[go: up one dir, main page]

CN108084945A - A kind of polyaminoester emulsion adhesive containing nano organic montmorillonite - Google Patents

A kind of polyaminoester emulsion adhesive containing nano organic montmorillonite Download PDF

Info

Publication number
CN108084945A
CN108084945A CN201711265922.5A CN201711265922A CN108084945A CN 108084945 A CN108084945 A CN 108084945A CN 201711265922 A CN201711265922 A CN 201711265922A CN 108084945 A CN108084945 A CN 108084945A
Authority
CN
China
Prior art keywords
mol
nano organic
emulsion adhesive
containing nano
organic montmorillonite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201711265922.5A
Other languages
Chinese (zh)
Other versions
CN108084945B (en
Inventor
丁逸峰
杭祖圣
王经逸
陈志峰
张国盛
周胜
周胜一
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 Guanghui Adhesive Technology Co Ltd
Original Assignee
Jiangsu Guanghui Adhesive Technology 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 Guanghui Adhesive Technology Co Ltd filed Critical Jiangsu Guanghui Adhesive Technology Co Ltd
Priority to CN201711265922.5A priority Critical patent/CN108084945B/en
Publication of CN108084945A publication Critical patent/CN108084945A/en
Application granted granted Critical
Publication of CN108084945B publication Critical patent/CN108084945B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/286—Oximes
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—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
    • C08G18/65—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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

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)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A kind of polyaminoester emulsion adhesive containing nano organic montmorillonite, end-capping reagent is done using nano organic montmorillonite, it plays reinforcement and induces the effect of polyurethane molecular chain crystallization, improve the initial bonding strength of adhesive, and using acetophenone oxime blocked isocyanate for it is potential can reactive group, it can further be reacted with the active group of bonding interface, improve the adhesive strength of adhesive.Adhesive for polyurethane obtained has the excellent properties such as initial bonding strength is high, crystallization rate is fast, crystallinity is high and adhesion strength is high.

Description

A kind of polyaminoester emulsion adhesive containing nano organic montmorillonite
Technical field
The present invention relates to adhesive for polyurethane field, more particularly to high initial bonding strength, crystallization rate is fast and crystallinity High High Performance Water Borne Polyurethane Emulsion adhesive.
Background technology
Aqueous Polyurethane Adhesives are increasingly becoming because it has many advantages, such as that pollution-free, easy transport is friendly with working environment The mainstream in adhesive market.But Aqueous Polyurethane Adhesives are there are slow drying speed, initial bonding strength is small and poor water resistance etc. lacks Point, particularly low initial bonding strength, has seriously affected the convenience for construction of adhesive for polyurethane, has limited Aqueous Polyurethane Adhesives Further development.
One of an important factor for polyurethane molecular chain crystallization rate is decision polyurethane initial bonding strength size.The crystallization of strand Speed is fast, and cohesive force increased dramatically polyurethane molecular chain in a short time, and initial bonding strength effectively improves.Moreover, it is high Crystallization rate can also improve the final adhesive strength of adhesive.Therefore it is to solve water simultaneously to improve polyurethane molecular chain crystallization rate Property polyurethane initial bonding strength and final adhesion strength one of effective scheme and one of research emphasis of aqueous polyurethane at present.
Nano filling is one of important component in high molecular material, can promote the crystal property of high molecular material, The intensity of high molecular material is improved, cost is reduced, improves the competitiveness of product.But when Nano filling is in water-borne polyurethane bond In application, there are serious agglomeration traits and the thing followed to settle in glutinous agent, can reduce instead product adhesion strength and Its workability.Therefore, reunion of the Nano filling in aqueous polyurethane how is solved, and improves Nano filling to polyurethane point The crystallization rate of subchain is the research direction in current Nano filling/adhesive for polyurethane field.But at present, both at home and abroad to water Property polyurethane research be concentrated mainly on new material utilization, such as crosslinking agent design with select, modified additive selection etc., to receiving Rice filler promotes the research of crystalline polyurethane speed to be rarely reported.
Nano imvite is a kind of inorganic material with special layer structure, there is high specific surface area, is possessed very strong Adsorption capacity, it is compound to reach good nanoscale with polyurethane molecular, while aqueous poly- ammonia cruel intensity is improved, The cruel original workability of aqueous poly- ammonia will not be damaged.
The content of the invention
Goal of the invention：The purpose of the invention is to overcome deficiency of the prior art, a kind of organic illiteracy containing nanometer is provided Take off the highly crystalline speed of soil, the aqueous polyurethane emulsion adhesive that initial bonding strength is big and adhesion strength is high.
Technical solution：In order to solve the above-mentioned technical problem, it is of the present invention a kind of containing the aqueous of nano organic montmorillonite Polyaminoester emulsion adhesive, it comprises the following steps,
Step 1：Under nitrogen protection, the polyadipate hexylene glycol ester dihydric alcohol of 1 mol and the toluene diisocyanate of 2 mol are added in Acid esters stirs 2 ~ 3 h at 60 ~ 70 DEG C of temperature, adds in 200g nano organic montmorillonites, adds in the di lauric dibutyl of 2wt% Tin continues 1 ~ 2 h of stirring at 80 ~ 90 DEG C of temperature, then reduces temperature, adds in 1 mol sealers, continues to stir 2 h, obtain pre- Aggressiveness A, wherein, 2wt% is on the basis of the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI)；
Step 2：Under the protection of dry nitrogen, the polyadipate hexylene glycol that 10 mol molecular weight are 4000 is added in a kettle Ester dihydric alcohol and 20 mol toluene di-isocyanate(TDI)s heat 60 DEG C, stir 2h, add in the dibutyl tin laurate of 2 wt%, after 2 h of continuous stirring, obtain performed polymer B, wherein, 2wt% is with the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) On the basis of；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added in, heating stirring is eventually adding 2 Mol trimethylolpropanes and 1 mol diglycols, with acetone regulation system viscosity to 2000 ~ 4000mPas, with 40 The rate of r/min stirs 3 h, 50 DEG C is cooled to, according to system and performed polymer A mass ratioes 1:It is obtained in 1 addition step 1 Performed polymer A, 40 r/min continue to stir 1 h, obtain polyurethane solutions；
Step 4：Under 50 r/min stirrings, the polyurethane solutions that step 3 is obtained are with 1:0.5 mass ratio adds in deionized water In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive containing nano organic montmorillonite.
Montmorillonite in step 1 is sodium-based montmorillonite, aspect ratio 30:1, specific surface area 600m2/ g, aperture are 30nm, surface hydroxyl number are 5.0 OH/nm2。
The structural formula of the performed polymer A obtained in step 1 is as follows：
。
In step 1,50 DEG C are reduced the temperature to, the sealer of addition is acetophenone oxime.
In step 3, after adding in dihydromethyl propionic acid, 1 ~ 2 h is stirred at 60 ~ 70 DEG C.
Advantageous effect：Compared with prior art, the present invention its remarkable advantage is：
（1）In polyaminoester emulsion adhesive, by using the polyester polyol of specified molecular weight and organic illiteracy of specific structure De- soil matches so that organo montmorillonite is dispersed stably in polyaminoester emulsion adhesive, has realized as end-capping reagent Machine montmorillonite improves the initial bonding strength and adhesion strength of adhesive to the nanometer supplement effect of adhesive for polyurethane；
（2）By organo montmorillonite to the induction crystallization of polyurethane molecular chain, the knot of adhesive for polyurethane is effectively increased Brilliant speed and crystallinity further increase the initial bonding strength adhesion strength of adhesive, improve the heat resistance of adhesive, obtained glue Glutinous agent has convenience for construction and good using effect.
Description of the drawings
Fig. 1 is the preparation technology flow chart of the polyaminoester emulsion adhesive containing nano organic montmorillonite.
Specific embodiment
With reference to embodiment and comparative example, the present invention is further illustrated.
Embodiment 1：
Step 1：Under nitrogen protection, the polyadipate hexylene glycol ester dihydric alcohol of 1 mol and the toluene diisocyanate of 2 mol are added in Acid esters stirs evenly, and 3 h are reacted under temperature 60 C, adds in 200g nano organic montmorillonites, adds in the tin dilaurate of 2 wt% Dibutyl tin continues at 90 DEG C of temperature to stir 1h, then reduces the temperature to 50 DEG C, adds in the acetophenone oxime of 1 mol, continue to stir 2 h obtain performed polymer A, wherein, 2wt% is for base with the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) It is accurate；
Step 2：Under the protection of dry nitrogen, the polyadipate hexylene glycol that 10 mol molecular weight are 4000 is added in a kettle Ester dihydric alcohol and 20 mol toluene di-isocyanate(TDI)s heat 60 DEG C, stir 2h, add in the dibutyl tin laurate of 2wt%, after 2 h of continuous stirring, obtain performed polymer B, wherein, 2wt% is with the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) On the basis of；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added in, 1 h are stirred at 70 DEG C, most After add in 2 mol trimethylolpropanes and 1 mol diglycols, with acetone regulation system viscosity to 2000mPas, with The rate of 40 r/min stirs 3 h, 50 DEG C is cooled to, according to system and performed polymer A mass ratioes 1:It is obtained in 1 addition step 1 Performed polymer A, 40 r/min continue to stir 1 h, obtain polyurethane solutions；
Step 4：Under 50 r/min stirrings, the polyurethane solutions that step 3 is obtained are with 1:0.5 mass ratio adds in deionized water In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive containing nano organic montmorillonite.
Adhesive performance is as shown in table 1.
Embodiment 2：
The method that embodiment 1 is repeated by each component content specified, but the first segment temperature in step 1 is 70 DEG C, stirring Time is 2 h；Second segment temperature is 80 DEG C, stirs 2 h；First segment temperature in step 3 is 60 DEG C, 2 h of mixing time, is glued Degree is adjusted to 4000mPas.
Adhesive performance is as shown in table 1.
Comparative example 1：
The method of embodiment 1 is repeated by each component content specified, but nano organic montmorillonite is not added in step 1.
Adhesive performance is as shown in table 1.
Comparative example 2：
The method that embodiment 1 is repeated by each component content specified, but the structure of the performed polymer A of the addition in step 3 is
。
Adhesive performance is as shown in table 1.
Comparative example 3：
The method that embodiment 1 is repeated by each component content specified, but the structure of the performed polymer A of the addition in step 3 For：
。
Adhesive performance is as shown in table 1.
Comparative example 4：
The method that embodiment 1 is repeated by each component content specified, but without reducing temperature in step 1.
Adhesive performance is as shown in table 1.
Comparative example 5：
The method that embodiment 1 is repeated by each component content specified, but the sealer added in step 1 is ethylene glycol ethyl ether.
Adhesive performance is as shown in table 1.
From upper table 1, polyaminoester emulsion adhesive of the invention possesses that high initial bonding strength, crystallization rate be fast, crystallinity It is high.
Polyaminoester emulsion adhesive obtained containing nano organic montmorillonite is tested for the property.
（1）Initial bonding strength：
Using GB/T2790 adhesive 180 degree peeling strength test methods.Flexibility is bent by one end not being glued of viscous test piece 180 °, rigidity is clamped in by viscous test piece on fixed collet, and flexible test piece is clamped on another collet.Pay attention to making collet Between sample be accurately positioned, to be distributed on the width of sample with ensureing applied tension uniform.It machines, makes collet up and down It is separated with constant rate.The rate of departure of collet is 100 ± 10mm/min.Write down the rate of departure of collet and when collet separates Suffered power during operation, until at least splicing length of 125 mm is stripped.Initial bonding strength is the bigger the better.Note：It was removing Cheng Zhong, the flex section of stripping are rubbed on part is glued sometimes, and in order to reduce friction, appropriate lubricant can be used, Such as glycerine or suds, as long as it does not influence adherend.
（2）Adhesion strength：
Adhesive obtained is tested with reference to GB 7124-86 adhesive tensile shear strength assay methods.Use gage measuring The length and width of sample faying surface, is accurate to 0.05mm.Sample is symmetrically clipped in upper and lower clamper, holding position is to taking It connects the distance at end and starts testing machine for 50 ± 1 mm., in 5 ± 1 mm/min, loaded with stabilized speed.Record sample shear is cut through Bad peak load.Glue is recorded by the type (cohesional failure, adhesive failure, metal failure) destroyed.
（3）Thermal stability：
Heat stability testing is carried out to Aqueous Polyurethane Adhesives obtained using TG methods of testing, TG curves are made, from curve Obtain temperature of the thermal weight loss corresponding to 5%T 5%Wherein, weightless temperature is higher, illustrates that the stability of adhesive is better.
（4）Crystal property：
The area that DSC curve and baseline surround is converted into heat enthalpy value by the test data based on DSC（Crystallization enthalpy Δ Hc）Side by side The temperature of peak crystallization is denoted as crystallization temperature T by tablec, the half-peak breadth FWHH of peak crystallization is denoted as crystallization relative velocity.Tc is bigger, Illustrate that sample is easier to crystallize, FWHH is smaller, illustrates that opposite crystalline rate is faster, Δ HcIt is bigger, illustrate that crystallinity is higher.

Claims (5)

1. a kind of polyaminoester emulsion adhesive containing nano organic montmorillonite, it is characterised in that：It comprises the following steps, step One：Under nitrogen protection, the polyadipate hexylene glycol ester dihydric alcohol of 1 mol and the toluene di-isocyanate(TDI) of 2 mol are added in, in temperature 2 ~ 3 h are stirred at 60 ~ 70 DEG C of degree, add in 200g nano organic montmorillonites, add in the dibutyl tin laurate of 2 wt%, temperature Continue 1 ~ 2 h of stirring at 80 ~ 90 DEG C, then reduce temperature, add in 1 mol sealers, continue to stir 2 h, obtain performed polymer A, Wherein, 2wt% is on the basis of the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI)；
Step 2：Under the protection of dry nitrogen, the polyadipate hexylene glycol that 10 mol molecular weight are 4000 is added in a kettle Ester dihydric alcohol and 20 mol toluene di-isocyanate(TDI)s heat 60 DEG C, stir 2h, add in the dibutyl tin laurate of 2 wt%, after 2 h of continuous stirring, obtain performed polymer B, wherein, 2wt% is with the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) On the basis of；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added in, heating stirring is eventually adding 2 Mol trimethylolpropanes and 1 mol diglycols, with acetone regulation system viscosity to 2000 ~ 4000mPas, with 40 The rate of r/min stirs 3 h, 50 DEG C is cooled to, according to system and performed polymer A mass ratioes 1:It is obtained in 1 addition step 1 pre- Aggressiveness A, 40 r/min continue to stir 1 h, obtain polyurethane solutions；
Step 4：Under 50 r/min stirrings, the polyurethane solutions that step 3 is obtained are with 1:0.5 mass ratio adds in deionized water In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive containing nano organic montmorillonite.
2. the polyaminoester emulsion adhesive according to claim 1 containing nano organic montmorillonite, it is characterised in that：It covers de- Soil is sodium-based montmorillonite, aspect ratio 30:1, specific surface area 600m2/ g, aperture 30nm, surface hydroxyl number are 5.0 OH/ nm2。
3. the polyaminoester emulsion adhesive according to claim 1 containing nano organic montmorillonite, it is characterised in that：Step 1 In the obtained structural formula of performed polymer A it is as follows：
。
4. the polyaminoester emulsion adhesive according to claim 1 containing nano organic montmorillonite, it is characterised in that：Step 1 In, 50 DEG C are reduced the temperature to, the sealer of addition is acetophenone oxime.
5. the polyaminoester emulsion adhesive according to claim 1 containing nano organic montmorillonite, it is characterised in that：Step 3 In, after adding in dihydromethyl propionic acid, 1 ~ 2 h is stirred at 60 ~ 70 DEG C.
CN201711265922.5A 2017-12-05 2017-12-05 Polyurethane emulsion adhesive containing nano organic montmorillonite Active CN108084945B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711265922.5A CN108084945B (en) 2017-12-05 2017-12-05 Polyurethane emulsion adhesive containing nano organic montmorillonite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711265922.5A CN108084945B (en) 2017-12-05 2017-12-05 Polyurethane emulsion adhesive containing nano organic montmorillonite

Publications (2)

Publication Number Publication Date
CN108084945A true CN108084945A (en) 2018-05-29
CN108084945B CN108084945B (en) 2020-08-07

Family

ID=62173695

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711265922.5A Active CN108084945B (en) 2017-12-05 2017-12-05 Polyurethane emulsion adhesive containing nano organic montmorillonite

Country Status (1)

Country Link
CN (1) CN108084945B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114214032A (en) * 2021-12-30 2022-03-22 英德市雅凯高新材料有限公司 Nanoscale wear-resistant weather-resistant waterproof adhesive and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942893A (en) * 2012-12-04 2013-02-27 苏州井上高分子新材料有限公司 Nano modified polyurethane adhesive and preparation method thereof
CN105778032A (en) * 2016-04-11 2016-07-20 浙江传化股份有限公司 Crystallization accelerating agent for crystallization/semi-crystallization polyurethane and preparing method and application thereof
US20170158838A1 (en) * 2014-06-24 2017-06-08 Byk-Chemie, Gmbh Polyurethane two-component or multi-component systems having a latent thickening tendency

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942893A (en) * 2012-12-04 2013-02-27 苏州井上高分子新材料有限公司 Nano modified polyurethane adhesive and preparation method thereof
US20170158838A1 (en) * 2014-06-24 2017-06-08 Byk-Chemie, Gmbh Polyurethane two-component or multi-component systems having a latent thickening tendency
CN105778032A (en) * 2016-04-11 2016-07-20 浙江传化股份有限公司 Crystallization accelerating agent for crystallization/semi-crystallization polyurethane and preparing method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
实用化学品配方手册编委会: "《实用化学品配方手册》", 31 March 2009, 四川科学技术出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114214032A (en) * 2021-12-30 2022-03-22 英德市雅凯高新材料有限公司 Nanoscale wear-resistant weather-resistant waterproof adhesive and preparation method thereof

Also Published As

Publication number Publication date
CN108084945B (en) 2020-08-07

Similar Documents

Publication Publication Date Title
CN107987777B (en) A kind of polyurethane emulsion adhesive containing nanocellulose whiskers and preparation method thereof
CN102010687B (en) Fast curing reaction type hot melt adhesive and preparation method thereof
KR102161969B1 (en) Surface protection film, method for manufacturing surface protection film, and optical member
US9659763B2 (en) Epoxy-based composition, adhesive film, dicing die-bonding film and semiconductor device
JP6012385B2 (en) Water-dispersed acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet
EP2275508A1 (en) Aqueous dispersion type acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape
CN107987776A (en) A kind of polyaminoester emulsion adhesive containing nano-attapulgite
CN102676062A (en) Low-temperature resistant rosin thickening resin, preparation method and usage thereof
KR102105211B1 (en) Aqueous dispersion type acrylic pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and optical member for repeeling
JP2017119753A (en) Surface protective film, method for manufacturing surface protective film, and optical member
CN108300401A (en) A kind of aqueous polyurethane emulsion adhesive and preparation method thereof of the multi-walled carbon nanotube containing acidification
US20120276284A1 (en) Method for preparing functional multilayer anisotropic conductive adhesive film
CN108084945A (en) A kind of polyaminoester emulsion adhesive containing nano organic montmorillonite
CN112143437A (en) Lithium battery aluminum plastic film outer layer adhesive resin and preparation and application thereof
TW202104491A (en) Surface protecting film and optical component
CN108300402A (en) A kind of aqueous polyurethane emulsion adhesive of nano-silica-containing and preparation method thereof
CN108034400A (en) A kind of polyaminoester emulsion adhesive containing superfine talcum powder
US5518571A (en) Use of polyester resins as hot-melt adhesives
CN112341967A (en) Pressure-sensitive adhesive applied to polyvinyl chloride film and preparation method and application thereof
WO2022210638A1 (en) Pressure-sensitive adhesive tape
CN114774057B (en) High-adhesive-strength impact-resistant black shading moisture-cured polyurethane hot melt adhesive and preparation method thereof
JP2020522898A (en) Dicing die bonding film
CN108424731A (en) A kind of preparation method of pressure sensitive adhesive
CN109762508B (en) Water-based hot melt adhesive with adjustable melting point and preparation method thereof
CN116355557A (en) A kind of low-temperature hot-melt 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
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A polyurethane lotion adhesive containing nano organic montmorillonite

Granted publication date: 20200807

Pledgee: Bank of Jiangsu Limited by Share Ltd. Wuxi branch

Pledgor: JIANGSU GUANGHUI ADHESIVE TECHNOLOGY Co.,Ltd.

Registration number: Y2024980013080