CN117844398A - Environment-friendly adhesive for preparing wooden composite material by modification of illite smectite clay - Google Patents
Environment-friendly adhesive for preparing wooden composite material by modification of illite smectite clay Download PDFInfo
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- CN117844398A CN117844398A CN202311739981.7A CN202311739981A CN117844398A CN 117844398 A CN117844398 A CN 117844398A CN 202311739981 A CN202311739981 A CN 202311739981A CN 117844398 A CN117844398 A CN 117844398A
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- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 title claims abstract description 148
- 239000004927 clay Substances 0.000 title claims abstract description 145
- 229910052900 illite Inorganic materials 0.000 title claims abstract description 134
- 229910021647 smectite Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 239000000853 adhesive Substances 0.000 title abstract description 31
- 230000001070 adhesive effect Effects 0.000 title abstract description 31
- 230000004048 modification Effects 0.000 title description 16
- 238000012986 modification Methods 0.000 title description 16
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 69
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 58
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 81
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 235000006408 oxalic acid Nutrition 0.000 claims description 27
- 150000007524 organic acids Chemical class 0.000 claims description 24
- 150000007522 mineralic acids Chemical class 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004135 Bone phosphate Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940000488 arsenic acid Drugs 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 61
- 238000002360 preparation method Methods 0.000 abstract description 16
- 239000000725 suspension Substances 0.000 abstract description 6
- 239000012790 adhesive layer Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 7
- 229910052901 montmorillonite Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- -1 ca 2 + Chemical compound 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to acid modified expanded illite-montmorillonite clay modified by acid and a preparation method thereof, and a green environment-friendly urea-formaldehyde resin adhesive for a wooden composite material containing the acid modified expanded illite-montmorillonite clay and a preparation method thereof. The acid modified puffed illite clay has good expansibility, better suspension property and rheological property, can form gel with good thixotropy, and can be uniformly and stably dispersed in urea-formaldehyde resin; the urea-formaldehyde resin adhesive containing the acid modified puffed illite smectite clay is simple in preparation method, better in adhesive layer mechanical property, more economical in production cost, lower in formaldehyde release amount and more environment-friendly.
Description
Technical Field
The invention relates to the field of illite clay modification, in particular to acid-modified puffed illite clay and a preparation method thereof, and green environment-friendly urea-formaldehyde resin adhesive for a wooden composite material containing the acid-modified puffed illite clay and a preparation method thereof.
Background
Illite clay is a silicate clay with a layered structure and lamellar crystals, and has a three-layer structure and is a main component of clay shale. Since the silicon atoms in the illite clay structure are substituted with aluminum atoms to a much lower degree than the aluminum atoms in montmorillonite are substituted with magnesium atoms, the radical exchange capacity of illite clay is located between montmorillonite and kaolinite, and thus the current commercial development value is much smaller than that of montmorillonite.
The hydrophilicity of the illite clay is larger than that of the kaolin and smaller than that of the montmorillonite, so that water between layers can freely enter and exit, however, the illite clay has poorer expansion performance, and the swelling phenomenon is not generated in the process. The reason is that illite clay belongs to a 2:1 type lattice, a crystal layer is formed by clamping 1 aluminum oxide octahedron by 2 silicon oxygen tetrahedrons, and the crystal layers are combined through potassium ions, so that the distance between the crystal layers is relatively fixed, the change is difficult, and the expansibility and the specific surface area are relatively small. The characteristic limits the matching property of the adhesive and urea-formaldehyde resin, precipitation delamination is easy to occur after the adhesive and the urea-formaldehyde resin are mixed, the adhesive layer is easy to be unstable after sizing, the defect of the adhesive layer occurs, and the cementing strength and the water resistance of the adhesive are affected. Therefore, in summary, the conventional illite clay mainly has the following three problems that (1) the swelling property is small; (2) poor hydrophilicity; (3) Unstable after being mixed with urea-formaldehyde resin, and is easy to precipitate and delaminate.
Therefore, the existing illite clay is modified so that the illite clay can be fully mixed with urea-formaldehyde resin, and the urea-formaldehyde resin adhesive which is low in formaldehyde release amount and does not damage cementing strength and water resistance is obtained, so that the illite clay has important practical value.
Disclosure of Invention
Problems to be solved by the invention
In order to solve the problems in the prior art, the invention provides acid modified puffed illite clay with large specific surface area, good expansion performance, lower price, better suspension property and rheological property and good thixotropy and a preparation method thereof, and provides a urea-formaldehyde resin adhesive containing the acid modified puffed illite clay with higher bonding strength, better suspension property, higher water resistance, stronger mechanical property after solidification, lower cost and lower formaldehyde release amount and a preparation method thereof.
Solution for solving the problem
The invention provides acid modified puffed illite clay, which is characterized in that the illite clay is modified by acid.
Further, the acid-modified puffed illite smectite clay as described above is characterized in that the acid is an organic acid or an inorganic acid;
further, the inorganic acid is a monobasic inorganic acid, a dibasic inorganic acid or a tribasic inorganic acid;
further, the organic acid is a monobasic organic acid, a dibasic organic acid or a tribasic organic acid;
further, the monobasic inorganic acid is hydrochloric acid, nitric acid, hydrobromic acid or hydrofluoric acid;
further, the dibasic inorganic acid is sulfuric acid or hydrogen sulfuric acid;
further, the ternary inorganic acid is phosphoric acid or arsenic acid;
further, the monobasic organic acid is benzoic acid, formic acid, acetic acid, propionic acid, acrylic acid, butyric acid or lactic acid;
further, the dibasic organic acid is oxalic acid, tartaric acid, oxalic acid or malic acid;
further, the ternary organic acid is citric acid or succinic acid;
further, the dibasic organic acid is oxalic acid.
The invention also provides a preparation method of the acid modified puffed illite smectite clay, which is characterized by comprising the following steps: (1) adding distilled water into illite clay for soaking, and then adding acid;
(2) Heating the sample obtained in the step (1);
(3) Filtering and rinsing the sample obtained in the step (2);
(4) Drying the sample obtained in the step (3);
(5) Sieving the sample obtained in the step (4) to obtain acid modified puffed illite smectite clay;
further, the temperature of the sample in the step (2) is raised to 80-100 ℃;
further, the temperature of the sample in the step (2) is raised to 90-100 ℃;
further, the sample in the step (2) is heated to boiling;
further, the sample in the step (4) is dried at 80-140 ℃;
further, the sample in the step (4) is dried at 90-130 ℃;
further, the sample in the step (4) is dried at 100-120 ℃;
further, the sample in the step (4) is dried at 110 ℃;
further, the sample in the step (4) is dried for 8-16 hours;
further, the sample in the step (4) is dried for 10-14 hours;
further, the sample in the step (4) is dried for 12 hours;
further, the sample in the step (5) is sieved by a sieve of 0.050-0.150 mm;
further, the sample in the step (5) is sieved by a sieve with 0.060-0.120 mm;
further, the sample in the step (5) is sieved by a sieve with 0.070-0.090 mm;
further, the sample in the step (5) was sieved through a 0.080mm sieve.
Further, the preparation method of the acid modified puffed illite smectite clay is characterized in that the acid is added in the step (1), and the pH value of the mixed solution is controlled to be 1-5;
further, the pH value of the mixed solution ranges from 1 to 3;
further, the pH value of the mixed solution is in the range of 1-2.
Further, the preparation method of the acid modified puffed illite clay is characterized in that in the step (1), the mass-volume ratio (g/ml) of the illite clay to distilled water is 1:3-6;
further, the mass-volume ratio (g/ml) of the illite clay to distilled water is 1:4-5;
further, the mass-to-volume ratio (g/ml) of illite clay to distilled water is 1:5.
Further, the preparation method of the acid modified puffed illite smectite clay is characterized in that the pH value of the obtained filtrate is 2-7 after the sample in the step (3) is subjected to suction filtration and rinsing;
further, the pH value of the filtrate is 3-6;
further, the pH value of the filtrate is 4-5.
The invention also provides a compound which is characterized by comprising urea-formaldehyde resin and the acid modified puffed illite smectite clay.
Further, the composite is characterized in that the addition proportion of the acid modified expanded illite smectite clay is 0.1-4wt%;
further, the acid modified puffed illite clay is added in a proportion of 1wt%,2wt%,3wt% or 4wt%;
further, the acid modified puffed illite clay is added in an amount of 4wt%.
The invention also provides a preparation method of the compound, which is characterized by comprising the following steps of: urea formaldehyde resin and acid modified expanded illite clay as described above were mixed.
The invention also provides the application of the acid modified puffed illite smectite clay or the compound in wood gluing.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention creatively discovers that the acid is utilized to modify the illite clay, and the obtained acid modified puffed illite clay has the following advantages:
(1) The acidification modification can break the combination of potassium ions between illite clay crystal layers, improves expansibility, has better suspension property and rheological property, can increase the coating consistency of urea-formaldehyde resin adhesive, and can form gel with good thixotropic property. The illite clay achieves a nanoscale effect through acidification and expansion so as to obtain larger specific surface area and strong interface interaction, so that the urea-formaldehyde resin polymer chain and the lamellar layer have strong Van der Waals force, and the illite clay can be uniformly and stably dispersed in the urea-formaldehyde resin;
(2) The acid modified puffed illite clay can improve the mechanical properties of the urea-formaldehyde resin adhesive layer;
(3) Under the condition that the urea-formaldehyde resin adhesive meets the requirement of the same mechanical property, the addition of the acid modified puffed illite smectite clay can reduce the consumption of the urea-formaldehyde resin base material, the cost of the adhesive is reduced by 12% -18%, and the production cost of the obtained urea-formaldehyde resin additive is more economic;
(4) The acid modified puffed illite clay can improve suspension property of urea-formaldehyde resin, improve construction brushing performance of plywood and improve mechanical property after solidification;
(5) The acid modified puffed illite smectite clay can reduce the formaldehyde release amount of urea-formaldehyde resin, and the obtained urea-formaldehyde resin adhesive is more environment-friendly.
Detailed Description
In order to make the technical scheme and the beneficial effects of the invention more obvious and understandable, the following detailed description is given by way of example. Unless defined otherwise, technical and scientific terms used herein have the same meaning as technical and scientific terms in the technical field to which this application belongs.
The term illite clay is silicate clay of lamellar structure and lamellar crystal formed by clamping 1 aluminum oxide octahedron with 2 silicon oxide tetrahedrons and combining potassium ions between crystal layers;
the term "urea-formaldehyde resin" is also known as urea-formaldehyde resin, and is an insoluble, infusible thermosetting resin.
The invention provides acid modified puffed illite clay, which is characterized in that the illite clay is modified by acid.
In certain embodiments, an acid-modified expanded illite clay as described above, characterized in that the acid is an organic acid or an inorganic acid;
in certain embodiments, the inorganic acid is a monobasic inorganic acid, a dibasic inorganic acid, or a tribasic inorganic acid;
in certain embodiments, the organic acid is a mono-, di-, or tri-organic acid;
in certain embodiments, the monobasic inorganic acid is hydrochloric acid, nitric acid, hydrobromic acid, or hydrofluoric acid;
in certain embodiments, the dibasic mineral acid is sulfuric acid or hydrogen sulfate;
in certain embodiments, the ternary inorganic acid is phosphoric acid or arsenic acid;
in certain embodiments, the monobasic organic acid is benzoic acid, formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, or lactic acid;
in certain embodiments, the dibasic organic acid is oxalic acid, tartaric acid, oxalic acid, or malic acid;
in certain embodiments, the ternary organic acid is citric acid or succinic acid;
in certain embodiments, the dibasic organic acid is oxalic acid.
The invention also provides a preparation method of the acid modified puffed illite smectite clay, which is characterized by comprising the following steps: (1) adding distilled water into illite clay for soaking, and then adding acid;
(2) Heating the sample obtained in the step (1);
(3) Filtering and rinsing the sample obtained in the step (2);
(4) Drying the sample obtained in the step (3);
(5) Sieving the sample obtained in the step (4) to obtain acid modified puffed illite smectite clay;
in certain embodiments, the sample in step (2) is warmed to 80-100 ℃;
in certain embodiments, the sample in step (2) is warmed to 90-100 ℃;
in certain embodiments, the sample in step (2) is warmed to boiling;
in certain embodiments, the sample in step (4) is dried at 80-140 ℃;
in certain embodiments, the sample in step (4) is dried at 90-130 ℃;
in certain embodiments, the sample in step (4) is dried at 100-120 ℃;
in certain embodiments, the sample in step (4) is dried at 110 ℃;
in certain embodiments, the sample in step (4) is dried for 8-16 hours;
in certain embodiments, the sample in step (4) is dried for 10-14 hours;
in certain embodiments, the sample in step (4) is dried for 12 hours;
in certain embodiments, the sample in step (5) is sieved through a 0.050-0.150mm sieve;
in certain embodiments, the sample in step (5) is sieved through a 0.060-0.120mm sieve;
in certain embodiments, the sample in step (5) is sieved through a 0.070-0.090mm sieve;
in certain embodiments, the sample in step (5) is sieved through a 0.080mm sieve.
In certain embodiments, the method for preparing acid-modified puffed illite clay as described above is characterized in that the acid is added in the step (1), and the pH value of the mixed solution is controlled to be in the range of 1-5;
in certain embodiments, the mixed solution has a pH in the range of 1 to 3;
in certain embodiments, the mixed solution has a pH in the range of 1 to 2.
In certain embodiments, the method for preparing acid-modified expanded illite clay as described above, characterized in that in the step (1), the mass-to-volume ratio (g/ml) of illite clay to distilled water is 1:3-6;
in certain embodiments, the mass to volume ratio (g/ml) of illite clay to distilled water is 1:4-5;
in certain embodiments, the mass to volume ratio (g/ml) of illite clay to distilled water is 1:5.
In certain embodiments, the method for preparing acid-modified puffed illite smectite clay as described above is characterized in that the pH of the filtrate obtained after the sample in step (3) is rinsed by suction filtration is 2-7;
in certain embodiments, the filtrate has a pH of 3 to 6;
in certain embodiments, the filtrate has a pH of 4 to 5.
The invention also provides a compound which is characterized by comprising urea-formaldehyde resin and the acid modified puffed illite smectite clay.
In certain embodiments, a composite as described above, characterized in that the acid-modified expanded illite clay is added in a proportion of 0.1 to 4wt%;
in certain embodiments, the acid-modified expanded illite clay is added in a proportion of 1wt%,2wt%,3wt%, or 4wt%;
in certain embodiments, the acid modified expanded illite clay is added in a proportion of 4wt%.
The invention also provides a preparation method of the compound, which is characterized by comprising the following steps of: urea formaldehyde resin and acid modified expanded illite clay as described above were mixed.
The invention also provides the application of the acid modified puffed illite smectite clay or the compound in wood gluing.
The process of the present invention is illustrated by the following specific examples, it being understood that these examples are illustrative of the basic principles, main features and advantages of the present invention, and the present invention is not limited by the scope of the following examples; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
EXAMPLE 1 oxalic acid activation modification treatment of illite clay
Weighing 20 g illite clay, placing in a 250 mL conical flask, soaking in 100 mL distilled water for 12h to disperse the illite clay, adding oxalic acid, controlling pH of the mixed solution to 1-2, heating to boil, and maintaining 4 h. After the treatment, the sample is filtered and rinsed until the pH value of the filtrate is 4-5, and then is placed in an electrothermal constant-temperature blast drying oven to be dried at 110 ℃ for 12 h. And (3) sieving the dried sample with a 0.080mm standard sieve, and placing the sample in a dryer for standby, wherein the sample is called oxalic acid puffed illite clay.
EXAMPLE 2 hydrochloric acid activation modification treatment of illite-montmorillonite clay
Weighing 20 g illite clay, placing in a 250 mL conical flask, soaking in 100 mL distilled water for 12h to disperse the illite clay, adding hydrochloric acid, controlling pH of the mixed solution to 1-2, heating to boil, and maintaining 4 h. After the treatment, the sample is filtered and rinsed until the pH value of the filtrate is 4-5, and then is placed in an electrothermal constant-temperature blast drying oven to be dried at 110 ℃ for 12 h. And (3) sieving the dried sample with a 0.080mm standard sieve, and placing the sample in a dryer for standby, wherein the sample is called hydrochloric acid puffed illite clay.
Example 3 specific surface area analysis of acid modified puffed illite smectite clay
In order to verify the influence of different modification treatment methods on the adsorption performance of the puffed illite clay, the specific surface areas of different types of puffed illite clay samples are tested by adopting a nitrogen adsorption and desorption method, and the test results are shown in table 1.
TABLE 1 example 1-2 acid modified puffed illite-montmorillonite clay specific surface area detection results
| Sample of | Specific surface area m 2 /g |
| Illite smectite clay | 45 |
| Hydrochloric acid modified puffed illite clay (example 2) | 68 |
| Oxalic acid modified puffed illite smectite clay (example 1) | 98 |
As shown in table 1, the specific surface area of the illite clay modified with oxalic acid in example 1 of the present invention was increased by more than one time compared to the unmodified illite clay, and also increased to a great extent compared to the illite clay modified with hydrochloric acid in example 2. The acid modified puffed illite clay is used for treating illite clay by acid, so that impurities in montmorillonite molecular structure channels are removed, and the channels become loose and porous; at the same time, H+ reacts with silicate in the interlayer structure of montmorillonite, ca 2 +、Na+、Mg 2 The +etc. metal cations are converted into soluble salt substances to enter water, so that the pore structure of the interlayer structure of montmorillonite is changed, and the specific surface area of illite clay is increased.
According to the invention, oxalic acid and hydrochloric acid are characterized by a specific surface area method to quantify the modification effect of the illite clay, and the BET specific surface area of the illite clay after reaction is determined by a nitrogen adsorption and desorption method. The experiment adopts a Tristar II 3020 porosity and specific surface area tester, utilizes the adsorption-condensation principle of low-temperature (77K) nitrogen (liquid nitrogen), utilizes the Van der Waals force between molecules to make the surface of an object generate adsorption phenomenon under the action of certain relative pressure, forms a single molecule nitrogen adsorption layer on the surface of an illite clay molecular layer, and when the relative pressure reaches or exceeds 0.4, the phenomenon of capillary energy aggregation can occur due to excessive liquid nitrogen adsorption until the pores in a sample are filled, and determines the volume of the pores through a BET equation and a Kelvin equation.
EXAMPLE 4 preparation of Urea-formaldehyde resin
The urea-formaldehyde resin used in the present invention is prepared by the following method (formaldehyde: urea molar ratio=1.02:1): firstly, adding a certain amount of formaldehyde solution into a three-neck flask, heating to 50 ℃, adjusting the pH value to 8.0 by using NaOH solution, adding a first batch of urea, heating to 90 ℃, adjusting the pH value to 5.4-5.6 by using formic acid solution, adding a second batch of urea, reacting for a certain time, adjusting the pH value to 7.5-8.0 by using NaOH solution, and adding a third batch of urea to enable the molar ratio of formaldehyde to urea to be 1.02:1, cooling to 65-70 ℃, reacting for 30min at a temperature of 30 ℃, and finally adjusting the pH value to 8.0 by using NaOH solution to obtain the urea-formaldehyde resin.
Example 5 preparation of acid-modified expanded illite-urea-formaldehyde resin composite
The acid modified puffed illite clay-urea resin compound obtained by the invention is prepared by the following method: the urea-formaldehyde resin prepared in example 4 was mixed with the acid-modified expanded illite clay to obtain an "acid-modified expanded illite clay-urea-formaldehyde resin" composite.
Polar genes in urea resin molecules, such as-OH, -NH and the like, can perform cation exchange with the puffed illite clay to form an illite clay-organic molecule composite. In urea-formaldehyde resin, illite clay connects urea-formaldehyde resin molecules into a three-dimensional net structure, and the urea-formaldehyde resin molecules are uniformly dispersed in a system, so that good suspension property is achieved, and sedimentation caused by different densities is avoided. And once the illite clay organic compound is generated, the illite clay organic compound is irreversibly cured at high temperature during pressing, and becomes a hydrophobic substance after water loss, so that the water resistance of the adhesive layer is increased.
EXAMPLE 6 determination of the glue Strength of Urea resin adhesive
The oxalic acid/hydrochloric acid modified expanded illite clay and the unmodified illite clay obtained in examples 1-2 were taken and prepared in the proportions of 0,1wt%,2wt%,3wt%,4wt% and the urea-formaldehyde resin prepared in example 4 according to the method in example 5, respectively, to obtain different types of "illite clay-urea-formaldehyde resin" composites, namely different types of urea-formaldehyde resin adhesives, and the bonding strength of the composites was measured, and the results are shown in tables 2-4.
Table 2: influence of the addition of unmodified illite clay on the bonding strength of urea-formaldehyde resin
| Unmodified illite-montmorillonite clay addition (wt%) | Dry Strength (MPa) | Wet strength (MPa) |
| 0 | 0.65 | Failure to pass |
| 1 | 0.68 | Failure to pass |
| 2 | 0.72 | Failure to pass |
| 3 | 0.81 | Failure to pass |
| 4 | 0.88 | Failure to pass |
Table 3: influence of hydrochloric acid modified puffed illite smectite clay addition on urea resin bonding strength
Table 4: influence of oxalic acid modified puffed illite smectite clay addition on urea resin bonding strength
| Oxalic acid modified expanded illite smectite clay (example 1) addition (wt%) | Dry Strength (MPa) | Wet strength (MPa) |
| 0 | 0.65 | Failure to pass |
| 1 | 0.66 | Failure to pass |
| 2 | 0.71 | Failure to pass |
| 3 | 0.83 | Disqualification (0.62) |
| 4 | 1.1 | Qualification (0.84) |
From tables 2 to 4, it can be seen that the bonding strength of the urea-formaldehyde resin adhesive gradually becomes stronger as the addition amount of the illite clay increases, and the bonding strength of the urea-formaldehyde resin adhesive is stronger when the acid-modified illite Meng Nian clay is added compared with the unmodified illite clay. In addition, when the addition amount of the puffed illite clay modified by oxalic acid in example 2 (example 1) was 4wt%, acceptable wet strength (0.84 MPa) was obtained on the premise that the dry strength reached 1.1 MPa. The bonding strength of the urea-formaldehyde resin adhesive obtained by adding 4wt% of the modified illite clay into urea-formaldehyde resin after acid modification, especially oxalic acid modification, is obviously improved, and the mechanical property after curing is better.
EXAMPLE 7 Urea resin adhesive viscosity determination
The oxalic acid/hydrochloric acid modified puffed illite clay and unmodified illite clay obtained in examples 1-2 were taken and prepared in the proportions of 0,1wt%,2wt%,3wt%,4wt% and the urea-formaldehyde resin prepared in example 4 according to the method in example 5, respectively, to obtain different types of illite clay-urea-formaldehyde resin composites, namely different types of urea-formaldehyde resin adhesives. The viscosity of the above-mentioned compound was measured using a 4-cup viscometer, and the results are shown in Table 5.
TABLE 5 influence of illite clay addition on urea-formaldehyde resin viscosity
As shown in table 5, the viscosity of the urea-formaldehyde resin adhesive gradually increased with the increase of the addition amount of the illite clay, and the viscosity of the urea-formaldehyde resin adhesive was stronger when the acid-modified illite Meng Nian clay was added than when the unmodified illite clay was added. In addition, the viscosity of the illite clay modified with oxalic acid in example 1 was more significantly improved than that modified with hydrochloric acid in example 2, and the viscosity was highest at an addition of 4wt%. The viscosity of the urea-formaldehyde resin adhesive obtained by adding 4 weight percent of the modified illite clay into urea-formaldehyde resin after acid modification, particularly oxalic acid modification, is obviously improved.
Example 8 determination of Formaldehyde Release amount of Urea resin adhesive
The oxalic acid/hydrochloric acid modified puffed illite clay and unmodified illite clay obtained in examples 1-2 were taken and prepared in the proportions of 0,1wt%,2wt%,3wt%,4wt% and the urea-formaldehyde resin prepared in example 4 according to the method in example 5, respectively, to obtain different types of illite clay-urea-formaldehyde resin composites, namely different types of urea-formaldehyde resin adhesives. Then, a crystallization dish containing (300+/-1) mL of distilled water and a metal bracket are placed at the bottom of a dryer with the diameter of 240mm and the volume of (1 L+/-2) L, and different groups of adhesives are manufactured into a certain number of small samples and placed on the metal bracket without mutual contact among various test pieces according to the requirements of GB/T17657-2013 on the physical and chemical property test method of artificial boards and veneer artificial boards. Placing the sample in the environment of (20+/-0.5) ℃ for 24 hours, absorbing formaldehyde released from the test piece by distilled water, and detecting the formaldehyde content by taking the solution as a liquid to be detected. The measurement results of the formaldehyde release amount of the urea-formaldehyde resin adhesive are shown in tables 6 to 8.
TABLE 6 influence of illite clay addition on the formaldehyde emission of urea-formaldehyde resins
| Unmodified illite-montmorillonite clay addition (wt%) | Formaldehyde emission (mg/L) |
| 0 | 1.7 |
| 1 | 1.5 |
| 2 | 1.2 |
| 3 | 0.9 |
| 4 | 1.3 |
TABLE 7 influence of the addition of hydrochloric acid modified expanded illite smectite clay on the formaldehyde emission of urea-formaldehyde resin
| Hydrochloric acid modified puffed illite clay (example 2) addition (wt%) | Formaldehyde emission (mg/L) |
| 0 | 1.7 |
| 1 | 1.3 |
| 2 | 1.1 |
| 3 | 0.9 |
| 4 | 1.1 |
TABLE 8 influence of oxalic acid modified expanded illite smectite clay addition on the Release of Urea-formaldehyde resin formaldehyde
| Oxalic acid modified expanded illite smectite clay (example 1) addition (wt%) | Formaldehyde emission (mg/L) |
| 0 | 1.7 |
| 1 | 1.2 |
| 2 | 0.8 |
| 3 | 0.7 |
| 4 | 0.9 |
As shown in tables 6 to 8, the formaldehyde release amount of the urea-formaldehyde resin adhesive gradually decreases with the increase of the addition amount of the illite clay, and the formaldehyde release amount of the urea-formaldehyde resin adhesive is lower when the acid-modified illite Meng Nian clay is added compared with the unmodified illite clay. In addition, the effect of the modified illite clay of example 1 on reducing formaldehyde emission of urea-formaldehyde resin was more remarkable than that of the hydrochloric acid modification of example 2. The formaldehyde release amount of the urea-formaldehyde resin adhesive obtained by adding the urea-formaldehyde resin after acid modification, particularly oxalic acid modification, of the illite clay is obviously reduced, and the illite clay is more environment-friendly.
It should be understood that the above examples are illustrative and are not intended to encompass all possible implementations encompassed by the claims. Various modifications and changes may be made in the above embodiments without departing from the scope of the disclosure. Likewise, the individual features of the above embodiments can also be combined arbitrarily to form further embodiments of the invention which may not be explicitly described. Therefore, the above examples merely represent several embodiments of the present invention and do not limit the scope of protection of the patent of the present invention.
Claims (10)
1. An acid-modified puffed illite clay is characterized in that the illite clay is modified by acid.
2. The acid-modified expanded illite clay according to claim 1, wherein the acid is an organic acid or an inorganic acid;
preferably, the inorganic acid is a monobasic inorganic acid, a dibasic inorganic acid or a tribasic inorganic acid;
preferably, the organic acid is a monobasic organic acid, a dibasic organic acid or a tribasic organic acid;
preferably, the monobasic inorganic acid is hydrochloric acid, nitric acid, hydrobromic acid or hydrofluoric acid;
preferably, the dibasic inorganic acid is sulfuric acid or hydrogen sulfuric acid;
preferably, the ternary inorganic acid is phosphoric acid or arsenic acid;
preferably, the monobasic organic acid is benzoic acid, formic acid, acetic acid, propionic acid, acrylic acid, butyric acid or lactic acid;
preferably, the dibasic organic acid is oxalic acid, tartaric acid, oxalic acid or malic acid;
preferably, the ternary organic acid is citric acid or succinic acid;
preferably, the dibasic organic acid is oxalic acid.
3. A method for preparing the acid-modified puffed illite smectite clay as claimed in claim 1 or 2, comprising the steps of:
(1) Soaking illite clay in distilled water, and adding acid;
(2) Heating the sample obtained in the step (1);
(3) Filtering and rinsing the sample obtained in the step (2);
(4) Drying the sample obtained in the step (3);
(5) Sieving the sample obtained in the step (4) to obtain acid modified puffed illite smectite clay;
preferably, the sample in the step (2) is heated to 80-100 ℃;
preferably, the sample in the step (2) is heated to 90-100 ℃;
preferably, the sample in step (2) is warmed to boiling;
preferably, the sample in step (4) is dried at 80-140 ℃;
preferably, the sample in step (4) is dried at 90-130 ℃;
preferably, the sample in step (4) is dried at 100-120 ℃;
preferably, the sample in step (4) is dried at 110 ℃;
preferably, the sample in the step (4) is dried for 8-16 hours;
preferably, the sample in the step (4) is dried for 10-14 hours;
preferably, the sample in the step (4) is dried for 12 hours;
preferably, the sample in step (5) is sieved through a 0.050-0.150mm sieve;
preferably, the sample in step (5) is sieved through a 0.060-0.120mm sieve;
preferably, the sample in step (5) is sieved through a 0.070-0.090mm sieve;
preferably, the sample in step (5) is sieved through a 0.080mm sieve.
4. The method for preparing acid-modified puffed illite clay according to claim 3, wherein the step (1) is performed by adding acid, and controlling the pH value of the mixed solution to be 1-5;
preferably, the pH value of the mixed solution ranges from 1 to 3;
preferably, the pH of the mixed solution is in the range of 1-2.
5. The method for preparing acid-modified puffed illite clay according to claim 3 or 4, wherein in the step (1), the mass-to-volume ratio (g/ml) of illite clay to distilled water is 1:3-6;
preferably, the mass-to-volume ratio (g/ml) of the illite clay to distilled water is 1:4-5;
preferably, the mass-to-volume ratio (g/ml) of illite clay to distilled water is 1:5.
6. The method for preparing acid-modified puffed illite smectite clay as claimed in any one of claims 3 to 5, wherein the pH of the filtrate obtained after the sample in step (3) is rinsed by suction filtration is 2 to 7;
preferably, the pH value of the filtrate is 3-6;
preferably, the pH of the filtrate is 4-5.
7. A composite comprising urea formaldehyde resin and the acid modified expanded illite clay of claims 1-6.
8. The composite of claim 7, wherein the acid-modified expanded illite clay is added in a proportion of 0.1 to 4wt%;
preferably, the acid modified puffed illite clay is added in a proportion of 1wt%,2wt%,3wt% or 4wt%;
preferably, the acid-modified expanded illite clay is added in an amount of 4wt%.
9. A method of preparing a composite according to claims 7-8, comprising the steps of: mixing urea formaldehyde resin with the acid modified expanded illite clay of claims 1-6.
10. Use of the acid modified expanded illite clay of claim 1 or 2 or the composite of claims 8-9 in wood gluing.
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| CN202311739981.7A CN117844398A (en) | 2023-12-18 | 2023-12-18 | Environment-friendly adhesive for preparing wooden composite material by modification of illite smectite clay |
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