CN108300402A - A kind of aqueous polyurethane emulsion adhesive of nano-silica-containing and preparation method thereof - Google Patents
A kind of aqueous polyurethane emulsion adhesive of nano-silica-containing and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/42—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
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A kind of aqueous polyurethane emulsion adhesive of nano-silica-containing and preparation method thereof, it is characterized in that doing end-capping reagent using nano silicon dioxide, 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 be 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, heat resistance is high and adhesion strength is high.
Description
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 and preparation method thereof.
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, especially low initial bonding strength have seriously affected the convenience for construction of adhesive for polyurethane, have 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, 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 at present aqueous polyurethane one of research emphasis.
Nano filling is one of the important component in high molecular material, can promote the crystal property of high molecular material,
The intensity for improving high molecular material, reduces cost, 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 currently, 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.
Invention content
The purpose of the present invention is to provide a kind of highly crystalline speed of nano-silica-containing, initial bonding strength is big and adhesion strength
High aqueous polyurethane emulsion adhesive and preparation method thereof.
Realize that the technical solution of the object of the invention is：
A kind of preparation method of the aqueous polyurethane emulsion adhesive of nano-silica-containing, includes the following steps：
Step 1：Under nitrogen protection, the toluene diisocyanate of polyadipate the hexylene glycol ester dihydric alcohol and 2 mol of 1 mol is added
Acid esters stirs 2 ~ 3 h at 60 ~ 70 DEG C of temperature, and 150 g nano silicon dioxides are added, and the di lauric dibutyl of 1 wt% is added
Tin continues 1 ~ 2 h of stirring at 80 ~ 90 DEG C of temperature, then reduces temperature, and 1 mol sealers are added, and continues to stir 2 h, obtain pre-
Aggressiveness A, wherein 1 wt% 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, and the dibutyl tin laurate of 1 wt% is added, after
2 h of continuous stirring, obtain performed polymer B, wherein 1 wt% be with polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) it
With on the basis of；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added, 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 the step of 1 addition one
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:Deionized water is added in 0.5 mass ratio
In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive of nano-silica-containing.
The specific surface area of nano silicon dioxide in the step 1 is 800 m2/ g, surface hydroxyl number are 5.0 OH/nm2。
The structural formula of the performed polymer A obtained in the step 1 is as follows：
In the step 1,50 DEG C are reduced the temperature to, the sealer of addition is acetophenone oxime.
In the step 3, the dihydromethyl propionic acid of addition is 5 mol, and 1 ~ 2 h is stirred at 60 ~ 70 DEG C；Three be added
Hydroxymethyl-propane is 2 mol, and the diglycol of addition is 1 mol.
The invention also discloses the polyaminoester emulsion adhesives for the nano-silica-containing being prepared using the above method.
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 the nanometer two of specific structure
Silica matches so that nano silicon dioxide is dispersed stably in as end-capping reagent in polyaminoester emulsion adhesive, is realized
Nanometer supplement effect of the nano silicon dioxide to adhesive for polyurethane, improves the initial bonding strength and adhesion strength of adhesive；
（2）By nano silicon dioxide to the induction crystallization of polyurethane molecular chain, adhesive for polyurethane is effectively increased
Crystallization rate and crystallinity further increase the initial bonding strength adhesion strength of adhesive, improve the heat resistance of adhesive, obtain
Adhesive has convenience for construction and good using effect.
Description of the drawings
Fig. 1 is the preparation technology flow chart of 1 polyaminoester emulsion adhesive of the embodiment of the present invention.
Specific implementation mode
A kind of preparation method of the polyaminoester emulsion adhesive of nano-silica-containing, includes the following steps：
Step 1：Under nitrogen protection, the toluene diisocyanate of polyadipate the hexylene glycol ester dihydric alcohol and 2 mol of 1 mol is added
Acid esters stirs 2 ~ 3 h at 60 ~ 70 DEG C of temperature, and 150 g nano silicon dioxides are added, and the di lauric dibutyl of 1 wt% is added
Tin continues 1 ~ 2 h of stirring at 80 ~ 90 DEG C of temperature, then reduces temperature, and 1 mol sealers are added, and continues to stir 2 h, obtain pre-
Aggressiveness A, wherein 1 wt% 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, and the dibutyl tin laurate of 1 wt% is added, after
2 h of continuous stirring, obtain performed polymer B, wherein 1 wt% be with polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) it
With on the basis of；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added, 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 the step of 1 addition one
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:Deionized water is added in 0.5 mass ratio
In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive of nano-silica-containing.
The aqueous polyurethane emulsion adhesive of nano-silica-containing obtained is tested for the property.
（1）Initial bonding strength：
Using GB/T2790 adhesive 180 degree peeling strength test methods.Flexibility is glued to one end bending of test piece not being glued
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 detached with constant rate.The rate of departure of collet is 100 ± 10mm/min.Write down the rate of departure of collet and when collet detaches
Suffered power when operation, until at least splicing length of 125 mm is stripped.Initial bonding strength is the bigger the better；
Note：In stripping process, the flex section of stripping is rubbed on being glued part sometimes, in order to reduce friction, can be made
With lubricant appropriate, such as glycerine or suds, as long as it does not influence adherend.
（2）Crystal property：
Test data based on DSC converts the area that DSC curve and baseline surround to heat enthalpy value（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.
（3）Adhesion strength：
Adhesive obtained is tested with reference to 7124 adhesive tensile shear strength assay methods of GB.It is tried with 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 to overlap joint
The distance at end is 50 ± 1 mm.Testing machine is started, in 5 ± 1 mm/min, is loaded with stabilized speed.Peel strength it is more big more
It is good.
（4）Thermal stability：
Heat stability testing is carried out to Aqueous Polyurethane Adhesives obtained using TG methods of testing, TG curves are made, from curve
It is the temperature corresponding to 5% to obtain thermal weight lossT 5%Wherein, weightless temperature is higher, illustrates that the stability of adhesive is better.
Below by embodiment and comparative example, the invention will be further described.
Embodiment 1
Step 1：Under nitrogen protection, the toluene diisocyanate of polyadipate the hexylene glycol ester dihydric alcohol and 2 mol of 1 mol is added
Acid esters stirs evenly, and 3 h are reacted under temperature 60 C, and 150 g specific surface areas, 800 m is added2/ g, several 5.0 OH/ of surface hydroxyl
nm2Nano silicon dioxide, the dibutyl tin laurate of 1 wt% is added, continues at 90 DEG C of temperature to stir 1h, then reduces temperature
Spend to 50 DEG C, be added 1 mol acetophenone oxime, continue stir 2 h, obtain performed polymer A, wherein 1 wt% be with polyadipate
On the basis of the sum of diol ester dihydric alcohol and toluene di-isocyanate(TDI)；
Step 2：Polyadipate hexylene glycol ester dihydric alcohol and the 20 mol first that 10 mol molecular weight are 4000 are added in a kettle
Phenylene diisocyanate heats 50 DEG C, stirs 2h, and the dibutyl tin laurate of 1 wt% is added, and continues to stir 2 h, obtains pre-polymerization
Body B, wherein 1 wt% is on the basis of the sum of polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI)；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added, 1 h are stirred at 70 DEG C, most
After 2 mol trimethylolpropanes and 1 mol diglycols are added, 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:Deionized water is added in 0.5 mass ratio
In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive of nano-silica-containing,
In, the preparation flow figure of aqueous polyurethane emulsion adhesive is as shown in Figure 1.Adhesive performance is as shown in table 1.
Embodiment 2
The method for repeating to implement 1 by specified each component content, but the first segment temperature in step 1 is 70 DEG C, when stirring
Between be 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, system
Viscosity is 4000mPas.Adhesive performance is as shown in table 1.
Comparative example 1
By the method that specified each component content repeats implementation 1, but nano silicon dioxide is not added in step 1.Adhesive
Performance is as shown in table 1.
Comparative example 2
By the method that specified each component content repeats implementation 1, but traditional silicon dioxide is added in step 1.Adhesive
It can be as shown in table 1.
Comparative example 3
By the method that specified each component content repeats implementation 1, 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 4
By the method that specified each component content repeats implementation 1, 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 5
By the method that specified each component content repeats implementation 1, but without reducing temperature in step 1.Adhesive performance such as table
Shown in 1.
Comparative example 6
By the method that specified each component content repeats implementation 1, but the sealer being added in step 1 is ethylene glycol ethyl ether.Glue
Glutinous agent performance is as shown in table 1.
Table 1
By upper table 1 it is found that the polyaminoester emulsion adhesive of the present invention, has that high initial bonding strength, crystallization rate are fast, crystallinity is high.
Claims (6)
1. a kind of preparation method of the aqueous polyurethane emulsion adhesive of nano-silica-containing, it is characterised in that including following step
Suddenly：
Step 1：Under nitrogen protection, the toluene diisocyanate of polyadipate the hexylene glycol ester dihydric alcohol and 2 mol of 1 mol is added
Acid esters stirs 2 ~ 3 h at 60 ~ 70 DEG C of temperature, and 150 g nano silicon dioxides are added, and the di lauric dibutyl of 1 wt% is added
Tin continues 1 ~ 2 h of stirring at 80 ~ 90 DEG C of temperature, then reduces temperature, and 1 mol sealers are added, and continues to stir 2 h, obtain pre-
Aggressiveness A, wherein 1 wt% 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, and the dibutyl tin laurate of 1 wt% is added, after
2 h of continuous stirring, obtain performed polymer B, wherein 1 wt% be with polyadipate hexylene glycol ester dihydric alcohol and toluene di-isocyanate(TDI) it
With on the basis of；
Step 3：In the performed polymer B obtained in step 2,5 mol dihydromethyl propionic acids are added, heating stirring is eventually adding 2
Mol trimethylolpropanes and 1 mol diglycols, with acetone regulation system viscosity to 2000 ~ 4000mPa s, with 40 r/
The rate of min stirs 3 h, 50 DEG C is cooled to, according to system and performed polymer A mass ratioes 1:The pre-polymerization obtained in 1 addition step 1
Body 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:Deionized water is added in 0.5 mass ratio
In, after stirring 1 h, solvent acetone is sloughed in vacuum distillation, obtains the aqueous polyurethane emulsion adhesive of nano-silica-containing.
2. the preparation method of the aqueous polyurethane emulsion adhesive of nano-silica-containing according to claim 1, special
Sign is that the specific surface area of the nano silicon dioxide in step 1 is 800 m2/ g, surface hydroxyl number are 5.0 OH/nm2。
3. the preparation method of the aqueous polyurethane emulsion adhesive of nano-silica-containing according to claim 1, special
Sign is that the structural formula of the performed polymer A obtained in step 1 is as follows：
。
4. the preparation method of the aqueous polyurethane emulsion adhesive of nano-silica-containing according to claim 1, special
Sign is, in step 1, reduces the temperature to 50 DEG C, the sealer of addition is acetophenone oxime.
5. the preparation method of the aqueous polyurethane emulsion adhesive of nano-silica-containing according to claim 1, special
Sign is, in step 3, stirs 1 ~ 2 h after the dihydromethyl propionic acid of addition at 60 ~ 70 DEG C.
6. a kind of aqueous polyurethane breast of nano-silica-containing being prepared according to any one of claim 1-5 the methods
Liquid adhesive.
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| CN2017111102680 | 2017-11-12 | ||
| CN201711110268 | 2017-11-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988538A (en) * | 2019-04-18 | 2019-07-09 | 李智远 | The preparation method of no-solvent type polyurethane adhesive |
| CN113336911A (en) * | 2021-05-24 | 2021-09-03 | 合肥科天水性科技有限责任公司 | Bio-based waterborne polyurethane hot melt adhesive and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153984A (en) * | 2011-01-26 | 2011-08-17 | 山西省应用化学研究所 | Method for preparing single-component high-heat-resistance aqueous polyurethane adhesive |
| 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 |
-
2017
- 2017-12-21 CN CN201711389545.6A patent/CN108300402A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153984A (en) * | 2011-01-26 | 2011-08-17 | 山西省应用化学研究所 | Method for preparing single-component high-heat-resistance aqueous polyurethane adhesive |
| 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)
| 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 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988538A (en) * | 2019-04-18 | 2019-07-09 | 李智远 | The preparation method of no-solvent type polyurethane adhesive |
| CN109988538B (en) * | 2019-04-18 | 2021-11-23 | 福建恒力达新材料有限公司 | Preparation method of solvent-free polyurethane adhesive |
| CN113336911A (en) * | 2021-05-24 | 2021-09-03 | 合肥科天水性科技有限责任公司 | Bio-based waterborne polyurethane hot melt adhesive and preparation method and application thereof |
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