CN107353387A - A kind of aqueous anionic polyurethane emulsion and preparation method and application - Google Patents
A kind of aqueous anionic polyurethane emulsion and preparation method and application Download PDFInfo
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- CN107353387A CN107353387A CN201710655677.2A CN201710655677A CN107353387A CN 107353387 A CN107353387 A CN 107353387A CN 201710655677 A CN201710655677 A CN 201710655677A CN 107353387 A CN107353387 A CN 107353387A
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
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- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- 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
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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Abstract
The invention discloses a kind of aqueous anionic polyurethane emulsion and preparation method and application, belong to fine polymer Material Field.Aqueous anionic polyurethane emulsion, including following raw material components and parts by weight:10 parts of pentaerythrite, 39.5 79 parts of dihydromethyl propionic acid A, N, 40 90 parts of N dimethylformamides, 0.005 0.09 parts of p-methyl benzenesulfonic acid, 200 350 parts of polyalcohol, 35 80 parts of isocyanates, 0.03 0.05 parts of catalyst, 5 10 parts of small molecule chain extender, 10 18 parts of dihydromethyl propionic acid B, 50 80 parts of N ethyl pyrrolidones, 6.7 13.5 parts of nertralizer, 270 480 parts of deionized water.Aqueous anionic polyurethane emulsion solid content obtained by the present invention is 40 50%, during for water vacuum plastics-absorption glue, water vacuum plastics-absorption glue is had excellent heat resistance, weatherability, low temperature viscosity stability and adhesion strength etc..
Description
Technical field
The present invention relates to fine polymer Material Field, more particularly to a kind of aqueous anionic polyurethane emulsion and preparation side
Method and application.
Background technology
Aqueous polyurethane emulsion can be separately as vacuum plastic-absorption, can also be multiple with ethylene-vinyl acetate emulsion etc.
Vacuum plastic-absorption is made into, but so far based on compounding.Vacuum forming technique is widely used in computer desk, dressing table, cupboard
In the manufacture of cabinet, door-plate and furniture.Vacuum plastic-absorption typically uses technique:By PVC film during heating and softening with glue spraying
Medium density fibre board (MDF) afterwards is pressed close to, and takes the air between PVC film and medium density fibre board (MDF) away using vacuum, makes by atmospheric pressure
PVC film is tightly pasted onto on medium density fibre board (MDF), and this technical process is referred to as vacuum forming.The characteristics of this technique maximum is
Spray paint or coating again are not needed, is that one kind exempts from lacquer craftwork, this feature is particularly important in the preparation of door-plate and furniture.
Aqueous polyurethane emulsion is embodied in applied to vacuum plastic-absorption leading indicator:(1) viscosity stability, it is generally desirable to glue
Glutinous agent has excellent viscosity stability, if with the change of storage temperature or the extension of time, the viscosity of adhesive occurs
Change can adversely affect to spraying application;(2) activity function, the activation temperature of adhesive is wished in actual use
Low, activation is abundant, and preferable activation effect is can reach in shorter soak time and relatively low activation temperature;(3) high temperature resistant
Performance, it is generally desirable to the heat resistance of adhesive is the higher the better;(4) blended characteristic;(5) cost factor.
The domestic aqueous polyurethane emulsion viscosity applied to vacuum plastic-absorption is not sufficiently stable at present, and portioned product has low temperature
The phenomenon of thickening, and it is larger per the fluctuation of batch range of viscosities, and for solid content typically below 40%, acetone smell is big, blending property
Can be not good enough the defects of.And the Bayer U-54 that import aqueous polyurethane emulsion product is for example German, its is expensive, and heat-resisting
Can be to 65 DEG C or so.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of aqueous anionic polyurethane breast
Liquid and preparation method and application, overcome the height of cost present in prior art, viscosity is unstable, resistance to elevated temperatures is poor, bonding is strong
The defects of degree is poor, blended characteristic difference.
To achieve these goals or other purposes, the present invention is achieved by the following technical solutions:
A kind of aqueous anionic polyurethane emulsion, including following raw material components and parts by weight:10 parts of pentaerythrite, dihydroxy
Methylpropanoic acid A 39.5-79 parts, N,N-dimethylformamide 40-90 parts, p-methyl benzenesulfonic acid 0.005-0.09 parts, polyalcohol 200-
350 parts, isocyanates 35-80 parts, catalyst 0.03-0.05 parts, small molecule chain extender 5-10 parts, dihydromethyl propionic acid B 10-
18 parts, N- ethyl pyrrolidone 50-80 parts, nertralizer 6.7-13.5 parts, deionized water 270-480 parts.
Further, the polyalcohol is adipic acid series PEPA.Preferably, the polyalcohol for gather oneself two
One or two kinds of combinations of acid -1,4- butanediol esters or polyadipate -1,6-HD ester.
Further, the isocyanates is toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate.Preferably, institute
It is toluene di-isocyanate(TDI) (TDI) to state isocyanates.
Further, the catalyst is selected from one or both of stannous octoate, dibutyl tin laurate.
Further, the small molecule chain extender be selected from diglycol, ethylene glycol, BDO, neopentyl glycol,
One or more combinations in 1,6-HD.
Further, the nertralizer is triethylamine or dimethylethanolamine.
Further, the dihydromethyl propionic acid A and dihydromethyl propionic acid B refer both to dihydromethyl propionic acid, are in the present invention
The addition of dihydromethyl propionic acid is distinguished, is represented respectively with dihydromethyl propionic acid A and dihydromethyl propionic acid B.
Present invention also offers the preparation method of above-mentioned aqueous anionic polyurethane emulsion, comprise the following steps:
(1) pentaerythrite and dihydromethyl propionic acid A are added in reaction vessel, add DMF, so
After add p-methyl benzenesulfonic acid, heat up and react at a constant temperature, after reaction terminates, vacuumize, acquisition hyper-branched polyester HBPE;
(2) polyalcohol and isocyanates are added in reaction vessel and reacted, be then added dropwise what step (1) obtained
HBPE and a small amount of catalyst, continue to react;
(3) reaction solution that step (2) is obtained is cooled to less than 70 DEG C, adds remaining catalyst, dihydroxymethyl
Propionic acid (B), small molecule chain extender, a small amount of N- ethyl pyrrolidones, continue to react after heating, then add remaining N- N-ethyl pyrrole Ns
Alkanone, 60 DEG C are cooled to, add nertralizer neutralization reaction 2-10min;
(4) in the case where high speed shear is scattered, deionized water is added in the reaction solution of step (3), after being uniformly dispersed i.e.
Obtain aqueous anionic polyurethane emulsion.
Further, pentaerythrite and dihydromethyl propionic acid A mol ratio are 1 in step (1):(4-8).
Further, 130-150 DEG C is warming up to after adding p-methyl benzenesulfonic acid in step (1), and constant temperature is anti-at this temperature
Answer 2.5-3.5h.
Preferably, at the end of step (1) reaction, the acid number of reactant mixture is less than 20mg KOH/g;Then carry out taking out very
Sky, pumpdown time 1h.
Further, polyalcohol and the isocyanates reaction condition in reaction vessel are in step (2):At 70-90 DEG C
1.5-3h is reacted, continues to react 0.5-1h after adding a small amount of catalyst and HBPE.Further, what is added in step (2) lacks
Amount catalyst accounts for the 40% of catalyst total amount, i.e., amount and the middle catalyst added of step (3) of the catalyst added in step (2)
Amount ratio be 2:3.
Further, remaining catalyst, dihydromethyl propionic acid B, small molecule chain extender, a small amount of N- are added in step (3)
After ethyl pyrrolidone, it is warming up to 75-85 DEG C and continues to react 2-3h.Further, the amount of a small amount of N- ethyl pyrrolidones accounts for N-
The 50% of ethyl pyrrolidone total amount, i.e. N- ethyl pyrrolidones are divided into two parts, add at twice.
Further, the scattered speed of step (4) high speed shearing is 800-1200 revs/min.
The solid content of aqueous anionic polyurethane emulsion obtained by the present invention is 40-50%.
Present invention also offers a kind of water vacuum plastics-absorption glue, including above-mentioned aqueous anionic polyurethane emulsion.
The water vacuum plastics-absorption glue includes following raw material components and parts by weight:Ethylene-vinyl acetate copolymer 30-70
Part, aqueous anionic polyurethane emulsion 70-30 parts, wetting agent 0.5-1 parts, thickener 0.1-0.5 parts, DMAE;
Wherein, the weight of DMAE accounts for 6/10000ths-one thousandth of ethylene-vinyl acetate copolymer weight.
Further, the ethylene-vinyl acetate copolymer parts by weight are with ethylene-vinyl acetate copolymer and water-based the moon
Ion polyaminoester emulsion sum is 100 parts of meters.
Further, the ethylene-vinyl acetate copolymer is selected from commercially available prod, the preferably DA-102 of Dalian chemistry or
DA-102H。
Further, the wetting agent is the JFC of AEO, preferably Jiangsu Hai'an petrochemical industry.
Further, the thickener is that polyurethane associative thickener or alkali soluble rise type thickener.Preferably, thickener
For polyurethane associative thickener, the bright good scientific and technological PU237 of RM-8W or Shenzhen selected from ROHM AND HAAS.
Present invention also offers the method for preparing above-mentioned water vacuum plastics-absorption glue, ethylene-vinyl acetate copolymer is added
Into Scattered Kettle, DMAE, stirring are added;Aqueous anionic polyurethane emulsion is added, stirs 5min;Continue addition profit
Humectant, stir 5min;Thickener is finally added, 10min is stirred, produces water vacuum plastics-absorption glue.
Preferably, 5min is stirred after adding DMAE.
Preferably, mixing speed is 400 revs/min.
Preferably, the final obtained water vacuum plastics-absorption glue pH value of the present invention:7.5-8.5, viscosity (25 DEG C):400-
800mPa.s。
Aqueous anionic polyurethane emulsion provided by the present invention, using the polyalcohol modified resin system of hyper-branched polyester,
So that aqueous anionic polyurethane emulsion solid content is heat-resisting in 30-100mpa.s, moment highest in 40-50%, viscosity (25 DEG C)
Temperature is 120-160 DEG C.During in water vacuum plastics-absorption glue, make water vacuum plastics-absorption glue that there is excellent heat resistance, resistance to
Hou Xing, low temperature viscosity stability and adhesion strength etc..
Embodiment
Illustrate embodiments of the present invention below by way of particular specific embodiment, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.The present invention can also be by different specific in addition
Embodiment is embodied or practiced, and the various details in this specification can also be based on different viewpoints and application, not carry on the back
Various modifications or alterations are carried out under spirit from the present invention.It should be noted that in the case where not conflicting, following examples and reality
Applying the feature in example can be mutually combined.
Aqueous polyurethane (or vacuum plastic-absorption) performance test methods are as follows in the embodiment of the present invention:
Determination of solid content
By a surface plate wash clean, dry at high temperature.Weigh out the quality m1 of surface plate in the balance;Weigh 1~2g breasts
For liquid in surface plate, it is m2 to measure quality;Dried under conditions of 105 DEG C, weigh the quality of now surface plate, write down during constant weight
Quality m3.Calculated by formula:
C (%)=(m3-m1)/(m2-m1) × 100%;
In formula:C:Solid content, %;m1:Dry the quality of surface plate, g;m2:Dry the matter of surface plate and unseasoned emulsion
Amount and g;m3:Dry the quality and g of surface plate solid content.
Heat activation temperature
A width of 1cm aqueous polyurethane glued membrane is placed in the drying oven of certain temperature and toasts one hour, then rapidly
Two battens are bonded, fitting area be 1cm × 1cm, is pressed with finger, and as glued membrane is activated, then two contact surfaces will be formed chemical
Key active force, obvious external force is needed to act on if separating two contact surfaces at once.The temperature needed for the effect is produced to be defined as
Heat activation temperature.
Adhesion strength
It is base material with PVC (or plane medium density fibre board (MDF) of 2cm thickness) thick 0.25mm, is cut into 25 × 150mm specifications.Will
The aqueous polyurethane of the present invention is uniformly coated on batten, is applied cloth length and is not less than 100mm, will not by vacuum forming technique
PVC and the batten fitting of gluing.After standing 24 hours its peel strength, draw speed 100mm/min are determined with puller system.
Heat resistance
Glued in the medium density fibre board (MDF) of the groove with certain depth, after drying by vacuum forming technique by PVC and
Medium density fibre board (MDF) is bonded, and is put in after standing 24 hours inside the insulating box of design temperature and is seen medium density fibre board (MDF) groove PVC
Whether come unglued situation.Record per hour once.
Embodiment 1
1st, the preparation of aqueous anionic polyurethane emulsion
Raw material components:10 parts of pentaerythrite (PE), 39.5 parts of dihydromethyl propionic acid A (DMPA), N,N-dimethylformamide
(DMF) 40 parts, 0.005 part of p-methyl benzenesulfonic acid, 200 parts of polyalcohol, 35 parts of TDI, 0.03 part of stannous octoate, dihydromethyl propionic acid B
10 parts, 5 parts of 1,4- butanediols, 50 parts of N- ethyl pyrrolidones, 7.5 parts of triethylamine, 270 parts of deionized water;
Method:(1) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add pentaerythrite 10 parts of (PE)
With 39.5 parts of dihydromethyl propionic acid A (DMPA), with 40 parts of DMFs (DMF) for solvent, p-methyl benzenesulfonic acid is added
0.005 part, 130 DEG C, isothermal reaction 2.5h are to slowly warm up to, until acid number is less than 20mg KOH/g, 1h is vacuumized, removes DMF,
Obtain hyper-branched polyester HBPE;
(2) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add polyalcohol Jing Guo dewater treatment
200 parts and 35 parts of TDI, 70 DEG C of reaction 3h, gained HBPE in step (1) is slowly added dropwise, adds 0.012 part of stannous octoate, after
Continuous reaction 0.5h;
(3) 70 DEG C are cooled to, adds 0.018 part of stannous octoate, 10 parts of dihydromethyl propionic acid B, 5 parts of Isosorbide-5-Nitrae-fourth two
Alcohol, 25 parts of N- ethyl pyrrolidones, 75 DEG C of reaction 2.5h are warming up to, add 25 parts of N- ethyl pyrrolidones, be cooled to 60
DEG C, add in 7.5 parts of triethylamine and 10min.
(4) 270 parts of deionized water in the case where high speed shear is scattered (rotating speed is 800 revs/min), is added to step (3)
In the material of gained, be uniformly dispersed to obtain aqueous anionic polyurethane emulsion;Gained aqueous anionic polyurethane emulsion solid content is
49.41%, viscosity (27 DEG C) is 100mpa.s, and moment highest heatproof is 120 DEG C.
2nd, the preparation of water vacuum plastics-absorption glue
Raw material components:60 parts of aqueous anionic polyurethane emulsion, ethylene-vinyl acetate emulsion DA-102 (Dalian chemistry)
40 parts, 0.035 part of dimethylethanolamine, 0.6 part of wetting agent jfc, 0.1 part of thickener PU237;
Wherein, wetting agent JFC, thickener are the RM-8W of ROHM AND HAAS;
Preparation method:According to formula, ethylene-vinyl acetate emulsion DA-102 is added in Scattered Kettle, adds diformazan
Ethylethanolamine, 5min is stirred with 400 revs/min of rotating speed;Aqueous anionic polyurethane emulsion is added, stirs 5min;Addition profit
Humectant, stir 5min;Thickener is finally added, 10min is stirred, produces water vacuum plastics-absorption glue.
The solid content of obtained water vacuum plastics-absorption glue is 51.64%, pH value 8.21, and viscosity (25 DEG C) is
610mPa.s, adhesion strength (PVC/ MDFs) are 3.0N/mm, and activation temperature is 60 DEG C, and heat-resisting 65 DEG C do not come unglued for 24 hours.
Embodiment 2
1st, the preparation of aqueous anionic polyurethane emulsion
Raw material components:10 parts of pentaerythrite (PE), 49.5 parts of dihydromethyl propionic acid A (DMPA), N,N-dimethylformamide
(DMF) 60 parts, 0.006 part of p-methyl benzenesulfonic acid, 245 parts of polyalcohol, 54 parts of TDI, 0.04 part of stannous octoate, dihydromethyl propionic acid B
12.5 parts, 7 parts of 1,6-HD, 56 parts of N- ethyl pyrrolidones, 8.3 parts of dimethylethanolamine, 450 parts of deionized water;
Preparation method:(1) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add pentaerythrite (PE)
10 parts and 49.5 parts of dihydromethyl propionic acid A (DMPA), with 60 parts of DMFs (DMF) for solvent, add to toluene
0.006 part of sulfonic acid, 135 DEG C, isothermal reaction 3h are to slowly warm up to, until acid number is less than 20mg KOH/g, vacuumize 1h, removed
DMF, obtain hyper-branched polyester HBPE.
(2) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add polyalcohol Jing Guo dewater treatment
245 parts and 54 parts of TDI, 80 DEG C of reaction 2.5h, gained HBPE in step 1 is slowly added dropwise, adds 0.016 part of stannous octoate, after
Continuous reaction 0.5h.
(3) be cooled to 65 DEG C, add 0.024 part stannous octoate, 12.5 parts of dihydromethyl propionic acid B, the 1,6- of 4.5 parts
Hexylene glycol, 28 parts of N- ethyl pyrrolidones, 85 DEG C of reaction 2h are warming up to, add 28 parts of N- ethyl pyrrolidones, be cooled to
60 DEG C, add in 8.3 parts of dimethylethanolamine and 2min.
(4) 450 parts of deionized water in the case where high speed shear is scattered (rotating speed is 1000 revs/min), is added to step (3)
In the material of gained, be uniformly dispersed to obtain aqueous anionic polyurethane emulsion, and gained aqueous anionic polyurethane emulsion solid content is
43.15%, viscosity (25 DEG C) is 35mpa.s, and moment highest heatproof is 135 DEG C.
2nd, the preparation of water vacuum plastics-absorption glue
Raw material components:60 parts of aqueous anionic polyurethane emulsion, ethylene-vinyl acetate emulsion DA-102 (Dalian chemistry)
40 parts, 0.035 part of dimethylethanolamine, 0.6 part of wetting agent jfc, 0.1 part of thickener PU237;
Preparation method:According to formula, ethylene-vinyl acetate emulsion DA-102 is added in Scattered Kettle, adds diformazan
Ethylethanolamine, stirred 5 minutes with 400 revs/min of rotating speed;Aqueous anionic polyurethane emulsion is added, is stirred 5 minutes;Addition
Wetting agent, stir 5 minutes;Thickener is finally added, 10min is stirred, produces water vacuum plastics-absorption glue.
Obtained water vacuum plastics-absorption glue, its solid content are 47.89%, pH value 8.02, and viscosity (25 DEG C) is
600mPa.s, adhesion strength (PVC/ MDFs) are 3.2N/mm, and activation temperature is 55 DEG C, and heat-resisting 70 DEG C do not come unglued for 24 hours.
Embodiment 3
1st, the preparation of aqueous anionic polyurethane emulsion
Raw material components:10 parts of pentaerythrite (PE), 59 parts of dihydromethyl propionic acid A (DMPA), N,N-dimethylformamide
(DMF) 70 parts, 0.009 part of p-methyl benzenesulfonic acid, 300 parts of polyalcohol, 70 parts of TDI, 0.05 part of stannous octoate, dihydromethyl propionic acid B
16.5 parts, 10 parts of 1,6-HD, 60 parts of N- ethyl pyrrolidones, 12.5 parts of triethylamine, 457 parts of deionized water;
Preparation method is:(1) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add pentaerythrite
(PE) 10 parts and 59 parts of dihydromethyl propionic acid A (DMPA), with 70 parts of DMFs (DMF) for solvent, add to first
0.006 part of benzene sulfonic acid, 145 DEG C, isothermal reaction 3h are to slowly warm up to, until acid number is less than 20mg KOH/g, vacuumize 1h, removed
DMF, obtain hyper-branched polyester HBPE;
(2) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add polyalcohol Jing Guo dewater treatment
300 parts and 70 parts of TDI, 90 DEG C of reaction 1.5h, gained HBPE in step 1 is slowly added dropwise, adds 0.02 part of stannous octoate, after
Continuous reaction 1h;
(3) be cooled to 65 DEG C, add 0.03 part stannous octoate, 16.5 parts of dihydromethyl propionic acid B, 10 parts of 1,6- oneself
Glycol, 30 parts of N- ethyl pyrrolidones, 85 DEG C of reaction 2h are warming up to, add 30 parts of N- ethyl pyrrolidones, be cooled to 60
DEG C, add in 12.5 parts of triethylamine and 10min;
(4) 457 parts of deionized water in the case where high speed shear is scattered (rotating speed is 1100 revs/min), is added to step (3)
In the material of gained, be uniformly dispersed to obtain aqueous anionic polyurethane emulsion, and gained aqueous anionic polyurethane emulsion solid content is
48.05%, viscosity (25 DEG C) is 65mpa.s, and moment highest heatproof is 150 DEG C.
2nd, the preparation of water vacuum plastics-absorption glue
Raw material components:50 parts of aqueous anionic polyurethane emulsion, ethylene-vinyl acetate emulsion DA-102 (Dalian chemistry)
50 parts, 0.05 part of dimethylethanolamine, 1 part of wetting agent jfc, 0.5 part of thickener PU237;
Preparation method:According to formula, ethylene-vinyl acetate emulsion DA-102 is added in Scattered Kettle, adds diformazan
Ethylethanolamine, stirred 5 minutes with 400 revs/min of rotating speed;Aqueous anionic polyurethane emulsion is added, is stirred 5 minutes;Addition
Wetting agent, stir 5 minutes;Thickener is finally added, 10min is stirred, produces water vacuum plastics-absorption glue.
Obtained water vacuum plastics-absorption glue, its solid content are 50.83%, pH value 8.15, and viscosity (25 DEG C) is
600mPa.s, adhesion strength (PVC/ MDFs) are 3.4N/mm, and activation temperature is 50 DEG C, and heat-resisting 72 DEG C do not come unglued for 24 hours.
Embodiment 4
1st, the preparation of aqueous anionic polyurethane emulsion
Raw material components:10 parts of pentaerythrite (PE), 79 parts of dihydromethyl propionic acid A (DMPA), N,N-dimethylformamide
(DMF) 90 parts, 0.008 part of p-methyl benzenesulfonic acid, 350 parts of polyalcohol, 80 parts of TDI, 0.05 part of stannous octoate, dihydromethyl propionic acid B
18 parts, 9 parts of 1,4- butanediols, 80 parts of N- ethyl pyrrolidones, 13.5 parts of triethylamine, 480 parts of deionized water;
Preparation method:(1) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add pentaerythrite (PE)
10 parts and 79 parts of dihydromethyl propionic acid A (DMPA), with 90 parts of DMFs (DMF) for solvent, add to toluene sulphur
0.008 part of acid, is to slowly warm up to 150 DEG C, isothermal reaction 3.5h, until acid number is less than 20mg KOH/g, vacuumizes 1h, removing
DMF, obtain hyper-branched polyester HBPE.
(2) equipped with mechanical agitation, thermometer, condenser pipe four-hole boiling flask in add polyalcohol Jing Guo dewater treatment
350 parts and TDI80 parts, 85 DEG C of reaction 2.5h, are slowly added dropwise gained HBPE in step 1, add 0.02 part of stannous octoate, continue
React 1h.
(3) 60 DEG C are cooled to, adds 0.03 part of stannous octoate, 18 parts of dihydromethyl propionic acid B, 9 parts of Isosorbide-5-Nitrae-fourth two
Alcohol, 40 parts of N- ethyl pyrrolidones, 80 DEG C of reaction 3h are warming up to, add 40 parts of N- ethyl pyrrolidones, be cooled to 60 DEG C,
Add in 13.5 parts of triethylamine and 10min.
(4) 750 parts of deionized water in the case where high speed shear is scattered (rotating speed is 1200 revs/min), is added to step (3)
In the material of gained, be uniformly dispersed to obtain aqueous anionic polyurethane emulsion, and gained aqueous anionic polyurethane emulsion solid content is
40.21%, viscosity (25 DEG C) is 45mpa.s, and moment highest heatproof is 160 DEG C.
2nd, the preparation of water vacuum plastics-absorption glue
Raw material components:30 parts of aqueous anionic polyurethane emulsion, ethylene-vinyl acetate emulsion DA-102 (Dalian chemistry)
70 parts, 0.06 part of dimethylethanolamine, 0.85 part of wetting agent jfc, 0.35 part of thickener PU237;
Preparation method:According to formula, ethylene-vinyl acetate emulsion DA-102 is added in Scattered Kettle, adds diformazan
Ethylethanolamine, stirred 5 minutes with 400 revs/min of rotating speed;Aqueous anionic polyurethane emulsion is added, is stirred 5 minutes;Addition
Wetting agent, stir 5 minutes;Thickener is finally added, 10min is stirred, produces water vacuum plastics-absorption glue.
Obtained water vacuum plastics-absorption glue, its solid content are 46.12%, pH value 7.90, and viscosity (25 DEG C) is
670mPa.s, adhesion strength (PVC/ MDFs) are 3.5N/mm, and activation temperature is 65 DEG C, and heat-resisting 75 DEG C do not come unglued for 24 hours.
The performance comparison of the water vacuum plastics-absorption glue of table 1
In summary, the aqueous anionic polyurethane emulsion obtained by the present invention is used in water vacuum plastics-absorption glue, is obtained
Water vacuum plastics-absorption glue resistance to elevated temperatures is good, adhesion strength is preferable, and more stable viscosity efficiently solves in the prior art
The defects of existing.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of aqueous anionic polyurethane emulsion, it is characterised in that including following raw material components and parts by weight:Pentaerythrite
10 parts, it is dihydromethyl propionic acid A39.5-79 parts, N,N-dimethylformamide 40-90 parts, p-methyl benzenesulfonic acid 0.005-0.09 parts, more
First alcohol 200-350 parts, isocyanates 35-80 parts, catalyst 0.03-0.05 parts, small molecule chain extender 5-10 parts, dihydroxymethyl third
Sour B 10-18 parts, N- ethyl pyrrolidone 50-80 parts, nertralizer 6.7-13.5 parts, deionized water 270-480 parts.
2. aqueous anionic polyurethane emulsion according to claim 1, it is characterised in that include any one of following feature
It is or multinomial:
The polyalcohol is adipic acid series PEPA;
The isocyanates is toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate;
The catalyst is selected from one or both of stannous octoate, dibutyl tin laurate;
The small molecule chain extender is in diglycol, ethylene glycol, 1,4- butanediols, neopentyl glycol, 1,6-HD
One or more combinations.
A kind of 3. method for preparing the aqueous anionic polyurethane emulsion as described in any one of claim 1 to 2, it is characterised in that
Comprise the following steps:
(1) pentaerythrite and dihydromethyl propionic acid A are added in reaction vessel, add DMF, Ran Houjia
Enter p-methyl benzenesulfonic acid, heat up and react at a constant temperature, after reaction terminates, vacuumize, obtain hyper-branched polyester HBPE;
(2) polyalcohol and isocyanates are added in reaction vessel and reacted, be then added dropwise HBPE that step (1) obtains, with
And a small amount of catalyst, continue to react;
(3) reaction solution that step (2) is obtained is cooled to less than 70 DEG C, adds remaining catalyst, dihydromethyl propionic acid
B, small molecule chain extender, a small amount of N- ethyl pyrrolidones, continue to react after heating, then add remaining N- ethyl pyrrolidones,
60 DEG C are cooled to, adds nertralizer neutralization reaction 2-10min;
(4) in the case where high speed shear is scattered, deionized water is added in the reaction solution of step (3), water is produced after being uniformly dispersed
Property anionic polyurethane emulsion.
4. according to the method for claim 3, it is characterised in that step (1) includes any one or multinomial of following feature:
Pentaerythrite and dihydromethyl propionic acid A mol ratio are 1:(4-8);
130-150 DEG C is warming up to, and reacts 2.5-3.5h at a constant temperature;
Acid number is less than 20mg KOH/g at the end of reaction.
5. according to the method for claim 3, it is characterised in that any one or multinomial also included the following features:
Step (2) reacts 1.5-3h at 70-90 DEG C, continues to react 0.5-1h after adding catalyst and HBPE;
The amount that a small amount of catalyst is added in step (2) accounts for the 40% of catalyst total amount;
The amount of a small amount of N- ethyl pyrrolidones accounts for the 50% of N- ethyl pyrrolidone total amounts in step (3);
The scattered speed of step (4) high speed shearing is 800-1200 revs/min.
6. according to the method for claim 3, it is characterised in that the solid content of obtained aqueous anionic polyurethane emulsion
For 40-50%.
7. a kind of water vacuum plastics-absorption glue, it is characterised in that including any one of claim 1 to the 2 water-based poly- ammonia of anion
Ester emulsion.
8. water vacuum plastics-absorption glue according to claim 7, it is characterised in that the water vacuum plastics-absorption glue includes following
Raw material components and parts by weight:Ethylene-vinyl acetate copolymer 30-70 parts, aqueous anionic polyurethane emulsion 70-30 parts, profit
Humectant 0.5-1 parts, thickener 0.1-0.5 parts, DMAE;
Wherein, the weight of DMAE accounts for 6/10000ths-one thousandth of ethylene-vinyl acetate copolymer weight.
A kind of 9. method for preparing the water vacuum plastics-absorption glue as described in any one of claim 7 to 8, it is characterised in that by ethene-
Acetate ethylene copolymer is added in Scattered Kettle, adds DMAE, stirring;Aqueous anionic polyurethane emulsion is added,
Stir 5min;Continue to add wetting agent, stir 5min;Thickener is finally added, 10min is stirred, produces water vacuum plastics-absorption glue.
10. according to the method for claim 9, it is characterised in that obtained water vacuum plastics-absorption glue pH value:7.5-8.5
Viscosity:400-800mPa.s.
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