CN101768418B - 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 onthe 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 chainextender 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 types of two components 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 situation, 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 like 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 propenoate, adopts 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 TEB 3K (MMA)/Bing Xisuandingzhi (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 " like 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, mixes with ydrogen peroxide 50 again; Leave standstill, inclining upper strata suspension-s; Suspension-s mixes with HCl solution, under the UW effect, stirs, and 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, under the UW effect, stirs, 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%, because the harmful monomer of removing residue formaldehyde in its sheet material, harm humans is healthy.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, and 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 through progressively polymerization and radical polymerization, generates modified polyurethane prepolymer; Subordinate phase be in salify after add recessed native suspension-s and carry out the dispersion of performed polymer; 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; Under 90 ℃, the vacuum tightness of 0.09～0.1Mpa, vacuumize 1h; Regulate then and just gather the isocyanate-monomer that adds metering under the temperature (65～90 ℃); Control R value is 1.02～2.0, the total ratio of the mole number of OH group in the R mole number that refers to total NCO group in the system and the system wherein, and 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 drip the mixed solution reaction 3～5h of modified monomer and initiator simultaneously, and make each material generation polycondensation and radical polymerization follow grafting, IPN simultaneously, regulate the viscosity of synthetic middle prepolymer through adding solvent;
Wherein said carboxylic monomer comprises that molecular weight is polyester polyol, polycarbonate, polycaprolactone, polyester polyethers polyol blend, polybutadiene diol, propenoate polyvalent alcohol, the castor-oil plant wet goods material of 800-5000; Be preferable over the polyethylene glycol adipate glycol, gather hexanodioic acid-1; 6-pinakon esterdiol, gather hexanodioic acid-1,4-butanediol ester glycol, poly-epsilon-caprolactone glycol, polycarbonate-1,6-pinakon esterdiol; More preferably in the polyethylene glycol adipate glycol, gather hexanodioic acid-1; 6-pinakon esterdiol, gather hexanodioic acid-1,4-butanediol ester glycol is most preferably in gathering hexanodioic acid-1; 4-butanediol ester glycol perhaps gathers 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 are 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 Bing Xisuandingzhi, TEB 3K, Hydroxyethyl acrylate, the vinylbenzene, is preferable over Bing Xisuandingzhi, Hydroxyethyl acrylate, and wherein modified monomer accounts for 1～6% of PU quality of material:
Wherein said initiator is Diisopropyl azodicarboxylate (ABIN), ABVN (ABVN), Lucidol (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), Lucidol (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-s 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, Pottasium Hydroxide, is preferable over triethylamine, Pottasium Hydroxide, and wherein neutralizing agent accounts for 2～6% of PU quality of material;
Wherein said recessed native suspension-s is original soil suspension-s, kation alkyl ammonium salt modified suspension, negatively charged ion sodium laurate modified suspension, silane coupling agent KH550 modified suspension, the acidified modified suspension-s of strong acid, high-temperature calcination modified suspension; Preferred original soil suspension-s, KH550 modified suspension; In the recessed native suspension-s that adds; Recessed native content counts 4～15% with massfraction, and used recessed native suspension-s 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, tetramethylenediamine, 1,6-pinakon, 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-s kinds; With recessed native suspension-s 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 (like goods such as wood veneer, 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 explain the present invention, but does not certainly limit the scope of the invention.
Comparative Examples 1: 21.85g is gathered hexanodioic acid-1, and 4-butanediol ester glycol (PBA-2000) and 1.6gDMPA add in the there-necked flask, and stirring is mixed in the fusing back, in the time of 90 ℃, vacuumizes 1h, 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 basically, (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 30 minutes salifies, change basic completion mutually after.Under high-speed stirring, add the 103g emulsifying water, 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 among 1.5g acetone and the 1.5g HEA 0.005gAIBN 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, in the time of 90 ℃, vacuumizes 1h, 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 drips off in 4h; 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 30 minutes salifies, change basic completion mutually after.Under high-speed stirring, add the recessed native suspension-s of 103g (recessed native content 4%) emulsification, 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-s of the 103g among the embodiment 1 (recessed native content 4% changes the recessed native suspension-s 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 the recessed native suspension-s after the KH550 modification, recessed native suspension-s changes 140g (recessed native content changes 10% into) into, beige emulsion (solid content 20%).
Embodiment 4: under embodiment 1 operational condition, recessed native suspension-s is changed to negatively charged ion sodium laurate modified suspension, recessed native suspension-s 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:
| Instance | 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:
1, with attapulgite/aqueous polyurethane compound binder when bonding and since wood-wood bonding all be that timber is broken, survey drawing of not plastic emitting and cut intensity, so all use Fe-Fe bonding, test to draw and cut intensity;
2, " recessed native content " expression is the massfraction that recessed native dry weight accounts for added recessed native suspension-s.
Claims (2)
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; Under 90 ℃, the vacuum tightness of 0.09～0.1MPa, vacuumize 1h; Regulate then and just gather 65～90 ℃ of isocyanate-monomers that add metering down of temperature; Control R value is 1.02～2.0, the total ratio of the mole number of OH group in the R mole number that refers to total NCO group in the system and the system wherein, and wherein the ratio of carboxylic monomer and hydrophilic monomer is controlled according to the size of R value; According to R size adjustment prepolymer molecular weight; And drip the mixed solution reaction 3～5h of modified monomer and initiator simultaneously, and make each material generation polycondensation and radical polymerization follow grafting, IPN simultaneously, regulate the viscosity of synthetic middle prepolymer through adding solvent;
Wherein hydrophilic monomer accounts for the 0.4-6% of PU quality of material;
Wherein said modified monomer is Bing Xisuandingzhi or Hydroxyethyl acrylate, and wherein modified monomer accounts for 1～6% of PU quality of material;
Described initiator is Diisopropyl azodicarboxylate, Lucidol (BPO) or tertbutyl peroxide, 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 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-s 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 the described neutralizing agent of step (2) is triethylamine or Pottasium Hydroxide, and wherein neutralizing agent accounts for 2～6% of PU quality of material;
Described recessed native suspension-s is original soil suspension-s or KH550 modified suspension; In the recessed native suspension-s that adds, recessed native content counts 4～15% with massfraction; Used recessed native suspension-s 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 chainextender accounts for 0.2～4% of PU quality of material;
Wherein the described carboxylic monomer of step (1) be molecular weight be polyethylene glycol adipate glycol, the molecular weight of 800-5000 be 800-5000 gather hexanodioic acid-1; 6-pinakon esterdiol, molecular weight be 800-5000 gather hexanodioic acid-1; 4-butanediol ester glycol, molecular weight are the poly-epsilon-caprolactone glycol of 800-5000 or the polycarbonate-1 that molecular weight is 800-5000; 6-pinakon 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,
Wherein the described chainextender of step (3) is quadrol or 1,4-butyleneglycol.
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) be molecular weight be polyethylene glycol adipate glycol, the molecular weight of 800-5000 be 800-5000 gather hexanodioic acid-1; 6-pinakon esterdiol or molecular weight be 800-5000 gather hexanodioic acid-1,4-butanediol ester glycol.
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| CN104232001B (en) * | 2014-09-19 | 2016-04-06 | 宝鸡文理学院 | Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof |
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| CN110003837A (en) * | 2019-04-17 | 2019-07-12 | 李智远 | Polyurethane binder and its preparation process |
| CN113831764A (en) * | 2021-09-22 | 2021-12-24 | 扬州工业职业技术学院 | Method for modifying attapulgite and attapulgite composite material |
| CN115651210B (en) * | 2022-10-28 | 2023-10-03 | 常州大学 | Preparation method of modified attapulgite-polyurethane composite thickener and product thereof |
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