CN109851629A - A kind of preparation method of single-component silicon rubber silanization alkynyl inhibitor - Google Patents
A kind of preparation method of single-component silicon rubber silanization alkynyl inhibitor Download PDFInfo
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- CN109851629A CN109851629A CN201910021026.7A CN201910021026A CN109851629A CN 109851629 A CN109851629 A CN 109851629A CN 201910021026 A CN201910021026 A CN 201910021026A CN 109851629 A CN109851629 A CN 109851629A
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- alkynyl
- inhibitor
- silicon rubber
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Abstract
The present invention relates to a kind of single-component silicon rubber preparation methods of silanization alkynyl inhibitor, comprising the following steps: (1) isocyanato silanes is dissolved in solvent, is stirred, isocyanato silanes solution is made；(2) it takes alkynyl compounds to be added drop-wise in the isocyanato silanes solution in step (1) again, is stirred, obtains mixed solution；(3) finally, catalyst is added into the mixed solution that step (2) is made into, reaction arrives purpose product after vacuum distillation.Compared with prior art, silanization alkynyl inhibitor and silicon rubber prepared by the present invention have preferable compatibility and volatility is very low, will not solidify, and have good inhibitory effect, can be used as inhibitor and be used to prepare single-component silicon rubber etc..
Description
Technical field
The invention belongs to organic compound synthesis technical fields, are related to a kind of single-component silicon rubber silanization alkynyl inhibition
The preparation method of agent.
Background technique
Addition-type silicon rubber has small shrinking percentage, excellent electric properties, chemical stability good, fine heat-resisting performance and vulcanization
The advantages that not generating any by-product in the process, is widely used in aerospace, automobile, telecommunications, health care, petroleum
The every field of the national economy such as work, machine-building.
Since the catalytic activity of addition-type silicon rubber catalyst is higher, addition-type silicon rubber is mainly bi-component addition at present
Type silicon rubber.Two kinds of components need to be uniformly mixed when use, it is not only inconvenient to use, and the holding time is shorter after mixing, holds
The problems such as easily causing waste.Single-component silicon rubber have many advantages, such as convenient for storage, transport and it is easy to use, be current add-on type silicon
One of development trend of rubber.
The key for developing single-component silicon rubber is to solve its stability stored at room temperature.Therefore it needs that inhibitor is added
It is coordinated with catalyst, catalyst is made to be unable to catalytic addition reaction at room temperature, being only heated to when certain temperature sizing material just can be with
Vulcanization.Common inhibitor is difficult to meet the requirement of single-component silicon rubber, as methyl butynol have boiling point is lower, volatility compared with
The shortcomings that high and organosilicon systems poor compatibility, ethynylcyclohexanol freezing point is low, and (fusing point of ethynylcyclohexanol is 30~33
DEG C), easily solidification is precipitated at room temperature, influences sizing material storage stability.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of single-component silicon rubbers
With the preparation method of silanization alkynyl inhibitor.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of single-component silicon rubber silanization alkynyl inhibitor, comprising the following steps:
(1) isocyanato silanes are dissolved in solvent, are stirred, isocyanato silanes solution is made；
(2) it takes alkynyl compounds to be added drop-wise in the isocyanato silanes solution in step (1) again, is stirred, obtains
Mixed solution；
(3) finally, catalyst is added into the mixed solution that step (2) is made into, reaction arrives mesh after vacuum distillation
Product.
Further, in step (1), the chemical general formula of the isocyanato silanes are as follows:
Wherein, R1、R2And R3It is independently-CH3、-OCH3Or-OCH2CH3, R4For saturated alkyl group, aryl radical
Group or group of naphthene base, such as-CH2CH2-,
Further, the solvent is tetrahydrofuran, toluene, ortho-xylene, paraxylene, meta-xylene, dimethyl Asia
One or more of sulfone, n-hexane or hexamethylene.
Further, in step (2), the general formula structure of the alkynyl compounds is CH ≡ C-R-OH or CH ≡ C-R-NH2,
Wherein, R is saturated alkyl group, aromatic hydrocarbon group or group of naphthene base, such as-CH2CH2,
Further, the catalyst is triethylamine, triethanolamine, triethylenediamine, propane diamine, tin dilaurate two
One or more of butyl tin or stannous octoate.
Further, isocyanato silanes and the addition molar ratio of alkynyl compounds are 1:1-1.2, solvent and reactant
Always the mass ratio of (i.e. isocyanato silanes and alkynyl compounds) is 1-10:1.
Further, the temperature of reaction is 25-70 DEG C, time 0.5-6h.
Further, the additive amount of catalyst is the 0.01-0.5% of mixed solution quality.
The preparation of silanization alkynyl inhibitor be by the isocyanato silanes-NCO group is in catalyst
Lower-the OH or-NH in the alkynyl compounds of effect2Addition reaction occurs and realizes.In the isocyanato silanes
- effect of NCO group is and-the OH or-NH in the alkynyl compounds2Addition reaction occurs and connects alkynyl compounds, silicon
The effect of groups is to enhance the compatibility of inhibitor and single-component silicon rubber.- OH or-NH in the alkynyl compounds2's
Effect is connection isocyanato silanes, and the effect of alkynyl group is to inhibit hydrosilylation.
In addition, the present invention has also carried out specific restriction, isocyanide to the type (group etc.) of the additive amount of each raw material, raw material
The addition molar ratio of acid esters base silane and alkynyl compounds is 1:1-1.2, it is therefore an objective to ensure that isocyanato silanes are reacted completely,
It prevents remaining in inhibitor-NCO group and water etc. from reacting, influences the performance of inhibitor.Agent and the total mass ratio of reactant are
1-10:1, solvent is very few so that reactant is completely dissolved, and solvent excessively will cause increased costs and the wasting of resources.Catalyst
Additive amount be mixed solution quality 0.01-0.5%, catalyst amount is too low, and reactivity can be too low, and yield is caused to drop
Low, catalyst amount is excessively high, and reactivity is too high, and initial reaction stage can be highly exothermic, be easy to cause danger.
Compared with prior art, the silanization alkynyl inhibitor and silicon rubber of preparation have preferable compatibility and volatilize
Property it is very low, will not solidify, have good inhibitory effect, can be used as inhibitor and be used to prepare single-component silicon rubber.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.The present embodiment is based on the technical solution of the present invention
Implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
The isocyanatopropyl trimethoxy silane of 10g is dissolved in the toluene of 50g, mechanical stirring 30 minutes, weighs 24.4g
Methyl butynol is added drop-wise in isocyanatopropyl trimethoxy silane solution dropwise and is stirred evenly with constant pressure funnel, is weighed
And the triethylamine that 0.14g (0.5%) is added reacts 6 hours under 70 degrees Celsius, as catalyst then 70 after mixing evenly
Vacuum distillation obtains silanization alkynyl inhibitor P1, yield 86.7% under degree Celsius.
Reaction equation is as follows:
Embodiment 2
The isocyanatopropyl triethoxysilane of 10g is dissolved in the tetrahydrofuran of 50g, mechanical stirring 30 minutes, is weighed
19.89g acetylene cyclohexanol is added drop-wise in isocyanatopropyl triethoxysilane solution dropwise with constant pressure funnel and is stirred
It is even, it weighs and the dibutyl tin dilaurate of 0.09g (0.3%) is added as catalyst, after mixing evenly at 50 c
Reaction 6 hours, then vacuum distillation obtains silanization alkynyl inhibitor P2, yield 82.3% at 50 c.
Reaction equation is as follows:
Embodiment 3
The isocyanatopropyl trimethoxy silane of 10g is dissolved in the tetrahydrofuran of 50g, mechanical stirring 30 minutes, is weighed
37.27g propargylamine is added drop-wise in isocyanatopropyl trimethoxy silane solution dropwise and is stirred evenly with constant pressure funnel, is claimed
Take and 0.0047g (0.01%) is added triethylenediamine as catalyst, react 0.5 under 25 degrees Celsius after mixing evenly
Hour, then vacuum distillation obtains silanization alkynyl inhibitor P3, yield 96.6% at 50 c.
Embodiment 4
The isocyanatopropyl trimethoxy silane of 10g is dissolved in the hexamethylene of 50g, mechanical stirring 30 minutes, is weighed
17.52g 4- acetylenylaniline is added drop-wise in isocyanatopropyl trimethoxy silane solution dropwise and is stirred with constant pressure funnel
Uniformly, weigh and 0.0083g (0.03%) is added propane diamine as catalyst, react 2 at 50 c after mixing evenly
Hour, then vacuum distillation obtains silanization alkynyl inhibitor P4, yield 98.6% at 50 c.
Embodiment 5-12
Compared with Example 1, the overwhelming majority is all identical, in addition to solvent employed in the present embodiment replaces with correspondence respectively
Tetrahydrofuran, ortho-xylene, paraxylene, meta-xylene, dimethyl sulfoxide, n-hexane, the hexamethylene of volume, or neighbour two
The mixed liquor of toluene and paraxylene (volume ratio 1:1).
Embodiment 13-17
Compared with Example 1, the overwhelming majority is all identical, in addition to catalyst employed in the present embodiment replaces with three respectively
Ethanol amine, triethylenediamine, propane diamine, dibutyl tin dilaurate, stannous octoate.
Embodiment 18
Compared with Example 1, the overwhelming majority is all identical, in addition in the isocyanato silanes in the present embodiment,
R1、R2And R3It is-CH3、-OCH3Or-OCH2CH3, R4For saturated alkyl group, aromatic hydrocarbon group or naphthenic base base
Group.
Further, in step (2), the general formula structure of the alkynyl compounds is CH ≡ C-R-OH or CH ≡ C-R-NH2,
Wherein, R is saturated alkyl group, aromatic hydrocarbon group or group of naphthene base.
Embodiment 19
Compared with Example 1, the overwhelming majority is all identical, in addition in the isocyanato silanes in the present embodiment,
R1、R2And R3It is-CH3、-OCH3Or-OCH2CH3, R4For saturated alkyl group, aromatic hydrocarbon group or naphthenic base base
Group.
Further, in step (2), the general formula structure of the alkynyl compounds is CH ≡ C-R-OH or CH ≡ C-R-NH2,
Wherein, R is saturated alkyl group, aromatic hydrocarbon group or group of naphthene base.
Embodiment 20
Compared with Example 1, the overwhelming majority is all identical, in addition in the isocyanato silanes in the present embodiment,
R1、R2And R3It is-CH3。
Embodiment 21
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment: isocyanato silanes and alkynyl chemical combination
The molar ratio of object is 1:1, and solvent and the total mass ratio of two kinds of reactants are 1:1, and the relative amount of rest materials remains unchanged.
Embodiment 22
Compared with Example 1, the overwhelming majority is all identical, in addition in the present embodiment: isocyanato silanes and alkynyl chemical combination
The molar ratio of object is 1:1.2, and solvent and the total mass ratio of two kinds of reactants are 10:1, and the relative amount of rest materials is kept not
Become.
Evaluation:
Below with regard to silanization alkynyl inhibitor P1, P2, P3 and P4 obtained in the above embodiment of the present invention and existing suppression
Preparation methyl butynol, acetylene cyclohexanol do performance and compare, the specific steps are as follows:
100g vinyl silicone oil, 10g containing hydrogen silicone oil and 1g inhibitor are mixed in a certain ratio, 10ppm platinum is added and urges
Agent, after mixing, vacuumizing and defoaming 30 minutes.
Its surface drying time at different temperatures is tested according to GB/T 13477.5-2002, the results are shown in Table 1.
The surface drying time of 1 Single-component addition-type silicone rubber of table
As can be seen from the table, silanization alkynyl inhibitor prepared by the present invention has excellent inhibition effect at room temperature
Fruit enhances the stability of single-component silicon rubber room temperature storage.And it can be solid at 10-12 minutes or so after being heated to 150 DEG C
Change, meets high temperature vulcanized requirement.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
Centainly refer to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
One or more embodiment or examples in can be combined in any suitable manner.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (8)
1. a kind of single-component silicon rubber preparation method of silanization alkynyl inhibitor, which comprises the following steps:
(1) isocyanato silanes are dissolved in solvent, are stirred, isocyanato silanes solution is made；
(2) it takes alkynyl compounds to be added drop-wise in the isocyanato silanes solution in step (1) again, is stirred, is mixed
Solution；
(3) finally, catalyst is added into the mixed solution that step (2) is made into, reaction is produced after vacuum distillation to get to purpose
Object.
2. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, in step (1), the chemical general formula of the isocyanato silanes are as follows:
Wherein, R1、R2And R3It is independently-CH3、-OCH3Or-OCH2CH3, R4For saturated alkyl group, aromatic hydrocarbon group or
Group of naphthene base.
3. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, the solvent is tetrahydrofuran, toluene, ortho-xylene, paraxylene, meta-xylene, dimethyl sulfoxide, n-hexane or ring
One or more of hexane.
4. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, in step (2), the general formula structure of the alkynyl compounds is CH ≡ C-R-OH or CH ≡ C-R-NH2, wherein R is saturation
Alkyl group, aromatic hydrocarbon group or group of naphthene base.
5. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, the catalyst is triethylamine, triethanolamine, triethylenediamine, propane diamine, dibutyl tin dilaurate or octanoic acid
One or more of stannous.
6. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, the molar ratio of isocyanato silanes and alkynyl compounds is 1:1-1.2, and solvent and two kinds of total mass ratioes of reactant are
1-10:1。
7. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, the temperature of reaction is 25-70 DEG C, time 0.5-6h.
8. a kind of preparation method of the single-component silicon rubber according to claim 1 with silanization alkynyl inhibitor, feature
It is, the additive amount of catalyst is the 0.01-0.5% of mixed solution quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111574717A (en) * | 2020-05-22 | 2020-08-25 | 广东标美硅氟新材料有限公司 | Inhibitor for LED (light-emitting diode) packaging silica gel and preparation method and application thereof |
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2019
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| JP2010241724A (en) * | 2009-04-06 | 2010-10-28 | Fujifilm Corp | Organosilicon compound, liquid composition, resin composition, and metal foil-clad film or metal foil-laminate, adhesive and coating agent using the same |
| CN103463639A (en) * | 2012-06-08 | 2013-12-25 | 华东理工大学 | Controlled release system and preparation method thereof |
| WO2014183164A1 (en) * | 2013-05-17 | 2014-11-20 | Naresh Kumar | Dihydropyrrolones and their use as antimicrobial agents |
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Cited By (2)
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| CN111574717A (en) * | 2020-05-22 | 2020-08-25 | 广东标美硅氟新材料有限公司 | Inhibitor for LED (light-emitting diode) packaging silica gel and preparation method and application thereof |
| CN111574717B (en) * | 2020-05-22 | 2021-09-10 | 广东标美硅氟新材料有限公司 | Inhibitor for LED (light-emitting diode) packaging silica gel and preparation method and application thereof |
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