CN101284980B - Preparation method of waterborne polyurethane adhesive and application in roads reflecting material - Google Patents
Preparation method of waterborne polyurethane adhesive and application in roads reflecting material Download PDFInfo
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Abstract
The invention relates to the nano-powder preparation field, in particular to a method for preparing nearly spherical nanometer oxide powder having good monodispersity and uniform particle size distribution with ultrasonic atomization. The method is characterized in that: the synthesis of water polyurethane is divided into three stages; a first stage is stepwise polymerization, i.e. polyurethane prepolymer is formed from oligomer polylol, hydrophilic monomers, modified monomers and isocyanate through stepwise polymerization; a second stage is the dispersion of the prepolymer in water after neutralization and salt formation; a third stage is the formation of water polyurethane emulsion after hydrophilic chain extender is added. The invention adopts a route of polymerizing modified monomers and polyurethane monomers jointly with different reaction mechanisms to ensure that modified monomers and polyurethane monomers are interpenetrated or grafted, thus obtained products have multiple material characteristics, i.e. the characteristics of acrylic acid, epoxy, hydroxyl silane and other materials are led into the products at the same time when the advantages of polyurethane material are maintained, so as to ensure that target products have stronger adaptability and better performance.
Description
Technical field
The present invention relates to a kind of tackiness agent, refer in particular to the preparation method of waterborne polyurethane adhesive and the application on roads reflecting material thereof.
Background technology
Waterborne polyurethane adhesive is meant that urethane is water-soluble or is scattered in the water and the tackiness agent that forms.
Get into 21 century, the critical role of environmental protection in people's daily life shows especially day by day, be industrial goods or family daily necessity all towards environmentally friendly trend development, this just provides wide application prospect for the use of novel environment friendly material.Water-based polyurethane adhesive is then complied with this market requirement and is produced.
The making of aqueous polyurethane generally comprises two key steps: 1, by oligomer polyol and polyisocyanates compound polymerization, form high-molecular weight urethane or middle high-molecular weight base polyurethane prepolymer for use as; 2, under high-speed stirring, in water, disperse.The base polyurethane prepolymer for use as of end NCO group can disperse or emulsification promptly outer emulsion process in water under shearing force suitable outer emulsifying agent and strong.Yet the dispersion liquid by this method makes is extremely coarse and very unstable.
In order better to improve the over-all properties of aqueous polyurethane; The broadened application scope; Go deep into along with what water-based polyurethane adhesive structure, performance were understood in recent years; Problem such as the stability of emulsion to its existence is poor, rate of drying slow,, original viscosity bad to the non-polar substrate wettability and water tolerance are low, many researchers further investigate.
So Ge Wen etc. uses epoxy resin modification urethane, prepares cation emulsion through high speed dispersion, is used to cohere Vestolen PP 7052 fine hair.Excellent propertys such as product sticking power, water tolerance, feel, but owing to be that the mechanical dispersion stability of emulsion is poor.
Wang Chunhui etc. utilize polyester diol, isophorone diisocyanate (IPDI), dimethylol propionic acid (DMPA), tetrabutyl titanate (TET); Adopt the sol-gel method preparation principle; Behind synthetic water based polyurethane performed polymer, add tetrabutyl titanate immediately; Mix, add emulsifying water, prepared nano-TiO
2/ anion aqueous polyurethane tackiness agent.The binder particles median size is 100nm, and freeze thaw stability reaches the non-polar substrate wettability is had some improvement.But this technical matters is complicated, and cost is higher.
Chinese patent 01144663.3 adopts IPN technology and seeded emulsion polymerization, makes the acrylic acid modified polyurethane tackiness agent of " nuclear-shell " structure with PU/PA polymer network IPN, and it is adjustable that its latex particle size is distributed in 20mm-200mm.This technology is to do polyaminoester emulsion earlier, is seed with this emulsion, adds emulsifying agent, and the dropwise addition of acrylic acid modified monomer is used the initiator initiated polymerization.The shortcoming of this way is: synthesize and carry out in two steps; Need add emulsifying agent in the reaction, the modified monomer consumption is limited; The gained stability of emulsion is poor.
Chinese patent 200610019567.9 has reported that " a kind of natural macromolecular composite aqueous polyurethane bond and preparation method thereof " its method is with emulsion blendings such as 10-25% polyaminoester emulsion and 40-100% starch, Sunlover 10, treated starch, modified soy proteins; Purpose is to reduce cost, and product is biodegradable.This technological shortcoming is that product is a co-mixing system, poor stability; The shared share of polyaminoester emulsion is lower, and performance is restricted.
Summary of the invention
The present invention is major ingredient and isocyanate-monomer pre-polymerization with the polyether glycol, through IPN, modified method such as crosslinked, has synthesized the anion-modified polyurethane binder water miscible liquid of self-emulsifying type.
Defective and deficiency to the prior art existence; Change prior art in synthetic and " do base polyurethane prepolymer for use as, water and milk earlier; add the method for modified monomer, emulsifying agent modification again "; Adopt modified monomer and the route of urethane monomer with different reaction mechanism co-polymerized, two steps of change synthesize a step, make modified monomer and base polyurethane prepolymer for use as IPN or grafting; Products obtained therefrom has plurality of material properties concurrently, promptly when keeping the polyurethane material advantage, introduces the speciality of materials such as vinylformic acid, epoxy, silicol.The gained emulsion is transparent or semitransparent shape, and good stability is water-fast, heat-resisting and weathering resistance is good.Target product flexibility is stronger, and performance is more excellent.
Aluminium sheet and film that synthetic aqueous polyurethane adhesive product of the present invention is used for light reflecting material is bonding, replace at present the generally solvent-borne type pressure sensitive adhesive of use, the production technique cleaning can reduce environmental pollution, reduces production safety hidden danger.
Operational path of the present invention is following:
The method for preparing the anion-modified polyurethane binder water miscible liquid of self-emulsifying type of the present invention is divided into three phases.Fs is progressively polymerization, promptly passes through progressively polymerization by oligomer polyol, hydrophilic monomer, modified monomer, isocyanic ester and generates base polyurethane prepolymer for use as; Subordinate phase be in salify after the dispersion of performed polymer in water; Phase III forms aqueous polyurethane emulsion after adding the wetting ability chainextender.
It adopts modified monomer and urethane monomer to add simultaneously; Wherein oligomer polyol comprises that molecular weight is polyether glycol, polyester polyol, polycarbonate, polycaprolactone, polybutadiene diol, the propenoate polyvalent alcohol of 500-4000, also has polyol blend: polyether-polyester, polyethers-polyhutadiene, polyester-polyhutadiene; Hydrophilic monomer comprises the monomer that contains carboxyl, sulfonic acid or sulfonate groups or secondary amine; Modified monomer comprises Bing Xisuandingzhi, TEB 3K, Hydroxyethyl acrylate, vinyl acetate; Isocyanic ester comprises: tolylene diisocyanate TDI, ditan-4; 4 '-vulcabond MDI, liquefied mdi, poly methylene poly phenyl poly isocyanate PAPI, hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, Methylcyclohexyl diisocyanate HTDI, wherein to account for the per-cent of the total material of reaction be 2%-7% to hydrophilic monomer; Modified monomer accounts for the 0%-10% of the total material of reaction; The per-cent that isocyanic ester accounts for the total material of reaction is 10%-30%, and the mol ratio that generates NCO/OH in the performed polymer is 1.00～1.30, and synthesis condition is: vacuum tightness is 0.080～0.1MPa; Just gather 70～95 ℃ of temperature; Just gather 2～6 hours reaction times, neutral temperature: 30～65 ℃, theoretical solid content (participating in the total material (it is outer with solvent to dewater) of reaction and the ratio of the total material of adding system) is 20～50%.
As previously mentioned, the anion-modified polyurethane binder water miscible liquid of self-emulsifying type of the present invention has following main repeat unit structure:
R wherein
1For being derived from the segment of oligomer polyol (polyether-type, polyester type and polyolefin-type etc.); Refer to that respectively molecular weight is the polyether glycol of 500-4000, polyester polyol, polycarbonate, polycaprolactone, polybutadiene diol, propenoate polyvalent alcohol) etc. segment, also have the segment of polyol blend types such as polyether-polyester, polyethers-polyhutadiene, polyester-polyhutadiene.R
2For being derived from the segment of isocyanic ester, i.e. the segment of isocyanic ester except that NCO can be divided into the segment of aromatic isocyanate type, aliphatic isocyanates type, alicyclic isocyanate type.R
3For being derived from the segment of wetting ability chainextender, promptly the segment beyond the chainextender hydroxyl-removal is respectively the segment that contains carboxyl, sulfonic acid (salt) group or secondary amine.Also contain modified monomer (epoxy, propenoate, organosilicon etc.) in this aqueous polyurethane; Epoxy resin and organosilicon are hydroxy-containing compounds; With polyurethane reaction in can branch point be introduced polyurethane backbone, make it part and form reticulated structure, these modified monomers and urethane monomer add simultaneously; And with different reaction mechanism co-polymerized; Make modified monomer and base polyurethane prepolymer for use as IPN or grafting, an amount of modified monomer and urethane copolymerization can obviously improve water-fast, the anti-solvent and the tack of product, make product performance more excellent.
In water-based polyurethane adhesive of the present invention, wherein generate R
1Comprise the segment that is derived from polyether glycol that molecular weight is 500-3000, polyester polyol, polycarbonate, polycaprolactone, polybutadiene diol, propenoate polyvalent alcohol etc.; The segment that also has polyol blend types such as polyether-polyester, polyethers-polyhutadiene, polyester-polyhutadiene; Be preferable over polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene tetrol, PTMG, polypropyleneoxide ether glycol, THF homopolymer propylene oxide copolymerization glycol, polyethylene glycol adipate glycol, gather hexanodioic acid-1; 6-pinakon esterdiol, gather hexanodioic acid-1; 4-butanediol ester glycol, poly-epsilon-caprolactone glycol, polycarbonate-1; The segment of 6-pinakon esterdiol, more preferably in polyoxypropyleneglycol, PTMG, gather hexanodioic acid-1, the segment of 4-butanediol ester glycol etc.; Most preferably in polyoxypropyleneglycol and polyoxytrimethylene triol, it is pressed mass ratio and mixed in 1: 12～3: 5.
In water-based polyurethane adhesive of the present invention, generate R
2Comprise that isocyanic ester is preferably tolylene diisocyanate (TDI), ditan-4; 4 '-vulcabond (MDI), liquefied mdi, poly methylene poly phenyl poly isocyanate (PAPI), 1; Hexamethylene-diisocyanate (HDI), isophorone diisocyanate (IPDI), methylene radical-dicyclohexyl-4,4 '-vulcabond (H
12MDI), the segment of Methylcyclohexyl diisocyanate (HTDI) etc., more preferably in liquefied mdi, isophorone diisocyanate (IPDI).Wherein to account for the per-cent of reaction mass be 12%-24% to MDI, and the per-cent that IPDI accounts for reaction mass is 10%-30%.
In aqueous polyurethane of the present invention, R
3The wetting ability chainextender of representative; Be respectively the segment that contains carboxyl, sulfonic acid (salt) group or secondary amine, be preferable over 2,2-dimethylol propionic acid (DMPA), quadrol base ethyl sulfonic acid sodium, 1; 4-butyleneglycol-2-sodium sulfonate and verivate thereof, N methyldiethanol amine are most preferably in DMPA.
In the preparation method of the anion-modified polyurethane binder water miscible liquid of self-emulsifying type of the present invention, synthesis modification is to accomplish in a step.Particularly, in synthesizing modified monomer and urethane monomer are added simultaneously, with different reaction mechanism co-polymerized.Modified monomer can be participated in the urethane polymerization and got into polyurethane backbone, carries out radical polymerization again and forms grafting, also can carry out radical polymerization and polyurethane backbone separately and form IPN.As: polyether glycol, DMPA and the synthetic performed polymer of MDI reaction; Modified monomer n-butyl acrylate and Hydroxyethyl acrylate carry out radical polymerization simultaneously; Make modified monomer and base polyurethane prepolymer for use as grafting, or modified monomer itself carries out radical polymerization and base polyurethane prepolymer for use as forms IPN.
Advantage of the present invention is:
Change prior art in synthetic and " do base polyurethane prepolymer for use as, water and milk earlier; add the method for modified monomer, emulsifying agent modification again ", adopt modified monomer and the route of urethane monomer, make modified monomer and base polyurethane prepolymer for use as IPN or grafting with different reaction mechanism co-polymerized; Products obtained therefrom has plurality of material properties concurrently; Promptly when keeping the polyurethane material advantage, introduce the speciality of materials such as vinylformic acid, epoxy, silicol, make target product flexibility stronger, performance is more excellent.
Prior art adopts seeded emulsion polymerization more, promptly does polyaminoester emulsion earlier, in this emulsion, adds emulsifying agent, drips modified monomer again, gets the modified aqueous polyurethane breast with the initiator initiated polymerization.The shortcoming of this way is: need add emulsifying agent in the reaction; The modified monomer consumption is limited; The gained stability of emulsion is poor.The present invention with modified monomer and urethane monomer add simultaneously, co-polymerized need not to add emulsifying agent, solved the emulsification problem of modified monomer, and production technique is simplified, and operate more easy to controlly, the gained dispersion particle size is littler, stability better.
The aluminium sheet and the film that the anion-modified polyurethane binder of synthetic self-emulsifying type of the present invention are used for light reflecting material are bonding; Sponge and PE plate are bonding, sponge with mould bondingly firmly, film and film are bonding etc.; Replace the present solvent-borne type pressure sensitive adhesive that generally uses; The employing cleaning procedure is produced, and can reduce environmental pollution, reduces production safety hidden danger.
Embodiment
The following example is used to explain the present invention, but does not certainly limit the scope of the invention.
Embodiment 1:
0.61g is gathered hexanodioic acid-1, and 4-butanediol ester glycol, 33.0g polyethers 330 and 2.2gDMPA add and mix stirring in the there-necked flask, in the time of 80 ℃, vacuumize dehydration 1.5h, and vacuum tightness is 0.095MPa.Add 1.9gNMP (1-Methyl-2-Pyrrolidone), 0.76gHEA (Hydroxyethyl acrylate), 7.54gIPDI and little amount of catalyst then successively, the nco value of reacting by heating in system gets prepolymer when reaching theoretical value basically, and begins cooling.Prepolymer is cooled to 60 ℃, earlier with the proper amount of acetone dilution, treat that viscosity reduces after, under high-speed stirring, drip the 1.2g triethylamine and carry out in the emulsification pretreatment and salify.Add 163.14g water after changing basic the completion mutually; Slowly drip chainextender 0.65g quadrol subsequently; Further the chain extension emulsion reaction is about 30 minutes, and (theoretical solid content (total material (it is outer with solvent to dewater) of promptly participating in reaction is divided by the total material of adding system) is 22.63% to obtain having a little the white emulsion of blue light.Wherein hydrophilic monomer accounts for 4%, and modified monomer accounts for 1%, and isocyanic ester accounts for 17%, and NCO/OH is 1.11.
Embodiment 2:
Under the operational condition of embodiment 1; To gather hexanodioic acid-1; 4-butanediol ester glycol consumption is adjusted into 20.85g, and polyethers 330 is adjusted into 3.0g, DMPA is 2.0g, and IPDI is adjusted into 8.05gMDI; Water consumption is 72.43g, obtains the translucent PU emulsion (theoretical solid content is 34.66%) that has a little blue light at last.Wherein hydrophilic monomer accounts for 5%, and modified monomer accounts for 2%, and isocyanic ester accounts for 22%, and NCO/OH is 1.00.
Embodiment 3:
Under the operational condition of embodiment 1; Change hydroxy component into 15.9g polyethers 330 and 5.4g polyethers 220, add 1.0g epoxy E-51 in addition, the IPDI consumption is 6.5g; Water consumption is 76.47g, obtains the PU emulsion (theoretical solid content is 31.59%) of zona pellucida blue light at last.Wherein hydrophilic monomer accounts for 7%, and modified monomer accounts for 2.4%, and isocyanic ester accounts for 21%, and NCO/OH is 1.07.
Embodiment 4:
Under the operational condition of embodiment 1, change hydroxy component into 11.9g polyethers 210, the DMPA consumption is 1.6g, and IPDI is 6.5g, and water consumption is 67.53g, obtains the emulsion (theoretical solid content is 26.71%) of milky white band blue light at last.Wherein hydrophilic monomer accounts for 7%, and modified monomer accounts for 3.3%, and isocyanic ester accounts for 28%, and NCO/OH is 1.13.
Embodiment 5:
Under the operational condition of embodiment 1, change hydroxy component into 21.9g polyethers 220, the DMPA consumption is 1.6g, and isocyanate component changes 7.33MDI into, and water consumption is 79.21g, obtains the emulsion (theoretical solid content is 30.85%) of semi-transparent zone blue light at last.Wherein hydrophilic monomer accounts for 5%, and modified monomer accounts for 2.3%, and isocyanic ester accounts for 22%, and NCO/OH is 1.03.
Embodiment 6:
On the basis of embodiment 3; Adopt tap funnel with the 0.76gHEA for preparing, 1.9gNMP, 2.4g modified monomer BA (n-butyl acrylate) simultaneously; Evenly be added drop-wise in the there-necked flask with 0.031g AIBN initiator mixed solution, subsequent step is according to embodiment 1 operation, and the water yield is a 44.41g water; Obtain having a little the white emulsion of blue light, at room temperature place and become comparatively transparent slightly yellowy PU emulsion (theoretical solid content is 40.56%) after 1 hour.Wherein hydrophilic monomer accounts for 6%, and modified monomer accounts for 9%, and isocyanic ester accounts for 18%, and NCO/OH is 1.07.
Embodiment 7:
Under the operational condition of embodiment 1, change polyethers 330 consumptions into 47.3g, the DMPA consumption is 1.6g, and IPDI changes 8.42g into, and water consumption is 118.75g, obtains the emulsion (theoretical solid content is 31.04%) that milky white has a little blue light at last.Wherein hydrophilic monomer accounts for 2.6%, modified monomer 1.2%, and isocyanic ester accounts for 14%, and NCO/OH is 1.25.
Testing method:
Measure 180 ° of stripping strengths and measure and press GB/T2790-1995, before the test prepared water-based polyurethane adhesive is evenly coated on the film and is affixed on the aluminium flake of handling mensuration after 24 hours after to be dried; Tack is measured and is pressed GB/T4852-1984; Hold viscosity and measure,, measure the sample required time of displacement 2cm the counterweight that is bonded at the obtained pressure sensitive adhesive sealing tape sample one end suspension predetermined weight (800g) on the test board by GB/T4851-1984.
The salient features of the foregoing description products obtained therefrom is listed in the table below:
Claims (8)
1. the preparation method of waterborne polyurethane adhesive; The synthetic three phases that is divided into that it is characterized in that aqueous polyurethane; Fs is progressively polymerization, promptly passes through progressively polymerization by oligomer polyol, hydrophilic monomer, modified monomer, isocyanic ester and generates base polyurethane prepolymer for use as; Subordinate phase be in salify after the dispersion of performed polymer in water; Phase III forms aqueous polyurethane emulsion after adding the wetting ability chainextender; Adopt modified monomer and urethane monomer to add simultaneously; Wherein oligomer polyol is that molecular weight is polyether glycol, polyester polyol, polycarbonate, polycaprolactone, polybutadiene diol, the propenoate polyvalent alcohol of 500-4000, or polyol blend: polyether-polyester, polyethers-polyhutadiene, polyester-polyhutadiene; Hydrophilic monomer is the monomer that contains carboxyl, sulfonic acid or sulfonate groups or secondary amine; Modified monomer is Bing Xisuandingzhi, TEB 3K, Hydroxyethyl acrylate, vinyl acetate; Isocyanic ester is tolylene diisocyanate TDI, ditan-4; 4 '-vulcabond MDI, liquefied mdi, poly methylene poly phenyl poly isocyanate PAPI, hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, Methylcyclohexyl diisocyanate HTDI, wherein to account for the per-cent of the total material of reaction be 2%-7% to hydrophilic monomer; Modified monomer accounts for the 1%-9% of the total material of reaction; The per-cent that isocyanic ester accounts for the total material of reaction is 10%-30%, and the mol ratio that generates NCO/OH in the performed polymer is 1.00～1.30, and synthesis condition is: vacuum tightness is 0.080～0.1MPa; Just gather 70～95 ℃ of temperature; Just gather 2～6 hours reaction times, neutral temperature: 30～65 ℃, theoretical solid content is 20～50%.
2. the preparation method of waterborne polyurethane adhesive according to claim 1; It is characterized in that oligomer polyol is polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene tetrol, PTMG, polypropyleneoxide ether glycol, THF homopolymer-propylene oxide copolymerization glycol, polyethylene glycol adipate glycol, gathers hexanodioic acid-1; 6-pinakon esterdiol, gather hexanodioic acid-1; 4-butanediol ester glycol, poly-epsilon-caprolactone glycol or polycarbonate-1,6-pinakon esterdiol.
3. the preparation method of waterborne polyurethane adhesive according to claim 2 is characterized in that oligomer polyol is polyoxypropyleneglycol, PTMG or gathers hexanodioic acid-1,4-butanediol ester glycol.
4. the preparation method of waterborne polyurethane adhesive according to claim 2 is characterized in that oligomer polyol is polyoxypropyleneglycol and polyoxytrimethylene triol, mixing in 1: 12～3: 5 that it presses mass ratio.
5. the preparation method of waterborne polyurethane adhesive according to claim 1; It is characterized in that isocyanic ester is liquefied mdi or isophorone diisocyanate IPDI; Wherein to account for the per-cent of reaction mass be 12%-24% to MDI, and the per-cent that IPDI accounts for reaction mass is 10%-30%.
6. the preparation method of waterborne polyurethane adhesive according to claim 1 is characterized in that hydrophilic monomer is 2,2-dimethylol propionic acid DMPA, quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and verivate or N methyldiethanol amine.
7. the preparation method of waterborne polyurethane adhesive according to claim 6 is characterized in that hydrophilic monomer is 2,2-dimethylol propionic acid DMPA.
8. the preparation method of waterborne polyurethane adhesive according to claim 1 is characterized in that modified monomer is Bing Xisuandingzhi or Hydroxyethyl acrylate.
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| CN103242794A (en) * | 2013-04-07 | 2013-08-14 | 武汉工程大学 | Method for preparing high-solid-content sulfonic-acid waterborne polyurethane adhesive |
| CN103242794B (en) * | 2013-04-07 | 2015-03-11 | 武汉工程大学 | Method for preparing high-solid-content sulfonic-acid waterborne polyurethane adhesive |
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| CN101284980A (en) | 2008-10-15 |
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