CN104232001A - Organic-attapulgite-modified water-based laminating adhesive and preparation method thereof - Google Patents
Organic-attapulgite-modified water-based laminating adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN104232001A CN104232001A CN201410482345.5A CN201410482345A CN104232001A CN 104232001 A CN104232001 A CN 104232001A CN 201410482345 A CN201410482345 A CN 201410482345A CN 104232001 A CN104232001 A CN 104232001A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- laminating adhesive
- organic
- aqueous
- distilled water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000012939 laminating adhesive Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229960000892 attapulgite Drugs 0.000 claims abstract description 222
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 222
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 29
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 29
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- -1 diisocyanate compound Chemical class 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 57
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 56
- 238000000746 purification Methods 0.000 claims description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 230000004048 modification Effects 0.000 claims description 46
- 238000012986 modification Methods 0.000 claims description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002689 soil Substances 0.000 claims description 34
- 238000010992 reflux Methods 0.000 claims description 32
- 238000000967 suction filtration Methods 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 230000003472 neutralizing effect Effects 0.000 claims description 22
- 239000003607 modifier Substances 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000605 extraction Methods 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000004945 emulsification Methods 0.000 claims description 17
- 230000027555 hydrotropism Effects 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 16
- 238000004062 sedimentation Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 10
- 229920001610 polycaprolactone Polymers 0.000 claims description 10
- 239000004632 polycaprolactone Substances 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- SGXQOOUIOHVMEJ-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCCCCCCCC Chemical compound N=C=O.N=C=O.CCCCCCCCCCCC SGXQOOUIOHVMEJ-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 4
- VMIORCIXXWGAGI-UHFFFAOYSA-N 2-(n-benzylanilino)ethanol Chemical compound C=1C=CC=CC=1N(CCO)CC1=CC=CC=C1 VMIORCIXXWGAGI-UHFFFAOYSA-N 0.000 claims description 4
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 235000005513 chalcones Nutrition 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229960002725 isoflurane Drugs 0.000 claims description 4
- YMGWAYYUKMLZCW-UHFFFAOYSA-N 1-(n-benzylanilino)propan-2-ol Chemical compound C=1C=CC=CC=1N(CC(O)C)CC1=CC=CC=C1 YMGWAYYUKMLZCW-UHFFFAOYSA-N 0.000 claims description 3
- MIZIOHLLYXVEHJ-UHFFFAOYSA-N 2-[benzyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CC1=CC=CC=C1 MIZIOHLLYXVEHJ-UHFFFAOYSA-N 0.000 claims description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 229960005082 etohexadiol Drugs 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 abstract 2
- 150000003077 polyols Chemical class 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000498 cooling water Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000003292 glue Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
一种有机凹凸棒土改性的水性复膜胶及其制备方法，包括14～23％的聚合物多元醇，12～22％的多异氰酸酯化合物，0.1～2％的有机改性凹凸棒土，2～9％的扩链剂，2～5％的中和剂，45-55％的去离子水；以聚合物多元醇、二异氰酸酯化合物、凹凸棒土和亲水扩链剂为主要原料，通过逐步聚合合成技术获得一种有机凹凸棒土改性的水性复膜胶。本发明所制备的复膜胶以水为溶剂，具有粘结力大和剥离强度大，耐热性好，绿色环保的优点。An organic attapulgite-modified water-based laminating adhesive and a preparation method thereof, comprising 14-23% of polymer polyols, 12-22% of polyisocyanate compounds, 0.1-2% of organically modified attapulgite, 2 ～9% chain extender, 2～5% neutralizer, 45-55% deionized water; with polymer polyol, diisocyanate compound, attapulgite and hydrophilic chain extender as the main raw materials, through A water-based laminating adhesive modified by organic attapulgite was obtained by stepwise polymerization synthesis technique. The laminating adhesive prepared by the invention uses water as a solvent, has the advantages of high cohesive force and peeling strength, good heat resistance, and 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 (made in NETZSCH-Gerate ball Co., 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 (10)
1. the aqueous laminating adhesive of an organic attapulgite modification, it is characterized in that, 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%.
2. a preparation method for the aqueous laminating adhesive of organic attapulgite modification as claimed in claim 1, is characterized in that, comprise 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.
3. a kind of preparation method being applicable to the organic attapulgite of aqueous laminating adhesive according to claim 2, 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.
4. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 2, 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.
5. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 2, is characterized in that, described organic modifiers is one or both in cats product, silane coupling agent.
6. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 5, 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.
7. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 2, 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, butanone, methylethylketone or acetone;
Described neutralizing agent is oxyacetic acid, diacetyl oxide or Glacial acetic acid.
8. the preparation method of the aqueous laminating adhesive of organic attapulgite modification according to claim 7, 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.
9. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 2, 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.
10. the preparation method of the aqueous laminating adhesive of a kind of organic attapulgite modification according to claim 9, 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, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410482345.5A CN104232001B (en) | 2014-09-19 | 2014-09-19 | Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410482345.5A CN104232001B (en) | 2014-09-19 | 2014-09-19 | Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104232001A true CN104232001A (en) | 2014-12-24 |
| CN104232001B CN104232001B (en) | 2016-04-06 |
Family
ID=52220925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410482345.5A Expired - Fee Related CN104232001B (en) | 2014-09-19 | 2014-09-19 | Aqueous laminating adhesive of a kind of organic attapulgite modification and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104232001B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280149A (en) * | 2018-08-28 | 2019-01-29 | 淮阴工学院 | Synthesis method of high weather resistance red waterborne polyurethane emulsion |
| CN109943249A (en) * | 2019-04-01 | 2019-06-28 | 广州秦耀照明电器有限公司 | A kind of flexible heat insulating compound film and its preparation process applied to collector surface |
| CN114262493A (en) * | 2021-12-13 | 2022-04-01 | 徐州盛安化工科技有限公司 | Attapulgite-polybutylene terephthalate toughened phenolic resin and preparation method thereof |
| CN116693987A (en) * | 2023-08-08 | 2023-09-05 | 深圳市新中元电子有限公司 | Functional chip aluminum electrolytic capacitor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180155A1 (en) * | 2003-03-13 | 2004-09-16 | Nguyen-Misra Mai T. | Moisture curable hot melt sealants for glass constructions |
| CN101768418A (en) * | 2010-01-21 | 2010-07-07 | 江苏工业学院 | Preparation method of attapulgite/aqueous polyurethane compound binder |
| CN103013420A (en) * | 2012-11-30 | 2013-04-03 | 三棵树涂料股份有限公司 | Environment-friendly anti-yellowing water-based universal polyurethane adhesive |
-
2014
- 2014-09-19 CN CN201410482345.5A patent/CN104232001B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180155A1 (en) * | 2003-03-13 | 2004-09-16 | Nguyen-Misra Mai T. | Moisture curable hot melt sealants for glass constructions |
| CN101768418A (en) * | 2010-01-21 | 2010-07-07 | 江苏工业学院 | Preparation method of attapulgite/aqueous polyurethane compound binder |
| CN103013420A (en) * | 2012-11-30 | 2013-04-03 | 三棵树涂料股份有限公司 | Environment-friendly anti-yellowing water-based universal polyurethane adhesive |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280149A (en) * | 2018-08-28 | 2019-01-29 | 淮阴工学院 | Synthesis method of high weather resistance red waterborne polyurethane emulsion |
| CN109280149B (en) * | 2018-08-28 | 2020-04-24 | 淮阴工学院 | Synthesis method of high-weather-resistance red water-based polyurethane emulsion |
| CN109943249A (en) * | 2019-04-01 | 2019-06-28 | 广州秦耀照明电器有限公司 | A kind of flexible heat insulating compound film and its preparation process applied to collector surface |
| CN114262493A (en) * | 2021-12-13 | 2022-04-01 | 徐州盛安化工科技有限公司 | Attapulgite-polybutylene terephthalate toughened phenolic resin and preparation method thereof |
| CN114262493B (en) * | 2021-12-13 | 2024-02-20 | 龚文洁 | A kind of attapulgite-polybutylene terephthalate toughened phenolic resin and its preparation method |
| CN116693987A (en) * | 2023-08-08 | 2023-09-05 | 深圳市新中元电子有限公司 | Functional chip aluminum electrolytic capacitor and preparation method thereof |
| CN116693987B (en) * | 2023-08-08 | 2023-10-24 | 深圳市新中元电子有限公司 | Functional chip aluminum electrolytic capacitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104232001B (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107828046B (en) | Preparation method of waterborne polyurethane/dopamine modified graphene nano composite emulsion | |
| Hu et al. | One-pot water-based hydrophobic surface modification of cellulose nanocrystals using plant polyphenols | |
| Zhang et al. | Synthesis and properties of UV-curable polyester-based waterborne polyurethane/functionalized silica composites and morphology of their nanostructured films | |
| CN102816515B (en) | Aqueous silicon dioxide-fluorinated acrylate polyurethane ultraviolet-curing coating, preparation method and application thereof | |
| CN101768418B (en) | Preparation method of attapulgite/aqueous polyurethane compound binder | |
| Lei et al. | Preparation and properties of amino-functional reduced graphene oxide/waterborne polyurethane hybrid emulsions | |
| CN103087291B (en) | Preparation method of high solid content waterborne polyurethane | |
| CN101225226B (en) | Preparation method and application of water-dispersed montmorillonite/organosilicon block polyurethane nanocomposite | |
| CN103360563B (en) | High-solid content waterborne polyurethane emulsion with particle size polydispersity and preparation method thereof | |
| CN105255348A (en) | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof | |
| CN101348704B (en) | Continuous production method of polyurethane water dispersion adhesive | |
| CN101787170B (en) | Preparation method of alcohol-soluble room temperature curing two-component polyurethane-acrylate resin | |
| CN105968306A (en) | Preparation method of nano-silicon-dioxide-modified water-based polyurethane | |
| CN105732940A (en) | Preparation method of waterborne polyurethane-silicon dioxide nano composite emulsion | |
| CN105462536B (en) | A kind of water-based silane-modified polyurethane adhesive and preparation method thereof | |
| CN101481451A (en) | High solid content latent curing polyurethane acroleic acid hybrid emulsion | |
| CN105622857A (en) | Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material | |
| TW200838907A (en) | Rheological additive in the form of a preactivated paste | |
| CN109810239B (en) | Waterborne polyurethane/modified graphene oxide composite emulsion and preparation method thereof | |
| CN103588951B (en) | A kind of preparation of high-strength hydrophobicity photocuring aqueous polyurethane nano composite emulsion | |
| CN103981716A (en) | A kind of preparation method and product of organosilicon-modified waterborne polyurethane for leather | |
| CN104232001A (en) | Organic-attapulgite-modified water-based laminating adhesive and preparation method thereof | |
| CN103382380B (en) | Two-component water-based polyurethane adhesive and preparation method thereof | |
| CN104341572A (en) | Preparation method of solvent-free water-based polyurethane resin | |
| CN106189298A (en) | A kind of novel emulsion asphalt modifier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160406 Termination date: 20190919 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |