CN104497313A

CN104497313A - Non-corrosive organic tin catalyst as well as preparation method and application thereof

Info

Publication number: CN104497313A
Application number: CN201410740356.9A
Authority: CN
Inventors: 黄永军; 翁祝强; 李彬彬
Original assignee: DONGGUAN ZHAOSHUN ORGANOSILICON NEW MATERIAL TECHNOLOGY Co Ltd
Current assignee: DONGGUAN ZHAOSHUN ORGANOSILICON NEW MATERIAL TECHNOLOGY Co Ltd
Priority date: 2014-12-05
Filing date: 2014-12-05
Publication date: 2015-04-08

Abstract

The invention provides a non-corrosive organic tin catalyst as well as a preparation method and application thereof. The catalyst is prepared from an oxide of alkyl tin and a chelating agent at the ratio of 1 to (1-1.2) in parts by weight. The preparation method comprises the following steps: (1) adding the oxide of alkyl tin to a reaction kettle as a raw material, stirring, filling protective gas and regulating temperature; and (2) dropping the chelating agent for reaction after the temperature achieves a requirement, and cooling after the reaction so as to obtain a finished product. The organic tin catalyst disclosed by the invention is synthesized by virtue of the non-corrosive chelating agent and the oxide of alkyl tin, so that the problem that an organic tin catalyst is corrosive to metal structures or electronic components in the prior art is solved.

Description

A kind of corrosion-free organotin catalysts and its production and use

Technical field

The invention belongs to organic synthesis field, particularly relate to a kind of corrosion-free organotin catalysts and its production and use.

Background technology

RTV silicon rubber, no matter be single component or two-pack, when formulated product, all will add a small amount of organotin and make catalyzer, conventional organotin catalysts is: R ¹ _nsn (OCOR ²) ₂, R in formula ¹for C ₄h ₉or C ₈h ₁₇, R ²for CH ₃, C ₇h ₁₅or C ₁₁h ₂₃deng, can also be the oxide compound of tin alkyl, but, the most frequently used still dibutyl tin laurate (C ₄h ₉) ₂sn (OOCC ₁₁h ₂₃) ₂.

The bright preparation method disclosing a kind of dibutyltin dilaurate catalyst of patent CN102516544A, comprises step: carry out stirring and heating after lauric acid and Dibutyltin oxide being fed intake, and when temperature is raised to 50 DEG C, reaction system starts to be with negative pressure; Continue heating, be warming up to 80 DEG C ~ 88 DEG C, maintenance system temperature successive reaction 2h, then stops negative pressure, adds acetic anhydride, then continues stirring reaction 1h; By the solution that is obtained by reacting according to certain mass than compound auxiliary, finally obtain finished product.

But this organotin catalysts often containing free organic acid, is corrosive for metal construction or electronic devices and components, the causing metal construction or electronic devices and components open circuit and affect water resistance of seriously corroded.Therefore need to find and a kind of not there is the catalyzer that corrosive organotin is used as RTV, reduce the corrosion to metal construction or electronic devices and components.

Summary of the invention

For above-mentioned existing organotin catalysts such as dibutyltin dilaurate catalyst etc., there is corrosive problem, the invention provides a kind of corrosion-free organotin catalysts and preparation method thereof.

For reaching this object, the present invention by the following technical solutions:

A kind of corrosion-free organotin catalysts, described catalyzer is prepared by the oxide compound of tin alkyl and sequestrant, and in the oxide compound of wherein said tin alkyl, alkyl is C ₁~ C ₁₈alkyl group, such as C ₁alkyl group, C ₂alkyl group, C ₃alkyl group, C ₅alkyl group, C ₇alkyl group, C ₁₀alkyl group, C ₁₃alkyl group, C ₁₅alkyl group, C ₁₇alkyl group or C ₁₈alkyl groups etc., are preferably Dibutyltin oxide.

Sequestrant is methyl aceto acetate and/or methyl ethyl diketone, such as the composition etc. of methyl aceto acetate, methyl ethyl diketone or methyl aceto acetate and methyl ethyl diketone.

The oxide compound of described tin alkyl and the ratio of weight and number of sequestrant are 1:1 ~ 1.2, such as 1:1,1:1.04,1:1.06,1:1.08,1:1.1,1:1.13,1:1.15,1:1.17 or 1:1.2 etc., preferred 1:1.04.

The preparation method of the above corrosion-free organotin catalysts, described preparation method comprises the following steps:

(1) oxide powder of raw material tin alkyl is added in reactor to open and stir, pass into shielding gas by emptying for the air in reactor and adjust temperature;

(2) after temperature reaches requirement, drip sequestrant to react, lower the temperature after completion of the reaction and obtain product.

In the oxide compound of described tin alkyl, alkyl is C ₁~ C ₁₈alkyl group, such as C ₁alkyl group, C ₂alkyl group, C ₃alkyl group, C ₅alkyl group, C ₇alkyl group, C ₁₀alkyl group, C ₁₃alkyl group, C ₁₅alkyl group, C ₁₇alkyl group or C ₁₈alkyl groups etc., are preferably Dibutyltin oxide.

Described sequestrant is methyl aceto acetate and/or methyl ethyl diketone, such as the composition etc. of methyl aceto acetate, methyl ethyl diketone or methyl aceto acetate and methyl ethyl diketone.

Shielding gas in described step (1) is the combination of any one or at least two kinds in nitrogen, helium, neon or argon gas; described combination typical case but limiting examples have: the combination of nitrogen and helium; the combination of helium and neon; the combination of neon and argon gas, the combination of nitrogen, helium, neon and argon gas.Passing into rare gas element is in order to starvation, is further oxided with the oxide compound of tin alkyl.

Pass into shielding gas in described step (1) and adjust temperature again after emptying for air in reactor.

Adjustment temperature to 95 ~ 105 DEG C in described step (1), such as 95 DEG C, 96 DEG C, 97 DEG C, 98 DEG C, 99 DEG C, 100 DEG C, 101 DEG C, 102 DEG C, 103 DEG C, 104 DEG C or 105 DEG C etc., preferably 100 DEG C.

Temperature of reaction in described step (2) is 135 ~ 145 DEG C, such as 135 DEG C, 136 DEG C, 137 DEG C, 138 DEG C, 139 DEG C, 140 DEG C, 141 DEG C, 142 DEG C, 143 DEG C, 144 DEG C or 145 DEG C etc., preferably 140 DEG C.

Reaction times in described step (2) is 2 ~ 6h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc.

Beneficial effect:

Adopt the oxide compound without corrosive sequestrant and tin alkyl to synthesize organotin catalysts in the present invention, to overcome in prior art organotin catalysts for metal construction or the mordant problem of electronic devices and components, to prepared obtain being coated in after the materials such as organotin catalysts and 107 glue mix copper base carries out two 85 test and contrast with the dibutyltin dilaurate catalyst etc. of routine, show that the colloid of the organotin catalysts adopted prepared by the present invention is to the corrosion-free phenomenon in copper base interface (see Fig. 1 and Fig. 2), as can be seen from the figure the copper base seriously corroded of ordinary method institute controlling catalyst is adopted, and adopt the copper base of institute of the present invention controlling catalyst substantially not corrode.

Accompanying drawing explanation

Fig. 1 is for adopting the corrosion condition figure of the copper base of ordinary method institute controlling catalyst;

Fig. 2 is for adopting the corrosion condition figure of the copper base of institute of the present invention controlling catalyst.

Embodiment

Technical scheme of the present invention is further illustrated below by embodiment.

Embodiment 1:

249 parts of Dibutyltin oxide powder are added in reactor, opens and stir, pass through N at powder surface ₂within 30 minutes, air is discharged, then temperature is adjusted to 100 DEG C, by the oxide compound of tin alkyl and sequestrant by ratio of weight and the number of copies 1:1.04 drip 260 parts of methyl aceto acetates, then 140 DEG C of reactions 3 hours, cooling i.e. obtained product.

Embodiment 2:

249 parts of methyl oxidation tin powder are added in reactor, open and stir, air was discharged in 30 minutes by helium at powder surface, then temperature is adjusted to 95 DEG C, by the oxide compound of tin alkyl and sequestrant by ratio of weight and the number of copies 1:1 drip 249 parts of methyl ethyl diketones, then 145 DEG C of reactions 2 hours, cooling i.e. obtained product.

Embodiment 3:

By 249 parts of C ₁₈alkyl-tin oxide powder adds in reactor, open and stir, air was discharged in 30 minutes by argon gas at powder surface, then temperature is adjusted to 105 DEG C, by the oxide compound of tin alkyl and sequestrant by ratio of weight and the number of copies 1:1.2 drip the mixture of 298.8 parts of methyl ethyl diketones and methyl aceto acetate, then 135 DEG C of reactions 6 hours, cooling i.e. obtained product.

Comparative example 1:

Comparative example is dibutyltin dilaurate catalyst.

Test experiments:

By 100 part of 107 glue, 3 parts of tetraethoxys, the catalyzer synthesized in respectively with 0.2 part of above-described embodiment 1-3 and comparative example, be coated in after stirring on copper base, solidify after 24 hours, carry out two 85 experiments and check whether colloid and copper base interface corrode, and experimental result is listed in table 1 after 72 hours.

Table 1: embodiment 1-3 and comparative example 1 test experiments result table

Result in integrated embodiment 1-3 and comparative example 1 can be found out, adopt the oxide compound without corrosive sequestrant and tin alkyl to synthesize organotin catalysts in the present invention, to overcome in prior art organotin catalysts for metal construction or the mordant problem of electronic devices and components, to prepared obtain being coated in after the materials such as organotin catalysts and 107 glue mix copper base carries out two 85 test and contrast with the dibutyltin dilaurate catalyst etc. of routine, show that the colloid of the organotin catalysts adopted prepared by the present invention is to the corrosion-free phenomenon in copper base interface.

Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims

1. a corrosion-free organotin catalysts, is characterized in that, described catalyzer is prepared by the oxide compound of tin alkyl and sequestrant, and in the oxide compound of wherein said tin alkyl, alkyl is C ₁~ C ₁₈alkyl group, sequestrant is methyl aceto acetate and/or methyl ethyl diketone.

2. catalyzer according to claim 1, is characterized in that, the oxide compound of described tin alkyl is Dibutyltin oxide.

3. catalyzer according to claim 1 and 2, is characterized in that, the oxide compound of described tin alkyl and the ratio of weight and number of sequestrant are 1:1 ~ 1.2;

Preferably, the oxide compound of described tin alkyl and the ratio of weight and number of sequestrant are 1:1.04.

4. the preparation method of catalyzer as described in any one of claim 1-3, it is characterized in that, described preparation method comprises the following steps:

(1) oxide powder of raw material tin alkyl is added in reactor to open and stir, pass into shielding gas and adjust temperature;

5. preparation method according to claim 4, is characterized in that, in the oxide compound of described tin alkyl, alkyl is C ₁~ C ₁₈alkyl;

Preferably, the oxide compound of described tin alkyl is Dibutyltin oxide;

Preferably, described sequestrant is methyl aceto acetate and/or methyl ethyl diketone;

Preferably, the oxide compound of described tin alkyl and the ratio of weight and number of sequestrant are 1:1 ~ 1.2;

6. the preparation method according to any one of claim 4 or 5, is characterized in that, the shielding gas in described step (1) is the combination of any one or at least two kinds in nitrogen, helium, neon or argon gas.

7. the preparation method according to any one of claim 4-6, is characterized in that, passes into shielding gas and adjust temperature again in described step (1) after emptying for air in reactor;

Preferably, adjustment temperature to 95 ~ 105 DEG C in described step (1);

Preferably, adjustment temperature to 100 DEG C in described step (1).

8. the preparation method according to any one of claim 4-7, is characterized in that, the temperature of reaction in described step (2) is 135 ~ 145 DEG C;

Preferably, the temperature of reaction in described step (2) is 140 DEG C.

9. the preparation method according to any one of claim 4-8, is characterized in that, the reaction times in described step (2) is 2 ~ 6h.

10. the purposes of the catalyzer as described in any one of claim 1-3.