CN101768418A - Preparation method of attapulgite/aqueous polyurethane compound binder - Google Patents
Preparation method of attapulgite/aqueous polyurethane compound binder Download PDFInfo
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Abstract
The invention relates to a preparation method of an attapulgite/aqueous polyurethane compound binder, belonging to the field of organic binders and comprising the following steps of: (1) modified polyurethane prepolymer preparation: vacuumizing hydroxy monomers and hydrophilic monomers at the temperature of 90 DEG C under the vacuum degree of 0.09-0.1MPa, then adding metric isocyanate monomers on the basis of regulating the prepolymerizing temperature to 65-90 DEG C, and controlling the R value at 1.02-2.0; (2) prepolymer neutralization and dispersion: lowering uniform temperature by 40-70 DEG C on the basis of the first step, and adding a neutralizer to neutralize into salt; after 30 minutes, controlling the solid content at 20-40 percent; dispersing metric attapulgite suspension into salt-formation modified polyurethane prepolymer and stirring at high speed for 30 minutes to prepare an attapulgite/aqueous polyurethane compound emulsion; and (3) chain extension stage: adding an chain extender on the basis of the second step, and continuously stirring for 30 minutes and discharging to prepare a final product of the emulsion of the attapulgite/aqueous polyurethane compound binder. The compound binder can be made into an artificial board which has excellent performance and meets the environmental protection requirements.
Description
Technical field
The invention belongs to the organic binder bond field, relate to a kind of preparation method of attapulgite/aqueous polyurethane compound binder.
Background technology
Aqueous polyurethane (PU) as dispersion medium, has nontoxicly, pollution-free with water, does not fire, and advantages such as environmental protection are a kind of application prospect " green materials " widely, have become scientific research personnel's research focus.Can be divided into single-component and two component two classes by type of service.Single-component water-based urethane is directly to use, or need not the aqueous polyurethane that linking agent can obtain required use properties; If use can not obtain required performance separately, must add linking agent, after adding linking agent, perhaps general single-component water-based urethane can improve adhesiveproperties, and in these situations, the two just forms two component systems aqueous polyurethane host and linking agent.Proposed a kind of preparation method of bi-component waterborne vinyl urethane tackiness agent as Chen Yuanwu, this glue is used for wood working, has characteristics such as good bonding strength, water-fast, anti-solvent.But because it is a two-component adhesive, use inconvenience, the storage time is restricted.
In order to address this problem, Hu Guowen has delivered the paper of the development of Viscotrol C and the dual modified aqueous polyurethane composite emulsion of acrylate, adopt 1 in the literary composition, the 4-butyleneglycol, dimethylol propionic acid (DMPA) and quadrol (EDA) are chainextender, Viscotrol C (C.O.) is a linking agent, aqueous polyurethane is carried out modification, obtain the aqueous polyurethane-acrylate composite emulsion of stable performance with methyl methacrylate (MMA)/butyl acrylate (BA) multipolymer.The Viscotrol C consumption increases, and water tolerance improves, and hardness increases, but the snappiness variation; The DMPA consumption increases, and emulsion appearance and stability all improve, and hardness increases, but the water tolerance variation; Along with the increase of BA consumption, the mechanical property of emulsion viscosity and film improves, but hardness diminishes.Preferable C.O. consumption is 15%-20%; The DMPA consumption is 7.45%; The BA consumption is 4.0%-6.0%, and gained emulsion over-all properties is better like this.But this emulsion has the monomer smell of a small amount of BA.
Nanotechnology and nano composite material have become the focus of scientific research and developing material in recent years, and become the frontier of interdisciplinary development.Attapulgite is called for short recessed soil.Recessed soil be a kind of porousness layer chain-like structure contain Shuifu County's magnesium alumino-silicate clays mineral, belong to natural porous nano mineral material.Recessed native crystal habit is bar-shaped or fibrous, the most 20～40nm of single crystal diameter, and length is 0.1～5 μ m, so it has very big length-to-diameter ratio, constitutional features belongs to the 1-dimention nano particle.Recessed soil has many excellent physical chemistry, and specific surface area is big, high adsorption capacity, and Heat stability is good also has characteristics such as thickening property, thixotropy, anti-heavy property, cementability.
Reported " preparation method of attapulgite (AT)/resol (PF) nano composite material " as Chinese patent 200910052605.4, this invention relates to the preparation method of attapulgite AT/ resol PF nano composite material, comprise: mix attapulgite AT original soil (1) with deionized water, stirred 0.5-2 hour, mix with hydrogen peroxide again, leave standstill, inclining upper strata suspension; Suspension mixes with HCl solution, stirs under the ultrasonic wave effect, is filtered to neutrality, and is air-dry, ball milling, drying; (2) resol PF is dissolved in the solvent, stirred 1-5 hour; (3) attapulgite that step (1) is made adds in the above-mentioned phenol resin solution, stirs under the ultrasonic wave effect, and vacuum defoamation is poured in the mould, solidifies.This invention is simple and easy to do, and equipment is simple, and cost is low, and the nano composite material that makes not only has the advantageous property of traditional material, and has improved the thermostability and the mechanical property of resol.
It mainly is that wood-based plate manufacturing and woodwork are produced two big fields that China's wood working is used tackiness agent." three urea formaldehydes " glue (urea-formaldehyde resin adhesive, Phenol aldehyde resin and melamine formaldehyde resin glue) is that wood working is used three maximum big synthetical glue kinds.Institute's panel market share is up to more than 80%, since the harmful monomer of removing residue formaldehyde in its sheet material, harm humans health.Therefore research and develop environment-protecting asepsis, the wood working that meets the technical requirements becomes the inevitable of development with glue.
The present invention utilizes the property of recessed soil, itself and aqueous polyurethane is compound, a small amount of organism free monomer in the adsorbable tackiness agent, remove the monomer smell, the hydroxyl on polyurethane molecular chain and the recessed soil reacts, adsorbs or twines simultaneously, improves the cohesive strength of product, thermotolerance and stability in storage, and composite prod is applied to wood processing field, and obtaining high-quality sheet material, its index can reach E0 or E1 sheet material requirement (this product is formaldehydeless).(E0 step burst size of methanal is smaller or equal to 0.5mg/L, and E1 step burst size of methanal is smaller or equal to 1.5mg/L)
Summary of the invention
The object of the invention is to provide the preparation method of attapulgite/aqueous polyurethane compound binder, and it is applied in wood processing field.
Operational path of the present invention is divided into three phases: the fs is prepolymerization, promptly by carboxylic monomer, the hydrophilic monomer (monomer that contains hydrophilic radical, be technical term), isocyanic ester, modified monomer be by progressively polymerization and radical polymerization, generates modified polyurethane prepolymer; Subordinate phase be in and add recessed native suspension and carry out the dispersion of performed polymer behind the salify; Phase III forms the attapulgite/aqueous polyurethane compound binder emulsion after adding chainextender.
The preparation method of attapulgite/aqueous polyurethane compound binder of the present invention, carry out according to following step:
(1) modified polyurethane prepolymer preparation: with carboxylic monomer and hydrophilic monomer, at 90 ℃, 0.09 vacuumize 1h under the vacuum tightness of～0.1Mpa, regulate the isocyanate-monomer that just poly-temperature (65～90 ℃) adds metering down then, control R value is 1.02～2.0, the ratio of the mole number of total OH group in the R mole number that refers in the system total NCO group and the system wherein, wherein the ratio of carboxylic monomer and hydrophilic monomer is controlled according to the size of R value, according to R adjustable size joint prepolymer molecular weight, and the mixed solution that drips modified monomer and initiator simultaneously reacts 3～5h, make each material generation polycondensation and radical polymerization follow grafting simultaneously, IPN is regulated the viscosity of synthetic middle prepolymer by adding solvent;
Wherein said carboxylic monomer comprises that molecular weight is the polyester polyol of 800-5000, polycarbonate, polycaprolactone, polyester polyethers polyol blend, polybutadiene diol, the acrylate polyvalent alcohol, castor-oil plant wet goods material, be preferable over the polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, the poly-epsilon-caprolactone glycol, polycarbonate-1,6-hexylene glycol esterdiol, more preferably in the polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, most preferably in poly-hexanodioic acid-1,4-butanediol ester glycol or poly-hexanodioic acid-1, the mixture of 4-butanediol ester glycol and Viscotrol C;
Wherein said isocyanate-monomer is 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), Methylcyclohexyl diisocyanate (HTDI), be preferable over tolylene diisocyanate (TDI), liquefied mdi, isophorone diisocyanate (IPDI);
Wherein said hydrophilic monomer is 2,2-dimethylol propionic acid (DMPA), quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate, N methyldiethanol amine, be preferable over 2,2-dimethylol propionic acid (DMPA) or N methyldiethanol amine, wherein hydrophilic monomer accounts for the 0.4-6% of PU quality of material;
Wherein said modified monomer is one or more the mixture in butyl acrylate, methyl methacrylate, Hydroxyethyl acrylate, the vinylbenzene, is preferable over butyl acrylate, Hydroxyethyl acrylate, and wherein modified monomer accounts for 1～6% of PU quality of material:
Wherein said initiator is Diisopropyl azodicarboxylate (ABIN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), benzoyl peroxide (BPO), dicumyl peroxide (DCP), ditertiary butyl peroxide (DTBP), isopropyl benzene hydroperoxide (CHP), tertbutyl peroxide (TBH) or di-isopropyl peroxydicarbonate (IPP), is preferable over Diisopropyl azodicarboxylate (ABIN), benzoyl peroxide (BPO) or tertbutyl peroxide (TBH).Wherein initiator accounts for 0.1～0.6% of PU quality of material;
Wherein said solvent is 1-Methyl-2-Pyrrolidone (NMP), N, and dinethylformamide, butanone, acetone, toluene are preferable over 1-Methyl-2-Pyrrolidone or acetone, and wherein solvent accounts for 1～10% of PU quality of material.
(2) neutralization of performed polymer and dispersion: on the basis of the first step, drop to 40～70 ℃ of certain temperatures, add in the neutralizing agent and salify, after 30 minutes, the control solid content is 20～40%, the recessed native suspension of metering is scattered in the modified polyurethane prepolymer behind the salify, and high-speed stirring made the attapulgite/aqueous polyurethane composite emulsion in 30 minutes;
Wherein said neutralizing agent is triethylamine, methylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide, is preferable over triethylamine, potassium hydroxide, and wherein neutralizing agent accounts for 2～6% of PU quality of material;
Wherein said recessed native suspension is original soil suspension, kation alkyl ammonium salt modified suspension, negatively charged ion sodium laurate modified suspension, silane coupling agent KH550 modified suspension, the acidified modified suspension of strong acid, high-temperature calcination modified suspension, preferred original soil suspension, KH550 modified suspension, in the recessed native suspension that adds, recessed native content counts 4～15% with massfraction, and used recessed native suspension accounts for 60～80% of total material;
(3) the chain extension stage: on the basis in second step, add chainextender, continue to stir discharging in 30 minutes, make attapulgite/aqueous polyurethane compound binder emulsion the finished product;
Wherein said chainextender is quadrol, diethylenetriamine, hexanediamine, butanediamine, 1,6-hexylene glycol, 1,4-butyleneglycol, glycol ether, and preferred quadrol, 1,4-butyleneglycol, wherein chainextender accounts for 0.2～4% of PU quality of material.
The present invention utilizes different recessed native suspension kinds, with recessed native suspension dispersed polyurethane performed polymer, hydroxyl on polyurethane molecular chain and the recessed soil reacts, adsorbs or twines, because this effect has limited the free movement of polyurethane molecular chain, over-all propertieies such as the corresponding mechanical property that improves matrix material, thermal stability, stability of emulsion, anti-heavy property.Can make the wood-based plate (as goods such as glued board, shaving board, wheat straw board and core-boards) of excellent performance, compliance with environmental protection requirements with synthetic attapulgite/aqueous polyurethane compound binder of the present invention, its sheet material can reach E0 or E1 level index request.
Embodiment
The following example is used to illustrate the present invention, but never limits the scope of the invention.
Comparative Examples 1: with the poly-hexanodioic acid-1 of 21.85g, 4-butanediol ester glycol (PBA-2000) and 1.6gDMPA add in the there-necked flask, and the mixing of fusing back is stirred, and vacuumizes 1h in the time of 90 ℃, and vacuum tightness is 0.1MPa.Cool to 70 ℃ then and add 1.9gNMP, 1.5gHEA (Hydroxyethyl acrylate), 5.89gTDI and 0.1g catalyzer (dibutyl tin laurate) successively, heating in water bath for reaction, nco value in system gets prepolymer when reaching theoretical value substantially, (the R value is 1.15 in this Comparative Examples) also begins cooling.Prepolymer is cooled to 50 ℃, earlier with acetone (3g) dilution, treat that viscosity reduces after, add the 1.2g triethylamine carry out in and 30 minutes salifies, change mutually finish substantially after.Add the 103g emulsifying water under high-speed stirring, slowly drip chainextender 0.65g quadrol subsequently, further the chain extension emulsion reaction obtained blueing light white emulsion (solid content 25%) about 30 minutes.
Comparative Examples 2: under Comparative Examples 1 operational condition, be dissolved in 0.005gAIBN among 1.5g acetone and the 1.5g HEA and the mixing dropping, be controlled in the 4h and drip off, drip 1.5g acetone and 0.005gAIBN mixing solutions 1h again, obtain blueing light white emulsion (solid content 25%).
Embodiment 1: 21.85g PBA-2000 and 1.6gDMPA are added in the there-necked flask, and stirring is mixed in the fusing back, vacuumizes 1h in the time of 90 ℃, and vacuum tightness is 0.1MPa.Cool to 70 ℃ then and add 1.9gNMP, 5.89gTDI and 0.1g catalyzer (dibutyl tin laurate) successively, R=1.15, begin to drip mixing solutions (0.005gAIBN is dissolved in 1.5g acetone and 1.5g HEA) simultaneously, heating in water bath for reaction, in 4h, drip off, and then drip 1.5g acetone and 0.005gAIBN mixing solutions 1h, and begin cooling.Prepolymer is cooled to 50 ℃, earlier with acetone (3g) dilution, treat that viscosity reduces after, add the 1.2g triethylamine carry out in and 30 minutes salifies, change mutually finish substantially after.Add the recessed native suspension of 103g (recessed native content 4%) emulsification under high-speed stirring, add chainextender 0.65g quadrol subsequently, further the chain extension emulsion reaction obtained beige emulsion (solid content 25%) about 30 minutes.
Embodiment 2: under embodiment 1 operational condition, with the recessed native suspension of the 103g among the embodiment 1 (recessed native content 4% changes the recessed native suspension of 52g (recessed native content 6%) into); Get beige emulsion (solid content 40%).
Embodiment 3: under embodiment 1 operational condition, recessed native emulsion is changed to recessed native suspension after the KH550 modification, recessed native suspension changes 140g (recessed native content changes 10% into) into, beige emulsion (solid content 20%).
Embodiment 4: under embodiment 1 operational condition, recessed native suspension is changed to negatively charged ion sodium laurate modified suspension, recessed native suspension changes 81g (recessed native content changes 15% into) into, gets beige emulsion (solid content 30%).
The salient features of the foregoing description products obtained therefrom is listed in the table below:
| Example | Viscosity (25 ℃)/mPaS | Outward appearance | Draw and cut intensity (Fe-Fe)/MPa | Free formaldehyde content/% | Relative No. 1 heat resisting temperature | Recessed native content/% |
| Comparative Examples 1 | ??10 | Milky white blueing is rare | ??1.83 | ??0 | ??- | ??0 |
| Comparative Examples 2 | ??12 | Milky white blueing is rare | ??2.11 | ??0 | Improve 5 ℃ | ??0 |
| Embodiment 1 | ??16 | The beige thickness | ??2.32 | ??0 | Improve 24 ℃ | ??4 |
| Embodiment 2 | ??20 | The beige thickness | ??2.56 | ??0 | Improve 38 ℃ | ??6 |
| Embodiment 3 | ??30 | The beige thickness | ??3.10 | ??0 | Improve 42 ℃ | ??10 |
| Embodiment 4 | ??42 | The beige thickness | ??3.33 | ??0 | Improve 45 ℃ | ??15 |
| The urea-formaldehyde resin carpenter's glue | ??10 | White inclusion-free uniform liquid | (1.22 wood-wood) | ??≤0.3 | ??- | ??0 |
Annotate:
When 1, using attapulgite/aqueous polyurethane compound binder bonding, all be that timber is broken, survey drawing of not plastic emitting and cut intensity that therefore all use Fe-Fe bonding, test is drawn and cut intensity owing to wood-wood is bonding;
2, " recessed native content " expression is the massfraction that recessed native dry weight accounts for added recessed native suspension.
Claims (6)
1. the preparation method of attapulgite/aqueous polyurethane compound binder is characterized in that carrying out according to following step:
(1) modified polyurethane prepolymer preparation: with carboxylic monomer and hydrophilic monomer, at 90 ℃, 0.09 vacuumize 1h under the vacuum tightness of～0.1Mpa, regulate 65～90 ℃ of isocyanate-monomers that add metering down of just poly-temperature then, control R value is 1.02～2.0, the ratio of the mole number of total OH group in the R mole number that refers in the system total NCO group and the system wherein, wherein the ratio of carboxylic monomer and hydrophilic monomer is controlled according to the size of R value, according to R adjustable size joint prepolymer molecular weight, and the mixed solution that drips modified monomer and initiator simultaneously reacts 3～5h, make each material generation polycondensation and radical polymerization follow grafting simultaneously, IPN is regulated the viscosity of synthetic middle prepolymer by adding solvent;
Wherein said carboxylic monomer comprises that molecular weight is polyester polyol, polycarbonate, polycaprolactone, polyester polyethers polyol blend, polybutadiene diol, acrylate polyvalent alcohol, the castor-oil plant wet goods material of 800-5000, wherein said isocyanate-monomer is 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), Methylcyclohexyl diisocyanate (HTDI), wherein said hydrophilic monomer is 2,2-dimethylol propionic acid (DMPA), quadrol base ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate, N methyldiethanol amine, wherein hydrophilic monomer accounts for the 0.4-6% of PU quality of material;
Wherein said modified monomer is one or more the mixture in butyl acrylate, methyl methacrylate, Hydroxyethyl acrylate, the vinylbenzene, and wherein modified monomer accounts for 1～6% of PU quality of material;
Wherein said initiator is Diisopropyl azodicarboxylate (ABIN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), benzoyl peroxide (BPO), dicumyl peroxide (DCP), ditertiary butyl peroxide (DTBP), isopropyl benzene hydroperoxide (CHP), tertbutyl peroxide (TBH) or di-isopropyl peroxydicarbonate (IPP), and wherein initiator accounts for 0.1～0.6% of Headquarters of the General Staff and reaction mass quality;
Wherein said solvent is 1-Methyl-2-Pyrrolidone (NMP), N, and dinethylformamide, butanone, acetone, toluene are preferable over 1-Methyl-2-Pyrrolidone or acetone, and wherein solvent accounts for 1～10% of PU quality of material.
(2) neutralization of performed polymer and dispersion: on the basis of the first step, drop to 40～70 ℃ of certain temperatures, add in the neutralizing agent and salify, after 30 minutes, the control solid content is 20～40%, the recessed native suspension of metering is scattered in the modified polyurethane prepolymer behind the salify, and high-speed stirring made the attapulgite/aqueous polyurethane composite emulsion in 30 minutes;
Wherein said neutralizing agent is triethylamine, methylamine, ammoniacal liquor, sodium hydroxide, potassium hydroxide, and wherein neutralizing agent accounts for 2～6% of PU quality of material;
Wherein said recessed native suspension is original soil suspension, kation alkyl ammonium salt modified suspension, negatively charged ion sodium laurate modified suspension, silane coupling agent KH550 modified suspension, the acidified modified suspension of strong acid, high-temperature calcination modified suspension, in the recessed native suspension that adds, recessed native content counts 4～15% with massfraction; Used recessed native suspension accounts for 60～80% of total material;
(3) the chain extension stage: on the basis in second step, add chainextender, continue to stir discharging in 30 minutes, make attapulgite/aqueous polyurethane compound binder emulsion the finished product;
Wherein said chainextender is quadrol, diethylenetriamine, hexanediamine, butanediamine, 1,6-hexylene glycol, 1,4-butyleneglycol, glycol ether, and wherein chainextender accounts for 0.2～4% of PU quality of material.
2. the preparation method of attapulgite/aqueous polyurethane compound binder according to claim 1, it is characterized in that the described carboxylic monomer of step (1) is polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-epsilon-caprolactone glycol, polycarbonate-1,6-hexylene glycol esterdiol, described isocyanate-monomer are tolylene diisocyanate (TDI), liquefied mdi or isophorone diisocyanate (IPDI); Described hydrophilic monomer is 2,2-dimethylol propionic acid (DMPA) or N methyldiethanol amine, described modified monomer is butyl acrylate or Hydroxyethyl acrylate, and described initiator is Diisopropyl azodicarboxylate (ABIN), benzoyl peroxide (BPO) or tertbutyl peroxide (TBH).
3. the preparation method of attapulgite/aqueous polyurethane compound binder according to claim 1 is characterized in that the described neutralizing agent of step (2) is triethylamine or potassium hydroxide, and described recessed native suspension is original soil suspension or KH550 modified suspension.
4. the preparation method of attapulgite/aqueous polyurethane compound binder according to claim 1 is characterized in that the described chainextender of step (3) is quadrol or 1,4-butyleneglycol.
5. the preparation method of attapulgite/aqueous polyurethane compound binder according to claim 2, it is characterized in that the described carboxylic monomer of step (1) is polyethylene glycol adipate glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1 or 4-butanediol ester glycol.
6. the preparation method of attapulgite/aqueous polyurethane compound binder according to claim 5, it is characterized in that the described carboxylic monomer of step (1) is poly-hexanodioic acid-1,4-butanediol ester glycol or poly-hexanodioic acid-1, the mixture of 4-butanediol ester glycol and Viscotrol C.
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