CN105713433A - Crosslinking agent, polymer composition containing same, and preparation method of crosslinking agent - Google Patents
Crosslinking agent, polymer composition containing same, and preparation method of crosslinking agent Download PDFInfo
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- CN105713433A CN105713433A CN201610283284.9A CN201610283284A CN105713433A CN 105713433 A CN105713433 A CN 105713433A CN 201610283284 A CN201610283284 A CN 201610283284A CN 105713433 A CN105713433 A CN 105713433A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
Abstract
The invention discloses a polymer composition. The composition comprises base polymer components and a crosslinking agent; the crosslinking agent comprises at least one compound selected a compound with the general formula I, a compound with the radical of the general formula II, and a compound with radical of the general formula III, or the combination thereof. The polymer composition can be used as powder coating.
Description
Technical field
The polymer composition that the present invention relates to the cross-linking agent containing chelating type zirconium titanium compound, comprises this cross-linking agent, its preparation method.
Background technology
At present, the kind of the cross-linking agent (firming agent) of widely used polymer powder coating particularly polyester powder coating mainly has: the cross-linking agent such as triglycidyl isocyanurate cross-linking agent, hydroxyalkyl amide class cross-linking agent, polyprotic acid ethylene oxidic ester cross-linking agent, isocyanuric acid three-Beta-methyl ethylene oxidic ester cross-linking agent, oxazolines cross-linking agent, polyester/blocked isocyanate, hydroxy resin/glycoluril, glycidyl acrylate/fatty acid.These cross-linking agent are had nothing in common with each other for powdery paints performance in weatherability, gloss, face effect, levelability, price etc., wherein the behaving oneself best of triglycidyl isocyanurate firming agent, its some performances are that other cross-linking agent is irreplaceable, therefore become the cross-linking agent (firming agent) of polyester powder coating main on market.
But, triglycidyl isocyanurate has certain carcinogenecity, and producing and in use procedure, contact people's overwhelming majority meeting severe allergy of its dust, therefore being prohibitted the use of by Europe, the powdery paints containing triglycidyl isocyanurate (TGIC) is also listed in developmental limitation intermediate item by China.Prior art is required for the substitute products of this cross-linking agent always.
Summary of the invention
On the one hand, the present invention provides a kind of cross-linking agent, and described cross-linking agent comprises at least one selected from following compound: have the compound of below general formula I, has the compound of the group of formula II, has the compound of the group of general formula III or its combination；
Formula I
Formula II
General formula III
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
The group that wave represents formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1～20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
On the other hand, the method for cross-linking agent is prepared in offer of the present invention, and it polyol including compound and formula V that use has formula (IV) reacts,
M(OR3)4
Formula IV
Wherein: when M occurs every time, be each independently Zr or Ti；
R3It is each independently the branched-chain or straight-chain alkyl of C2-C10, particularly C when occurring every time2H5, C3H7, C4H9；
HO-R4-OH
Formula V
Wherein: R4It is each independently when occurring: the branched-chain or straight-chain alkyl of bivalence C2-C10 every time；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base；
Thus generating at least one in following compound: there is the compound of below general formula I, there is the compound of the group of formula II, there is the compound of the group of general formula III or its combination；
Formula I
Formula II
General formula III
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
The group that wave represents formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
On the other hand, the present invention provides a kind of polymer composition, and it comprises base polymer component and cross-linking agent,
Wherein said cross-linking agent comprises at least one selected from following compound: have the compound of below general formula I, has the compound of the group of formula II, has the compound of the group of general formula III or its combination；
Formula I
Formula II
General formula III
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
Wave (～) represent that the group of formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1～20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
In some embodiments, described polymer composition is powdery paints.
On the other hand, the method for polymer composition is prepared in offer of the present invention, and it includes mixing all components of polymer composition, extrusion, cooling, and pulverizes formation final products.
In some embodiments, described extrusion carries out the temperature of 90 to 120 DEG C.In some embodiments, described final products are the fine powder of 150 to 300 orders.In some embodiments, described final products are the fine powder of 200 orders.
Detailed description of the invention
Term " cross-linking agent " and " firming agent " can exchange use in this application.
In this application, statement " fine powders of 200 orders " refers to that this fine powder can pass through the sieve of 200 orders." fine powders of 150 to 300 orders " refer to that this fine powder can pass through the sieve of 150 to 300 orders.
Chelating type zirconium titanium compound well known in the prior art or chelating type zirconium titanate esters are mainly single chelating type compound of alkoxyl or phosphate-based or phosphorous acid ester group or pyrophosphoric acid ester group or sulfonate group, Main Function is coupling agent, is applied to the fields such as filler modified, plastics, rubber, liquid coating, ink.In these chelating type zirconium titanium compounds, alcoxyl fundamental mode has reactivity, but meets water decomposition and just lose reactivity；Phosphate-based or phosphorous acid ester group or pyrophosphoric acid ester group or sulphonic acid ester fundamental mode do not have reactivity, therefore cannot function as crosslinking (solidification) agent.It is known that zirconate or titanate esters can with the compound containing hydroxyl and carboxyl, especially with the macromolecular compound generation cross-linking reaction of hydroxyl and carboxyl.But general zirconate or titanate esters are met water decomposition and lost reactivity, therefore, these chelating type zirconium titanium compounds of the prior art are unsuitable for being used as the cross-linking agent of polymer, are not suitable for use in the cross-linking agent of polymer powder coating in other words.
Having inventors have surprisingly discovered that a kind of chelating type zirconium titanium compound, it had both retained the activity of cross-linking reaction of zirconate or titanate esters, ensured that again they do not decompose under meeting regimen condition.
Therefore, on the one hand, the present invention provides a kind of cross-linking agent, and described cross-linking agent comprises at least one selected from following compound: have the compound of below general formula I, has the compound of the group of formula II, there is the compound of the group of general formula III or its combination；
Formula I
Formula II
General formula III
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
The group that wave represents formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1～20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
" bivalence C2-C10 branched-chain or straight-chain alkyl " described herein can be such as bivalence C3-C10 branched-chain or straight-chain alkyl, bivalence C4-C10 branched-chain or straight-chain alkyl, bivalence C5-C10 branched-chain or straight-chain alkyl, bivalence C6-C10 branched-chain or straight-chain alkyl, bivalence C7-C10 branched-chain or straight-chain alkyl, bivalence C8-C10 branched-chain or straight-chain alkyl or bivalence C9-C10 branched-chain or straight-chain alkyl.
In some embodiments, there is the compound of group of general formula III selected from the compound with below general formula described in:
Wherein M, X1There is when occurring with R implication defined above every time independently of one another.
In some embodiments, described cross-linking agent also comprises at least one selected from following compound: beta-hydroxy alkylamide, epoxide, or its combination.
In some embodiments, there is the compound of below general formula I, there is the compound of the group of formula II, have general formula III group compound at least one for selected from following compound:
In other words, in some embodiments, described cross-linking agent comprises at least one selected from above compound.
The cross-linking agent that embodiments of the invention provide can act as the cross-linking agent of polymer.In some embodiments, the base polymer containing this cross-linking agent is used as powdery paints.Powdery paints containing this cross-linking agent has excellent filming performance.
Therefore, on the other hand, the present invention provides a kind of polymer composition, and it comprises base polymer component and above-described cross-linking agent.
In some embodiments, described base polymer component comprises selected from following polymer: polyester resin such as hydroxy polyester resin, carboxyl-type polyester resin；Alkyd resin；Epoxy resin is bisphenol A epoxide resin such as；Polyurethane；Acrylic resin such as oh type acrylic resin, carboxylic acid type acrylic resin, acrylic resin containing epoxy radicals.
In some embodiments, in described polymer composition, the content of described cross-linking agent is 1wt% to 10wt%, or 1.5wt% to 8wt%, or 1.8wt% to 6wt%, or 2.0wt% to 5.6wt%, or 2.3wt% to 5wt%, or 2.5wt% to 4.5wt%, or 3wt% to 4wt%, based on the gross weight of cross-linking agent and base polymer.
In some embodiments, described polymer composition also includes being selected from following at least one component: levelling agent and filler.
In some embodiments, described filler is selected from: titanium dioxide, barium sulfate and combination thereof.
In some embodiments, described polymer composition is powdery paints.
The thin film of 60 to 150 micron thickness can be formed on the surface of metal or other goods by this powdery paints.Film build method can adopt electrostatic spraying mode.
The thin film formed by this powdery paints has the following performance of excellence: gloss (60 °), the positive intensity of counter assault of 490N cm, adhesive force, bending property and visual appearance.
On the other hand, the method for cross-linking agent is prepared in offer of the present invention, and it polyol including compound and formula V that use has formula (IV) reacts,
M(OR3)4
Formula IV
Wherein: when M occurs every time, be each independently Zr or Ti；
R3It is each independently the branched-chain or straight-chain alkyl of C2-C10, particularly C when occurring every time2H5, C3H7, C4H9；
HO-R4-OH
Formula V
Wherein: R4It is each independently when occurring: the branched-chain or straight-chain alkyl of bivalence C2-C10 every time；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base；
Thus generating at least one in following compound: there is the compound of below general formula I, there is the compound of the group of formula II, there is the compound of the group of general formula III or its combination；
Formula I
Formula II
General formula III
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
The group that wave represents formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
In some embodiments, the compound of described formula V comprises the compound with three hydroxyls.
In some embodiments, the proportioning of the polyol of the compound of formula (IV) and formula V makes in the compound of formula (IV) molal quantity of M atom with the ratio of the molal quantity of the hydroxyl in the polyol of formula V equal to or more than 1:4.In some embodiments, this ratio can also be slightly less than 1:4, for instance for equal to or more than 1:5.In some embodiments, this ratio can also be less than 1:3.
In some embodiments, the compound of its formula of IV is selected from following at least one: metatitanic acid four methyl ester, tetraethyl titanate, tetraisopropyl titanate, metatitanic acid four n-propyl, tetra-n-butyl titanate, tetrabutyl titanate, metatitanic acid four tert-butyl ester, metatitanic acid four pentyl ester, metatitanic acid four monooctyl ester, zirconic acid four methyl ester, zirconic acid tetra-ethyl ester, zirconic acid four isopropyl ester, zirconic acid four n-propyl, the positive butyl ester of zirconic acid four, zirconic acid four isobutyl ester, zirconic acid four tert-butyl ester, zirconic acid four pentyl ester, zirconic acid four monooctyl ester；With
The polyol of its formula of V is selected from following at least one: ethylene glycol, diethylene glycol, triethylene glycol, TEG, Polyethylene Glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,3 butylene glycol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-PD, hexanediol, neopentyl glycol, dimethyl hexanediol, trimethylolpropane, tetramethylolmethane, diethanolamine, triethanolamine, diisopropanolamine (DIPA), triisopropanolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-methyl diisopropanolamine (DIPA), N-ethyl diisopropanolamine (DIPA), N-ethoxy diisopropanolamine (DIPA), N, N-dihydroxy ethyl isopropanolamine, N butyl diethanol amine, stearyl diethanolamine, Lauryl Diethanolamine, tallow diethanolamine, cocoyl diethanolamine, N-butyl diisopropanolamine (DIPA), stearyl diisopropanolamine (DIPA), lauryl diisopropanolamine (DIPA), tallow diisopropanolamine (DIPA), cocoyl diisopropanolamine (DIPA).
In some embodiments, use the compound of formula IV and formula V 20-150 DEG C of reaction.Concrete reaction temperature depends on the needs, as long as making this reaction system stably.
In some embodiments, the compound of formula V meets the following conditions, R4It is each independently when occurring: the branched-chain or straight-chain alkyl of bivalence C2-C10 every time；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen or the branched-chain or straight-chain alkyl of monovalence C2-C10 when occurring every time,
So that generate the compound of formula I, wherein X, Y are each independently when occurring every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n。
In some embodiments, the compound of formula V meets the following conditions, R4It is each independently when occurring :-R every time '-N (R ")-R '-, wherein, when R ' occurs every time, it is each independently bivalence C2-C10 branched-chain or straight-chain alkyl；R " it is each independently hydrogen or the branched-chain or straight-chain alkyl of monovalence C2-C10 when occurring every time,
So that generate the compound of formula I, wherein X, Y are each independently when occurring every time :-R '-N (R ")-R '-.
In some embodiments, the compound of formula V meets the following conditions, R in the compound of a part (such as half) formula V4It is each independently when occurring: the branched-chain or straight-chain alkyl of bivalence C2-C10 every time；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen or the branched-chain or straight-chain alkyl of monovalence C2-C10 when occurring every time；R in the compound of a part (such as half) formula V4It is each independently when occurring :-R every time '-N (R ")-R '-, wherein, when R ' occurs every time, it is each independently bivalence C2-C10 branched-chain or straight-chain alkyl；R " it is each independently hydrogen or the branched-chain or straight-chain alkyl of monovalence C2-C10 when occurring every time,
So that generate the compound of formula I, wherein in X, Y is each independently when occurring every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Independently be when another in X, Y occurs every time-R '-N (R ")-R '-.
In some embodiments, the compound of formula V meets the following conditions, R4It is each independently when occurring :-R every time '-N (R ")-R '-, wherein, when R ' occurs every time, it is each independently bivalence C2-C10 branched-chain or straight-chain alkyl；R " it is each independently side chain or the straight chain alkanol of monovalence C2-C10 when occurring every time,
So that generate the compound of below general formula,
Wherein X1 is each independently when occurring every time :-R '-N (R '-)-R '-, it is each independently bivalence C2-C10 branched-chain or straight-chain alkyl when R ' occurs every time.
In some embodiments, the compound of formula V meets the following conditions, R in the compound of a part (such as half) formula V4It is each independently when occurring: the branched-chain or straight-chain alkyl of bivalence C2-C10 every time；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen or the branched-chain or straight-chain alkyl of monovalence C2-C10 when occurring every time；R in the compound of a part (such as half) formula V4It is each independently when occurring :-R every time '-N (R ")-R '-, wherein, when R ' occurs every time, it is each independently bivalence C2-C10 branched-chain or straight-chain alkyl；R " it is each independently side chain or the straight chain alkanol of monovalence C2-C10 when occurring every time,
So that generate the compound of below general formula,
Wherein X1 is each independently when occurring every time :-R '-N (R '-)-R '-, it is each independently bivalence C2-C10 branched-chain or straight-chain alkyl when R ' occurs every time；It is each independently when R occurs every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n。
On the other hand, the method for polymer composition is prepared in offer of the present invention, and it includes mixing all components of polymer composition, extrusion, cooling, and pulverizes formation final products.
In some embodiments, described extrusion carries out the temperature of 90 to 120 DEG C.In some embodiments, described final products are the fine powder of 150 to 300 orders.In some embodiments, described final products are the fine powder of 200 orders.
Embodiment
Using following raw material in embodiments herein, these raw materials are all conventional, it is possible to prepared by conventional method or can buy from the market:
Table 1: raw material sources and character
Preparation embodiment 1
Diethanolamine (molecular weight 105.14) 105.14 grams is joined equipped with agitator, condenser, in 500 milliliters of four-hole boiling flasks of constant pressure funnel and thermometer, under agitation drip tetraisopropyl titanate (TiPT, molecular weight 284) 142 grams, exothermic heat of reaction, cool down with water-bath, temperature is controlled 25-30 DEG C of dropping, completion of dropwise addition in about 1 hour, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction to terminate to reaction for 2 hours, first air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steam to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, cooling curing beats powder, obtain beige white powder, obtain the compound 123 grams of following formula, yield 96.8%, elementary analysis result: TiO2%=31.2% (theoretical value 31.5%).
Take in the water that the said goods 10 grams is dissolved in 90 grams, for transparent solution, it does not have produce the precipitation of titanium dioxide.Being dried, obtain the solid that class is white, elementary analysis result is TiO2%=31.2%.Prove this chelating type titanium compound, meet water and do not decompose.
Preparation embodiment 2
Diethanolamine (molecular weight 105.14) 105.14 grams is joined equipped with agitator, condenser, in 500 milliliters of four-hole boiling flasks of constant pressure funnel and thermometer, the lower dropping positive butyl ester of the zirconic acid four (NBZ of stirring, molecular weight 383.68) 192 grams, exothermic heat of reaction, cool down with water-bath, temperature is controlled 25-30 DEG C of dropping, completion of dropwise addition in about 1 hour, obtain glassy yellow transparency liquid, it is warming up to 100-110 DEG C of back flow reaction 2 hours, first air-distillation, reclaim n-butyl alcohol, reducing pressure steams to the greatest extent by alcohol again, steam to temperature 150 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, cooling curing beats powder, obtain beige white powder 141 grams, yield 94.6%, elementary analysis result: ZrO2%=40.9 (theoretical value 41.4%).
Take in the water that the said goods 10 grams is dissolved in 90 grams, for transparent solution, it does not have produce the precipitation of zirconium dioxide.Being dried, obtain the solid that class is white, elementary analysis result is ZrO2%=40.9.Prove this chelating type zirconium compounds, meet water and do not decompose.
Preparation embodiment 3
Diisopropanolamine (DIPA) (molecular weight 133.2) 133.2 grams is joined equipped with agitator, condenser, in 500 milliliters of four-hole boiling flasks of constant pressure funnel and thermometer, tetraisopropyl titanate (TiPT is dripped under stirring, molecular weight 284) 142 grams, exothermic heat of reaction, cool down with water-bath, temperature is controlled 25-30 DEG C of dropping, completion of dropwise addition in about 1 hour, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, first air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steam to temperature 150 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, cooling curing beats powder, obtain beige white powder 152.2 grams, yield 98.1%, elementary analysis result: TiO2%=25.1% (theoretical value 25.8%).
Take in the water that the said goods 10 grams is dissolved in 90 grams, for transparent solution, it does not have produce the precipitation of titanium dioxide.Being dried, obtain the solid that class is white, elementary analysis result is TiO2%=25.1%.Prove this chelating type titanium compound, meet water and do not decompose.(it should be noted that all products of preparation embodiment 1-27 have all been carried out soluble test, the experimental result obtained is all similar, and therefore this part no longer enumerates in following preparation embodiment.)
Preparation embodiment 4
Diisopropanolamine (DIPA) (molecular weight 133.2) 133.2 grams is joined equipped with agitator, condenser, in 500 milliliters of four-hole boiling flasks of constant pressure funnel and thermometer, the lower dropping positive butyl ester of the zirconic acid four (NBZ of stirring, molecular weight 383.68) 192 grams, exothermic heat of reaction, cool down with water-bath, temperature is controlled 25-30 DEG C of dropping, completion of dropwise addition in about 1 hour, obtain glassy yellow transparency liquid, it is warming up to 100-110 DEG C of back flow reaction 2 hours, first air-distillation, reclaim n-butyl alcohol, reducing pressure steams to the greatest extent by alcohol again, steam to temperature 140 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, cooling curing beats powder, obtain beige white powder 171 grams, yield 96.5%, elementary analysis result: ZrO2%=34.5 (theoretical value 34.7%).
Preparation embodiment 5
Diethylene glycol (molecular weight 106.11) 106.2 grams is joined equipped with agitator, condenser, in 500 milliliters of four-hole boiling flasks of constant pressure funnel and thermometer, tetraisopropyl titanate (TiPT is dripped under stirring, molecular weight 284) 142 grams, exothermic heat of reaction, cool down with water-bath, temperature is controlled 25-30 DEG C of dropping, completion of dropwise addition in about 1 hour, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, first air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steam to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, cooling curing beats powder, obtain beige white powder 121.2 grams, yield 94.5%, elementary analysis result: TiO2%=31.2 (theoretical value 31.3%).
Preparation embodiment 6
Diethylene glycol (molecular weight 106.11) 53.1 grams is joined equipped with in 500 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, exothermic heat of reaction, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diisopropanolamine (DIPA) (molecular weight 133.2) 66.8 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 150 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 132 grams, yield 93%, elementary analysis result: TiO2%=28.1% (theoretical value 28.2%).
Preparation embodiment 7
Diethanolamine (molecular weight 105.14) 52.6 grams is joined equipped with in 500 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction slightly to lower the temperature for 2 hours, add dipropylene glycol (molecular weight 134.2) 67.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 135 grams, yield 95.3%, elementary analysis result: TiO2%=28.0% (theoretical value 28.2%).
Preparation embodiment 8
Lauryl Diethanolamine (molecular weight 273.45) 137 grams and isopropanol 100 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add dipropylene glycol (molecular weight 134.2) 67.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 218 grams, yield 96.4%, elementary analysis result: TiO2%=25.2 (theoretical value 25.7%).
Preparation embodiment 9
Lauryl Diethanolamine (molecular weight 273.45) 274 grams and isopropanol 100 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 140 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 291 grams, yield 98.3%, elementary analysis result: TiO2%=13.2% (theoretical value 13.5%).
Preparation embodiment 10
Lauryl Diethanolamine (molecular weight 273.45) 274 grams and isopropanol 100 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower positive butyl ester of the fast drop zirconic acid four (NBZ of stirring, molecular weight 383.68) 192 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, be warming up to 100-110 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim n-butyl alcohol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 140 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 320 grams, yield 92.5%, elementary analysis result: ZrO2%=19.1% (theoretical value 19.5%).
Preparation embodiment 11
Lauryl Diethanolamine (molecular weight 273.45) 137 grams and isopropanol 100 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diethanolamine (molecular weight 105.14) 52.6 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 205 grams, yield 96.9%, elementary analysis result: TiO2%=18.7% (theoretical value 19.0%).
Preparation embodiment 12
Lauryl Diethanolamine (molecular weight 273.45) 137 grams and isopropanol 100 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diisopropanolamine (DIPA) (molecular weight 133.2) 66.8 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 216 grams, yield 95.6%, elementary analysis result: TiO2%=17.4% (theoretical value 17.7%).
Preparation embodiment 13
Stearyl diethanolamine (molecular weight 357.45) 358 grams and isopropanol 300 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 361 grams, yield 95%, elementary analysis result: TiO2%=10.3% (theoretical value 10.5%).
Preparation embodiment 14
Stearyl diethanolamine (molecular weight 357.45) 178.8 grams and isopropanol 200 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diethanolamine (molecular weight 105.14) 52.6 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 150 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 248 grams, yield 97.8%, elementary analysis result: TiO2%=15.2% (theoretical value 15.8%).
Preparation embodiment 15
Stearyl diethanolamine (molecular weight 357.45) 178.8 grams and isopropanol 200 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diisopropanolamine (DIPA) (molecular weight 133.2) 66.8 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 261 grams, yield 97.5%, elementary analysis result: TiO2%=14.8% (theoretical value 15.0%).
Preparation embodiment 16
Lauryl Diethanolamine (molecular weight 273.45) 137 grams and isopropanol 100 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diethylene glycol (molecular weight 106.11) 53.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 160 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 206 grams, yield 97.1%, elementary analysis result: TiO2%=18.1% (theoretical value 18.8%).
Preparation embodiment 17
Lauryl Diethanolamine (molecular weight 273.45) 137 grams and isopropanol 200 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add dipropylene glycol (molecular weight 134.2) 67.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 180 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 213.5 grams, yield 94.4%, elementary analysis result: TiO2%=17.3% (theoretical value 17.7%).
Preparation embodiment 18
Stearyl diethanolamine (molecular weight 357.45) 178.8 grams and isopropanol 200 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add diethylene glycol (molecular weight 106.11) 53.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 180 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 238.9 grams, yield 94%, elementary analysis result: TiO2%=15.3 (theoretical value 15.8%).
Preparation embodiment 19
Stearyl diethanolamine (molecular weight 357.45) 178.8 grams and isopropanol 200 grams are joined equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower fast drop tetraisopropyl titanate (TiPT of stirring, molecular weight 284) 142 grams, heat release, temperature is warming up to 40-50 DEG C voluntarily, obtain glassy yellow transparency liquid, it is warming up to 75-85 DEG C of back flow reaction 2 hours, slightly lower the temperature, add dipropylene glycol (molecular weight 134.2) 67.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 190 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 254 grams, yield 96.2%, elementary analysis result: TiO2%=14.4% (theoretical value 15.0%).
Preparation embodiment 20
By tetraisopropyl titanate (TiPT, molecular weight 284) 284 grams join equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, triethanolamine (molecular weight 149) 149 grams is dripped under stirring, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, 75-85 DEG C of back flow reaction it is warming up to 2 hours after completion of dropwise addition, slightly lower the temperature, add diethylene glycol (molecular weight 106.11) 53.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 240 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 233 grams, yield 94.6%, elementary analysis result: TiO2%=17.1% (theoretical value 17.8%).
Preparation embodiment 21
By tetraisopropyl titanate (TiPT, molecular weight 284) 284 grams join equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, triethanolamine (molecular weight 149) 149 grams is dripped under stirring, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, 75-85 DEG C of back flow reaction it is warming up to 2 hours after completion of dropwise addition, slightly lower the temperature, add dipropylene glycol (molecular weight 134.2) 67.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 240 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 239 grams, yield 92%, elementary analysis result: TiO2%=15.1% (theoretical value 15.3%).
Preparation embodiment 22
By tetraisopropyl titanate (TiPT, molecular weight 284) 284 grams join equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, triisopropanolamine (molecular weight 191) 191 grams is dripped under stirring, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, 75-85 DEG C of back flow reaction it is warming up to 2 hours after completion of dropwise addition, slightly lower the temperature, add diethylene glycol (molecular weight 106.11) 53.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 240 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 269 grams, yield 93.4%, elementary analysis result: TiO2%=13.2% (theoretical value 13.8%).
Preparation embodiment 23
By tetraisopropyl titanate (TiPT, molecular weight 284) 284 grams join equipped with in 1000 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, triisopropanolamine (molecular weight 191) 191 grams is dripped under stirring, exothermic heat of reaction, cool down with water-bath, glassy yellow glassy yellow transparency liquid, 75-85 DEG C of back flow reaction it is warming up to 2 hours after completion of dropwise addition, slightly lower the temperature, add dipropylene glycol (molecular weight 134.2) 67.1 grams, then be warming up to 75-85 DEG C of back flow reaction 2 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 240 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 286 grams, yield 94.6%, elementary analysis result: TiO2%=13.0% (theoretical value 13.2%).
Preparation embodiment 24
Triethanolamine (molecular weight 149) 59.6 grams is joined equipped with in 250 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, tetraisopropyl titanate (TiPT is dripped under stirring, molecular weight 284) 85.2 grams, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, be warming up to 75-85 DEG C of back flow reaction after completion of dropwise addition 4 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 260 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 69 grams, yield 94.8%, elementary analysis result: TiO2%=32.2% (theoretical value 33.0%).
Preparation embodiment 25
Triethanolamine (molecular weight 149) 59.6 grams is joined equipped with in 250 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower dropping positive butyl ester of the zirconic acid four (NBZ of stirring, molecular weight 383.68) 115.1 grams, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, be warming up to 100-110 DEG C of back flow reaction after completion of dropwise addition 4 hours.Then air-distillation, reclaim n-butyl alcohol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 260 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 82 grams, yield 95.4%, elementary analysis result: ZrO2%=41.3% (theoretical value 41.9%).
Preparation embodiment 26
Triisopropanolamine (molecular weight 191) 76.4 grams is joined equipped with in 250 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, tetraisopropyl titanate (TiPT is dripped under stirring, molecular weight 284) 85.2 grams, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, be warming up to 100-110 DEG C of back flow reaction after completion of dropwise addition 4 hours.Then air-distillation, reclaim isopropanol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 260 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 88 grams, yield 98.2%, elementary analysis result: TiO2%=25.4% (theoretical value 26.8%).
Preparation embodiment 27
Triisopropanolamine (molecular weight 191) 76.4 grams is joined equipped with in 250 milliliters of four-hole boiling flasks of agitator, condenser, constant pressure funnel and thermometer, the lower dropping positive butyl ester of the zirconic acid four (NBZ of stirring, molecular weight 383.68) 115.1 grams, exothermic heat of reaction, cool down with water-bath, obtain glassy yellow transparency liquid, be warming up to 100-110 DEG C of back flow reaction after completion of dropwise addition 4 hours.Then air-distillation, reclaim n-butyl alcohol, reducing pressure steams to the greatest extent by alcohol again, steams to temperature 260 DEG C, during vacuum 25-30mmHg, stop distillation, residual liquid is poured in dish while hot, and cooling curing beats powder, obtains beige white powder 98 grams, yield 95.4%, elementary analysis result: ZrO2%=34.8% (theoretical value 35.9%).
Embodiment 1-27 to prepare Data Summary as follows:
Application Example
Respectively by some products (beige white powder) in above-described embodiment, mix with polyester resin (wherein the total amount of polyester resin and beige white powder is 360 grams) in different ratios, add 6 grams of levelling agents, 120 grams of titanium dioxides and 150 grams of barium sulfate, mix homogeneously, through double screw extruder 110 DEG C of extrusions, after cooling, it is ground into the fine powder of 200 orders.
Being sprayed on aluminium flake or iron plate by the mode of above-mentioned powder electrostatic spraying, coating thickness, at 60-150 μm, then toasts 15 minutes at 210 DEG C.
Aluminium flake or iron plate, film and the performance test results after baking are as follows:
Method of testing: test according to national standard " thermosetting powder coating HG/T2006-2006 ".
1) oh type polyester resin (hydroxyl value 26-34)
2) carboxyl-type polyester resin (acid number 20-25)
Claims (15)
1. a polymer composition, it comprises base polymer component and cross-linking agent,
Wherein said cross-linking agent comprises at least one selected from following compound: have the compound of below general formula I, has the compound of the group of formula II, has the compound of the group of general formula III or its combination；
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
Wave (～) represent that the group of formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1～20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
2. the polymer composition of claim 1, the compound of the wherein said group with general formula III is selected from the compound with below general formula:
Wherein M, X1There is independently of one another implication defined above with R.
3. the polymer composition of claim 1, wherein said base polymer component comprises selected from following polymer: polyester resin such as hydroxy polyester resin, carboxyl-type polyester resin；Alkyd resin；Epoxy resin is bisphenol A epoxide resin such as；Polyurethane；Acrylic resin such as oh type acrylic resin, carboxylic acid type acrylic resin, acrylic resin containing epoxy radicals.
4. the polymer composition of claim 1, wherein the content of cross-linking agent is 1wt% to 10wt%, or 1.5wt% to 8wt%, or 1.8wt% to 6wt%, or 2.0wt% to 5.6wt%, or 2.3wt% to 5wt%, or 2.5wt% to 4.5wt%, or 3wt% to 4wt%, based on the gross weight of cross-linking agent and base polymer.
5. the polymer composition of claim 1, wherein said cross-linking agent also comprises selected from following at least one: beta-hydroxy alkylamide, epoxide, or its combination.
6. the polymer composition of claim 1, wherein said polymer composition also includes being selected from following at least one component: levelling agent and filler.
7. the polymer composition of claim 6, wherein said filler is selected from: titanium dioxide, barium sulfate and combination thereof.
8. the polymer composition of claim 1, wherein said polymer composition is powdery paints.
9. the polymer composition of claim 1, wherein said cross-linking agent comprises at least one selected from following compound:
10. a cross-linking agent, described cross-linking agent comprises at least one selected from following compound: have the compound of below general formula I, has the compound of the group of formula II, has the compound of the group of general formula III or its combination；
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
The group that wave represents formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1～20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
11. the cross-linking agent of claim 10, the compound of the wherein said group with general formula III is selected from the compound with below general formula:
Wherein M, X1There is when occurring with R implication defined above every time independently of one another.
12. the cross-linking agent of claim 10, it also comprises at least one selected from following compound: beta-hydroxy alkylamide, epoxide, or its combination.
13. the method preparing cross-linking agent, it polyol including compound and formula V that use has formula (IV) reacts,
M(OR3)4
Formula IV
Wherein: when M occurs every time, be each independently Zr or Ti；
R3It is each independently the branched-chain or straight-chain alkyl of C2-C10, particularly C when occurring every time2H5, C3H7, C4H9；
HO-R4-OH
Formula V
Wherein: R4It is each independently when occurring: the branched-chain or straight-chain alkyl of bivalence C2-C10 every time；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base；
Thus generating at least one in following compound: there is the compound of below general formula I, there is the compound of the group of formula II, there is the compound of the group of general formula III or its combination；
In formula I, II, III:
Zr or Ti it is each independently when M occurs every time；
It is each independently when X, R, Y occur every time: the branched-chain or straight-chain alkyl of bivalence C2-C10；Divalent ether radicals group, such as-R '-O-R '-；[-R '-O-R '-]n；Bivalence polyether group, such as-R ' [-O-R '-]n；Or-R '-N (R ")-R '-；
The group that wave represents formula II or III is connected with the other parts of the compound comprising it；
It is each independently when X1 occurs every time :-R '-N (R '-)-R '-；
Wherein, R ' is each independently bivalence C2-C10 branched-chain or straight-chain alkyl every time when occurring；1-20 it is each independently when n occurs every time；R " it is each independently hydrogen when occurring every time, or the branched-chain or straight-chain alkyl of monovalence C2-C10 or silane alcohol base.
14. the method for claim 13, the compound of wherein said formula V comprises the compound with three hydroxyls.
15. the method for claim 13, the proportioning of the compound of its formula of (IV) and the polyol of formula V makes in the compound of formula (IV) molal quantity of M atom with the ratio of the molal quantity of the hydroxyl in the polyol of formula V equal to or more than 1:4.
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Citations (6)
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| US4461848A (en) * | 1981-11-20 | 1984-07-24 | Tioxide Group Plc. | Production of vesiculated polymer beads |
| CN1104663A (en) * | 1993-05-19 | 1995-07-05 | 泰奥塞特殊品有限公司 | Polyester resin powder coating compositions |
| CN1125245A (en) * | 1994-06-28 | 1996-06-26 | 泰奥塞特殊品有限公司 | Polyester resin powder coating compositions |
| CN1148071A (en) * | 1995-08-05 | 1997-04-23 | 泰奥塞特殊品有限公司 | Polyester resin powder coating compositions |
| US5908497A (en) * | 1997-12-19 | 1999-06-01 | Ppg Industries Ohio, Inc. | Water soluble titanium complexes and use as fiber glass sizing |
| CN102775436A (en) * | 2011-05-09 | 2012-11-14 | 常州市亚邦亚宇助剂有限公司 | Alcohol amine type titanate coupling agent |
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2016
- 2016-04-29 CN CN201610283284.9A patent/CN105713433A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4461848A (en) * | 1981-11-20 | 1984-07-24 | Tioxide Group Plc. | Production of vesiculated polymer beads |
| CN1104663A (en) * | 1993-05-19 | 1995-07-05 | 泰奥塞特殊品有限公司 | Polyester resin powder coating compositions |
| CN1125245A (en) * | 1994-06-28 | 1996-06-26 | 泰奥塞特殊品有限公司 | Polyester resin powder coating compositions |
| CN1148071A (en) * | 1995-08-05 | 1997-04-23 | 泰奥塞特殊品有限公司 | Polyester resin powder coating compositions |
| US5908497A (en) * | 1997-12-19 | 1999-06-01 | Ppg Industries Ohio, Inc. | Water soluble titanium complexes and use as fiber glass sizing |
| CN102775436A (en) * | 2011-05-09 | 2012-11-14 | 常州市亚邦亚宇助剂有限公司 | Alcohol amine type titanate coupling agent |
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