CN104232001B - Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof - Google Patents
Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof Download PDFInfo
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- CN104232001B CN104232001B CN201410482345.5A CN201410482345A CN104232001B CN 104232001 B CN104232001 B CN 104232001B CN 201410482345 A CN201410482345 A CN 201410482345A CN 104232001 B CN104232001 B CN 104232001B
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Abstract
Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof, comprises the polymer polyatomic alcohol of 14 ~ 23%, the polyisocyanate compound of 12 ~ 22%, the organically-modified attapulgite of 0.1 ~ 2%, the chainextender of 2 ~ 9%, the neutralizing agent of 2 ~ 5%, the deionized water of 45-55%; With polymer polyatomic alcohol, diisocyanate cpd, attapulgite and hydrophilic chain extender for main raw material, obtain a kind of aqueous laminating adhesive of organic attapulgite modification by being progressively polymerized synthetic technology.Multiple film glue prepared by the present invention take water as solvent, has the large and stripping strength of cohesive force greatly, good heat resistance, the advantage of environmental protection.
Description
Technical field
The invention belongs to the preparation field of macromolecular material, relate to aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof.
Background technology
Attapulgite is that a kind of layer chain contains Shuifu County's magnesium silicate mineral, and it has special layer chain crystalline structure and a large amount of micropore canals, and easier Redispersion, be therefore suitable as very much the packing material of polymeric matrix.But nano-attapulgite has very high surface energy and surfactivity, therefore easily reunites in polymeric matrix.In order to improve the dispersive ability of nano-attapulgite, strengthening the bonding force of nano material and polymer interface simultaneously, usually needing to carry out modification to nano-attapulgite, to improve the avidity of nanoparticle and organic phase, weaken the surface polarity of nanoparticle.
Aqueous laminating adhesive with water to replace organic solvent, environmental protection, extremely rising at flexible packaging industry.At present, in food flexible packing, the multiple film glue of water-borne acrylic type is well bonding to aluminium plating film, but to the tack of plastic film with to hold viscosity all lower.Again because second-order transition temperature is higher, so there is hot sticky cold crisp shortcoming, frozen product can not be used for.Aqueous adhesives for laminated film is better to plastics film cementability, and second-order transition temperature is lower, can be used for normal temperature or Frozen Food Packaging.So aqueous adhesives for laminated film has wide market.But the sticking power also existed on a plastic film due to pure aqueous adhesives for laminated film is low, therefore the not good feature of thermotolerance becomes focus to the modification of aqueous polyurethane.
Summary of the invention
The object of the invention is to overcome the problems of the prior art, providing aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof, obtained aqueous laminating adhesive take water as solvent, has the large and stripping strength of cohesive force greatly, the advantage of good heat resistance.
For achieving the above object, the present invention adopts following technical scheme:
A kind of aqueous laminating adhesive of organic attapulgite modification, by mass percentage, comprise the polymer polyatomic alcohol of 14 ~ 23%, the polyisocyanate compound of 12 ~ 22%, the organically-modified attapulgite of 0.1 ~ 2%, the chainextender of 2 ~ 9%, the neutralizing agent of 2 ~ 5% and the deionized water of 45 ~ 55%.
A preparation method for the aqueous laminating adhesive of organic attapulgite modification as claimed in claim 1, comprises the following steps:
1) by sedimentation after original soil and distilled water mix and blend, get top suspension and carry out suction filtration, dry, obtain purification attapulgite; Add in mineral acid by purification attapulgite, reflux, centrifugation after cooling, distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is (1 ~ 2): (10 ~ 20);
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add organic modifiers, after ultrasonic vibration at 70 ~ 80 DEG C stirring and refluxing 10 ~ 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polymer polyatomic alcohol of 14 ~ 23% and 0.1 ~ 2% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the polyisocyanate compound of 12 ~ 22% after being cooled to and at 75 ~ 95 DEG C, react 2 ~ 4h, obtain aqueous prepolymer; Then in hydrotropisms's prepolymer drip 2 ~ 9% chainextender and organic solvent after at 58 ~ 80 DEG C, continue reaction 4 ~ 6h after, be down to room temperature, after adding the neutralizing agent of 2 ~ 5% again, under agitation add the deionized water emulsification of 45 ~ 55%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of organic solvent is 30 ~ 50% of aqueous prepolymer and chainextender total mass.
Described original soil grain diameter is 20 ~ 40nm, and length is 1 ~ 2m, and in the crystallization of one dimension fibre shape.
The hydrochloric acid of described mineral acid to be concentration be 2 ~ 4mol/L, sulfuric acid, nitric acid or phosphoric acid; The volume ratio of purification attapulgite and mineral acid is 1:10; Return time is 6-8h.
Described organic modifiers is one or both in cats product, silane coupling agent.
Described cats product is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride, and silane coupling agent is 3-aminopropyl triethoxysilane or urea propyl-triethoxysilicane.
Described polymer polyatomic alcohol is polycaprolactone diols, PCDL or polyether Glycols;
Chainextender is the mixture of tertiary amine compound and small molecules trivalent alcohol, or the mixture of tertiary amine compound, small molecules trivalent alcohol and small molecules dibasic alcohol;
Described organic solvent is tetrahydrofuran (THF), ethyl acetate, butanone, methylethylketone or acetone;
Described neutralizing agent is oxyacetic acid, diacetyl oxide or Glacial acetic acid.
Described tertiary amine compound is diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanolamine, N-benzyl diethanolamine, tertiarybutyldiethanolamine, dimethylethanolamine, two (2-hydroxyethyl) benzylaniline or two (2-hydroxypropyl) benzylaniline;
Described small molecules dibasic alcohol is ethylene glycol, 1,2-propylene glycol, 1,3-PD, BDO, 1,3-butyleneglycol, 1,4-butylene glycol, Isosorbide-5-Nitrae-butynediol, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, dimethyltrimethylene glycol, 1,4 cyclohexane dimethanol, 2-methyl isophthalic acid, one or more in ammediol, divinyl glycol, triethylene glycol, four ethylene glycols, dipropylene glycol, dibutylene glycol;
Described small molecules trivalent alcohol is one or more in glycerine, TriMethylolPropane(TMP), BT.
The chemical formula of described polyisocyanate compound is X (NCO)
n, wherein, X is the aliphatic group containing 4 ~ 12 carbon atoms, containing the alicyclic of 6 ~ 12 carbon atoms or aryl radical, containing one or both in the aromatic-aliphatic alkyl of 7 ~ 15 carbon atoms, and n=2.
When described X is containing the aliphatic group of 4 ~ 12 carbon atoms, polyisocyanate compound is one or both in tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane diisocyanate, trimethylene hexane diisocyanate;
When X is containing the alicyclic or aryl radical of 6 ~ 12 carbon atoms, polyisocyanate compound is one or both in Isosorbide-5-Nitrae-cyclohexyl diisocyanate, isoflurane chalcone diisocyanate, 2,2-bis-propane-4-cyclohexyl diisocyanates;
When X is the aromatic-aliphatic alkyl containing 7 ~ 15 carbon atoms, polyisocyanate compound is 1,4-bis-phenylcarbimide, Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, to 4-phenyl-dimethyl vulcabond, terephthalylidene vulcabond, a tetramethyl-xylylene diisocyanate, to one or both in tetramethyl-xylylene diisocyanate.
Compared with prior art, the beneficial effect that the present invention has: first prepare organically-modified attapulgite in the present invention, polymer polyatomic alcohol and organically-modified attapulgite are in temperature controlled water bath after ultrasonic mixing, vacuum hydro-extraction, then add polyisocyanate compound and prepare isocyanate-terminated prepolymer, add hydrophilic chain extender again, question response terminates to be down to room temperature and adds neutralizing agent neutralization, then water-based resin is emulsified into slowly adding ionized water, vacuum removal organic solvent, products obtained therefrom is attapulgite modified aqueous laminating adhesive.
The present invention, by being progressively polymerized the aqueous laminating adhesive that synthetic technology obtains a kind of organic attapulgite modification, because organic modifiers has unique backbone, well improves the dispersiveness of attapulgite and the consistency with aqueous laminating adhesive.Prepared multiple film glue is solvent with water, and have the large and stripping strength of cohesive force greatly, the sticking power on nylon reaches 5 grades, and the sticking power on PET polyester reaches 4 grades, good heat resistance, the advantage of environmental protection.
Further, because tensio-active agent or silane coupling agent have unique backbone, the dispersiveness of attapulgite and the consistency with aqueous laminating adhesive is well improved.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph (SEM) of the multiple film glue of organic attapulgite modified water-soluble of the present invention.
Embodiment
Described the present invention by specific embodiment below in conjunction with accompanying drawing.
STA449C type (madeinNETZSCH-GerateballCo., Germany) thermal gravimetric analyzer is adopted to measure film thermal weight loss rate in the present invention: N
2atmosphere, temperature rise rate 10 DEG C/min; JSM-6400 type scanning electronic microscope (SEM) is adopted to observe film coated surface pattern; Adopt cross-hatching test sticking power.
Embodiment 1
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 20%, the organically-modified attapulgite of 1%, the polyisocyanate compound of 20%, the chainextender of 9%, the neutralizing agent of 5% and the deionized water of 45%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add cetyl trimethylammonium bromide, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 20% and 1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the tetramethylene diisocyanate of 20% after being cooled to 60 DEG C, and react 4h at 75 DEG C, obtain aqueous prepolymer; Then diethanolamine and the 2-methyl isophthalic acid of 9% is dripped in hydrotropisms's prepolymer, after continuing reaction 6h after the mixture of ammediol arbitrary proportion and tetrahydrofuran (THF) at 65 DEG C, be down to room temperature, after adding the oxyacetic acid of 5% again, under agitation slowly add the deionized water emulsification of 45%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of tetrahydrofuran (THF) is 30% of aqueous prepolymer and diethanolamine total mass.
Embodiment 2
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the organically-modified attapulgite of 0.1%, the polyisocyanate compound of 18.9%, the chainextender of 6%, the neutralizing agent of 2% and the deionized water of 50%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the sulfuric acid of 3mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 6h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add 3-aminopropyl triethoxysilane, after ultrasonic vibration at 80 DEG C stirring and refluxing 10h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the PCDL of 23% and 0.1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the dodecane diisocyanate of 18.9% after being cooled to 60 DEG C, and react 2h at 95 DEG C, obtain aqueous prepolymer; Then after continuing reaction 5h after dripping the N-ethyldiethanolamine of 6% and the mixture of triethylene glycol arbitrary proportion and ethyl acetate in hydrotropisms's prepolymer at 75 DEG C, be down to room temperature, after adding the diacetyl oxide of 2% again, under agitation slowly add the deionized water emulsification of 50%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of ethyl acetate is 40% of aqueous prepolymer and N-ethyldiethanolamine total mass.
Embodiment 3
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 14%, the organically-modified attapulgite of 2%, the polyisocyanate compound of 15%, the chainextender of 9%, the neutralizing agent of 5% and the deionized water of 55%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the nitric acid of 4mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 7h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:20;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add urea propyl-triethoxysilicane, after ultrasonic vibration at 75 DEG C stirring and refluxing 11h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polyether Glycols of 14% and 2% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, the hexamethylene diisocyanate of 15% and the mixture of trimethylene hexane diisocyanate arbitrary proportion is added after being cooled to 60 DEG C, and 4h is reacted at 80 DEG C, obtain aqueous prepolymer; Then after continuing reaction 4h after dripping the dimethylethanolamine of 9% and the mixture of dipropylene glycol arbitrary proportion and butanone in hydrotropisms's prepolymer at 80 DEG C, be down to room temperature, after adding the Glacial acetic acid of 5% again, under agitation slowly add the deionized water emulsification of 55%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of butanone is 50% of aqueous prepolymer and dimethylethanolamine total mass.
Embodiment 4
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 18%, the organically-modified attapulgite of 0.6%, the polyisocyanate compound of 22%, the chainextender of 2%, the neutralizing agent of 3% and the deionized water of 54.4%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the phosphoric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 6h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:20;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add the mixture of palmityl trimethyl ammonium chloride and urea propyl-triethoxysilicane arbitrary proportion, after ultrasonic vibration at 70 DEG C stirring and refluxing 11h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 18% and 0.6% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the Isosorbide-5-Nitrae-cyclohexyl diisocyanate of 22% after being cooled to 60 DEG C, and 3h is reacted at 85 DEG C, obtain aqueous prepolymer; Then two (2-hydroxyethyl) benzylanilines and 1 of 2% are dripped in hydrotropisms's prepolymer, after continuing reaction 4h after the mixture of 6-hexylene glycol arbitrary proportion, methylethylketone at 80 DEG C, be down to room temperature, after adding the Glacial acetic acid of 3% again, under agitation slowly add the deionized water emulsification of 54.5%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of methylethylketone is aqueous prepolymer and number-average molecular weight is 300gmol
-1polyvalent alcohol total mass 35%.
Embodiment 5
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the organically-modified attapulgite of 1.5%, the polyisocyanate compound of 12%, the chainextender of 5.5%, the neutralizing agent of 5% and the deionized water of 53%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:12;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add palmityl trimethyl ammonium chloride, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 23% and 1.5% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, the isoflurane chalcone diisocyanate and 2 of 12% is added after being cooled to 60 DEG C, the mixture of 2-bis-propane-4-cyclohexyl diisocyanate arbitrary proportion, and 3h is reacted at 90 DEG C, obtain aqueous prepolymer; Then the tertiarybutyldiethanolamine and 1 of 5.5% is dripped in hydrotropisms's prepolymer, after continuing reaction 6h after the mixture of 4-butyleneglycol arbitrary proportion and acetone at 58 DEG C, be down to room temperature, after adding the Glacial acetic acid of 5% again, under agitation slowly add the deionized water emulsification of 53%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of acetone is aqueous prepolymer and number-average molecular weight is 6000gmol
-1polyvalent alcohol total mass 45%.
Embodiment 6
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 19%, the organically-modified attapulgite of 2%, the polyisocyanate compound of 14%, the chainextender of 9%, the neutralizing agent of 4% and the deionized water of 52%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:15;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add 3-aminopropyl triethoxysilane, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 20% and 1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the Toluene-2,4-diisocyanate of 20% after being cooled to 60 DEG C, 4-vulcabond, and 4h is reacted at 75 DEG C, obtain aqueous prepolymer; Then the N-benzyl diethanolamine and 1 of 9% is dripped in hydrotropisms's prepolymer, after continuing reaction 6h after the mixture of 2-propylene glycol arbitrary proportion and tetrahydrofuran (THF) at 65 DEG C, be down to room temperature, after adding the oxyacetic acid of 5% again, under agitation slowly add the deionized water emulsification of 45%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of tetrahydrofuran (THF) is 30% of aqueous prepolymer and 1,2-PD total mass.
Embodiment 7
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 16%, the organically-modified attapulgite of 1%, the polyisocyanate compound of 22%, the chainextender of 9%, the neutralizing agent of 5% and the deionized water of 47%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:15;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add cetyl trimethylammonium bromide, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 16% and 1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add after being cooled to 60 DEG C 22% to 4-phenyl-dimethyl vulcabond, and react 4h at 75 DEG C, obtain aqueous prepolymer; Then two (2-hydroxypropyl) benzylanilines, 1 of 9% are dripped in hydrotropisms's prepolymer, 4-butylene glycol, dimethyltrimethylene glycol, 1, after continuing reaction 6h after the mixture of 4-cyclohexanedimethanol arbitrary proportion and tetrahydrofuran (THF) at 65 DEG C, be down to room temperature, after adding the oxyacetic acid of 5% again, under agitation slowly add the deionized water emulsification of 47%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of tetrahydrofuran (THF) is 30% of aqueous prepolymer and Isosorbide-5-Nitrae-butylene glycol total mass.
Embodiment 8
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 20%, the organically-modified attapulgite of 1%, the polyisocyanate compound of 20%, the chainextender of 9%, the neutralizing agent of 5% and the deionized water of 45%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add cetyl trimethylammonium bromide, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 20% and 1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, the terephthalylidene vulcabond of 20% and the mixture of a tetramethyl-xylylene diisocyanate arbitrary proportion is added after being cooled to 60 DEG C, and 4h is reacted at 75 DEG C, obtain aqueous prepolymer; Then after continuing reaction 6h after dripping the trolamine of 9%, dibutylene glycol, the mixture of glycerine arbitrary proportion and tetrahydrofuran (THF) in hydrotropisms's prepolymer at 65 DEG C, be down to room temperature, after adding the oxyacetic acid of 5% again, under agitation slowly add the deionized water emulsification of 45%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of tetrahydrofuran (THF) is 30% of aqueous prepolymer and diethanolamine total mass.
Embodiment 9
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 20%, the organically-modified attapulgite of 1%, the polyisocyanate compound of 20%, the chainextender of 9%, the neutralizing agent of 5% and the deionized water of 45%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add cetyl trimethylammonium bromide, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 20% and 1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, the tetramethylene diisocyanate of 20% and the mixture of isoflurane chalcone diisocyanate arbitrary proportion is added after being cooled to 60 DEG C, and 4h is reacted at 75 DEG C, obtain aqueous prepolymer; Then the ethylene glycol, 1 of 9% is dripped in hydrotropisms's prepolymer, 8-ethohexadiol, four ethylene glycols, TriMethylolPropane(TMP) and 1,2, the mixture of 4-trihydroxybutane arbitrary proportion and tetrahydrofuran (THF), after then continuing reaction 6h at 65 DEG C, be down to room temperature, after adding the oxyacetic acid of 5% again, under agitation slowly add the deionized water emulsification of 45%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of tetrahydrofuran (THF) is 30% of aqueous prepolymer and diethanolamine total mass.
Embodiment 10
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 20%, the organically-modified attapulgite of 1%, the polyisocyanate compound of 20%, the chainextender of 9%, the neutralizing agent of 5% and the deionized water of 45%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the hydrochloric acid of 2mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 8h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 1:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add cetyl trimethylammonium bromide, after ultrasonic vibration at 70 DEG C stirring and refluxing 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polycaprolactone diols of 20% and 1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, 20% 2 are added after being cooled to 60 DEG C, 2-bis-propane-4-cyclohexyl diisocyanate and the mixture to tetramethyl-xylylene diisocyanate arbitrary proportion, and 4h is reacted at 75 DEG C, obtain aqueous prepolymer; Then mixture and the tetrahydrofuran (THF) of two (2-hydroxyethyl) benzylaniline, four ethylene glycols and the glycerine arbitrary proportions of 9% is dripped in hydrotropisms's prepolymer, then after continuing reaction 6h at 65 DEG C, be down to room temperature, after adding the oxyacetic acid of 5% again, under agitation slowly add the deionized water emulsification of 45%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of tetrahydrofuran (THF) is 30% of aqueous prepolymer and diethanolamine total mass.
Comparative example 1
A kind of aqueous laminating adhesive, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the polyisocyanate compound of 19%, the chainextender of 6%, the neutralizing agent of 2% and the deionized water of 50%.
The preparation method of above-mentioned aqueous laminating adhesive is: by mass percentage, and the PCDL of 23% is carried out vacuum hydro-extraction, adds the dodecane diisocyanate of 19% after being cooled to 60 DEG C, and reacts 2h at 95 DEG C, obtains aqueous prepolymer; Then after continuing reaction 5h after dripping the N-ethyldiethanolamine of 6% and the mixture of triethylene glycol arbitrary proportion and ethyl acetate in hydrotropisms's prepolymer at 75 DEG C, be down to room temperature, after adding the diacetyl oxide of 2% again, under agitation slowly add the deionized water emulsification of 50%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of ethyl acetate is 40% of aqueous prepolymer and N-ethyldiethanolamine total mass.
Embodiment 11
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the organically-modified attapulgite of 0.1%, the polyisocyanate compound of 19%, the chainextender of 6%, the neutralizing agent of 2% and the deionized water of 49.9%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the sulfuric acid of 3mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 6h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add 3-aminopropyl triethoxysilane, after ultrasonic vibration at 80 DEG C stirring and refluxing 10h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the PCDL of 23% and 0.1% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the dodecane diisocyanate of 19% after being cooled to 60 DEG C, and react 2h at 95 DEG C, obtain aqueous prepolymer; Then after continuing reaction 5h after dripping the N-ethyldiethanolamine of 6% and the mixture of triethylene glycol arbitrary proportion and ethyl acetate in hydrotropisms's prepolymer at 75 DEG C, be down to room temperature, after adding the diacetyl oxide of 2% again, under agitation slowly add the deionized water emulsification of 49.9%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of ethyl acetate is 40% of aqueous prepolymer and N-ethyldiethanolamine total mass.
Embodiment 12
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the organically-modified attapulgite of 0.2%, the polyisocyanate compound of 19%, the chainextender of 6%, the neutralizing agent of 2% and the deionized water of 49.8%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the sulfuric acid of 3mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 6h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add 3-aminopropyl triethoxysilane, after ultrasonic vibration at 80 DEG C stirring and refluxing 10h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the PCDL of 23% and 0.2% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the dodecane diisocyanate of 19% after being cooled to 60 DEG C, and react 2h at 95 DEG C, obtain aqueous prepolymer; Then after continuing reaction 5h after dripping the N-ethyldiethanolamine of 6% and the mixture of triethylene glycol arbitrary proportion and ethyl acetate in hydrotropisms's prepolymer at 75 DEG C, be down to room temperature, after adding the diacetyl oxide of 2% again, under agitation slowly add the deionized water emulsification of 49.8%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of ethyl acetate is 40% of aqueous prepolymer and N-ethyldiethanolamine total mass.
Embodiment 13
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the organically-modified attapulgite of 0.3%, the polyisocyanate compound of 19%, the chainextender of 6%, the neutralizing agent of 2% and the deionized water of 49.7%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the sulfuric acid of 3mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 6h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add 3-aminopropyl triethoxysilane, after ultrasonic vibration at 80 DEG C stirring and refluxing 10h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the PCDL of 23% and 0.3% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the dodecane diisocyanate of 19% after being cooled to 60 DEG C, and react 2h at 95 DEG C, obtain aqueous prepolymer; Then after continuing reaction 5h after dripping the N-ethyldiethanolamine of 6% and the mixture of triethylene glycol arbitrary proportion and ethyl acetate in hydrotropisms's prepolymer at 75 DEG C, be down to room temperature, after adding the diacetyl oxide of 2% again, under agitation slowly add the deionized water emulsification of 49.7%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of ethyl acetate is 40% of aqueous prepolymer and N-ethyldiethanolamine total mass.
Embodiment 14
An aqueous laminating adhesive for organic attapulgite modification, by mass percentage, comprises the polymer polyatomic alcohol of 23%, the organically-modified attapulgite of 0.4%, the polyisocyanate compound of 19%, the chainextender of 6%, the neutralizing agent of 2% and the deionized water of 49.6%.
The preparation method of the aqueous laminating adhesive of above-mentioned organic attapulgite modification, comprises the following steps:
1) be 20 ~ 40nm by particle diameter, length is 1 ~ 2m, and sedimentation after original soil in the crystallization of one dimension fibre shape and distilled water mix and blend, get top suspension and carry out suction filtration, drying, obtains purification attapulgite; Purification attapulgite being added concentration is in the sulfuric acid of 3mol/L, and the volume ratio of purification attapulgite and hydrochloric acid is 1:10, reflux 6h, centrifugation after cooling, and distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is 2:10;
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add 3-aminopropyl triethoxysilane, after ultrasonic vibration at 80 DEG C stirring and refluxing 10h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the PCDL of 23% and 0.4% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the dodecane diisocyanate of 19% after being cooled to 60 DEG C, and react 2h at 95 DEG C, obtain aqueous prepolymer; Then after continuing reaction 5h after dripping the N-ethyldiethanolamine of 6% and the mixture of triethylene glycol arbitrary proportion and ethyl acetate in hydrotropisms's prepolymer at 75 DEG C, be down to room temperature, after adding the diacetyl oxide of 2% again, under agitation slowly add the deionized water emulsification of 49.6%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of ethyl acetate is 40% of aqueous prepolymer and N-ethyldiethanolamine total mass.
For the test that the performance of the aqueous laminating adhesive of comparative example 1 and the obtained organic attapulgite modification of embodiment of the present invention 11-embodiment 14 is carried out, refer to table 1.
The sticking power of the multiple film glue of table 1 organic attapulgite modified water-soluble of the present invention and temperature resistance data
Note: the decomposition temperature of quality 50% is temperature when taking mass-burning decomposition half.
As seen from Table 1, record the aqueous laminating adhesive sticking power had on nylon prepared by the present invention and reach 5 grades, the sticking power on PET polyester reaches 4 grades, and decomposition temperature is higher, has good thermotolerance as seen.
Fig. 1 is the stereoscan photograph of the multiple film glue of organic attapulgite modified water-soluble of the present invention, as seen from Figure 1, organically-modified attapulgite embeds in aqueous laminating adhesive matrix with homogeneously dispersed state, this is because tensio-active agent or silane coupling agent have unique backbone, well improves the dispersiveness of attapulgite and the consistency with aqueous laminating adhesive.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. a preparation method for the aqueous laminating adhesive of organic attapulgite modification, is characterized in that, comprises the following steps:
1) by sedimentation after original soil and distilled water mix and blend, get top suspension and carry out suction filtration, dry, obtain purification attapulgite; Add in mineral acid by purification attapulgite, reflux, centrifugation after cooling, distilled water drip washing gained solid is to neutral, and vacuum-drying, obtains acidifying attapulgite; Wherein, the mass ratio of original soil and distilled water is (1 ~ 2): (10 ~ 20);
Join in distilled water by acidifying attapulgite, stirred at ambient temperature makes acidifying attapulgite be scattered in completely in water; Then add organic modifiers, after ultrasonic vibration at 70 ~ 80 DEG C stirring and refluxing 10 ~ 12h, then carry out suction filtration, washing, drying, obtain organically-modified attapulgite; Wherein, the mass ratio of acidifying attapulgite, distilled water, organic modifiers is 1:20:1;
2) by mass percentage, by the polymer polyatomic alcohol of 14 ~ 23% and 0.1 ~ 2% the mixing of organically-modified attapulgite after carry out vacuum hydro-extraction, add the polyisocyanate compound of 12 ~ 22% after being cooled to and at 75 ~ 95 DEG C, react 2 ~ 4h, obtain aqueous prepolymer; Then in hydrotropisms's prepolymer drip 2 ~ 9% chainextender and organic solvent after at 58 ~ 80 DEG C, continue reaction 4 ~ 6h after, be down to room temperature, after adding the neutralizing agent of 2 ~ 5% again, under agitation add the deionized water emulsification of 45 ~ 55%, then vacuum removal organic solvent, obtains aqueous laminating adhesive; Wherein, the add-on of organic solvent is 30 ~ 50% of aqueous prepolymer and chainextender total mass.
2. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 1, is characterized in that, described original soil grain diameter is 20 ~ 40nm, and length is 1 ~ 2 μm, and in the crystallization of one dimension fibre shape.
3. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 1, is characterized in that, the hydrochloric acid of described mineral acid to be concentration be 2 ~ 4mol/L, sulfuric acid, nitric acid or phosphoric acid; The volume ratio of purification attapulgite and mineral acid is 1:10; Return time is 6-8h.
4. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 1, is characterized in that, described organic modifiers is one or both in cats product, silane coupling agent.
5. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 4, it is characterized in that, described cats product is cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride, and silane coupling agent is 3-aminopropyl triethoxysilane or urea propyl-triethoxysilicane.
6. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 1, is characterized in that, described polymer polyatomic alcohol is polycaprolactone diols, PCDL or polyether Glycols;
Chainextender is the mixture of tertiary amine compound and small molecules trivalent alcohol, or the mixture of tertiary amine compound, small molecules trivalent alcohol and small molecules dibasic alcohol;
Described organic solvent is tetrahydrofuran (THF), ethyl acetate, methylethylketone or acetone;
Described neutralizing agent is oxyacetic acid, diacetyl oxide or Glacial acetic acid.
7. the preparation method of the aqueous laminating adhesive of organic attapulgite modification according to claim 6, it is characterized in that, described tertiary amine compound is diethanolamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanolamine, N-benzyl diethanolamine, tertiarybutyldiethanolamine, dimethylethanolamine, two (2-hydroxyethyl) benzylaniline or two (2-hydroxypropyl) benzylaniline;
Described small molecules dibasic alcohol is ethylene glycol, 1,2-propylene glycol, 1,3-PD, BDO, 1,3-butyleneglycol, 1,4-butylene glycol, Isosorbide-5-Nitrae-butynediol, 1,5-PD, 1,6-hexylene glycol, 1,8-ethohexadiol, dimethyltrimethylene glycol, 1,4 cyclohexane dimethanol, 2-methyl isophthalic acid, one or more in ammediol, divinyl glycol, triethylene glycol, four ethylene glycols, dipropylene glycol, dibutylene glycol;
Described small molecules trivalent alcohol is one or more in glycerine, TriMethylolPropane(TMP), BT.
8. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 1, is characterized in that, the chemical formula of described polyisocyanate compound is X (NCO)
n, wherein, X is the aliphatic group containing 4 ~ 12 carbon atoms, containing the alicyclic of 6 ~ 12 carbon atoms or aryl radical, containing one or both in the aromatic-aliphatic alkyl of 7 ~ 15 carbon atoms, and n=2.
9. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 8, it is characterized in that, when described X is containing the aliphatic group of 4 ~ 12 carbon atoms, polyisocyanate compound is one or both in tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane diisocyanate, trimethylene hexane diisocyanate;
When X is containing the alicyclic or aryl radical of 6 ~ 12 carbon atoms, polyisocyanate compound is one or both in Isosorbide-5-Nitrae-cyclohexyl diisocyanate, isophorone diisocyanate, 2,2-bis-propane-4-cyclohexyl diisocyanates;
When X is the aromatic-aliphatic alkyl containing 7 ~ 15 carbon atoms, polyisocyanate compound is Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, to 4-phenyl-dimethyl vulcabond, terephthalylidene vulcabond, a tetramethyl-xylylene diisocyanate, to one or both in tetramethyl-xylylene diisocyanate.
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