CN107057629A - Environment-friendly high-intensity sealant composition and preparation method thereof - Google Patents

Environment-friendly high-intensity sealant composition and preparation method thereof Download PDF

Info

Publication number
CN107057629A
CN107057629A CN201710312112.4A CN201710312112A CN107057629A CN 107057629 A CN107057629 A CN 107057629A CN 201710312112 A CN201710312112 A CN 201710312112A CN 107057629 A CN107057629 A CN 107057629A
Authority
CN
China
Prior art keywords
parts
aqueous
intensity
environment
sealant composition
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.)
Withdrawn
Application number
CN201710312112.4A
Other languages
Chinese (zh)
Inventor
吴德斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Hok Seal Material Co Ltd
Original Assignee
Jiangsu Hok Seal Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu Hok Seal Material Co Ltd filed Critical Jiangsu Hok Seal Material Co Ltd
Priority to CN201710312112.4A priority Critical patent/CN107057629A/en
Publication of CN107057629A publication Critical patent/CN107057629A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6576—Compounds of group C08G18/69
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Sealing Material Composition (AREA)

Abstract

The present invention discloses a kind of environment-friendly high-intensity sealant composition, by Acrylate Modified Aqueous Polyurethane, modified vegetable protein glue, water-based thickener, waterborne curing agent, aqueous levelling agent, aqueous antioxidant part, Nano-meter SiO_22, aqueous dispersion composition.Compared with prior art, environment-friendly high-intensity sealant composition of the invention is low by introducing modified vegetable protein glue, cost, is all significantly improved in terms of water resistance and adhesion strength；Acrylate Modified Aqueous Polyurethane is introduced, occurs graft reaction using acrylate quasi-oligomer and the polyurethane of hydroxyl, then by cross-linking agents formation network structure, react more abundant, realize that level of residual monomers is low；SiO2 is surface-treated using poly- epoxy prapanol, the adhesion between sizing material is improved, colloid combination property is improved；The environment-friendly high-intensity sealant composition preparation method of the present invention meets environmental requirement, it is to avoid the harm of formaldehyde, and simple production process, cost be low.

Description

Environment-friendly high-intensity sealant composition and preparation method thereof
Technical field
The present invention relates to sealant composition field, more particularly to a kind of environment-friendly high-intensity sealant composition and its preparation Method.
Background technology
Fluid sealant is that one kind is deformed with sealing surface shape, is difficult trickling, there is the encapsulant of certain caking property.Be for Fill configuration gap, the adhesive to play sealing function.It is a kind of flowing when in use or the unsetting material that can squeeze Material, energy pointing closure seam is volatilized by drying, temperature change, solvent, is chemically crosslinked and bonded with base material stabilization, it is gradually Sizing turns into plasticity solid-state, viscoelastic state or elaxtic seal.
With people's environmental protection, the enhancing of consciousness, it is the low stain of representative, environment-protective sealing agent to promote aqueous sealant Development.Aqueous polyurethane fluid sealant refers to polyurethane being dissolved in water or adhesive formed by being dispersed in water, nontoxic non-ignitable, Nuisanceless, no danger, smell is small, free from environmental pollution, saves the energy, and viscosity is relatively low, can be adjusted with water-soluble thickener and water Section, easy to operate, cull can be cleared up with water；By the hardness of polyurethane coating film is high, adhesive force is strong, erosion resistant, solvent resistance are good The advantages of be combined with the low VOC content of water paint, and polyether polyols have cut property, using molecular design theory, With reference to new synthesis and crosslinking technological, the Nomenclature Composition and Structure of Complexes of film-coating polymer can be effectively controlled.
The defect of prior art：Due to the presence of the hydrophilic radical in aqueous polyurethane molecular backbone structure, it result in The water resistance of aqueous polyurethane fluid sealant, tack and solvent-resisting are poor, and the solid content of aqueous polyurethane fluid sealant The defect such as low, activation temperature is high.
The content of the invention
To solve above technical problem, the present invention provides environment-friendly high-intensity sealant composition and preparation method thereof, to solve Certainly low monomer residue, the problem of improving aqueous polyurethane fluid sealant mechanical property, temperature tolerance and water resistance.
The technical solution adopted by the present invention is as follows：A kind of environment-friendly high-intensity sealant composition, key is by following matter Measure the raw material composition of number：
30~50 parts of Acrylate Modified Aqueous Polyurethane, 25~40 parts of modified vegetable protein glue, 3~8 parts of water-based thickener, 3~7 parts of waterborne curing agent, 0.2~3 part of aqueous levelling agent, 0.05~1 part of aqueous antioxidant, Nano-meter SiO_2210~20 parts, 0.5~5 part of aqueous dispersion；
The Acrylate Modified Aqueous Polyurethane is made up of the raw material of following mass fraction：
15~20 parts of acrylic monomers, 0.1~1 part of azodiisobutyronitrile, 40~55 parts of dihydric alcohol, 2,2- dihydroxymethyls third Acid 4~10 parts, 35~50 parts of hexamethylene diisocyanate, 1~3 part of dibutyl tin laurate, 8~20 parts of triethanolamine, 10~15 parts of trimethylolethane, 2~5 parts of BDO, 18~33 parts of ethyl acetate and appropriate deionized water.
It is preferred that, the mass fraction of the raw material is：35 parts of Acrylate Modified Aqueous Polyurethane, modified vegetable protein glue 28 Part, 5 parts of water-based thickener, 6 parts of waterborne curing agent, 0.5 part of aqueous levelling agent, 0.1 part of aqueous antioxidant, Nano-meter SiO_22 12 Part, 1.5 parts of aqueous dispersion；The Acrylate Modified Aqueous Polyurethane is by 18 parts of acrylic monomers, azodiisobutyronitrile 0.4 Part, 45 parts of dihydric alcohol, 6 parts of 2,2- dihydromethyl propionic acids, 38 parts of hexamethylene diisocyanate, dibutyl tin laurate 1.5 Part, 10 parts of triethanolamine, 13 parts of trimethylolethane, 4 parts of BDO, 27 parts of ethyl acetate and appropriate deionized water.
It is preferred that, the Acrylate Modified Aqueous Polyurethane is obtained using following methods：The second of addition 2/3 in reaction vessel Acetoacetic ester, is warming up to 55~85 DEG C, and acrylic ester monomer, azodiisobutyronitrile and remaining acetic acid are added dropwise at reflux The mixture of ethyl ester, 1~2h is dripped off, and after 3~5h of insulation, obtains acrylic acid oligomer；By dihydric alcohol and 2,2- dihydroxymethyls third Acid is cooled to 60~85 DEG C after 90~110 DEG C, 1~2h of vacuum dehydration, adds hexamethylene diisocyanate, the propylene After acid oligomer and dibutyl tin laurate, 1.0~3.0h of reaction, 40~50 DEG C are cooled to, triethanolamine is added and neutralizes into Salt, reacts 0.5~1.0h, is warming up to 60~85 DEG C, adds trimethylolethane and is neutralized into salt, react 0.5h~ 4.0h, makes prepolymer formation subnetwork structure, and appropriate amount of deionized water is then added under high velocity agitation and emulsifies 0.5~1.0h, BDO chain extending reaction 0.5h is added, the Acrylate Modified Aqueous Polyurethane is obtained.
It is preferred that, the Nano-meter SiO_22Obtained using following methods：The Nano-meter SiO_22Obtained using following methods：Will SiO is added in 0.5mol/L sodium methoxide solution2, solution and SiO2Mass ratio be 3: 1, ultrasonic vibration 5~10 minutes, continue React after 1h, washed with absolute methanol, drying, grinding obtains the SiO2 of sodium methoxide surface treatment；By the sodium methoxide The SiO2 of surface treatment is added in epoxy prapanol, in 105-115 DEG C of temperature, nitrogen protection, and centrifugation divides after reaction 40-55 minute From and being washed with ethanol, through dry the nanosized SiO_2.
It is preferred that, the modified vegetable protein glue is obtained using following methods：It will be added in the mixture of sucrose and urea Mass fraction is the 35% NaOH aqueous solution, and the mass ratio of sucrose, urea and the NaOH aqueous solution is 10-20：1：8~15, heating Until sucrose and urea dissolve, 60~90 DEG C are then warming up to, soybean protein is added, the mass ratio of soybean protein and urea is 5 ~10:1, and constant temperature stirring is carried out, 30min is reacted, modified vegetable protein glue is obtained.
It is preferred that, the acrylic monomers is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate In one kind；The dihydric alcohol is one in polyethylene glycol adipate glycol, polybutadiene diol or polytetrahydrofuran diol Kind.
It is preferred that, the water-based thickener is water-based thickener in ROHM AND HAAS RM-12W, RM-2020 or RM-8W One kind；Aqueous levelling agent is one kind in BYK-380N, BYK-381 or BYK-307.
It is preferred that, waterborne curing agent is one kind in DesmodurD, BayhydurXP2655 or BayhydurXP2547.
It is preferred that, aqueous antioxidant is irgasfos 168 or antioxidant 1010；Aqueous dispersion is polyethylene glycol, poly- third Olefin(e) acid or Sodium Polyacrylate.
A kind of preparation method of environment-friendly high-intensity sealant composition, key is to carry out according to the following steps：
Step 1: preparing Acrylate Modified Aqueous Polyurethane, modified vegetable protein glue and Nano-meter SiO_2 respectively2；
Step 2: adding water after Acrylate Modified Aqueous Polyurethane, modified vegetable protein glue and water-based thickener are mixed Property levelling agent, aqueous antioxidant, with dispersion machine with 50~1000rpm rotating speed, stir 30~50min, base-material be made；
Step 3: base-material, waterborne curing agent, nanosized SiO_2 and aqueous dispersion are mixed, with dispersion machine with 50~ 1000rpm revs/min of rotating speed, stirs 35~100min, obtains finished product.
Beneficial effect：Compared with prior art, environment-friendly high-intensity sealant composition of the invention is by introducing modified plant Thing protein adhesive, the natural material resource of use, cost is low；Modification has been carried out to vegetable protein, gluing is effectively increased The adhesion strength of agent, is all significantly improved in terms of water resistance and adhesion strength；Acrylate Modified Aqueous Polyurethane is introduced, is adopted Occur graft reaction with the acrylate quasi-oligomer and polyurethane of hydroxyl, then by cross-linking agents formation network structure, Product is post-processed using redox initiation system, reacts more abundant, realizes that level of residual monomers is low；Using polycyclic oxygen third Alcohol is surface-treated to SiO2, the poly- epoxy prapanol of SiO2 nanoparticle surface situ-formed grafts, and special cladding is formed to grey body Structure, is applied to the preparation of polyurethane sealant, it is uniformly and stably dispersed in reaction system, improves and sizing material Between adhesion, make the combination properties such as elongation, tensile strength, the bin stability of colloid improve；The environment-friendly, high-intensity of the present invention Degree sealant composition preparation method meets environmental requirement, it is to avoid the harm of formaldehyde, simple production process, cost are low, give birth to The sealant composition of production has preferable water resistance, weatherability and resistance to low temperature, and adhesive force is strong, and pliability preferably, is sealed Function admirable.
Embodiment
To make those skilled in the art be better understood from technical scheme, with reference to subordinate list and specific embodiment party Formula elaborates to the present invention.
First, a kind of environment-friendly high-intensity sealant composition
Embodiment 1：The configuration proportion of each raw material in environment-friendly high-intensity sealant composition
By each raw material in environment-friendly high-intensity sealant composition, the mass fraction as described in table 1 is mixed respectively, obtains 3 groups Environment-friendly high-intensity sealant composition I~III of different mixing proportion.
The environment-friendly high-intensity sealant composition of the different mixing proportion of table 1 (mass fraction)
Embodiment 2：The preparation method of environment-friendly high-intensity sealant composition
Step 1: the preparation of Acrylate Modified Aqueous Polyurethane：12 parts of ethyl acetate is added in reaction vessel, 55 are warming up to ~85 DEG C, the mixing of 6 parts of 15 parts of hydroxy-ethyl acrylate, 0.1 part of azodiisobutyronitrile and ethyl acetate is added dropwise at reflux Thing, 1~2h is dripped off, and after 3~5h of insulation, obtains acrylic acid oligomer；By 40 parts of polyethylene glycol adipate glycol and 2,2- bis- 4 parts of hydroxymethyl propionic acid is cooled to 60~85 DEG C after 90~110 DEG C, 1~2h of vacuum dehydration, adds the isocyanic acid of hexa-methylene two After 1 part of 35 parts of ester, the acrylic acid oligomer and dibutyl tin laurate, 1.0~3.0h of reaction, 40~50 DEG C are cooled to, Add 8 parts of triethanolamine and neutralize into salt, react 0.5~1.0h, be warming up to 60~85 DEG C, add 10 parts of progress of trimethylolethane Salt is neutralized into, 0.5h~4.0h is reacted, makes prepolymer formation subnetwork structure, then adds and go in right amount under high velocity agitation Ion 0.5~1.0h of water emulsification, adds 2 parts of chain extending reaction 0.5h of BDO, obtains the acrylic modified waterborne and gathers Urethane, the molecular weight of the Acrylate Modified Aqueous Polyurethane is that the 50000, degree of polymerization is 20.
The preparation of modified vegetable protein glue：The NaOH water that mass fraction is 35% will be added in the mixture of sucrose and urea Solution, the mass ratio of sucrose, urea and the NaOH aqueous solution is 10-20：1：8~15, heating are until sucrose and urea dissolve, then It is warming up to 60~90 DEG C, adds soybean protein, the mass ratio of soybean protein and urea is 5~10:1, and constant temperature stirring is carried out, instead 30min is answered, modified vegetable protein glue is obtained.
Nano-meter SiO_22Preparation：SiO will be added in 0.5mol/L sodium methoxide solution2, solution and SiO2Mass ratio be 3: 1, ultrasonic vibration 5~10 minutes continues to react after 1h, washed with absolute methanol, drying, grinding obtains sodium methoxide surface The SiO2 of processing；The SiO2 that the sodium methoxide is surface-treated is added in epoxy prapanol, and in 105-115 DEG C of temperature, nitrogen is protected Centrifugation after shield, reaction 40-55 minute, and is washed with ethanol, through dry the nanosized SiO_2.
Step 2: by 30 parts of Acrylate Modified Aqueous Polyurethane, 25 parts of modified vegetable protein glue and ROHM AND HAAS RM-12W3 0.2 part of BYK-380N, 0.2 part of irgasfos 168 are added after part mixing, with dispersion machine with 50~1000rpm rotating speed, stirring 30~ 50min, is made base-material；
Step 3: by base-material, 3 parts of BayhydurXP2655, Nano-meter SiO_2s210 parts and the mixing of 0.5 part of polyethylene glycol, with point Machine is dissipated with 50~1000rpm revs/min of rotating speed, is stirred 35~100min, is obtained finished product.
Embodiment 3：The preparation method of environment-friendly high-intensity sealant composition
Step 1: the preparation of Acrylate Modified Aqueous Polyurethane：22 parts of ethyl acetate is added in reaction vessel, 55 are warming up to ~85 DEG C, the mixed of 11 parts of 20 parts of hydroxyethyl methacrylate, 1 part of azodiisobutyronitrile and ethyl acetate is added dropwise at reflux Compound, 1~2h is dripped off, and after 3~5h of insulation, obtains acrylic acid oligomer；By 55 parts of polybutadiene diol and 2,2- dihydroxymethyl 10 parts of propionic acid is cooled to 60~85 DEG C after 90~110 DEG C, 1~2h of vacuum dehydration, adds hexamethylene diisocyanate 50 After 3 parts of part, the acrylic acid oligomer and dibutyl tin laurate, 1.0~3.0h of reaction, 40~50 DEG C, addition are cooled to 20 parts of triethanolamine neutralizes into salt, reacts 0.5~1.0h, is warming up to 60~85 DEG C, adds in 15 parts of progress of trimethylolethane With into salt, react 0.5h~4.0h, make prepolymer formation subnetwork structure, then add under high velocity agitation it is appropriate go from Sub- 0.5~1.0h of water emulsification, adds 5 parts of chain extending reaction 0.5h of BDO, obtains the poly- ammonia of the acrylic modified waterborne Ester, the molecular weight of the Acrylate Modified Aqueous Polyurethane is that the 100000, degree of polymerization is 25.
The preparation of modified vegetable protein glue：The NaOH water that mass fraction is 35% will be added in the mixture of sucrose and urea Solution, the mass ratio of sucrose, urea and the NaOH aqueous solution is 10~20：1：8~15, heating are until sucrose and urea dissolve, so After be warming up to 60~90 DEG C, add soybean protein, the mass ratio of soybean protein and urea is 5~10:1, and carry out constant temperature stirring, 30min is reacted, modified vegetable protein glue is obtained.
Nano-meter SiO_22Preparation：SiO will be added in 0.5mol/L sodium methoxide solution2, solution and SiO2Mass ratio be 3: 1, ultrasonic vibration 5~10 minutes continues to react after 1h, washed with absolute methanol, drying, grinding obtains sodium methoxide surface The SiO2 of processing；The SiO2 that the sodium methoxide is surface-treated is added in epoxy prapanol, and in 105-115 DEG C of temperature, nitrogen is protected Centrifugation after shield, reaction 40-55 minute, and is washed with ethanol, through dry the nanosized SiO_2.
Step 2: 50 parts of Acrylate Modified Aqueous Polyurethane, 40 parts and 8 parts RM-2020 of modified vegetable protein glue are mixed 3 parts of BYK-381,2 parts of irgasfos 168s are added afterwards, with dispersion machine with 50~1000rpm rotating speed, are stirred 30~50min, are made Base-material；
Step 3: by base-material, 7 parts of DesmodurD, Nano-meter SiO_2s220 parts and the mixing of 5 parts of polyacrylic acid, with dispersion machine with 50~1000rpm revs/min of rotating speed, stirs 35~100min, obtains finished product.
Embodiment 4：The preparation method of environment-friendly high-intensity sealant composition
Step 1: the preparation of Acrylate Modified Aqueous Polyurethane：18 parts of ethyl acetate is added in reaction vessel, 55 are warming up to ~85 DEG C, 9 parts of 18 parts of hydroxy propyl methacrylate, 0.4 part of azodiisobutyronitrile and ethyl acetate are added dropwise at reflux Mixture, 1~2h is dripped off, and after 3~5h of insulation, obtains acrylic acid oligomer；By 45 parts of polytetrahydrofuran diol and 2,2- dihydroxy 6 parts of methylpropanoic acid is cooled to 60~85 DEG C after 90~110 DEG C, 1~2h of vacuum dehydration, adds hexamethylene diisocyanate After 1.5 parts of 38 parts, the acrylic acid oligomer and dibutyl tin laurate, 1.0~3.0h of reaction, 40~50 DEG C are cooled to, Add 10 parts of triethanolamine and neutralize into salt, react 0.5~1.0h, be warming up to 60~85 DEG C, add 13 parts of trimethylolethane and enter Row neutralizes into salt, reacts 0.5h~4.0h, makes prepolymer formation subnetwork structure, then adds under high velocity agitation appropriate Deionized water emulsifies 0.5~1.0h, adds 4 parts of chain extending reaction 0.5h of BDO, obtains the acrylic modified waterborne Polyurethane, the molecular weight of the Acrylate Modified Aqueous Polyurethane is that the 100000, degree of polymerization is 25.
The preparation of modified vegetable protein glue：The NaOH water that mass fraction is 35% will be added in the mixture of sucrose and urea Solution, the mass ratio of sucrose, urea and the NaOH aqueous solution is 10~20：1：8~15, heating are until sucrose and urea dissolve, so After be warming up to 60~90 DEG C, add soybean protein, the mass ratio of soybean protein and urea is 5~10:1, and carry out constant temperature stirring, 30min is reacted, modified vegetable protein glue is obtained.
Nano-meter SiO_22Preparation：SiO will be added in 0.5mol/L sodium methoxide solution2, solution and SiO2Mass ratio be 3: 1, ultrasonic vibration 5~10 minutes continues to react after 1h, washed with absolute methanol, drying, grinding obtains sodium methoxide surface The SiO2 of processing；The SiO2 that the sodium methoxide is surface-treated is added in epoxy prapanol, and in 105-115 DEG C of temperature, nitrogen is protected Centrifugation after shield, reaction 40-55 minute, and is washed with ethanol, through dry the nanosized SiO_2.
Step 2: after 35 parts of Acrylate Modified Aqueous Polyurethane, 28 parts and 5 parts RM-8W of modified vegetable protein glue are mixed 0.5 part of BYK-307,0.5 part of antioxidant 1010 are added, with dispersion machine with 50~1000rpm rotating speed, 30~50min, system is stirred Into base-material；
Step 3: by base-material, 6 parts of BayhydurXP2547, Nano-meter SiO_2s212 parts and 1.5 parts of mixing of Sodium Polyacrylate, are used Dispersion machine is stirred 35~100min, is obtained finished product with 50~1000rpm revs/min of rotating speed.
The comparative example of embodiment 5
Equipment and operation be the same as Example 4, unlike the consumption of modified vegetable protein glue is changed to 0, other raw materials and its Consumption is constant, and resulting sealant composition code name is IV.
The comparative example of embodiment 6
Equipment and operation be the same as Example 4, unlike by Nano-meter SiO_22Consumption be changed to 0, other raw materials and its consumption are not Become, resulting sealant composition code name is V.
2nd, the sealant composition for respectively preparing the various embodiments described above carries out performance test and comparison：
(1) method of testing
1st, the general condition of test
The environmental condition of test site
Standard state：23 ± 2 DEG C of temperature, relative humidity 60 ± 5%.
Off-rating：5-35 DEG C of temperature, relative humidity 45-85%.
2nd, sampling method
The sample of upper, middle and lower three is taken to be tested according to the position of kettle per kettle product.
3rd, test piece steel plate
Automobile cold-rolled calendering steel plate, is 25mm × 100mm × 0.1mm per chip size.
4th, key instrument device：WD-5 type electronic universal testers, hot blast constant temperature oven, is beaten constant temperature thermostat, balance Glue device, tensile testing machine.
5th, the measure of hardness
A devices：Shore A durometer, glass plate.
B methods：Fluid sealant is applied on clean glass plate, the size for the film painted is 6mm × 50mm × 50mm. 168h is placed under standard state.Test piece is used as after being fully cured.Hardness is measured with Shore A durometer, each point point of measure is not away from Less than 6mm, measurement point is not less than 10mm apart from sample edge.
C results：Take the arithmetic mean of instantaneous value of 5 measured values.
6th, tensile strength and the measure of elongation
A devices：Tensile testing machine, blanking die, cut-off knife (the dumb-bell shape cut-off knife for meeting 1 type in standard GB/T 528).
B methods：On glass plate (200mm × 300mm), fluid sealant is painted into the thick glued membranes of 2.0 ± 0.3mm, in standard Under state, 168h is placed.It is cut into No. 1 dumb-bell shape cut-off knife and takes dumbbell-shaped test piece.
The position at dumbbell-shaped test piece center is measured with measurer, and marks vertical center line aa ', Zai center both sides apart Vertical graticule bb ' and cc ' is drawn at each 10mm of center line, two clampers of tensile testing machine are clipped on normal line respectively.Open Dynamic tensile testing machine, it is 500 ± 2mm/min to make translational speed.Load when sample extends one times is recorded, when sample is destroyed most Big load and tensile elongation (test position must not have stomata).
C results：As a result the arithmetic mean of instantaneous value of 5 parallel samples is taken.
7th, the measure of tearing strength
A devices：Tensile testing machine, glass plate (200mm × 300mm), cut-off knife (meets nothing as defined in standard GB/T 530 Scarfing square style).
B methods：In coating the thick glued membranes of 2.0 ± 0.3mm on glass plate, 168h is placed in normal conditions.Test piece is used Cut-off knife is cut into lambdoid test piece, accurately measures the thickness of right angle tip position, is accurate to 0.01mm.The clamp of tensile testing machine Two ends are clamped, test piece, peak load when record is broken are broken with 500 ± 2mm/min draw speed.
C results：5 samples are determined, its arithmetic mean of instantaneous value is taken.The each measured value of sample and the difference of average value cannot be greater than 15%.
8th, the measure of water resistance
The thick glued membranes of 2.0 ± 0.3mm are coated on glass plate, after being fully cured, the glass plate for scribbling glued membrane is placed on 100 DEG C water in, record time for coming off of glued membrane.
As a result：5 samples are determined, its arithmetic mean of instantaneous value is taken.The each measured value of sample and the difference of average value cannot be greater than 15%.
(2) test result
The performance test results contrast of each sealant composition of table 2
From the data of upper table, the combination property of environment-friendly high-intensity sealant composition of the invention has significantly Improve；Composition III is compared with composition IV, due to introducing modified vegetable protein glue, its solidfied material compact structure, crosslink density Height, tearing strength and water resistance are greatly improved；Composition III introduces Nano-meter SiO_2 compared with composition V2, SiO2 nanometers The poly- epoxy prapanol of particle surface situ-formed graft, makes it uniformly and stably be dispersed in reaction system, improves the knot between sizing material With joint efforts, improve the combination properties such as elongation, tensile strength, the bin stability of colloid.
Finally it is to be appreciated that foregoing description is only the preferred embodiments of the present invention, those skilled in the art is in the present invention Enlightenment under, on the premise of without prejudice to present inventive concept and claim, expression as multiple types can be made, it is such to become Change and each fall within protection scope of the present invention.

Claims (10)

1. a kind of environment-friendly high-intensity sealant composition, it is characterised in that be made up of the raw material of following mass fraction：
It is 30~50 parts of Acrylate Modified Aqueous Polyurethane, 25~40 parts of modified vegetable protein glue, 3~8 parts of water-based thickener, aqueous 3~7 parts of curing agent, 0.2~3 part of aqueous levelling agent, 0.5~2 part of aqueous antioxidant, Nano-meter SiO_2210~20 parts, aqueous point 0.5~5 part of powder；
The Acrylate Modified Aqueous Polyurethane is made up of the raw material of following mass fraction：
15~20 parts of acrylic monomers, 0.1~1 part of azodiisobutyronitrile, 40~55 parts of dihydric alcohol, 2,2- dihydromethyl propionic acids 4 ~10 parts, 35~50 parts of hexamethylene diisocyanate, 1~3 part of dibutyl tin laurate, 8~20 parts of triethanolamine, three hydroxyls 10~15 parts of methyl ethane, 2~5 parts of BDO, 18~33 parts of ethyl acetate and appropriate deionized water.
2. environment-friendly high-intensity sealant composition according to claim 1, it is characterised in that the mass fraction of the raw material For：35 parts of Acrylate Modified Aqueous Polyurethane, 28 parts of modified vegetable protein glue, 5 parts of water-based thickener, 6 parts of waterborne curing agent, water 0.5 part of levelling agent of property, 0.5 part of aqueous antioxidant, Nano-meter SiO_2212 parts, 1.5 parts of aqueous dispersion；It is described acrylic acid modified Aqueous polyurethane by 18 parts of acrylic monomers, 0.4 part of azodiisobutyronitrile, 45 parts of dihydric alcohol, 6 parts of 2,2- dihydromethyl propionic acids, 38 parts of hexamethylene diisocyanate, 1.5 parts of dibutyl tin laurate, 10 parts of triethanolamine, 13 parts of trimethylolethane, 1, 4 parts of 4- butanediols, 27 parts of ethyl acetate and appropriate deionized water.
3. environment-friendly high-intensity sealant composition according to claim 1 or 2, it is characterised in that：It is described acrylic acid modified Aqueous polyurethane is obtained using following methods：The ethyl acetate of addition 2/3, is warming up to 55~85 DEG C in reaction vessel, in backflow The mixture of acrylic ester monomer, azodiisobutyronitrile and remaining ethyl acetate is added dropwise under state, 1~2h is dripped off, insulation 3 After~5h, acrylic acid oligomer is obtained；By dihydric alcohol and 2,2- dihydromethyl propionic acids are in 90~110 DEG C, 1~2h of vacuum dehydration Afterwards, 60~85 DEG C are cooled to, hexamethylene diisocyanate, the acrylic acid oligomer and dibutyl tin laurate is added, React after 1.0~3.0h, be cooled to 40~50 DEG C, add triethanolamine and neutralize into salt, react 0.5~1.0h, it is warming up to 60~ 85 DEG C, add trimethylolethane and neutralized into salt, react 0.5h~4.0h, make prepolymer formation subnetwork structure, Then appropriate amount of deionized water is added under high velocity agitation and emulsifies 0.5~1.0h, is added BDO chain extending reaction 0.5h, is obtained To the Acrylate Modified Aqueous Polyurethane, the molecular weight of the Acrylate Modified Aqueous Polyurethane is 50000~100000, gathered Right is 20~25.
4. environment-friendly high-intensity sealant composition according to claim 1 or 2, it is characterised in that：The Nano-meter SiO_22Using Following methods are obtained：SiO will be added in 0.5mol/L sodium methoxide solution2, solution and SiO2Mass ratio be 3: 1, ultrasonic vibration 5~10 minutes, continue to react after 1h, washed with absolute methanol, drying, grinding obtains sodium methoxide surface treatment SiO2；The SiO2 that the sodium methoxide is surface-treated is added in epoxy prapanol, in 105-115 DEG C of temperature, nitrogen protection, reaction Centrifuge, and washed with ethanol after 40-55 minutes, through dry the nanosized SiO_2.
5. environment-friendly high-intensity sealant composition according to claim 1 or 2, it is characterised in that：The improved plant egg White glue is obtained using following methods：The NaOH aqueous solution that mass fraction is 35%, sugarcane will be added in the mixture of sucrose and urea The mass ratio of sugar, urea and the NaOH aqueous solution is 10-20：1：8~15, heating are until sucrose and urea dissolving, are then warming up to 60~90 DEG C, soybean protein is added, the mass ratio of soybean protein and urea is 5~10:1, and constant temperature stirring is carried out, react 30min, obtains modified vegetable protein glue.
6. environment-friendly high-intensity sealant composition according to claim 1 or 2, it is characterised in that：The acrylic monomers For one kind in hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate；The dihydric alcohol is polyadipate One kind in glycol ester glycol, polybutadiene diol or polytetrahydrofuran diol.
7. environment-friendly high-intensity sealant composition according to claim 1, it is characterised in that：The water-based thickener is water The one kind of property thickener in ROHM AND HAAS RM-12W, RM-2020 or RM-8W；Aqueous levelling agent is BYK-380N, BYK- One kind in 381 or BYK-307.
8. environment-friendly high-intensity sealant composition according to claim 3, it is characterised in that：Waterborne curing agent is One kind in DesmodurD, BayhydurXP2655 or BayhydurXP2547.
9. environment-friendly high-intensity sealant composition according to claim 4, it is characterised in that：Aqueous antioxidant is antioxygen Agent 168 or antioxidant 1010；Aqueous dispersion is polyethylene glycol, polyacrylic acid or Sodium Polyacrylate.
10. the preparation method of the environment-friendly high-intensity sealant composition according to claim any one of 1-9, it is characterised in that Carry out according to the following steps：
Step 1: preparing Acrylate Modified Aqueous Polyurethane, modified vegetable protein glue and Nano-meter SiO_2 respectively2；
Step 2: adding aqueous flow after Acrylate Modified Aqueous Polyurethane, modified vegetable protein glue and water-based thickener are mixed Flat agent, aqueous antioxidant, with dispersion machine with 50~1000rpm rotating speed, stir 30~50min, base-material are made；
Step 3: by base-material, waterborne curing agent, Nano-meter SiO_22With aqueous dispersion mixing, with dispersion machine with 50~1000rpm turn/ The rotating speed divided, stirs 35~100min, obtains finished product.
CN201710312112.4A 2017-05-05 2017-05-05 Environment-friendly high-intensity sealant composition and preparation method thereof Withdrawn CN107057629A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710312112.4A CN107057629A (en) 2017-05-05 2017-05-05 Environment-friendly high-intensity sealant composition and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710312112.4A CN107057629A (en) 2017-05-05 2017-05-05 Environment-friendly high-intensity sealant composition and preparation method thereof

Publications (1)

Publication Number Publication Date
CN107057629A true CN107057629A (en) 2017-08-18

Family

ID=59596692

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710312112.4A Withdrawn CN107057629A (en) 2017-05-05 2017-05-05 Environment-friendly high-intensity sealant composition and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107057629A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108118563A (en) * 2017-11-17 2018-06-05 南宁科天水性科技有限责任公司 A kind of formaldehydeless Mould Resistant MDF of compound adhesive and its manufacturing process
CN109294510A (en) * 2018-08-30 2019-02-01 合肥瑞来宝电源技术有限公司 A kind of sealant for dipulse oxidation power supply adapter
CN110669433A (en) * 2018-07-02 2020-01-10 深圳市裕展精密科技有限公司 Sealing glue and workpiece gap vacuum sealing method using same
CN112126399A (en) * 2020-09-28 2020-12-25 浙江伟涛包装材料有限公司 Reactive polyurethane adhesive material for textiles and preparation process thereof
CN113755002A (en) * 2021-09-22 2021-12-07 莆田市涵江怡丰鞋业有限公司 Preparation method of washable women's shoes
CN118580750A (en) * 2024-08-01 2024-09-03 山东应强新材料科技有限公司 Wear-resistant weather-resistant nano paint and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108118563A (en) * 2017-11-17 2018-06-05 南宁科天水性科技有限责任公司 A kind of formaldehydeless Mould Resistant MDF of compound adhesive and its manufacturing process
CN110669433A (en) * 2018-07-02 2020-01-10 深圳市裕展精密科技有限公司 Sealing glue and workpiece gap vacuum sealing method using same
CN109294510A (en) * 2018-08-30 2019-02-01 合肥瑞来宝电源技术有限公司 A kind of sealant for dipulse oxidation power supply adapter
CN112126399A (en) * 2020-09-28 2020-12-25 浙江伟涛包装材料有限公司 Reactive polyurethane adhesive material for textiles and preparation process thereof
CN113755002A (en) * 2021-09-22 2021-12-07 莆田市涵江怡丰鞋业有限公司 Preparation method of washable women's shoes
CN118580750A (en) * 2024-08-01 2024-09-03 山东应强新材料科技有限公司 Wear-resistant weather-resistant nano paint and preparation method thereof

Similar Documents

Publication Publication Date Title
CN107057629A (en) Environment-friendly high-intensity sealant composition and preparation method thereof
EP0932652B1 (en) Use of polymer dispersions as binding agents for sealing compounds and coating compounds
CN104099046B (en) Silane primer for improving the adhesiveness of adhesive tape on hydrophilic surfaces, especially on the glass surface
CN109054570B (en) Environment-friendly high-strength elastic coating and preparation method thereof
CN103946323B (en) The acrylic latex of hydroxyethyl cellulose grafting
CN104099047B (en) For improving black silane primer of the adhesive tape to the cohesive of glass surface
Wang et al. Combinations of soy protein and polyacrylate emulsions as wood adhesives
Parvate et al. Insights into the preparation of water-based acrylic interior decorative paint: tuning binder’s properties by self-crosslinking of allyl acetoacetate-hexamethylenediamine
EP0778870B1 (en) Physically and/or chemically setting binders
CN110655620B (en) Aqueous hyperbranched polyacrylate emulsion, preparation method and application thereof
CN108690172B (en) Acrylic resin polymer polyether polyol and preparation method thereof
CN109593400B (en) Application of nano-scale aqueous acrylic copolyester with narrow molecular weight distribution
CN109485797A (en) A kind of resin emulsion and preparation method thereof
CN117070149B (en) Water-based EAU plastic track adhesive and preparation method thereof
CN108424731A (en) A kind of preparation method of pressure sensitive adhesive
Fotoohi et al. Investigation of the mechanical and thermal properties of reactive AAEM-co-MMA adhesive
CN109180885A (en) A kind of preparation method of water polyacrylic acid lotion
CN103339215B (en) Pressure sensitive adhesive composition for optical members, pressure sensitive adhesive, adhesion type optical component and image display device
CN107459618A (en) A kind of preparation method of woodcare paint water-based acrylic resin and the product of acquisition
KR101104149B1 (en) Method for manufacturing floor material comprising ethylene vinyl acetate and hydroxyacrylate and floor material made thereby
KR102705727B1 (en) Formaldehyde-free adhesive composition
JPH07310041A (en) Pigment dispersion paste and water-based coating composition containing the paste
CN112759715B (en) High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof
KR101240740B1 (en) Acrylic polymeric plasticizer and plastisol comprising the same
CN115216257B (en) Water-based acrylate composite adhesive and preparation method thereof

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
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20170818