CN104774142B - A kind of no-solvent process for preparing solid organic acid titanium - Google Patents
A kind of no-solvent process for preparing solid organic acid titanium Download PDFInfo
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- CN104774142B CN104774142B CN201510014190.7A CN201510014190A CN104774142B CN 104774142 B CN104774142 B CN 104774142B CN 201510014190 A CN201510014190 A CN 201510014190A CN 104774142 B CN104774142 B CN 104774142B
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Abstract
The present invention provides a kind of no-solvent process for preparing solid organic acid titanium, using tetravalent titanium compound, organic acid and acylate as raw material, titanic, organic acid and acylate are progressively mixed under normal temperature, by grinding distribution, titanic and organic acid mixture solid phase reaction, abundant after-ripening, the solid organic acid titanium of solubility is obtained, the wherein mol ratio of titanic and organic acid and acylate is 1: 18: 03.The preparation method of solid organic acid titanium of the present invention, without using any solvent, also without other acid-base reagents, the acid-base value of product is selected and burden control by titanic, organic acid and acylate, and material consumption is low.The preparation method of the present invention is without using heating, and energy expenditure is low.The present invention is not related to or comprising precipitation, filtering and evaporation, drying and other steps, concise in technology, it is not necessary to special installation, easily industrialization.
Description
Technical field
The invention belongs to Chemical composition that preparation field and technical field of fertilizers, specifically belong to the new of organic acid titanium preparation
Technology, content is related to using titanic as titanium source, and with organic acid sequestering agent, solid organic acid is prepared with simple solid phase reaction process
The method of titanium.
Background technology
Organic acid titanium has broad application prospects, one of focus as scientific research in recent years and technological development.Such as
Organic acid titanium is used as new crop growth conditioning agent and the micro- expanded application of fertilizer of feature.Meanwhile, organic acid titanium is still
Prepare catalytic self-cleaning material, material for air purification, anti-biotic material, anti misting materials and special electrode material, microwave-medium
The presoma of the titanium-based functional materials such as material, chemical synthesis catalysis material.Titanium is played in many ways in plant growth and development process
The effect in face：Such as improve the nitrogen fixing capacity of plant, promote plant to nitrogen, phosphorus, potassium and other trace element molybdenums, boron, iron, zinc, copper,
The uptake and transport of manganese；Chlorophyll content is improved, promotes the accumulation etc. of photosynthesis and carbohydrate.But titanium ion easily water
Solve and generate precipitation, it is difficult to be absorbed by plants, and reduce its bioactivity, so the organic acid titanium of Chelating state is usually as titanium
Source is employed.
Patent document CN1003302B discloses titanium-ascorbic acid solid chemical compound of a plant growth regulators
Preparation method；Patent document CN1052302A discloses the technical side for synthesizing plant growth regulator with citric acid with titanium tetrachloride
Method；Patent document CN101838159A discloses the coordination such as titanium sulfate and tartaric acid, citric acid, malic acid, mandelic acid, lactic acid
The method that body prepares the multi-Functional Fertilizers containing titanium complex.Patent document CN102557919A discloses one kind microwave chelating technique
By the method for new metatitanic acid precipitate synthesizing citric acid titanium.
The prior art literature for being related to organic acid titanium shows：At present, the method for preparing organic acid titanium：It is general to use titanium chlorination
Thing, the sulfate of titanium or new metatitanic acid precipitate are as titanium source, using organic acid as chelating agent, anti-in aqueous or in organic solvent
Should, chelated by carboxylic acid ion and titanium ion and constitute stable organic acid titanium solution.One prepared is chelated in aqueous
As be to obtain organic acid titanium solution.Organic acid titanium solution need to be through further evaporation and concentration, recrystallization or salt precipitation and mistake
Solid citric acid titanium can just be finally given by being filtered dry the process such as dry.Due to titanium (vi) ion facile hydrolysis characteristic, liquid Lemon acid titanium storage
Deposit stability not good, liquid Lemon acid titanium packed and transported also be not as convenient as solid citric acid titanium economy, have impact on organic acid titanium and answer
With effect, it is limited to a certain degree and is being applied on a large scale.And the Titanium Citrate aqueous solution by evaporation drying, recrystallization or
Salt precipitation is obtained during solid citric acid titanium, evaporation drying technique not only consumed energy and also overheat may cause titanium (vi)
Ion is hydrolyzed, and recrystallization or salt precipitation technique cause supplies consumption and waste liquid, waste gas to produce.In a word there is work in prior art
Skill is comparatively laborious, and material energy consumption is higher, and part produces the defects such as three-waste pollution environment.A kind of simple and easy to do, green of exploitation
The preparation technology of the organic acid titanium of environmental protection and economical and efficient is applied for the Technique Popularizing of organic acid titanium has significantly actual anticipate
Justice.
In the last few years, Green Chemical Technology was developed rapidly, and a collection of low-energy-consumption, low supplies consumption, low environment are dirty
Dyeing technique technology is widely adopted.The Green Chemistry way of thinking and technological means are applied to the preparation of organic acid titanium and ground by inventor
Study carefully, realize satisfactory results.
Through retrieving the disclosed patent document and scientific paper that are related to organic acid titanium delivered, solid organic acid titanium is not found
The same as the present application no-solvent process for preparing solid organic acid titanium of no-solvent process report.
The content of the invention
In view of the above-mentioned problems of the prior art, present invention offer is a kind of to prepare the solvent-free of solid organic acid titanium
Method, using titanic, organic acid and acylate as raw material, progressively mix titanic, organic acid and acylate under normal temperature,
By grinding distribution, titanic and organic acid mixture solid phase reaction, abundant after-ripening, the solid organic acid titanium of solubility is obtained,
Wherein the mol ratio of titanic, organic acid and acylate is 1: 1-8: 0-3.
Preferably, the titanic is titanium tetrachloride or titanium sulfate or their any scalemic thereof.
Preferably, the organic acid be citric acid, tartaric acid, ascorbic acid, ethylenediamine tetra-acetic acid in any one or
Their any scalemic thereof.
Preferably, material mixing keeps temperature of charge to be less than 120 DEG C.
Preferably, material mixing keeps temperature of charge to be room temperature, and production process had not both included heating or should not cooling step.
Preferably, the grinding distribution time is 1-72 hours, preferably 1-24 hours.
Preferably, titanic and organic acid mixture solid phase reaction time are 1-72 hours, preferably 1-24 hours.
Preferably, ripening time is 1-48 hours, preferably 1-24 hours..
Preferably, the mol ratio of titanic and organic acid preferably 1: 1.5-3, preferred mol ratio is 1: 2.
The advantage of the invention is that：
1st, the preparation method of solid organic acid titanium of the present invention, without using any solvent, is also tried without other soda acids
Agent, the acid-base value of product is selected and burden control by titanic, organic acid and acylate, and material consumption is low.
2nd, the preparation method of solid organic acid titanium of the present invention, without using heating, without cooling, but passes through tetravalence
Titanium, organic acid and acylate mixing velocity and the anti-thermal control reaction of solid phase reaction, energy expenditure are low.
3rd, the preparation method of solid organic acid titanium of the present invention, liquid or solid waste is not produced, environmentally safe.
4th, the present invention is not related to or comprising precipitation, filtering and evaporation, drying and other steps, concise in technology, it is not necessary to special to set
It is standby, easily industrialization.
5th, the method for the invention prepare solid organic acid titanium be generally organic acid titanium chelate and excess organic acid and
The mixture of its salt.
Embodiment
Clear, complete description will be carried out to the technical scheme of various embodiments of the present invention below, it is clear that described implementation
Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is general
Logical technical staff all other embodiment resulting on the premise of creative work is not made, belongs to the present invention and is protected
The scope of shield.
Embodiment 1
The proportioning of titanium tetrachloride and citric acid is 1 mole: 1 mole.210 grams of Citric Acid Mono is placed in and possesses tail gas absorption
In the reaction vessel of device, tail gas is absorbed with sig water, and the tetrachloro into 190 grams is slowly added dropwise into citric acid under stirring at room temperature
Change titanium (by citric acid be added in titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than
120℃；By titanic and organic acid mixture material by being fully ground, milling time is -24 hours 1 hour；Titanic and have
Machine acid blend solid phase reaction, the solid phase reaction time is -72 hours 1.0 hours；Mixed material, after solid phase reaction, room temperature
Post curing -48 hours 1 hour, that is, obtain solid citric acid titanium of the present invention.
Embodiment 2
The proportioning of titanium tetrachloride and citric acid is 1 mole: 2 mole.420 grams of Citric Acid Mono is placed in and possesses tail gas absorption
In the reaction vessel of device, tail gas is absorbed with sig water, and the tetrachloro into 190 grams is slowly added dropwise into citric acid under stirring at room temperature
Change titanium (by citric acid be added in titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than
120℃；By titanic and organic acid mixture material by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room
Warm post curing -48 hours 1 hour, that is, obtain solid citric acid titanium of the present invention.
Embodiment 3
The proportioning of titanium tetrachloride and citric acid is 1 mole: 3 mole.580 grams of anhydrous citric acid is placed in and possesses tail gas absorption
In the reaction vessel of device, tail gas is absorbed with sig water, and the tetrachloro into 190 grams is slowly added dropwise into citric acid under stirring at room temperature
Change titanium (by citric acid be added in titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than
120℃；By titanic and organic acid mixture material by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room
Warm post curing -48 hours 1 hour, that is, obtain solid citric acid titanium of the present invention.
Embodiment 4
The proportioning of titanium tetrachloride, citric acid and sodium citrate is 1 mole: 1 mole: 1 mole.By 210 grams of Citric Acid Mono
With the 294 grams of mixing of sodium citrate or ammonium salt, it is placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water,
Citric acid (is added in titanium tetrachloride also by the titanium tetrachloride for being slowly added dropwise 190 grams into citric acid under stirring at room temperature
Can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；By titanic and organic acid mixture material
By grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain this hair
Bright described solid citric acid titanium.
Embodiment 5
The proportioning of titanium tetrachloride, citric acid and sodium citrate is 1 mole: 2 mole: 1 mole.By 420 grams of anhydrous citric acid
With the 260 grams of mixing of sewage sodium citrate, it is placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water,
Be stirred at room temperature it is lower 190 grams are slowly added dropwise into citric acid titanium tetrachloride (by citric acid be added in titanium tetrachloride also can),
Material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；Titanic and organic acid mixture material are passed through
Grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain institute of the present invention
The solid citric acid titanium stated.
Embodiment 6
The proportioning of titanium tetrachloride, citric acid and sodium citrate is 1 mole: 1.5 mole: 1 mole.By Citric Acid Mono 315
Gram and the mixing of 294 grams of sodium citrate, be placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room
Temperature stirring under be slowly added dropwise into citric acid 190 grams titanium tetrachloride (by citric acid be added in titanium tetrachloride also can), thing
Material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；By titanic and organic acid mixture material by grinding
Mill -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain of the present invention
Solid citric acid titanium.
Embodiment 7
The proportioning of titanium tetrachloride and tartaric acid is 1 mole: 1 mole.150 grams of tartaric acid is placed in and possesses device for absorbing tail gas
Reaction vessel in, tail gas is absorbed with sig water, and the titanium tetrachloride into 190 grams is slowly added dropwise into tartaric acid under stirring at room temperature
(by tartaric acid be added in titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than 120
℃；By titanic and organic acid mixture material by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；After room temperature
Curing -48 hours 1 hour, that is, obtain solid tartaric acid titanium of the present invention.
Embodiment 8
The proportioning of titanium tetrachloride and tartaric acid is 1 mole: 2 mole.300 grams of tartaric acid is placed in and possesses device for absorbing tail gas
Reaction vessel in, tail gas is absorbed with sig water, and the titanium tetrachloride into 190 grams is slowly added dropwise into tartaric acid under stirring at room temperature
(by tartaric acid be added in titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than 120
℃；By titanic and organic acid mixture material by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；After room temperature
Curing -48 hours 1 hour, that is, obtain solid tartaric acid titanium of the present invention.
Embodiment 9
The proportioning of titanium tetrachloride and tartaric acid is 1 mole: 3 mole.450 grams of tartaric acid is placed in and possesses device for absorbing tail gas
Reaction vessel in, tail gas is absorbed with sig water, and the titanium tetrachloride into 190 grams is slowly added dropwise into tartaric acid under stirring at room temperature
(by tartaric acid be added in titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than 120
℃；By titanic and organic acid mixture material by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；After room temperature
Curing -48 hours 1 hour, that is, obtain solid tartaric acid titanium of the present invention.
Embodiment 10
The proportioning of titanium tetrachloride, tartaric acid and sodium potassium tartrate tetrahydrate is 1 mole: 1 mole: 1 mole.By 150 grams of tartaric acid and
282 grams of mixing of sodium potassium tartrate tetrahydrate, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room temperature
Tartaric acid (is added to four by the titanium tetrachloride being slowly added dropwise under stirring into tartaric acid and potassium tartrate sodium compound into 190 grams
In titanium chloride also can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；By titanic and organic
Acid blend material was by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour,
Obtain solid tartaric acid titanium of the present invention.
Embodiment 11
The proportioning of titanium tetrachloride, tartaric acid and sodium potassium tartrate tetrahydrate is 1 mole: 2 mole: 1 mole.By 300 grams of tartaric acid and
282 grams of mixing of sodium potassium tartrate tetrahydrate, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room temperature
Tartaric acid (is added to four by the titanium tetrachloride being slowly added dropwise under stirring into tartaric acid and potassium tartrate sodium compound into 190 grams
In titanium chloride also can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；By titanic and organic
Acid blend material was by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour,
Obtain solid tartaric acid titanium of the present invention.
Embodiment 12
The proportioning of titanium tetrachloride, tartaric acid and sodium potassium tartrate tetrahydrate is 1 mole: 1.5 mole: 1 mole.By 225 grams of tartaric acid
With 282 grams of mixing of sodium potassium tartrate tetrahydrate, it is placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room
Tartaric acid (is added to by the titanium tetrachloride being slowly added dropwise under temperature stirring into tartaric acid and potassium tartrate sodium compound into 190 grams
In titanium tetrachloride also can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；Titanic and will have
Machine acid blend material was by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing 1 hour -48 is small
When, that is, obtain solid tartaric acid titanium of the present invention.
Embodiment 13
The proportioning of titanium sulfate, citric acid and sodium citrate is 1 mole: 1 mole: 1 mole.By 210 grams of Citric Acid Mono and
294 grams of mixing of sodium citrate, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, are stirred in room temperature
Mix it is lower 402 grams are slowly added into citric acid titanium sulfate (by citric acid be added in titanium sulfate also can), material stirring and add
Acceleration should keep mixed material temperature to be less than 120 DEG C；By titanic and organic acid mixture material by grinding 1 hour -24
Hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain solid citric of the present invention
Sour titanium.
Embodiment 14
The proportioning of titanium sulfate, citric acid and sodium citrate is 1 mole: 2 mole: 1 mole.By 420 grams of anhydrous citric acid and
The 260 grams of mixing of sewage sodium citrate, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room
Temperature stirring under be slowly added into citric acid 402 grams titanium sulfate (by citric acid be added in titanium sulfate also can), material stirring
With adding speed mixed material temperature should be kept to be less than 120 DEG C；Titanic and organic acid mixture material is small by grinding 1
When -24 hours；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain of the present invention solid
Body Titanium Citrate.
Embodiment 15
The proportioning of titanium sulfate, citric acid and sodium citrate is 1 mole: 1.5 mole: 1 mole.By 315 grams of Citric Acid Mono
With 294 grams of mixing of sodium citrate, it is placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room temperature
Be slowly added dropwise under stirring into citric acid 402 grams titanium sulfate (by citric acid be added in titanium sulfate also can), material stirring
With adding speed mixed material temperature should be kept to be less than 120 DEG C；Titanic and organic acid mixture material is small by grinding 1
When -24 hours；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain of the present invention solid
Body Titanium Citrate.
Embodiment 16
The proportioning of titanium sulfate, tartaric acid and sodium potassium tartrate tetrahydrate is 1 mole: 1 mole: 1 mole.By 150 grams of tartaric acid and wine
The 282 grams of mixing of sodium of stone acid potassium, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, are stirred in room temperature
Mix lower be slowly added dropwise into tartaric acid and potassium tartrate sodium compound and (tartaric acid is added to titanium sulfate into 402 grams of titanium sulfate
In also can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；Titanic and organic acid are mixed
Material was by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain
Solid tartaric acid titanium of the present invention.
Embodiment 17
The proportioning of titanium sulfate, tartaric acid and sodium potassium tartrate tetrahydrate is 1 mole: 2 mole: 1 mole.By 300 grams of tartaric acid and wine
The 282 grams of mixing of sodium of stone acid potassium, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, are stirred in room temperature
Mix lower be slowly added dropwise into tartaric acid and potassium tartrate sodium compound and (tartaric acid is added to titanium sulfate into 402 grams of titanium sulfate
In also can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；Titanic and organic acid are mixed
Material was by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, that is, obtain
Solid tartaric acid titanium of the present invention.
Embodiment 18
The proportioning of titanium sulfate, tartaric acid and sodium potassium tartrate tetrahydrate is 1 mole: 1.5 mole: 1 mole.By 225 grams of tartaric acid and
282 grams of mixing of sodium potassium tartrate tetrahydrate, are placed in the reaction vessel for possessing device for absorbing tail gas, tail gas is absorbed with sig water, in room temperature
Tartaric acid (is added to sulfuric acid by the titanium sulfate being slowly added dropwise under stirring into tartaric acid and potassium tartrate sodium compound into 402 grams
In titanium also can), material stirring and adding speed should keep mixed material temperature to be less than 120 DEG C；Titanic and organic acid are mixed
Compound material was by grinding -24 hours 1 hour；Solid phase reaction -72 hours 1.0 hours；Room temperature post curing -48 hours 1 hour, is produced
To solid tartaric acid titanium of the present invention.
Other organic acids or salt substitute the organic acid or salt in above example, by substantially close processing step, also may be used
To obtain solid tartaric acid titanium of the present invention.
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention, appoint
What those skilled in the art, without departing from the scope of the present invention, when in the technology using the disclosure above
Hold the equivalent embodiment made a little change or be modified to equivalent variations, as long as being the content without departing from technical solution of the present invention,
Any simple modification, equivalent variations and modification that technical spirit according to the present invention is made to above example, still fall within this
In the range of inventive technique scheme.
Claims (6)
1. a kind of no-solvent process for preparing solid organic acid titanium, it is characterized in that, using titanic, organic acid and acylate as original
Titanic, organic acid and acylate are progressively mixed under material, normal temperature, by grinding distribution, titanic and organic acid mixture
Solid phase reaction, abundant after-ripening, obtain mole of the solid organic acid titanium, wherein titanic, organic acid and acylate of solubility
Than for 1: 1-8: 0-3, wherein titanic is titanium tetrachloride or titanium sulfate or their any scalemic thereof；Material mixing is kept
Temperature of charge is less than 120 DEG C；Material mixing keeps material to carry out at room temperature, and production process had not both included heating or should not cool down step
Suddenly；Room temperature post curing -48 hours 1 hour.
2. the no-solvent process according to claim 1 for preparing solid organic acid titanium, it is characterised in that the organic acid is
Any one in citric acid, tartaric acid, ascorbic acid, the sodium salt of ethylenediamine tetra-acetic acid, sylvite, ammonium salt or their any ratio
Example mixture.
3. the no-solvent process for preparing solid organic acid titanium according to claims 1 or 2, it is characterised in that：Grinding point
The time of dissipating is 1-72 hours.
4. the no-solvent process for preparing solid organic acid titanium according to claims 1 or 2, it is characterised in that：Titanic
It it is 1-72 hours with the organic acid mixture solid phase reaction time.
5. the no-solvent process for preparing solid organic acid titanium according to claims 1, it is characterised in that：It is preferred that grinding point
The time of dissipating is 1-24 hours.
6. the no-solvent process for preparing solid organic acid titanium according to claims 1, it is characterised in that：It is preferred that titanic
Mol ratio with organic acid is 1: 1.5-3.
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| CN85107690A (en) * | 1985-10-22 | 1987-04-29 | 北京有色金属研究总院 | Synthesizing of the titanium that plant-growth regulator is used-xitix solid chemical compound |
| US5021171A (en) * | 1989-03-20 | 1991-06-04 | E. I. Du Pont De Nemours And Company | Organotitanium compositions useful for cross-linking |
| CN1052302A (en) * | 1989-11-28 | 1991-06-19 | 北京有色金属研究总院 | Titanium compound for plant growing regulating agent and synthetic |
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| JPS5646835A (en) * | 1979-09-27 | 1981-04-28 | Ichiro Kijima | Preparation of organic titanium compound in aqueous system |
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| US5021171A (en) * | 1989-03-20 | 1991-06-04 | E. I. Du Pont De Nemours And Company | Organotitanium compositions useful for cross-linking |
| CN1052302A (en) * | 1989-11-28 | 1991-06-19 | 北京有色金属研究总院 | Titanium compound for plant growing regulating agent and synthetic |
| JP5646835B2 (en) * | 2009-10-23 | 2014-12-24 | 日東シンコー株式会社 | Bundling tape for wire harness and bundling tape manufacturing method |
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