CN1763050A - Preparation method of cation aluminium zirconium metal-organic complex coupling agent - Google Patents
Preparation method of cation aluminium zirconium metal-organic complex coupling agent Download PDFInfo
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- CN1763050A CN1763050A CN 200510096302 CN200510096302A CN1763050A CN 1763050 A CN1763050 A CN 1763050A CN 200510096302 CN200510096302 CN 200510096302 CN 200510096302 A CN200510096302 A CN 200510096302A CN 1763050 A CN1763050 A CN 1763050A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007822 coupling agent Substances 0.000 title claims description 34
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 title claims description 11
- 150000001768 cations Chemical class 0.000 title claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 aluminium chlorohydroxide-propylene glycol Chemical compound 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000010992 reflux Methods 0.000 claims description 28
- 239000002585 base Substances 0.000 claims description 22
- 239000007998 bicine buffer Substances 0.000 claims description 20
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 229910018580 Al—Zr Inorganic materials 0.000 abstract 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 abstract 2
- CCALPSCGTRJNTD-UHFFFAOYSA-K aluminum propane-1,2-diol trichloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].CC(O)CO CCALPSCGTRJNTD-UHFFFAOYSA-K 0.000 abstract 2
- 150000004696 coordination complex Chemical class 0.000 abstract 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract 2
- 229960004063 propylene glycol Drugs 0.000 abstract 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 229940015043 glyoxal Drugs 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000012764 mineral filler Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The preparation process of the cationic Al-Zr organic metal complex coupler includes the following steps: dissolving glyoxal and diethanolamine in water to react, adding anhydrous ethanol to separate out white crystal and stoving to obtain organic dentate N, N-dihydroxyethyl glycine; dissolving basic aluminum chloride in water, dropping hydrochloric acid, adding methanol and 1, 2-propylene glycol to react, evaporating methanol and stoving to obtain basic aluminum chloride-propylene glycol complex; and final reacting zirconium hydroxide, 1, 2-propylene glycol, and N, N-dihydroxyethyl glycine or dodecyl dimethyl betaine via mixing and heating, adding basic aluminum chloride-propylene glycol complex and decompression extraction to eliminate solvent and obtain the cationic Al-Zr organic metal complex coupler. The coupler has high stability, and may be used in modifying inorganic stuffing.
Description
Technical field
The present invention relates to a kind of preparation method of metal-organic complex coupling agent, particularly a kind of preparation method who is applicable to the cation aluminium zirconium metal-organic complex coupling agent of aqueous systems modification such as pigment in paper grade (stock) filler/latex coating.
Background technology
Mineral filler is behind super-refinement, and its specific surface area significantly increases, and surface energy is very high, and particle is in unsteady state, thereby has and attract each other strongly and reach stable tendency.This tendency makes particle produce gathering and influence effect subsequently.In fact, the Applications of Ultrafine Sized Materials process is the mutual fusion of ultrafine particle interface and other material interface, interactional process.Mineral filler is directly used in that polymkeric substance is compound will to influence its dispersion in polymkeric substance, causes the composite property variation.So, need carry out surface modification to ultrafine particle for the ease of the bonding force between ultrafine particle dispersion and increase particle and the polymkeric substance, mainly be the surperficial energy state that reduces particle, improve the avidity of particle and organic phase, weaken the surface polarity of particle etc.From molecular structure, the properties-correcting agent that is used for inorganic mineral filler and surface of pigments modification should be a class have more than one can with the functional group of mineral surface and more than one with organic polymer bonded group.A kind of material and coupling agent comes to this with both sexes structure, a part of group in its molecular structure can with the various functional group reactionses of powder microparticle surfaces, form strong chemical bonding, another part can some chemical reaction take place with organic polymer or physics twines, thereby two kinds of very big materials of nature difference are combined, between mineral filler or pigment and organic polymer, produce " molecule bridge " with specific function.Common coupling agent only has the coordination coupled action, and do not possess cationic electric charge, and most of coupling agent is be used for rubber and the used filler of plastics organically-modified, can not be used for water-soluble system, use the modification of powder filler, pigment seldom to relate to institutes such as papermaking, water milk coating, leather, water color inks.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of easily synthetic, cost is low and the preparation method of the water-soluble cationic aluminium zirconium metal-organic complex coupling agent that the coupling performance is good.
For achieving the above object, the preparation method that the present invention adopts is:
1) organic coordination base N, N-bicine N-synthetic
By mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 80～100 parts the water, be heated to 50～70 ℃, react 40～70 minutes postcooling to room temperature, add 20～30ml dehydrated alcohol again and separate out white crystals, in 30～60 ℃ of baking ovens, dry;
2) aluminium chlorohydroxide-propylene glycol complex compound is synthetic
By mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 20～50 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 20～30 minutes, add 15 parts of methyl alcohol again, add 1 part 1 after the reflux again, the 2-propylene glycol, reacted 40～60 minutes, in 60～70 ℃ steam methyl alcohol after, in 90～110 ℃ of baking ovens, dry again;
3) the aluminum-zirconium metal-organic complex coupling agent is synthetic
Press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the Varion CDG-K of N-bicine N-or 4.5 parts mixes, be heated to 50～75 ℃, reacted 20～40 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 50～75 ℃ of reactions 40～60 minutes down, be decompressed to 0.07～0.09Mpa and extract solvent out, get faint yellow viscous liquid.
Coupling agent by method preparation of the present invention is the oligopolymer that contains the organic complex of aluminium and zr element, and its chemical structural formula is: [Al (OR
1O)
aCl
b(OH)
e]
x[OC (R
2) O]
y[ZrCl
d(OH)
e]
z, x wherein, y, z=1-100; 2a+b+c=4; D+e=z;-OR
1O-is base organic the joining of containing bifunctional, and it gives coupling agent good hydroxyl stability and stability to hydrolysis;-OR
2The O-dentate has cation group, give coupling agent good organic affinity or reactivity, synthetic positively charged ion coupling agent is applied to Surface Modification Of Inorganic Fillers, can obviously change the viscosity of filler suspension, the bonding force of reinforcing filler and matrix, improve the application performance of filler in water-soluble system, its structure is:
R is an organic functions base, can provide coupling agent good organic affinity and reactivity.
Embodiment
Embodiment 1: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 96 parts the water, be heated to 50 ℃, react 70 minutes postcooling to room temperature, add the 20ml dehydrated alcohol again and separate out white crystals, in 45 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 20 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 30 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 60 minutes, in 70 ℃ steam methyl alcohol after, in 110 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 75 ℃, reacted 20 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 60 ℃ of reactions 50 minutes down, be decompressed to 0.07Mpa and extract solvent out, get faint yellow viscous liquid.
Embodiment 2: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 100 parts the water, be heated to 70 ℃, react 40 minutes postcooling to room temperature, add the 25ml dehydrated alcohol again and separate out white crystals, in 30 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 35 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 26 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 45 minutes, in 68 ℃ steam methyl alcohol after, in 98 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 63 ℃, reacted 30 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 63 ℃ of reactions 52 minutes down, be decompressed to 0.08Mpa and extract solvent out, get faint yellow viscous liquid.
Embodiment 3: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 80 parts the water, be heated to 60 ℃, react 55 minutes postcooling to room temperature, add the 30ml dehydrated alcohol again and separate out white crystals, in 60 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 25 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 28 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 52 minutes, in 62 ℃ steam methyl alcohol after, in 105 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 50 ℃, reacted 40 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 50 ℃ of reactions 60 minutes down, be decompressed to 0.09Mpa and extract solvent out, get faint yellow viscous liquid.
Embodiment 4: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 90 parts the water, be heated to 64 ℃, react 48 minutes postcooling to room temperature, add the 23ml dehydrated alcohol again and separate out white crystals, in 50 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 40 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 24 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 58 minutes, in 65 ℃ steam methyl alcohol after, in 93 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 60 ℃, reacted 26 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 75 ℃ of reactions 40 minutes down, be decompressed to 0.08Mpa and extract solvent out, get faint yellow viscous liquid.
Embodiment 5: aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 50 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 20 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 40 minutes, in 60 ℃ steam methyl alcohol after, in 100 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the Varion CDG-K of 2-propylene glycol and 4.5 parts mixes, be heated to 55 ℃, reacted 35 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, reacted 55 minutes down at 55 ℃, be decompressed to 0.09Mpa and extract solvent out, get faint yellow viscous liquid.
Embodiment 6: aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 30 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 25 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 50 minutes, in 64 ℃ steam methyl alcohol after, in 90 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the Varion CDG-K of 2-propylene glycol and 4.5 parts mixes, be heated to 68 ℃, reacted 31 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, reacted 45 minutes down at 68 ℃, be decompressed to 0.07Mpa and extract solvent out, get faint yellow viscous liquid.
The present invention is applied to the surface modification of lime carbonate, and its consumption is 0.1～1% of a light calcium carbonate consumption, can reduce the viscosity of this system greatly.To be used for filler in the papermaking slurry through the lime carbonate of modification, and not only can increase retention, and can improve the intensity of page.Be used for the modification that paper is coated with cloth filler, can obviously improve the oil absorbency of White Board and improve gigging speed.
Claims (7)
1, the preparation method of cation aluminium zirconium metal-organic complex coupling agent is characterized in that:
1) organic coordination base N, N-bicine N-synthetic
By mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 80～100 parts the water, be heated to 50～70 ℃, react 40～70 minutes postcooling to room temperature, add 20～30ml dehydrated alcohol again and separate out white crystals, in 30～60 ℃ of baking ovens, dry;
2) aluminium chlorohydroxide-propylene glycol complex compound is synthetic
By mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 20～50 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 20～30 minutes, add 15 parts of methyl alcohol again, add 1 part 1 after the reflux again, the 2-propylene glycol, reacted 40～60 minutes, in 60～70 ℃ steam methyl alcohol after, in 90～110 ℃ of baking ovens, dry again;
3) the aluminum-zirconium metal-organic complex coupling agent is synthetic
Press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the Varion CDG-K of N-bicine N-or 4.5 parts mixes, be heated to 50～75 ℃, reacted 20～40 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 50～75 ℃ of reactions 40～60 minutes down, be decompressed to 0.07～0.09Mpa and extract solvent out, get faint yellow viscous liquid.
2, the preparation method of cation aluminium zirconium metal-organic complex coupling agent according to claim 1, it is characterized in that: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 96 parts the water, be heated to 50 ℃, react 70 minutes postcooling to room temperature, add the 20ml dehydrated alcohol again and separate out white crystals, in 45 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 20 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 30 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 60 minutes, in 70 ℃ steam methyl alcohol after, in 110 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 75 ℃, reacted 20 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 60 ℃ of reactions 50 minutes down, be decompressed to 0.07Mpa and extract solvent out, get faint yellow viscous liquid.
3, the preparation method of cation aluminium zirconium metal-organic complex coupling agent according to claim 1, it is characterized in that: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 100 parts the water, be heated to 70 ℃, react 40 minutes postcooling to room temperature, add the 25ml dehydrated alcohol again and separate out white crystals, in 30 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 35 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 26 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 45 minutes, in 68 ℃ steam methyl alcohol after, in 98 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 63 ℃, reacted 30 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 63 ℃ of reactions 52 minutes down, be decompressed to 0.08Mpa and extract solvent out, get faint yellow viscous liquid.
4, the preparation method of cation aluminium zirconium metal-organic complex coupling agent according to claim 1, it is characterized in that: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 80 parts the water, be heated to 60 ℃, react 55 minutes postcooling to room temperature, add the 30ml dehydrated alcohol again and separate out white crystals, in 60 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 25 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 28 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 52 minutes, in 62 ℃ steam methyl alcohol after, in 105 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 50 ℃, reacted 40 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 50 ℃ of reactions 60 minutes down, be decompressed to 0.09Mpa and extract solvent out, get faint yellow viscous liquid.
5, the preparation method of cation aluminium zirconium metal-organic complex coupling agent according to claim 1, it is characterized in that: organic coordination base N, N-bicine N-synthetic: by mass fraction the diethanolamine of 15 parts oxalic dialdehyde and 10 parts is dissolved in 90 parts the water, be heated to 64 ℃, react 48 minutes postcooling to room temperature, add the 23ml dehydrated alcohol again and separate out white crystals, in 50 ℃ of baking ovens, dry; Aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 40 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 24 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol reacted 58 minutes, in 65 ℃ steam methyl alcohol after, in 93 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the organic coordination base N of 2-propylene glycol and 2.5 parts, the N-bicine N-mixes, be heated to 60 ℃, reacted 26 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, 75 ℃ of reactions 40 minutes down, be decompressed to 0.08Mpa and extract solvent out, get faint yellow viscous liquid.
6, the preparation method of cation aluminium zirconium metal-organic complex coupling agent according to claim 1, it is characterized in that: aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 50 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 20 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol, reacted 40 minutes, in 60 ℃ steam methyl alcohol after, in 100 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the Varion CDG-K of 2-propylene glycol and 4.5 parts mixes, be heated to 55 ℃, reacted 35 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, reacted 55 minutes down at 55 ℃, be decompressed to 0.09Mpa and extract solvent out, get faint yellow viscous liquid.
7, the preparation method of cation aluminium zirconium metal-organic complex coupling agent according to claim 1, it is characterized in that: aluminium chlorohydroxide-propylene glycol complex compound synthetic: by mass fraction with the water of 7 parts aluminium chlorohydroxide and 10 parts band stir and the there-necked flask of reflux in be stirred to aluminum chloride and dissolve fully, at 30 ℃ down is 36% hydrochloric acid with 1 part of concentration of dropping in 25 minutes, add 15 parts of methyl alcohol again, after the reflux, add 1 part 1 again, the 2-propylene glycol, reacted 50 minutes, in 64 ℃ steam methyl alcohol after, in 90 ℃ of baking ovens, dry again; Aluminum-zirconium metal-organic complex coupling agent synthetic: press mass fraction with 1.1 parts zirconium oxychloride, 10 parts 1, the Varion CDG-K of 2-propylene glycol and 4.5 parts mixes, be heated to 68 ℃, reacted 31 minutes, and then add aluminium chlorohydroxide-propylene glycol complex compound of 1.5 parts, reacted 45 minutes down at 68 ℃, be decompressed to 0.07Mpa and extract solvent out, get faint yellow viscous liquid.
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| CN101407643B (en) * | 2008-11-04 | 2011-04-27 | 华南理工大学 | Preparation of anionic aluminum-zirconium coupling agent |
| CN101407644B (en) * | 2008-11-04 | 2011-08-17 | 华南理工大学 | Preparation of aluminum-zirconium coupling agent |
| CN101423674B (en) * | 2007-11-02 | 2012-04-25 | 俞明康 | Master batch for preparing titanium dioxide ethylene glycol slurry and preparation method thereof |
| CN106591877A (en) * | 2016-11-14 | 2017-04-26 | 江苏科技大学 | Coupling agent with convertible central atoms and preparing method of coupling agent |
| CN108660851A (en) * | 2018-05-18 | 2018-10-16 | 俞小峰 | A kind of environment protecting paper and preparation method thereof |
| CN116380602A (en) * | 2023-06-05 | 2023-07-04 | 深圳市森盈生物科技有限公司 | Liquid-based cytology and immunocytochemistry double-slide staining kit and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101423674B (en) * | 2007-11-02 | 2012-04-25 | 俞明康 | Master batch for preparing titanium dioxide ethylene glycol slurry and preparation method thereof |
| CN101407643B (en) * | 2008-11-04 | 2011-04-27 | 华南理工大学 | Preparation of anionic aluminum-zirconium coupling agent |
| CN101407644B (en) * | 2008-11-04 | 2011-08-17 | 华南理工大学 | Preparation of aluminum-zirconium coupling agent |
| CN106591877A (en) * | 2016-11-14 | 2017-04-26 | 江苏科技大学 | Coupling agent with convertible central atoms and preparing method of coupling agent |
| CN108660851A (en) * | 2018-05-18 | 2018-10-16 | 俞小峰 | A kind of environment protecting paper and preparation method thereof |
| CN116380602A (en) * | 2023-06-05 | 2023-07-04 | 深圳市森盈生物科技有限公司 | Liquid-based cytology and immunocytochemistry double-slide staining kit and application thereof |
| CN116380602B (en) * | 2023-06-05 | 2023-09-08 | 深圳市森盈生物科技有限公司 | Liquid-based cytology and immunocytochemistry double-slide staining kit and application thereof |
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