CN109135656A - A kind of water-based polyurethane adhesive and preparation method thereof - Google Patents
A kind of water-based polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN109135656A CN109135656A CN201810831644.3A CN201810831644A CN109135656A CN 109135656 A CN109135656 A CN 109135656A CN 201810831644 A CN201810831644 A CN 201810831644A CN 109135656 A CN109135656 A CN 109135656A
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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
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of water-based polyurethane adhesives, are mainly prepared from the following raw materials: waterborne polyurethane resin, polyisocyanates, nanoparticle suspension, hydrophilic chain extender, chain extender, salt forming agent, thickener, defoaming agent and levelling agent.The adhesive introduces the nanoparticle suspension of different-grain diameter size, aqueous polyurethane is modified by the nanoparticle in situ for adulterating different-grain diameter, it can effectively solve the dispersion of the nanoparticle in waterborne polyurethane resin, to improve the quality of adhesive.The object of the invention is also to provide the preparation methods of above-mentioned water-based polyurethane adhesive, and the preparation method is environmentally protective, and production cost is low, construction is simple.
Description
Technical field
The invention belongs to adhesive technology fields, and in particular to a kind of water-based polyurethane adhesive and preparation method thereof.
Background technique
Polyurethane adhesive has good adhesive property and safe and healthy performance, occupies in food, drug packing field
Absolute leadership status.Current polyurethane adhesive market is still accounted for solvent adhesive leading.Since solvent was being produced using journey
In can pollute air, endanger workers ' health, or even the health of consumer can be endangered.
With deepening constantly for people's environmental consciousness, being gradually improved for environmental regulation organises to toxic, volatilization with various countries
Close the increasingly stringent of object limitation, water-based polyurethane adhesive is because of its safety and sanitation, environmentally protective, and easy to operate, safety in fortune
Etc. advantages, every field constantly expand application.However, single Property of Waterborne Polyurethane is bad, it is mainly shown as pair
Non-polar substrate wetability is poor, adhesive strength is low, initial bonding strength is low etc., is not able to satisfy the needs of multiple fields.It is aqueous poly- to improve
The performance of urethane, the application field for expanding aqueous polyurethane, need to be modified aqueous polyurethane.
Nano material provides short-range diffusion approach due to dispersivity and large interface with height, for atom, makes nanometer
Material has high diffusivity rate, creep and superplasticity and big chemical activity.It is that current one kind has the function of application prospect very much
Material.Currently, dispersity of the inorganic particle in final adhesive being blended based on simple physical often serious out of control, this pole
The earth affects the promotion of adhesive quality and giving full play to for functional particulate effect.
Summary of the invention
The purpose of the present invention is to provide a kind of water-based polyurethane adhesive, which introduces different-grain diameter size
Nanoparticle suspension is modified aqueous polyurethane by the nanoparticle in situ for adulterating different-grain diameter, can effectively be solved
Certainly the dispersion of the nanoparticle in waterborne polyurethane resin, to improve the quality of adhesive.
The object of the invention is also to provide the preparation method of above-mentioned water-based polyurethane adhesive, the preparation method green rings
It protects, production cost is low, construction is simple.
Above-mentioned first purpose of the invention is achieved through the following technical solutions: a kind of aqueous polyurethane gluing
Agent is mainly made of the raw material of following proportion by weight:
In above-mentioned each raw material of water-based polyurethane adhesive of the present invention:
Waterborne polyurethane resin of the present invention preferably passes through small molecule polyacid and small molecule polyol passes through polycondensation
What reaction prepared.
Further, waterborne polyurethane resin of the present invention is preferably prepared by the following method acquisition:
S1: small molecule polyacid and small molecule polyol are chosen, by 1.1~1.4:1 of molar ratio of alcohol to acid, reaction vessel is added
In, it is gradually heated to 220~230 DEG C of anti-1.5~2.0h of heat preservation under nitrogen protection；
S2: it is decompressed to -0.095~-0.1MPa under the conditions of 220~230 DEG C, is stopped after acid value drops to 1.0 or less anti-
Should to get arrive waterborne polyurethane resin.
In the preparation method of the waterborne polyurethane resin:
Step S1Described in small molecule polyacid be preferably adipic acid, terephthalic acid (TPA), M-phthalic acid, terephthalic acid (TPA)
One or more of dimethyl ester, decanedioic acid, phthalic anhydride, trimellitic anhydride and maleic anhydride.
Step S1Described in small molecule polyol be preferably neopentyl glycol, methyl propanediol, 1,2- ethylene glycol, 1,4- fourth two
The pure and mild poly- tetrahydro of alcohol, diglycol, 1,2- propylene glycol, trimethylolpropane, polyoxypropyleneglycol, polypropylene oxide three
One or more of furans ether glycol.
Wherein the number-average molecular weight Mn of polyoxypropyleneglycol is preferably 400,1000 and 2000；Polypropylene oxide triol
Number-average molecular weight Mn is preferably 400,1000 and 2000；The number-average molecular weight Mn of polytetrahydrofuran ether glycol is preferably 1000 Hes
2000。
The preparation method of waterborne polyurethane resin is usually to pass through esterification and polycondensation to be made, and key technology is to resin structure
Design.
The present invention do not select outsourcing sold resin preferentially and it is preferred that using above method preparation waterborne polyurethane resin, the
First is that the considerations of to end properties, can rationally design polyurethane molecular structure；It is also to cost consideration, adopts simultaneously
Preparation cost is less expensive in aforementioned manners.
Polyisocyanates of the present invention is preferably tetramethyl m-xylylene diisocyanate (TMXDI), toluene two
Isocyanates (TDI), isophorone diisocyanate (IPDI), '-diphenylmethane diisocyanate (MDI) and hexa-methylene two are different
The mixture of one or more of cyanate (HDI).
Nanoparticle suspension of the present invention is coupling agent modified nanometer titanium dioxide silicon suspension, the idol in the present invention
Join the partial size of the modified nano silica of agent, it is compound not adhesive can be regulated and controled according to the performance requirement of water-based polyurethane adhesive
Same structure, the partial size of the requirement difference nanoparticle of peel strength, particle size are controllable in 20~500nm.
Further, coupling agent modified nanometer titanium dioxide silicon suspension of the present invention is preferably made by the following method
: 40~50 DEG C of insulated and stirreds are warming up to after selection dehydrated alcohol and ammonium hydroxide mixing and obtain solution a, then weigh dehydrated alcohol and positive silicon
Acetoacetic ester obtains solution b after mixing, and solution b is instilled in solution a, and constant temperature is added dropwise and stirs 1.5~2.0h, nano-silica is made
SiClx suspension is warming up to 90~95 DEG C, adds coupling agent constant temperature and stirs 23~25h, obtains coupling agent modified nanometer two
Aoxidize silicon suspension.
In the preparation method of the coupling agent modified nanometer titanium dioxide silicon suspension:
Preferably, the proportion by weight of dehydrated alcohol described in solution a and ammonium hydroxide is 200~250:13~60；In solution b
The proportion by weight of the dehydrated alcohol and ethyl orthosilicate is 45~60:10~25, the proportion by weight of solution a and solution b
Preferably 2.5~6.0:1；Constant pressure funnel is used to instill solution b in solution a with 3~4 drops/minute rate.
Preferably, the coupling agent is silane coupling agent gamma-aminopropyl-triethoxy-silane, and dosage is nanometer titanium dioxide
The 0.8~2.0% of silicon suspension gross mass.
The present invention prepares coupling agent modified nanometer titanium dioxide silicon suspension using the above method, passes through solution a and solution b
Different ratio can prepare the nano silica of different-grain diameter, and that centrifugation is not carried out to nanoparticle is dry by the present invention
It is dry, but directly suspension is added in water-based polyurethane adhesive, the functional characteristic of nanoparticle has been given full play to, thus
To high performance water-based polyurethane adhesive.
Nanoparticle in the present invention can be added in water-based polyurethane adhesive by the method adulterated in situ, not only be had
Effect inhibits the reunion of nanoparticle, ensure that effective dispersion of the nanoparticle in adhesive, gives full play to nanoparticle
Effect, while greatly improving the quality of water-based polyurethane adhesive.
Preferably, hydrophilic chain extender of the present invention is dihydromethyl propionic acid.
Preferably, chain extender of the present invention is one or both of 1,4-butanediol and trimethylolpropane.
Preferably, salt forming agent of the present invention is triethylamine.
Preferably, thickener of the present invention is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Preferably, defoaming agent of the present invention is polyoxy enol amidogen ether class defoaming agent.
Preferably, levelling agent of the present invention is modified organic silicon class levelling agent.
Above-mentioned second purpose of the invention is achieved through the following technical solutions: above-mentioned water-based polyurethane adhesive
Preparation method, comprising the following steps:
(1) waterborne polyurethane resin is chosen, is warming up to 108~110 DEG C, is evacuated to -0.90~-0.1MPa, vacuum is de-
2.0~3.0h of water is cooled to 50~60 DEG C；
(2) dosage relation is pressed, polyisocyanates is added, then 1.5~2.0h of insulation reaction under the conditions of 50~55 DEG C heats up
To 80~95 DEG C of continuation 1.5~2.0h of insulation reaction, performed polymer is obtained；
(3) pre-polymerization temperature is down to 45~50 DEG C, by dosage relation, acetone and hydrophilic chain extender is added, then rises
Temperature is to 70~80 DEG C of 2.0~4.0h of insulation reaction；
(4) 40~50 DEG C are then cooled to, chain extender is added, then heats to 70~80 DEG C of 2.0~3.0h of insulation reaction；
(5) 40~50 DEG C then are cooled to, salt forming agent, 1.0~1.5h of insulation reaction is added by dosage relation；
(6) press dosage relation, be added nanoparticle suspension adjust revolving speed be 1000~1500r/min stirring 30~
It after 60min, adds thickener, defoaming agent and levelling agent and stirs evenly, then acetone is sloughed in decompression, is down to room temperature, was discharged
Filter is packed up to water-based polyurethane adhesive.
Acetone is wherein added in step (3) can reduce viscosity, and decompression is sloughed before discharging in step (6).
Compared with prior art, the invention has the following advantages that
(1) that there are adhesive strengths is low, initial bonding strength is low etc. for current water-based polyurethane adhesive by the present invention, is not able to satisfy more
The problems such as needs of field of kind is modified it by the nanoparticle in situ for adulterating different-grain diameter, and the present invention is effective
It solves the dispersion of nanoparticle in the base, gives full play to the functional effect of nanoparticle, improve adhesive energetically
Quality meets the requirement of water-based polyurethane adhesive higher standard；
(2) preparation method of the present invention passes through small molecule polyacid and small molecule polyol first and prepares water by polycondensation reaction
Property polyurethane resin, then obtained by prepolymerization reaction-chain extending reaction-neutralization reaction (be added that step of salt forming agent be neutralization reaction)
The different-grain diameter prepared by sol-gel method is finally added and with occasionally in Waterborne Polyurethane Prepolymer under high shear agitation
Join the Nano-meter SiO_2 of agent processing2Suspension, obtains having that adhesive strength is high, viscosity is low, water-fast solvent resistant, in-situ nano doping
Water-based polyurethane adhesive；
(3) present invention in the experimental results showed that, all had using the composite membrane of the water-based polyurethane adhesive in the present invention
There are good initial bonding strength and peel strength；
(4) preparation method of the invention is not only environmentally protective, and production cost is low, construction is simple, and the aqueous poly- ammonia prepared
Ester gum stick has excellent performance, for exploitation green environment protection adhesion agent and pushes green environment protection adhesion agent in drug, food
Extensive use in packaging provides a new way.
Specific embodiment
Embodiment 1
Water-based polyurethane adhesive provided in this embodiment is mainly made of the raw material of following proportion by weight:
Wherein:
Waterborne polyurethane resin is prepared via a method which to obtain: in terms of proportion by weight, under nitrogen protection, by 80 parts
Adipic acid, 7 parts of maleic anhydrides, 50 parts of diglycols, 10 parts of trimethylolpropanes, 10 parts of methyl propanediols, 30 parts of molecules
Amount is added in reaction kettle for 400 polyoxypropyleneglycol, is warming up to 230 DEG C of heat preservation esterification 2h, be then slowly decompressed to-
0.1MPa stops reaction after acid value drops to 1 or less, obtains waterborne polyurethane resin.
Nanoparticle suspension is prepared via a method which to obtain: weighing 250 parts of dehydrated alcohols, 16 parts of ammonium hydroxide are added anti-
It answers in kettle, is gradually heated to 40 DEG C of insulated and stirreds after mixing and obtains solution a；Weigh 60 parts of dehydrated alcohols, 15 parts of positive silicic acid second
Ester obtains solution b after mixing, use constant pressure funnel with the solution a of the speed instillation reaction kettle of 3~4 drop per second solution b
In, rear constant temperature stirring 2h, the Nano-meter SiO_2 that obtained partial size is about 20~50nm is added dropwise2Suspension.
Polyisocyanates is tetramethyl m-xylylene diisocyanate.
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA).
Chain extender is 1,4- butanediol.
Salt forming agent is triethylamine.
Thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Defoaming agent is polyoxy enol amidogen ether class defoaming agent.
Levelling agent is modified organic silicon class levelling agent.
The preparation method of the water-based polyurethane adhesive, comprising the following steps:
(1) proportion by weight is pressed, 50 parts of waterborne polyurethane resins is weighed and is added in reaction kettle, be warming up to 108~110 DEG C,
It is evacuated to -0.1MPa, vacuum dehydration 2h is cooled to 55 DEG C；
(2) above-mentioned dosage relation is pressed, 16 parts of polyisocyanates are slowly dropped in reaction kettle, is kept the temperature under the conditions of 55 DEG C anti-
2h is answered, 80 DEG C of continuation insulation reaction 2h is then heated to, obtains performed polymer；
(3) pre-polymerization temperature is down to 50 DEG C, by above-mentioned dosage relation, by 20 parts of acetone and 6 parts of hydrophilic chain extenders two
Hydroxymethyl propionic acid is added dropwise to reaction kettle, then heats to 75 DEG C of insulation reaction 4h；
(4) then cooling degree is to 50 DEG C, by above-mentioned dosage relation, reaction kettle is added in 7 parts of chain extender 1,4-butanediol, so
After be warming up to 75 DEG C of insulation reaction 2h；
(5) 45 DEG C are cooled to, 5 parts of salt forming agents, insulation reaction 1h is added；
(6) 60 parts of SiO are added into reaction kettle2Suspension, adjusting revolving speed is 1500r/min high-speed stirred 30min, then is pressed
Above-mentioned dosage relation is added thickener, defoaming agent and levelling agent and stirs evenly, and then acetone is sloughed in decompression, is down to room temperature, discharges
It filters and packages up to water-based polyurethane adhesive.
Different packaging materials is chosen, spread is controlled in 3.5~4.0g/m2。
Good membrane sample first places 12h at room temperature again, then moves into 50 DEG C of curing room again, cures 48h.State is pressed after curing
Composite membrane is cut into the Test strips of 15mm × 200mm by mark, and its initial bonding strength is tested on XLW Intelligent electronic tensil testing machine
And peel strength, test result are shown in Table 1.
The properties of product testing result that 1 embodiment 1 of table obtains
Embodiment 2 (comparative example)
Water-based polyurethane adhesive provided in this embodiment is mainly made of the raw material of following proportion by weight:
Wherein:
Waterborne polyurethane resin is prepared via a method which to obtain: under nitrogen protection, by 80 parts of adipic acids, 7 parts of Malaysias
The polyoxygenated that acid anhydrides, 50 parts of diglycols, 10 parts of trimethylolpropanes, 10 parts of methyl propanediols, 30 parts of molecular weight are 400
Propylene glycol is added in reaction kettle, is warming up to 230 DEG C of heat preservation esterification 2h, is then slowly decompressed to -0.1MPa, drops to acid value
Stop reaction after to 1 or less, obtains waterborne polyurethane resin.
Polyisocyanates is tetramethyl m-xylylene diisocyanate.
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA).
Chain extender is 1,4- butanediol.
Salt forming agent is triethylamine.
Thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Defoaming agent is polyoxy enol amidogen ether class defoaming agent.
Levelling agent is modified organic silicon class levelling agent.
The preparation method of the water-based polyurethane adhesive, comprising the following steps:
(1) 50 parts of waterborne polyurethane resins are accurately weighed to be added in reaction kettle, are warming up to 108~110 DEG C, be evacuated to-
0.1MPa, vacuum dehydration 2h are cooled to 55 DEG C；
(2) 16 parts of polyisocyanates are slowly dropped in reaction kettle, insulation reaction 2h, then heats under the conditions of 55 DEG C
80 DEG C of continuation insulation reaction 2h, obtain performed polymer；
(3) pre-polymerization temperature is down to 50 DEG C, 20 parts of acetone and 6 parts of hydrophilic chain extender dihydromethyl propionic acids is added dropwise to
Reaction kettle then heats to 75 DEG C of insulation reaction 4h；
(4) 7 parts of 1,4-butanediol (chain extender) are added reaction kettle, then heat to 75 DEG C of heat preservations by cooling degree to 50 DEG C
React 2h；
(5) 45 DEG C are cooled to, 5 parts of salt forming agents, insulation reaction 1h is added；
(6) 60 parts of distilled water are added into reaction kettle, high-speed stirred 30min adds thickener, defoaming agent and levelling agent
It stirs evenly, then acetone is sloughed in decompression, is down to room temperature, and discharging filters and packages up to water-based polyurethane adhesive.
Different packaging materials is chosen, spread is controlled in 3.5~4.0g/m2。
Good membrane sample first places 12h at room temperature again, then moves into 50 DEG C of curing room again, cures 48h.State is pressed after curing
Composite membrane is cut into the Test strips of 15mm × 200mm by mark, and its initial bonding strength is tested on XLW Intelligent electronic tensil testing machine
And peel strength, test result are shown in Table 2.
The properties of product testing result that 2 embodiment 2 of table obtains
| Test structure | Initial bonding strength (N/15mm) | Peel strength (N/15mm) |
| PET//PE | 0.6 | 1.8 |
| PET//BOPP | 0.2 | 0.4 |
| PET//VMPET | 1.0 | 2.0 |
Embodiment 3
Water-based polyurethane adhesive provided in this embodiment is mainly made of the raw material of following proportion by weight:
Wherein:
Waterborne polyurethane resin is prepared via a method which to obtain: by proportion by weight, under nitrogen protection, by 85 parts oneself
Diacid, 5 parts of dimethyl terephthalate (DMT)s, 20 parts of diglycols, 5 parts of trimethylolpropanes, 42 parts of methyl propanediols, 25 parts
The polyoxypropyleneglycol that polyoxypropyleneglycol that molecular weight is 400,30 parts of molecular weight are 1000 is added in reaction kettle, heating
To 230 DEG C of heat preservation esterification 2h, it is then slowly decompressed to -0.1MPa, stops reaction after acid value drops to 1 or less, obtains water
Property polyurethane resin.
Nanoparticle suspension is coupling agent modified nanometer titanium dioxide silicon suspension.
Coupling agent modified nanometer titanium dioxide silicon suspension is prepared via a method which to obtain: by proportion by weight, weighing
200 parts of dehydrated alcohols, 13 parts of ammonium hydroxide are added in reaction kettle, are gradually heated to 40 DEG C of insulated and stirreds after mixing and obtain solution a；
50 parts of dehydrated alcohols are weighed, 12 parts of ethyl orthosilicates obtain solution b, use constant pressure funnel with per second 3 solution b after mixing
The speed of~4 drops instills in the solution a of reaction kettle, rear constant temperature stirring 2h is added dropwise, obtained partial size is about receiving for 20~50nm
Rice SiO2, 95 DEG C are warming up to, 5 parts of silane coupling agent gamma-aminopropyl-triethoxy-silane constant temperature stirrings is added for 24 hours, obtains idol
Join the modified nanometer titanium dioxide silicon suspension of agent.
Polyisocyanates is isophorone diisocyanate.
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA).
Chain extender is 1,4- butanediol.
Salt forming agent is triethylamine.
Thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Defoaming agent is polyoxy enol amidogen ether class defoaming agent.
Levelling agent is modified organic silicon class levelling agent.
The preparation method of the water-based polyurethane adhesive, comprising the following steps:
(1) 50 parts of waterborne polyurethane resins are accurately weighed to be added in reaction kettle, are warming up to 108~110 DEG C, be evacuated to-
0.1MPa, vacuum dehydration 2h are cooled to 55 DEG C；
(2) 14 parts of polyisocyanates are slowly dropped in reaction kettle, insulation reaction 2h, then heats under the conditions of 55 DEG C
80 DEG C of continuation insulation reaction 2h, obtain performed polymer；
(3) pre-polymerization temperature is down to 50 DEG C, 25 parts of acetone and 6 parts of dihydromethyl propionic acids (hydrophilic chain extender) is added dropwise
Enter reaction kettle, then heats to 75 DEG C of insulation reaction 4h；
(3) 6 parts of 1,4-butanediol (chain extender) are added reaction kettle, then heat to 75 DEG C of heat preservations by cooling degree to 50 DEG C
React 2h；
(4) 45 DEG C are cooled to, 5 parts of salt forming agents, insulation reaction 1h is added；
(5) 58 parts of coupling agent modified nanoparticle suspensions are added into reaction kettle, adjusting revolving speed is 1200r/min high
Speed stirring 30min, adds thickener, defoaming agent and levelling agent and stirs evenly, and then acetone is sloughed in decompression, is down to room temperature, out
Material filters and packages up to water-based polyurethane adhesive.
Different packaging materials is chosen, spread is controlled in 3.5~4.0g/m2。
Good membrane sample first places 12h at room temperature again, then moves into 50 DEG C of curing room again, cures 48h.State is pressed after curing
Composite membrane is cut into the Test strips of 15mm × 200mm by mark, and its initial bonding strength is tested on XLW Intelligent electronic tensil testing machine
And peel strength, test result are shown in Table 3.
The properties of product testing result that 3 embodiment 3 of table obtains
| Test structure | Initial bonding strength (N/15mm) | Peel strength (N/15mm) |
| PET//PE | 1.5 | 3.8 |
| PET//BOPP | 0.5 | 1.1 |
| PET//VMPET | 2.0 | 4.3 |
Embodiment 4
Water-based polyurethane adhesive provided in this embodiment is mainly made of the raw material of following proportion by weight:
Wherein:
Waterborne polyurethane resin is prepared via a method which to obtain: under nitrogen protection, by 90 parts of adipic acids, 5 parts of adjacent benzene
Dicarboxylic acid anhydride, 25 parts of diglycols, 6 parts of trimethylolpropanes, 30 parts of methyl propanediols, 150 parts of molecular weight are 1000
Polyoxypropyleneglycol is added in reaction kettle, is warming up to 230 DEG C of heat preservation esterification 2h, is then slowly decompressed to -0.1MPa, to
Acid value stops reaction after dropping to 1 or less, obtains waterborne polyurethane resin.
Coupling agent modified nanometer titanium dioxide silicon suspension is prepared via a method which to obtain: 200 parts of dehydrated alcohols are weighed,
22 parts of ammonium hydroxide are added in reaction kettle, are gradually heated to 40 DEG C of insulated and stirreds after mixing and obtain solution a；Weigh 50 parts of anhydrous second
Alcohol, 11 parts of ethyl orthosilicates obtain solution b after mixing, use constant pressure funnel to instill with the speed of 3~4 drop per second solution b
In the solution a of reaction kettle, rear constant temperature stirring 2h, the Nano-meter SiO_2 that obtained partial size is about 50~100nm is added dropwise2, it is warming up to 90
It~95 DEG C, adds 4 parts of coupling agent constant temperature and stirs 23~25h, obtain coupling agent modified nanometer titanium dioxide silicon suspension.
Polyisocyanates is toluene di-isocyanate(TDI).
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA).
Chain extender is trimethylolpropane.
Salt forming agent is triethylamine.
Thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Defoaming agent is polyoxy enol amidogen ether class defoaming agent.`
Levelling agent is modified organic silicon class levelling agent.
The preparation method of the water-based polyurethane adhesive, comprising the following steps:
(1) 50 parts of waterborne polyurethane resins are accurately weighed to be added in reaction kettle, are warming up to 108~110 DEG C, be evacuated to-
0.1MPa, vacuum dehydration 2h are cooled to 55 DEG C；
(2) 11 parts of polyisocyanates are slowly dropped in reaction kettle, insulation reaction 2h, then heats under the conditions of 55 DEG C
80 DEG C of continuation insulation reaction 2h, obtain performed polymer；
(3) pre-polymerization temperature is down to 50 DEG C, 20 parts of acetone and 7 parts of hydrophilic chain extenders is added dropwise to reaction kettle, then
It is warming up to 75 DEG C of insulation reaction 4h；
(3) 4 parts of trimethylolpropanes (chain extender) are added reaction kettle, then heat to 75 DEG C of guarantors by cooling degree to 50 DEG C
Temperature reaction 2h；
(4) 45 DEG C are cooled to, 5 parts of salt forming agents, insulation reaction 1h is added；
(5) 55 parts of nanoparticle suspensions are added into reaction kettle, adjusting revolving speed is 1500r/min high-speed stirred 30min,
It adds thickener, defoaming agent and levelling agent to stir evenly, then acetone is sloughed in decompression, is down to room temperature, and discharging filters and packages i.e.
Obtain water-based polyurethane adhesive.
Different packaging materials is chosen, spread is controlled in 3.5~4.0g/m2。
Good membrane sample first places 12h at room temperature again, then moves into 50 DEG C of curing room again, cures 48h.State is pressed after curing
Composite membrane is cut into the Test strips of 15mm × 200mm by mark, and its initial bonding strength is tested on XLW Intelligent electronic tensil testing machine
And peel strength, test result are shown in Table 4.
The properties of product testing result that 4 embodiment 4 of table obtains
| Test structure | Initial bonding strength (N/15mm) | Peel strength (N/15mm) |
| PET//PE | 1.4 | 3.3 |
| PET//BOPP | 0.5 | 0.8 |
| PET//VMPET | 1.8 | 3.8 |
Embodiment 5
Water-based polyurethane adhesive provided in this embodiment is mainly made of the raw material of following proportion by weight:
Wherein:
Waterborne polyurethane resin is prepared via a method which to obtain: under nitrogen protection, by 75 parts of adipic acids, 10 parts of isophthalic
The polyoxygenated third that dioctyl phthalate, 20 parts of ethylene glycol, 10 parts of trimethylolpropanes, 20 parts of methyl propanediols, 50 parts of molecular weight are 1000
The polyoxypropyleneglycol that enediol, 50 parts of molecular weight are 2000 is added in reaction kettle, is warming up to 230 DEG C of heat preservation esterifications
Then 3h is slowly decompressed to -0.1MPa, stop reaction after acid value drops to 1 or less, obtain waterborne polyurethane resin.
Coupling agent modified nanometer titanium dioxide silicon suspension is prepared via a method which to obtain: 200 parts of dehydrated alcohols are weighed,
50 parts of ammonium hydroxide are added in reaction kettle, are gradually heated to 40 DEG C of insulated and stirreds after mixing and obtain solution a；Weigh 45 parts of anhydrous second
Alcohol, 15 parts of ethyl orthosilicates obtain solution b after mixing, use constant pressure funnel to instill with the speed of 3~4 drop per second solution b
In the solution a of reaction kettle, rear constant temperature stirring 2h, the Nano-meter SiO_2 that obtained partial size is about 200~500nm is added dropwise2, it is warming up to
It 90~95 DEG C, adds 6 parts of coupling agent constant temperature and stirs 23~25h, obtain coupling agent modified nanometer titanium dioxide silicon suspension.
Polyisocyanates is methyl diphenylene diisocyanate
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA).
Chain extender is trimethylolpropane.
Salt forming agent is triethylamine.
Thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Defoaming agent is polyoxy enol amidogen ether class defoaming agent.
Levelling agent is modified organic silicon class levelling agent.
The preparation method of the water-based polyurethane adhesive, comprising the following steps:
(1) 55 parts of waterborne polyurethane resins are accurately weighed to be added in reaction kettle, are warming up to 108~110 DEG C, be evacuated to-
0.1MPa, vacuum dehydration 2h are cooled to 55 DEG C；
(2) 20 parts of polyisocyanates are slowly dropped in reaction kettle, insulation reaction 2h, then heats under the conditions of 55 DEG C
80 DEG C of continuation insulation reaction 2h, obtain performed polymer；
(3) pre-polymerization temperature is down to 50 DEG C, 20 parts of acetone and 7 parts of hydrophilic chain extenders is added dropwise to reaction kettle, then
It is warming up to 75 DEG C of insulation reaction 4h；
(3) 3 parts of trimethylolpropanes (chain extender) are added reaction kettle, then heat to 75 DEG C of guarantors by cooling degree to 50 DEG C
Temperature reaction 2h；
(4) 45 DEG C are cooled to, 5 parts of salt forming agents, insulation reaction 1h is added；
(5) 60 parts of nanoparticle suspensions are added into reaction kettle, high-speed stirred 30min adds thickener, defoaming agent
It is stirred evenly with levelling agent, then acetone is sloughed in decompression, is down to room temperature, and discharging filters and packages up to water-based polyurethane adhesive.
Different packaging materials is chosen, spread is controlled in 3.5~4.0g/m2。
Good membrane sample first places 12h at room temperature again, then moves into 50 DEG C of curing room again, cures 48h.State is pressed after curing
Composite membrane is cut into the Test strips of 15mm × 200mm by mark, and its initial bonding strength is tested on XLW Intelligent electronic tensil testing machine
And peel strength, test result are shown in Table 5.
The properties of product testing result that 5 embodiment 5 of table obtains
Embodiment 6
Water-based polyurethane adhesive provided in this embodiment is mainly made of the raw material of following proportion by weight:
Wherein:
Waterborne polyurethane resin is prepared via a method which to obtain: under nitrogen protection, by 85 parts of adipic acids, 6 parts of adjacent benzene
The polyoxy that dicarboxylic acid anhydride, 10 parts of neopentyl glycols, 5 parts of trimethylolpropanes, 50 parts of methyl propanediols, 100 parts of molecular weight are 2000
Change propylene glycol to be added in reaction kettle, is warming up to 220 DEG C of heat preservation esterification 2h, -0.1MPa is then slowly decompressed to, to acid value
Stop reaction after dropping to 1 or less, obtains waterborne polyurethane resin.
Nanoparticle suspension is coupling agent modified nanometer titanium dioxide silicon suspension.
Coupling agent modified nanometer titanium dioxide silicon suspension is prepared via a method which to obtain: 250 parts of dehydrated alcohols are weighed,
60 parts of ammonium hydroxide are added in reaction kettle, are gradually heated to 40 DEG C of insulated and stirreds after mixing and obtain solution a；Weigh 60 parts of anhydrous second
Alcohol, 25 parts of ethyl orthosilicates obtain solution b after mixing, use constant pressure funnel to instill with the speed of 3~4 drop per second solution b
In the solution a of reaction kettle, rear constant temperature stirring 2h, the Nano-meter SiO_2 that obtained partial size is about 20~50nm is added dropwise2, it is warming up to 95
DEG C, it adds 6.5 parts of silane coupling agent gamma-aminopropyl-triethoxy-silane constant temperature stirrings for 24 hours, obtains coupling agent modified nanometer
Silica suspension.
Polyisocyanates is tetramethyl m-xylylene diisocyanate.
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA).
Chain extender is trimethylolpropane.
Salt forming agent is triethylamine.
Thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener.
Defoaming agent is polyoxy enol amidogen ether class defoaming agent.
Levelling agent is modified organic silicon class levelling agent.
The preparation method of the water-based polyurethane adhesive, comprising the following steps:
(1) 60 parts of waterborne polyurethane resins are accurately weighed to be added in reaction kettle, are warming up to 108~110 DEG C, be evacuated to-
0.1MPa, vacuum dehydration 3h are cooled to 50 DEG C；
(2) 20 parts of polyisocyanates are slowly dropped in reaction kettle, insulation reaction 2h, then heats under the conditions of 50 DEG C
80 DEG C of continuation insulation reaction 2h, obtain performed polymer；
(3) pre-polymerization temperature is down to 50 DEG C, 25 parts of acetone and 8 parts of hydrophilic chain extenders is added dropwise to reaction kettle, then
It is warming up to 80 DEG C of insulation reaction 4h；
(3) 4 parts of trimethylolpropanes (chain extender) are added reaction kettle, then heat to 75 DEG C of guarantors by cooling degree to 45 DEG C
Temperature reaction 2h；
(4) 45 DEG C are cooled to, 6 parts of salt forming agents, insulation reaction 1h is added；
(5) 55 parts of nanoparticle suspensions are added into reaction kettle, high-speed stirred 30min adds thickener, defoaming agent
It is stirred evenly with levelling agent, then acetone is sloughed in decompression, is down to room temperature, and discharging filters and packages up to water-based polyurethane adhesive.
Different packaging materials is chosen, spread is controlled in 3.5~4.0g/m2。
Good membrane sample first places 12h at room temperature again, then moves into 50 DEG C of curing room again, cures 48h.State is pressed after curing
Composite membrane is cut into the Test strips of 15mm × 200mm by mark, and its initial bonding strength is tested on XLW Intelligent electronic tensil testing machine
And peel strength, test result are shown in Table 6.
The properties of product testing result that 6 embodiment 6 of table obtains
| Test structure | Initial bonding strength (N/15mm) | Peel strength (N/15mm) |
| PET//PE | 1.6 | 3.9 |
| PET//BOPP | 0.5 | 1.2 |
| PET//VMPET | 2.0 | 4.4 |
The main distinction of embodiment 1 and embodiment 2 is to adulterate unmodified nanoparticle in situ in embodiment 1, implement
Undoped with nanoparticle in example 2；The main distinction of embodiment 1 and embodiment 3 is that the nanoparticle in embodiment 1 does not pass through idol
It is modified to join agent, and the nanoparticle of embodiment 3 pass through it is coupling agent modified.Therefrom it can be concluded that nanoparticle is adulterated by situ,
Greatly improve the initial bonding strength and peel strength of water-based polyurethane adhesive；The addition of coupling agent, is also beneficial to aqueous polyurethane
The raising of Adhensive performance.
The main distinction of embodiment 3 and embodiment 4, embodiment 5 is that the partial size of nanoparticle is different, can therefrom obtain
Out, nano particle diameter is smaller, is more conducive to the functional characteristic for playing nanoparticle, improves the performance of aqueous polyurethane.It is different
Polyisocyanates and polyester soft segment can have an impact to the performance of aqueous polyurethane, the chain extender performance that can generate cross-linked structure is excellent
It is connect in the chain extension of straight chain.
A part of specific embodiment is enumerated above, and the present invention will be described, it is necessary to which indicated herein is the above specific reality
It applies example and is served only for that the invention will be further described, do not represent limiting the scope of the invention.Other people are according to the present invention
The some nonessential modifications and adjustment made still fall within protection scope of the present invention.
Claims (10)
1. a kind of water-based polyurethane adhesive, it is characterized in that being mainly made of the raw material of following proportion by weight:
2. water-based polyurethane adhesive according to claim 1, it is characterized in that: the waterborne polyurethane resin pass through it is following
Method is made:
S1: small molecule polyacid and small molecule polyol are chosen, by 1.1~1.4:1 of molar ratio of alcohol to acid, is added in reaction vessel,
220~230 DEG C of anti-1.5~2.0h of heat preservation are gradually heated under nitrogen protection；
S2: it is decompressed to -0.095~-0.1MPa under the conditions of 220~230 DEG C, stops reaction after acid value drops to 1.0 or less, i.e.,
Obtain waterborne polyurethane resin.
3. water-based polyurethane adhesive according to claim 2, it is characterized in that: step S1Described in small molecule polyacid be
Adipic acid, terephthalic acid (TPA), M-phthalic acid, dimethyl terephthalate (DMT), decanedioic acid, phthalic anhydride, trimellitic anhydride
One or more of with maleic anhydride；Step S1Described in small molecule polyol be neopentyl glycol, methyl propanediol, 1,2- second
Glycol, 1,4- butanediol, diglycol, 1,2- propylene glycol, trimethylolpropane, polyoxypropyleneglycol, polyoxygenated third
One or more of pure and mild polytetrahydrofuran ether glycol of alkene three.
4. water-based polyurethane adhesive according to claim 1, it is characterized in that: the polyisocyanates is tetramethyl isophthalic
Dimethylene diisocyanate, toluene di-isocyanate(TDI), isophorone diisocyanate, '-diphenylmethane diisocyanate and six are sub-
The mixture of one or more of methyl diisocyanate.
5. water-based polyurethane adhesive according to claim 1, it is characterized in that: the nanoparticle suspension is coupling agent
Modified nanometer titanium dioxide silicon suspension, wherein the particle size of coupling agent modified nano silica is 20~500nm.
6. water-based polyurethane adhesive according to claim 5, it is characterized in that: the coupling agent modified nanometer titanium dioxide
Silicon suspension is made by the following method: being warming up to 40~50 DEG C of insulated and stirreds after selection dehydrated alcohol and ammonium hydroxide mixing and obtains solution
A, then solution b is obtained after weighing dehydrated alcohol and ethyl orthosilicate mixing, solution b is instilled in solution a, constant temperature stirring is added dropwise
1.5~2.0h is made nanometer titanium dioxide silicon suspension, is warming up to 90~95 DEG C, adds coupling agent constant temperature and stirs 23~25h,
Obtain coupling agent modified nanometer titanium dioxide silicon suspension.
7. water-based polyurethane adhesive according to claim 6, it is characterized in that: dehydrated alcohol described in solution a and ammonium hydroxide
Proportion by weight be 200~250:13~60；The proportion by weight of dehydrated alcohol described in solution b and ethyl orthosilicate is 45
2.5~6.0:1 of proportion by weight of~60:10~25, solution a and solution b, use constant pressure funnel with 3~4 drops/minute
Rate will solution b instill solution a in.
8. water-based polyurethane adhesive according to claim 6, it is characterized in that: the coupling agent is silane coupling agent γ-
Aminopropyl triethoxysilane, dosage are the 0.8~2.0% of nanometer titanium dioxide silicon suspension gross mass.
9. water-based polyurethane adhesive according to claim 1, it is characterized in that: the hydrophilic chain extender is dihydroxymethyl third
Acid, the chain extender are one or both of 1,4-butanediol and trimethylolpropane；The salt forming agent is triethylamine；Institute
Stating thickener is carboxymethylcellulose sodium and/or non-ionic associative type thickener；The defoaming agent is that polyoxy enol amidogen ether class disappears
Infusion；The levelling agent is modified organic silicon class levelling agent.
10. the preparation method of any one of the claim 1-9 water-based polyurethane adhesive, it is characterized in that the following steps are included:
(1) waterborne polyurethane resin is chosen, 108~110 DEG C is warming up to, is evacuated to -0.90~-0.1MPa, vacuum dehydration 2.0
~3.0h is cooled to 50~60 DEG C；
(2) dosage relation is pressed, polyisocyanates is added, 1.5~2.0h of insulation reaction under the conditions of 50~55 DEG C then heats to 80
~95 DEG C of continuation 1.5~2.0h of insulation reaction, obtain performed polymer；
(3) pre-polymerization temperature is down to 45~50 DEG C, by dosage relation, acetone and hydrophilic chain extender is added, then heats to
70~80 DEG C of 2.0~4.0h of insulation reaction；
(4) 40~50 DEG C are then cooled to, chain extender is added, then heats to 70~80 DEG C of 2.0~3.0h of insulation reaction；
(5) 40~50 DEG C then are cooled to, salt forming agent, 1.0~1.5h of insulation reaction is added by dosage relation；
(6) dosage relation is pressed, after nanoparticle suspension adjusting revolving speed is added as 1000~1500r/min stirring, 30~60min,
It adds thickener, defoaming agent and levelling agent to stir evenly, then acetone is sloughed in decompression, is down to room temperature, and discharging filters and packages i.e.
Obtain water-based polyurethane adhesive.
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| CN109988538A (en) * | 2019-04-18 | 2019-07-09 | 李智远 | The preparation method of no-solvent type polyurethane adhesive |
| CN110484185A (en) * | 2019-08-16 | 2019-11-22 | 福建省统一环保科技有限公司 | A kind of unilateral water-based adhesion agent and preparation method thereof |
| CN111908883A (en) * | 2020-07-31 | 2020-11-10 | 上海航烯环保科技有限公司 | Composite binder and permeable surface layer coated particles and permeable material prepared from same |
| CN114395359A (en) * | 2021-10-13 | 2022-04-26 | 南京伊戈高分子复合新材料科技有限公司 | High-strength water-based polyurethane adhesive and preparation method thereof |
| CN117363300A (en) * | 2023-11-22 | 2024-01-09 | 佛山市尚峰高分子科技有限公司 | Preparation method of special aqueous adhesive for intelligent shoe machine |
| CN117987067A (en) * | 2024-03-29 | 2024-05-07 | 四川汇利实业有限公司 | Preparation method of polyurethane adhesive for medicine packaging composite film and composition of polyurethane adhesive |
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| CN109988538A (en) * | 2019-04-18 | 2019-07-09 | 李智远 | The preparation method of no-solvent type polyurethane adhesive |
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| CN114395359A (en) * | 2021-10-13 | 2022-04-26 | 南京伊戈高分子复合新材料科技有限公司 | High-strength water-based polyurethane adhesive and preparation method thereof |
| CN117363300A (en) * | 2023-11-22 | 2024-01-09 | 佛山市尚峰高分子科技有限公司 | Preparation method of special aqueous adhesive for intelligent shoe machine |
| CN117987067A (en) * | 2024-03-29 | 2024-05-07 | 四川汇利实业有限公司 | Preparation method of polyurethane adhesive for medicine packaging composite film and composition of polyurethane adhesive |
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