded on formation level, improves the construction reliability of waterproof material；It can also be used for asphalt water-proof coiled material or macromolecule
The maintenance of waterproof roll.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe being preferable to carry out for the present invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without should be limited by embodiments set forth herein.Phase
Instead, there is provided these embodiments are of the invention more thorough and complete in order to make, and can be by the scope of the present invention intactly
It is communicated to those skilled in the art.
The first aspect of the present invention provides a kind of dual-component polyurethane waterproof containing non-polar polymer modified compound
Coating, the double-composition polyurethane waterproof paint include component A and B component；
The component A is base polyurethane prepolymer for use as, and in terms of parts by weight, the base polyurethane prepolymer for use as is by 3-15 parts of isocyanates
It is made for 2-40 parts with the first polyalcohol；
In terms of parts by weight, the B component includes：Second 2-20 parts of polyalcohol, main chain contain the non-of multiple C=C double bonds
0.1-2 parts of 2-30 parts of the epoxidation modification compound of polar polymer, 2-15 parts of chain extender and catalyst.
Non-polar polymer progress of the water-repellent paint of the present invention by containing multiple C=C double bonds to main chain is epoxidised
Chemical modification, carries out oxidation reaction by the C=C double bonds in non-polar polymer molecular structure, produces a certain amount of epoxidation base
Group or hydroxyl group, further chemically react with base polyurethane prepolymer for use as, and molecule combines, and prepare a kind of and asphalt water-proof coiled material
There is the Two-component Waterproof Polyurethane Coating of good bonding with non-polar materials such as polymer membranes, rolled up for asphalt waterproofing
Being bonded of material or polymer membranes, compound or maintenance, solve the application problem in Practical Project.
In accordance with the present invention it is preferred that the weight ratio of the component A and the B component is 1：(0.25-4).
Preferably, in use, A, B component are uniformly mixed according to a certain ratio, you can construction.
In accordance with the present invention it is preferred that the main chain contains the epoxidation modification of the non-polar polymer of multiple C=C double bonds
Compound occurs epoxidation reaction with organic peroxide acid by the non-polar polymer that main chain contains multiple C=C double bonds and is made.
Beat the double bond in the strand for the non-polar polymer that main chain contains multiple C=C double bonds using organic peroxide acid
Open, epoxidation reaction occurs, generates a certain amount of epoxidation group or hydroxyl group.
In accordance with the present invention it is preferred that the non-polar polymer that the main chain contains multiple C=C double bonds is line style or star-like
At least one of block copolymer, line style or star-like homopolymer, line style or star-like random copolymer, preferred molecular weight 1-12
Ten thousand linear copolymers, more preferably s-B-S (SBS), butadiene-styrene rubber (SBR) and polybutadiene
At least one of (PB).
The organic peroxide acid is at least one of peroxidating formic acid, peracetic acid, monoperoxyphthalic acid.
Organic peroxide acid can be made by organic acid and peroxide reactions, can also be commercially available.
Inventor, which studies, to be found：Backbone molecule contains the non-polar polymer of substantial amounts of C=C double bonds, such as styrene-fourth
Styrene (SBS), butadiene-styrene rubber (SBR) and polybutadiene (PB) etc., due to its structure and surface energy and pitch,
Polyethylene is close, there is certain compatibility and adhesive effect to nonpolar, low-surface-energy pitch or polythene material, but its with
Polyurethane poor compatibility, therefore in polyurethane water-proof paint, addition backbone molecule contains the nonpolar of substantial amounts of C=C double bonds
Separating out or separating, easily occur in polymer, only physical mixed, and additive amount is limited, it is necessary to contain in advance to backbone molecule largely
The non-polar polymers of C=C double bonds carry out chemical modification, then by being chemically reacted with base polyurethane prepolymer for use as to improve main chain
Molecule contains the non-polar polymer of substantial amounts of C=C double bonds and the compatibility of polyurethane.
In accordance with the present invention it is preferred that the isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate,
At least one of isophorone diisocyanate and hexamethylene-diisocyanate；First polyalcohol and the second polyalcohol
It is each independently the end hydroxy polyether polyalcohol or polyester polyols that molecular weight is 500-5000, hydroxyl value is 40-400mgKOH/g
Alcohol, is preferably end hydroxy polyether polyalcohol, more preferably in polyether Glycols, polyether-tribasic alcohol and polyethers tetrahydroxylic alcohol extremely
Few one kind.
In accordance with the present invention it is preferred that the chain extender is binary amine chain extender, di-alcohols chain extender and alcamines expand
At least one of chain agent；The binary amine chain extender is chloro- 4, the 4- diaminodiphenyl-methanes (MOCA) of 3,3'- bis-；Institute
Di-alcohols chain extender is stated as at least one in 1,4- butanediols, ethylene glycol, propane diols, diglycol and neopentyl glycol
Kind；The alcamines chain extender is monoethanolamine, diethanol amine, triethanolamine, triisopropanolamine and double (2- hydroxypropyls) benzene of N, N'-
At least one of amine.
The catalyst is urged for organo-metallic catalyst, fatty amines catalyst, alicyclic ring amines catalyst and aromatic amine
At least one of agent.
In accordance with the present invention it is preferred that the component A further includes：0-40 parts of plasticizer, 0-20 parts of solvent, auxiliary agent 0-2 weight
Part；The B component further includes：5-30 parts of plasticizer, 5-30 parts of solvent, 10-80 parts of pigment, 0.1-2 parts of auxiliary agent.
The plasticizer is preferably chlorinated paraffin, aromatic naphtha, phthalic ester plasticizer and citric acid ester type plasticising
At least one of agent.The phthalic ester plasticizer is preferably dioctyl phthalate, two fourth of phthalic acid
At least one of ester and diisononyl phthalate.
The solvent is preferably toluene, dimethylbenzene, hexamethylene, 120# solvent naphthas, 150# solvent naphthas, ethyl acetate and acetic acid
At least one of butyl ester.
The pigment be preferably carbon black, titanium dioxide, iron oxide yellow, kaolin, cement, coarse whiting, barium sulfate, magnesia, calcium oxide,
At least one of wollastonite, silicon powder and talcum powder.
The auxiliary agent be preferably in defoamer, dispersant, levelling agent, anti-settling agent, coupling agent, antioxidant and retarder extremely
Few one kind.The auxiliary agent is commonly used in this field, and those skilled in the art can rule of thumb adjust the species and use of auxiliary agent
Amount.
In the present invention, the plasticizer, solvent, auxiliary agent and pigment in component A and B component can be identical or different.
The second aspect of the present invention provides a kind of preparation method of above-mentioned double-composition polyurethane waterproof paint, the preparation method
For one of following two modes；
Mode one：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and isocyanates haptoreaction；After cooling, go out in the presence of an inert gas
Material, is made component A；
The preparation of B component：
I) non-polar polymer and organic peroxide acid that main chain is contained to multiple C=C double bonds carries out haptoreaction, and master is made
Chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii the second polyalcohol after vacuum dehydration and solid chain extender) are contained into the non-of multiple C=C double bonds with the main chain
The epoxidation modification compound of polar polymer is uniformly mixed, and obtains mixture；After cooling, the mixture is mixed with catalyst
Close uniformly, cool down again, discharge in the presence of an inert gas, B component is made.
Mode two：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and isocyanates haptoreaction；After cooling, in the presence of an inert gas go out
Material, is made component A；
The preparation of B component：
I) non-polar polymer and organic peroxide acid that main chain is contained to multiple C=C double bonds carries out haptoreaction, and master is made
Chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii) the second polyalcohol after vacuum dehydration and the main chain are contained to the non-polar polymer of multiple C=C double bonds
Epoxidation modification compound is uniformly mixed, and obtains mixture；After cooling, the mixture, catalyst and liquid chain extender are mixed
Close uniformly, cool down again, discharge in the presence of an inert gas, B component is made.
Preferably, B component preparation step ii) in, preferably cool to 50-60 DEG C after the cooling.
The third aspect of the present invention provides a kind of preparation method of above-mentioned double-composition polyurethane waterproof paint, the preparation method
For one of following two modes；
Mode one：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and plasticizer and isocyanates haptoreaction；After cooling, add solvent and
Auxiliary agent, cools down again, discharges in the presence of an inert gas, and component A is made；
The preparation of B component：
I) non-polar polymer that main chain contains multiple C=C double bonds, partial solvent with organic peroxide acid contact anti-
Should, obtained main chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii) the second polyalcohol, plasticizer, pigment and the solid chain extender after vacuum dehydration are contained with the main chain multiple
The epoxidation modification compound of the non-polar polymer of C=C double bonds is uniformly mixed, and obtains mixture；After cooling, by the mixing
Thing, catalyst, residual solvent and auxiliary agent are uniformly mixed, and are cooled down again, are discharged in the presence of an inert gas, and B component is made.
Mode two：
The preparation of component A：
By the first polyalcohol after vacuum dehydration and plasticizer and isocyanates haptoreaction；After cooling, add solvent and
Auxiliary agent, cools down again, discharges in the presence of an inert gas, and component A is made；
The preparation of B component：
I) non-polar polymer that main chain contains multiple C=C double bonds, partial solvent with organic peroxide acid contact anti-
Should, obtained main chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；
Ii the second polyalcohol, plasticizer and the pigment after vacuum dehydration and the main chain) are contained into multiple C=C double bonds
The epoxidation modification compound of non-polar polymer is uniformly mixed, and obtains mixture；After cooling, by the mixture, catalyst,
Liquid chain extender, residual solvent and auxiliary agent are uniformly mixed, and are cooled down again, are discharged in the presence of an inert gas, and B component is made.
Preferably, the step ii in the preparation of component A with the preparation of B component) in, preferably dropped after the cooling
Temperature arrives 50-60 DEG C.
In accordance with the present invention it is preferred that the condition of the vacuum dehydration includes：Temperature be 100-120 DEG C, -0.09MPa with
Under vacuum condition under be dehydrated 2-8h；The temperature of the discharging is 30-40 DEG C；In the preparation of component A：The isocyanates adds
Heating degree is less than 80 DEG C, and the catalytic temperature is 60-100 DEG C, time 2-5h；In the preparation of B component：It is described to connect
The temperature for touching reaction is 30-100 DEG C, time 2-10h.
Preferably, preparing each raw material of the water-repellent paint of the present invention can be commercially available.
The present invention is further illustrated by the following examples：
Embodiment 1
The present embodiment provides a kind of double-composition polyurethane waterproof paint containing non-polar polymer modified compound, with weight
Number meter is measured, preparing the composition of raw materials of component A includes：10 parts of isocyanates (TDI), 20 parts of polyether Glycols (2000D), polyethers
10 parts of trihydroxylic alcohol (330N)；Preparing the composition of raw materials of B component includes：10 parts of polyether-tribasic alcohol (330N), two fourth of phthalic acid
10 parts of ester (DBP), 15 parts of type SBS polymer, 1 part of peroxidating formic acid, MOCA6 parts of chain extender, 50 parts of pigment (coarse whiting) are organic
0.2 part of tin catalyst (T-12), 0.5 part of defoamer, 0.2 part of dispersant, 20 parts of dimethylbenzene.
Specific preparation process is as follows：
The preparation of component A：
By 20 parts of polyether Glycols (2000D), 10 parts of mixing of polyether-tribasic alcohol (330N), are warming up to 110 DEG C, vacuum pressure
For when dehydration 5 is small under conditions of -0.095MPa；Less than 80 DEG C are reduced the temperature to, adds isocyanates isocyanates (TDI) 10
Part, at 90 DEG C, when reaction 3 is small；35 DEG C are reduced the temperature to, is filled with inert gas shielding, discharging obtains component A；
The preparation of B component：
10 parts of 15 parts of type SBS polymer and dimethylbenzene are added in reaction vessel, after heating stirring and dissolving, is added dropwise advance
1 part of completely reacted peroxidating formic acid, when 65 DEG C of reactions 6 are small, prepares the epoxidation modification compound of SBS；By polyethers ternary
10 parts of alcohol (330N), 10 parts of dibutyl phthalate (DBP), 6 parts of chain extender MOCA, 50 parts of stirring heatings of pigment (coarse whiting)
To 110 DEG C, when dehydration 6 is small under conditions of vacuum pressure is -0.095MPa；Moisture is less than less than 5/10000ths, and addition has been made
The epoxidation modification compound of the SBS got ready, stirs evenly；55 DEG C are reduced the temperature to, adds organotin catalysts (T-12) 0.2
Part, 0.5 part of defoamer, 0.2 part of dispersant, 10 parts of dimethylbenzene, when stirring 1-2 is small, is cooled to 35 DEG C, nitrogen charging gas shielded, discharges
Obtain B component.
Embodiment 2
The present embodiment provides a kind of double-composition polyurethane waterproof paint containing non-polar polymer modified compound, with weight
Number meter is measured, preparing the composition of raw materials of component A includes：15 parts of isocyanates (MDI-50), 20 parts of polyether Glycols (2000D),
10 parts of polyether-tribasic alcohol (330N)；10 parts of chlorinated paraffin；Preparing the composition of raw materials of B component includes：Polyether-tribasic alcohol (330N) 10
Part, 10 parts of chlorinated paraffin, 15 parts of star-shaped sbs polymer, 1 part of peroxidating formic acid, 6 parts of chain extender MOCA, pigment (coarse whiting) 50
Part, 0.2 part of organotin catalysts (T-12), 0.5 part of defoamer, 0.2 part of dispersant, 20 parts of dimethylbenzene.
Specific preparation process is as follows：
The preparation of component A：
By 10 parts of 20 parts of polyether Glycols (2000D), 10 parts of polyether-tribasic alcohol (330N) and chlorinated paraffin mixing, it is warming up to
110 DEG C, when dehydration 6 is small under conditions of vacuum pressure is -0.09MPa；Less than 80 DEG C are reduced the temperature to, adds isocyanates
(MDI-50) 15 parts, at 90 DEG C, when reaction 3 is small；35 DEG C are reduced the temperature to, is filled with inert gas shielding, discharging obtains A groups
Part；
The preparation of B component：
10 parts of 15 parts of type SBS polymer and dimethylbenzene are added in reaction vessel, after heating stirring and dissolving, is added dropwise advance
1 part of completely reacted peroxidating formic acid, when 65 DEG C of reactions 6 are small, prepares the epoxidation modification compound of SBS；By polyethers ternary
10 parts of alcohol (330N), 10 parts of chlorinated paraffin, 6 parts of chain extender MOCA, 50 parts of stirrings of pigment (coarse whiting) are warming up to 110 DEG C, in vacuum
When dehydration 6 is small under conditions of pressure is -0.09MPa；Moisture is less than less than 5/10000ths, adds the epoxy of the SBS prepared
Change modified compound, stir evenly；Reduce the temperature to 55 DEG C, add 0.2 part of organotin catalysts (T-12), 0.5 part of defoamer,
0.2 part of dispersant, 10 parts of dimethylbenzene, when stirring 1-2 is small, is cooled to 35 DEG C, nitrogen charging gas shielded, discharging obtains B component.
Embodiment 3
The present embodiment provides a kind of double-composition polyurethane waterproof paint containing non-polar polymer modified compound, with weight
Number meter is measured, preparing the composition of raw materials of component A includes：15 parts of isocyanates (MDI-50), 20 parts of polyether Glycols (2000D),
10 parts of polyether-tribasic alcohol (330N)；10 parts of chlorinated paraffin；Preparing the composition of raw materials of B component includes：Polyether-tribasic alcohol (330N) 10
Part, 10 parts of chlorinated paraffin, 15 parts of styrene-butadiene polymer (SBR), 1 part of peracetic acid, 6 parts of chain extender MOCA, pigment (coarse whiting) 50
Part, 0.2 part of organotin catalysts (T-12), 0.5 part of defoamer, 0.2 part of dispersant, 20 parts of 200# solvent naphthas.
Specific preparation process is as follows：
The preparation of component A：
By 20 parts of polyether Glycols (2000D), the 10 parts of mixing of 10 parts of polyether-tribasic alcohol (330N) and chlorinated paraffin, are warming up to
110 DEG C, when dehydration 6 is small under conditions of vacuum pressure is -0.09MPa；Less than 80 DEG C are reduced the temperature to, adds isocyanates
(MDI-50) 15 parts, at 90 DEG C, when reaction 3 is small；35 DEG C are reduced the temperature to, is filled with inert gas shielding, discharging obtains A groups
Part；
The preparation of B component：
10 parts of 15 parts of styrene-butadiene polymer (SBR) and 200# solvent naphthas are added in reaction vessel, after heating stirring and dissolving, drop
Add 1 part completely reacted in advance of peroxidating formic acid, when 65 DEG C of reactions 6 are small, prepare the epoxidation modification compound of SBS；Will be poly-
10 parts of ether trihydroxylic alcohol (330N), 10 parts of chlorinated paraffin and 50 parts of stirrings of pigment (coarse whiting) are warming up to 110 DEG C, be in vacuum pressure-
When dehydration 6 is small under conditions of 0.09MPa；Moisture is less than less than 5/10000ths, adds the epoxidation modification of the SBS prepared
Compound, stirs evenly；Reduce the temperature to 55 DEG C, add 0.2 part of organotin catalysts (T-12), 2 parts of chain extender 1,4-butanediol,
0.5 part of defoamer, 0.2 part of dispersant, 10 parts of 200# solvent naphthas, when stirring 1-2 is small, are cooled to 35 DEG C, nitrogen charging gas shielded, discharges
Obtain B component.
Embodiment 4
The present embodiment provides a kind of double-composition polyurethane waterproof paint containing non-polar polymer modified compound, with weight
Number meter is measured, preparing the composition of raw materials of component A includes：15 parts of isocyanates (MDI-50), 20 parts of polyether Glycols (2000D),
10 parts of polyether-tribasic alcohol (330N)；10 parts of chlorinated paraffin；Preparing the composition of raw materials of B component includes：Polyether-tribasic alcohol (330N) 10
Part, 10 parts of chlorinated paraffin, 15 parts of polybutadiene rubber, 1 part of peroxidating formic acid, 6 parts of chain extender MOCA, 50 parts of pigment (coarse whiting),
0.2 part of organotin catalysts (T-12), 0.5 part of defoamer, 0.2 part of dispersant, 20 parts of dimethylbenzene.
Specific preparation process is as follows：
The preparation of component A：
By 20 parts of polyether Glycols (2000D), the 10 parts of mixing of 10 parts of polyether-tribasic alcohol (330N) and chlorinated paraffin, are warming up to
110 DEG C, when dehydration 6 is small under conditions of vacuum pressure is -0.09MPa；Less than 80 DEG C are reduced the temperature to, adds isocyanates
(MDI-50) 15 parts, at 90 DEG C, when reaction 3 is small；35 DEG C are reduced the temperature to, is filled with inert gas shielding, discharging obtains A groups
Part；
The preparation of B component：
10 parts of 15 parts of polybutadiene rubber and dimethylbenzene are added in reaction vessel, after heating stirring and dissolving, is added dropwise advance
1 part of completely reacted peroxidating formic acid, when 65 DEG C of reactions 6 are small, prepares the epoxidation modification compound of SBS；By polyethers ternary
10 parts of alcohol (330N), 10 parts of chlorinated paraffin, 6 parts of chain extender MOCA, 50 parts of stirrings of pigment (coarse whiting) are warming up to 110 DEG C, in vacuum
When dehydration 6 is small under conditions of pressure is -0.09MPa；Moisture is less than less than 5/10000ths, adds the epoxy of the SBS prepared
Change modified compound, stir evenly；Reduce the temperature to 55 DEG C, add 0.2 part of organotin catalysts (T-12), 0.5 part of defoamer,
0.2 part of dispersant, 10 parts of dimethylbenzene, when stirring 1~2 is small, is cooled to 35 DEG C, nitrogen charging gas shielded, discharging obtains B component.
Comparative example
This comparative example provides a kind of bi-component modified polyurethane water-repellent paint, in terms of parts by weight, prepares the raw material of component A
Formula includes：15 parts of isocyanates (MDI-50), 20 parts of polyether Glycols (2000D), 10 parts of polyether-tribasic alcohol (330N)；Chlorination
10 parts of paraffin；Preparing the composition of raw materials of B component includes：10 parts of polyether-tribasic alcohol (330N), 10 parts of chlorinated paraffin, chain extender MOCA
6 parts, 50 parts of pigment (coarse whiting), 0.2 part of organotin catalysts (T-12), 0.5 part of defoamer, 0.2 part of dispersant, dimethylbenzene 10
Part.
Specific preparation process is as follows：
The preparation of component A：
By 20 parts of polyether Glycols (2000D), the 10 parts of mixing of 10 parts of polyether-tribasic alcohol (330N) and chlorinated paraffin, are warming up to
110 DEG C, when dehydration 6 is small under conditions of vacuum pressure is -0.09MPa；Less than 80 DEG C are reduced the temperature to, adds isocyanates
(MDI-50) 15 parts, at 90 DEG C, when reaction 3 is small；35 DEG C are reduced the temperature to, is filled with inert gas shielding, discharging obtains A groups
Part；
The preparation of B component：
By 10 parts of polyether-tribasic alcohol (330N), 10 parts of chlorinated paraffin, 6 parts of chain extender MOCA, 50 parts of stirrings of pigment (coarse whiting)
110 DEG C are warming up to, when dehydration 6 is small under conditions of vacuum pressure is -0.09MPa；Moisture is less than less than 5/10000ths, is cooled to
55 DEG C, 0.2 part of organotin catalysts (T-12) are added, 0.5 part of defoamer, 0.2 part of dispersant, 10 parts of dimethylbenzene, it is small to stir 1-2
When, 35 DEG C are cooled to, nitrogen charging gas shielded, discharging obtains B component.
Test case
According to the weight ratio of A, B component it is 1 by Two-component Waterproof Polyurethane Coating prepared by embodiment 1-4 and comparative example：1
It is uniformly mixed, film；Then according to GB/T 19250-2013《Polyurethane water-proof paint》Middle type-I standard is to two component polyurethane
Water-repellent paint paint film is tested for the property, and test result is shown in Table 1.
Table 1
By test result, the dual-component polyurethane waterproof of the invention containing non-polar polymer modified compound
The adhesive strength of coating and asphalt water-proof coiled material and polymer membranes is better than comparative example.
Various embodiments of the present invention are described above, described above is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
- A kind of 1. double-composition polyurethane waterproof paint containing non-polar polymer modified compound, it is characterised in that this pair of group Part polyurethane water-proof paint includes component A and B component；The component A is base polyurethane prepolymer for use as, and in terms of parts by weight, the base polyurethane prepolymer for use as is by 3-15 parts of isocyanates and the One 2-40 parts of polyalcohol is made；In terms of parts by weight, the B component includes：Second 2-20 parts of polyalcohol, main chain contain the nonpolar of multiple C=C double bonds 0.1-2 parts of 2-30 parts of the epoxidation modification compound of polymer, 2-15 parts of chain extender and catalyst.
- 2. double-composition polyurethane waterproof paint according to claim 1, wherein, the weight of the component A and the B component Than for 1：(0.25-4).
- 3. double-composition polyurethane waterproof paint according to claim 1, wherein, the main chain contains multiple C=C double bonds The epoxidation modification compound of non-polar polymer is contained the non-polar polymer and organic peroxy of multiple C=C double bonds by main chain Acid occurs epoxidation reaction and is made.
- 4. double-composition polyurethane waterproof paint according to claim 3, wherein, the main chain contains multiple C=C double bonds Non-polar polymer is in line style or star block copolymer, line style or star-like homopolymer, line style or star-like random copolymer At least one, preferred molecular weight are the linear copolymers of 1-12 ten thousand, more preferably s-B-S, butylbenzene At least one of rubber and polybutadiene；The organic peroxide acid is peroxidating formic acid, peracetic acid, single peroxidating neighbour's benzene At least one of dioctyl phthalate.
- 5. double-composition polyurethane waterproof paint according to claim 1, wherein, the isocyanates is toluene diisocynate At least one of ester, methyl diphenylene diisocyanate, isophorone diisocyanate and hexamethylene-diisocyanate；Institute State the first polyalcohol and the second polyalcohol is each independently the end that molecular weight is 500-5000, hydroxyl value is 40-400mgKOH/g Hydroxy polyethers polyalcohol or polyester polyol, are preferably end hydroxy polyether polyalcohol, more preferably polyether Glycols, polyethers At least one of trihydroxylic alcohol and polyethers tetrahydroxylic alcohol.
- 6. double-composition polyurethane waterproof paint according to claim 1, wherein, the chain extender is binary amine chain extension At least one of agent, di-alcohols chain extender and alcamines chain extender；The binary amine chain extender is 3,3'- bis- chloro- 4, 4- diaminodiphenyl-methanes；The di-alcohols chain extender is 1,4- butanediols, ethylene glycol, propane diols, diglycol At least one of with neopentyl glycol；The alcamines chain extender is monoethanolamine, diethanol amine, triethanolamine, triisopropanolamine And at least one of double (2- hydroxypropyls) aniline of N, N'-；The catalyst is organo-metallic catalyst, fatty amines are catalyzed At least one of agent, alicyclic ring amines catalyst and aromatic amine catalyst.
- 7. double-composition polyurethane waterproof paint according to claim 1, wherein, the component A further includes：Plasticizer 0-40 Part, 0-20 parts of solvent, auxiliary agent 0-2 parts by weight；The B component further includes：5-30 parts of plasticizer, 5-30 parts of solvent, pigment 10-80 Part, 0.1-2 parts of auxiliary agent；The plasticizer is preferably in chlorinated paraffin, aromatic naphtha, phthalic ester plasticizer and citric acid ester plasticizer At least one；The solvent is preferably toluene, dimethylbenzene, hexamethylene, 120# solvent naphthas, 150# solvent naphthas, ethyl acetate and butyl acetate At least one of；The pigment is preferably carbon black, titanium dioxide, iron oxide yellow, kaolin, cement, coarse whiting, barium sulfate, magnesia, calcium oxide, silicon ash At least one of stone, silicon powder and talcum powder；The auxiliary agent is preferably at least one in defoamer, dispersant, levelling agent, anti-settling agent, coupling agent, antioxidant and retarder Kind.
- 8. the preparation method of the double-composition polyurethane waterproof paint in claim 1-6 described in any one, it is characterised in that should Preparation method is one of following two modes；Mode one：The preparation of component A：By the first polyalcohol after vacuum dehydration and isocyanates haptoreaction；After cooling, discharge, make in the presence of an inert gas Obtain component A；The preparation of B component：I) non-polar polymer and organic peroxide acid that main chain is contained to multiple C=C double bonds carries out haptoreaction, and obtained main chain contains There is the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；Ii the second polyalcohol after vacuum dehydration and solid chain extender) are contained into the nonpolar of multiple C=C double bonds with the main chain The epoxidation modification compound of polymer is uniformly mixed, and obtains mixture；After cooling, the mixture is mixed with catalyst It is even, cool down again, discharge in the presence of an inert gas, B component is made；Mode two：The preparation of component A：By the first polyalcohol after vacuum dehydration and isocyanates haptoreaction；After cooling, in the presence of an inert gas discharge, make Obtain component A；The preparation of B component：I) non-polar polymer and organic peroxide acid that main chain is contained to multiple C=C double bonds carries out haptoreaction, and obtained main chain contains There is the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；Ii) the second polyalcohol after vacuum dehydration and the main chain are contained to the epoxy of the non-polar polymer of multiple C=C double bonds Change modified compound to be uniformly mixed, obtain mixture；After cooling, the mixture, catalyst and liquid chain extender are mixed equal It is even, cool down again, discharge in the presence of an inert gas, B component is made.
- 9. the preparation method of the double-composition polyurethane waterproof paint described in claim 7, it is characterised in that the preparation method be with One of lower two ways；Mode one：The preparation of component A：By the first polyalcohol after vacuum dehydration and plasticizer and isocyanates haptoreaction；After cooling, solvent and auxiliary agent are added, Cool down again, discharge in the presence of an inert gas, component A is made；The preparation of B component：I) non-polar polymer, partial solvent and organic peroxide acid that main chain contains multiple C=C double bonds are subjected to haptoreaction, Obtained main chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；Ii the second polyalcohol, plasticizer, pigment and the solid chain extender after vacuum dehydration and the main chain) are contained into multiple C=C The epoxidation modification compound of the non-polar polymer of double bond is uniformly mixed, and obtains mixture；After cooling, by the mixture, Catalyst, residual solvent and auxiliary agent are uniformly mixed, and are cooled down again, are discharged in the presence of an inert gas, and B component is made；Mode two：The preparation of component A：By the first polyalcohol after vacuum dehydration and plasticizer and isocyanates haptoreaction；After cooling, solvent and auxiliary agent are added, Cool down again, discharge in the presence of an inert gas, component A is made；The preparation of B component：I) non-polar polymer, partial solvent and organic peroxide acid that main chain contains multiple C=C double bonds are subjected to haptoreaction, Obtained main chain contains the epoxidation modification compound of the non-polar polymer of multiple C=C double bonds；Ii) the second polyalcohol, plasticizer and pigment after vacuum dehydration and the main chain are contained to the non-pole of multiple C=C double bonds The epoxidation modification compound of property polymer is uniformly mixed, and obtains mixture；After cooling, by the mixture, catalyst, liquid Chain extender, residual solvent and auxiliary agent are uniformly mixed, and are cooled down again, are discharged in the presence of an inert gas, and B component is made.
- 10. preparation method according to claim 8 or claim 9, wherein, the condition of the vacuum dehydration includes：It is 100- in temperature 120 DEG C, 2-8h is dehydrated under the vacuum condition of below -0.09MPa；The temperature of the discharging is 30-40 DEG C；In the preparation of component A： The addition temperature of the isocyanates is less than 80 DEG C, and the catalytic temperature is 60-100 DEG C, time 2-5h；B groups In the preparation divided：The catalytic temperature is 30-100 DEG C, time 2-10h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110499134A (en) * | 2018-05-17 | 2019-11-26 | 西安光启尖端技术研究院 | Adhesive, preparation method and covering |
| WO2021022923A1 (en) * | 2019-08-02 | 2021-02-11 | 江苏凯伦建材股份有限公司 | Two-component osmotic reaction-type waterproof paint, preparation method therefor and use thereof |
| CN112500777A (en) * | 2020-11-30 | 2021-03-16 | 四川奥星建材科技有限公司 | PFS polyurethane waterproof coating and preparation and use methods thereof |
| CN112760985A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of aqueous emulsion type carbon fiber sizing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110499134A (en) * | 2018-05-17 | 2019-11-26 | 西安光启尖端技术研究院 | Adhesive, preparation method and covering |
| WO2021022923A1 (en) * | 2019-08-02 | 2021-02-11 | 江苏凯伦建材股份有限公司 | Two-component osmotic reaction-type waterproof paint, preparation method therefor and use thereof |
| CN112760985A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of aqueous emulsion type carbon fiber sizing agent |
| CN112760986A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of aqueous emulsion type carbon fiber sizing agent |
| CN112500777A (en) * | 2020-11-30 | 2021-03-16 | 四川奥星建材科技有限公司 | PFS polyurethane waterproof coating and preparation and use methods thereof |
| CN112500777B (en) * | 2020-11-30 | 2022-01-25 | 四川奥星建材科技有限公司 | PFS polyurethane waterproof coating and preparation and use methods thereof |
| CN113698565A (en) * | 2021-08-19 | 2021-11-26 | 山东一诺威聚氨酯股份有限公司 | Method for reducing crystallization point of polyester type modified MDI |
| CN115505336A (en) * | 2022-10-25 | 2022-12-23 | 江苏凯伦建材股份有限公司 | Single-component asphalt polyurethane waterproof coating and preparation method and application thereof |
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