CN85109471A - Ethanolamine titanate isopropyl ester synthetic method and application - Google Patents

Abstract

The present invention is the synthetic method and the application of ethanolamine titanate isopropyl ester.This technology is the completely closed loop process that is made of esterification and chelatropic reaction two portions.

At first carrying out esterification (the reactant Virahol itself is made solvent) with Virahol and titanium tetrachloride and get the intermediate isopropyl titanate, is that sequestrant and isopropyl titanate get the ethanolamine titanate isopropyl ester through chelatropic reaction again with the alcohol amine compound.This compound has good dispersiveness, thixotropy, ultraviolet-absorbing, is applied to do in the coating dispersion agent, UV light absorber and thixotropic agent.

Description

Ethanolamine titanate isopropyl ester synthetic method and application

The present invention is the synthetic method and the application thereof of organic titanic compound.

Ethanolamine titanate isopropyl ester (hereinafter to be referred as TAE-3), water-soluble and oily, and there is not decomposing phenomenon, to coating particularly water-borne coatings (latex coating) good dissemination is arranged, compare with the dispersion agent hexametaphosphate that domestic current is used, except that having good dispersing property, also have ultraviolet-absorbing, thixotropy.

In recent years, the organic titanium based compound has been widely used in process industries such as plastics, rubber, binding agent, coating, still, does not still have the document record for synthetic method and the application of TAE-3.

United States Patent (USP) (VS-3,119,852), French Patent (Fr-1396951) introduced the intermediate isopropyl titanate of TAE-3 to adopt normal heptane in synthetic has been solvent, Japan " technical chemistry magazine " 62.77-9(1959) report, adopting normal hexane is the synthetic isopropyl titanate of solvent, domestic Beijing chemical reagent factory once adopted benzene to make solvent and produced isopropyl titanate, owing to adopted solvent, the technical process of reclaiming solvent increases, and retrieving arrangement is huge, investment is big, and production cost is higher.

The object of the present invention is to provide simple, the safe and reliable method of producing TAE-3 of a kind of technology and this application of compound.

Content of the present invention and implementation method comprise esterification and two steps of chelatropic reaction, and existing division is as follows:

1, esterification: Virahol is added in the reactor, and the reactant Virahol is originally as solvent.10～30 ℃ of following agitation and dropping titanium tetrachlorides 10～50 minutes, the weight ratio of titanium tetrachloride and Virahol is 1: (4～10), 50～70 rev/mins of stirring velocitys, reduce to 10～40 ℃ in temperature, stir and fed ammonia 90～200 minutes, cross filtering white chloride precipitation thing, filtrate is through distillation, refining, removes Virahol and gets pure isopropyl titanate and be sent to the chelatropic reaction operation.

2, chelatropic reaction: with the alcohol amine compound is sequestrant, under agitation isopropyl titanate is added in the reactor, the mole ratio of isopropyl titanate and thanomin is 1: (1.8～2.1), reacted 30～90 minutes down at 80～120 ℃, when gas phase temperature reaches 80 ℃.There is Virahol to distillate, when overhead product reaches theoretical value, under vacuum, extracts residual isopropanol out, promptly get TAE-3.

The Virahol that reclaims in esterification and the chelatropic reaction is sent to esterifier and recycles.

Main chemical reactions is:

The technological process of invention sees Fig. 1, Fig. 2 for details.

Fig. 1 is the synthesis technique schematic flow sheet of isopropyl titanate.

Fig. 2 is the synthesis technique schematic flow sheet of TAE-3.

TAE-3 has good dispersiveness, and ultraviolet-absorbing and thixotropy are applied to do in the coating dispersant. Ultra-violet absorber and thixotropic agent. Its dispersive property sees Table 1. By table 1 as seen, various Pigments are in the medium of some, and not adding TAE-3 does not all have flowability before, when adding 0.5%TAE-3, has changed the interface character between pigment and medium, and the viscosity of pigments system obviously reduces.

Table 1 TAE-3 is to the impact of different pigments system flowabilities

The absorbing ultraviolet spectrum property sees Table 2. UV absorbing properties by the visible TAE-3 of table 2 is better.

Table 2 concentration is the mensuration of the TAE-3 ultra-violet absorption spectrum of 1000PPm

Wavelength X 200 250 270 280 290 300 310 320

Light transmittance T 0000003 25.3

Optical density A ∞ ∞ ∞ ∞ ∞ ∞ 1.53 0.597

Wavelength X 330 340 350 360 370 380 390 400

Light transmittance T 62.3 85.5 94.5 96.5 97.2 97.8 98.0 98.8

Optical density A 0.207 0.068 0.025 0.015 0.012 0.010 0.008 0.005

Thixotropic property shows TAE-3 added thickening effect in the coating, brushing easily, sagging not.

TAE-3 synthetic method provided by the present invention, technology is simple, is a totally-enclosed circulation technology flow process; Synthetic isopropyl titanate does not need freezing, itself makes solvent with the reactant Virahol; In TAE-3 is synthetic, not high to the content requirement of sequestrant thanomin, can be one, two, the mixture of trolamine; Technical indicator advanced person, the isopropyl titanate yield can reach 80～85%, and titanium content is 16～18%, and cl content is below 1%, and the TAE-3 yield can reach 95～97%; Side product sodium chloride can be used as chemical fertilizer and uses, not output " three wastes "; TAE-3 has ultraviolet-absorbing, thixotropy concurrently as dispersion agent result of use excellence, is the multifunctional assistant of coating.

Non-limiting examples of the present invention:

Example 1:TAE-3's is synthetic

Raw material: titanium tetrachloride, Virahol, thanomin, liquefied ammonia.

Main processes: esterification, chelatropic reaction.

The esterification condition: titanium tetrachloride and Virahol were than (weight) 1: 5

Dropping titanium tetrachloride temperature＜15 ℃

Drip 30～40 minutes titanium tetrachloride time

Dehydrochlorination temperature＜20 ℃

120～150 minutes dehydrochlorination time

The thick ester of batching temperature of reaction

Solvent ratio titanium tetrachloride Virahol drips the titanium tetrachloride dehydrochlorination must measure yield

(weight) (gram) (℃) (℃) (gram) (%)

1∶5 303.4 1550 11～27 20-43 390 85.90

1∶5 303.4 1550 10～30 20-43 395 87.00

The chelatropic reaction condition:

Ratio of components (ester/amine mole ratio) 1: 2

Temperature of reaction: 80～100 ℃

Reaction times: 50～70 minutes

The product and the index that obtain:

The test result analysis result feeds intake

The different ethanol of metatitanic acid reclaims pure TAE-3 yield unhindered amina viscosity proportion

Propyl ester amine

(gram) (gram) (gram) (gram) be (gram) (25 ℃ of centipoises) d (%) ₄25

426 447 201 659.5 95.17 11.19 3000 1.1850

426 447 196 677 97.69 11.31 3000 1.1810

Example 2:TAE-3 is applied in the general white slurry

TAE-3 is applied in the general white slurry, and compare dispersing property with Sodium hexametaphosphate 99 good, and thickening effectiveness is arranged.

Example 3:TAE-3 is applied in the naval vessel in the aqueous latex paint of cabin

In the naval vessel in the aqueous latex paint of cabin, adopt TAE-3 and Sodium hexametaphosphate 99 to be used, its dispersion effect significantly improves than use Sodium hexametaphosphate 99 separately, and colo(u)rant dispersion is even, does not occur growing dim, phenomenon such as yellowing; Better than benzene one third, vinyl acetate-acrylic latex paint UV resistant irradiation performance; Strong adhesion, the brightness height; Scrubbing resistance; Oil resistant-water, water-fast, salt water resistance soak 15 days no auxiliary agents and separate out phenomenon.

Example 4:TAE-3 has been applied to light latex finish paint

Light latex finish paint is arranged, and main pigment is titanium dioxide, adopts Sodium hexametaphosphate 99 liquid (accounting for amount of pigment 6～10%) sanding mill 30 minutes, and fineness can reach below the 30u, and adopt TAE-3(account for amount of pigment 0.34%) sanding mill 15 minutes, fineness can reach below the 30u.

Example 5:TAE-3 is applied to the iron oxide red latex primer

The main pigment of iron oxide red latex primer is red iron oxide, zinc network Huang etc., below the fineness requirement 50u, adopts Sodium hexametaphosphate 99 liquid (Sodium hexametaphosphate 99 account for amount of pigment 6～10%) sanding mill to need 7 hours, and with TAE-3(account for amount of pigment 1%), then got final product in 3～4 hours.

Find out that by example 4 and example 5 TAE-3 has good dispersiveness, and emulsion paint is had thickening effectiveness, paint film property is had no adverse effects, sagging not in the brushing process.

Claims (4)

1, a kind of synthetic method of organic titanic compound is characterized in that:

1.1 with the reactant Virahol this as solvent, 10～30 ℃ of following agitation and dropping titanium tetrachlorides 10～50 minutes, stirred the feeding ammonia down 90～200 minutes for 10～40 ℃ in temperature, remove by filter ammonium chloride, filtrate is through distillation, refining that isopropyl titanate send the chelatropic reaction operation, and the Virahol that removes is sent reactor cycles back to and used.

1.2 with the alcohol amine compound is sequestrant, stirs to add isopropyl titanate down, 80～120 ℃ of reactions 30～90 minutes down, through distillation, refining ethanolamine titanate isopropyl ester, reclaims Virahol and send esterifier to recycle.

2, according to the synthetic method of claim 1, the weight ratio that it is characterized in that titanium tetrachloride and Virahol is 1: (4～10), stirring velocity are 50～70 rev/mins.

3, synthetic method according to claim 1, the mole ratio that it is characterized in that isopropyl titanate and thanomin is 1: (1.8～2.1), stirring velocity are 50～70 rev/mins.

4, organic titanic compound according to claim 1 the invention reside in dispersion agent, UV light absorber and the thixotropic agent of this compound as coating.

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