CN1101059A

CN1101059A - High-temperature (350 deg.C) silicon sulfide at room-temperature

Info

Publication number: CN1101059A
Application number: CN 93117927
Authority: CN
Inventors: 谢择民; 王金亭; 王清正; 师彤
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 1993-09-30
Filing date: 1993-09-30
Publication date: 1995-04-05
Anticipated expiration: 2013-09-30
Also published as: CN1037353C

Abstract

The vulcanized thermophilic (350 degree C) room-temp. silicon sulfide rubber is made up by using silazine polymer as cross linking agent. This invention provides a glue-stock formula and the dosage-range of the silazine polymer to be added. The domestic 107, 108 or 106. SDL series of silicon rubber can be substituted for said glue-stock to obtain thermophilic 100-temp. silicon-sulfide rubber. The invented glue has better thermal stability, mechanical performance and adhesive performance.

Description

High-temperature (350 deg.C) silicon sulfide at room-temperature

The present invention relates to a kind of organosilicon macromolecule material of high-temperature resistant.

Two component condensed room temperature vulcanized silicone rubbers are linking agent usually with the ethyl orthosilicate, carry out crosslinking reaction with dibutyl tin laurate as catalyzer obtains cross-linked rubber:

Because this class glue has the performance of many excellences, processing and easy to use simultaneously is so obtained using widely.But this class glue also exists the problem of several aspects, and some use is restricted.The one, because siloxane bond polarity height, so remaining catalyzer can cause the main chain degraded rapidly when temperature is high, particularly this degraded is more outstanding under sealing and inert atmosphere, so this class glue can only use about 200 ℃.Silicon hydroxyl and water also can cracking silica chains in addition.Brit.1434528 once was reported in and added a small amount of 2 in this class glue, and the 4-dichlorobenzoperoxide makes cross-linked rubber increase cross-linking set when temperature is high, the result makes the heat resistance of this class glue bring up to 250 ℃, aboveground Kev (chemical と industry, 1987,40(12), 1034) report; With filler of hydroxyl not etc., the result can make anti-300 ℃ of this class glue.The 2nd, remaining catalyzer can reduce the electrical property of this class glue when high temperature [Polym.Eng.Sci., 1986,26(13), 940].The 3rd, the adhesive property of this class glue is relatively poor, usually by the coated bed material or with coupling agents to improve (Adhesives Age.1974,17(6) 27).The 4th, what this class glue was used is the polysiloxane of lower molecular weight, so mechanical property is lower than hot-vulcanized silicone rubber, will waits with high enhanced filler usually and improve its mechanical property.

The objective of the invention is to overcome the defective of prior art, with the vulcanizing agent of a kind of new linking agent as the self cure sizing material, make this class glue carry out the cross-linking vulcanized main chain degraded of eliminating the catalyzer initiation of on-catalytic, thereby the heat resistance that makes this class glue is brought up to 350 ℃, can improve its mechanical property and adhesiveproperties again simultaneously.

Content of the present invention is to add silicon-nitrogen polymer C in silicone rubber compounds, as the self cure linking agent, makes the heat resistance of sulfuration back silicon rubber bring up to 350 ℃.The component of this high-temperature resistant silicon rubber (weight) is

100 parts of silicone rubber compounds

Silicon-nitrogen polymer C 3-7 part

Described silicone rubber compounds can use hydroxy silicon oil (as 107 or 108, viscosity 2000-10000CP) or this hydroxy silicon oil add the silicone rubber compounds A that filler and additive etc. are mixed with, also can be with homemade 106 or the requirement of any high-temperature-resisting silicon rubber sizing material all according to the invention of sizing material of SDL series etc.

Contain following component among the silicone rubber compounds A:

(weight)

100 parts of hydroxy silicon oils (107 or 108, viscosity 2000-10000CP)

SiO ₂(vapor phase process 2#) 12-30 part

CaCO ₃0-50 part

TiO ₂0-25 part

ZnO ₂0-25 part

Fe ₂O ₃0-5 part

MM ^NOr D ^N ₃1.5-3 part

The preparation steps of sizing material A is:

With antistructurizing agent hexamethyldisilazane (MM ^N) or pregnancy basic ring three silazane (D ^N ₃), be added in 107 glue, add SiO after mixing well again ₂Deng, and in kneader kneading 1-2 hour, take out the back on three roller rubber mixing machines mixing 1-2 time, the sizing material that obtains dried by the fire 2-4 hour in 120-150 ℃ baking oven, after the cooling again on three roller rubber mixing machines freshening can obtain the product sizing material 1-3 time.

The best of high-temperature-resisting silicon rubber sizing material A of the present invention is formed (weight)

100 parts of hydroxy silicon oils (107 glue, viscosity 2000-10000CP)

SiO ₂(vapor phase process 2#) 15 parts

CaCO ₃30 parts

TiO ₂20 parts

MM ^N1.8 part

Described its structural formula of silicon-nitrogen polymer C is:

n＝1～2 m＝100～200

Its synthetic method is: the MeSiCl that adds 1mol in there-necked flask ₃, the Me of 0.5mol ₂SiCL ₂With 800ml toluene, under stirring and water-bath cooling, feed NH ₃16 hours, and suitably turn down logical NH ₃Speed, logical again NH ₃About two hours, stopped reaction removes by filter ammonium chloride, uses toluene wash ammonium chloride again three times, removes with distillation and underpressure distillation and desolvates and oligomer makes silicon-nitrogen polymer C.

The sulfuration process of high-temperature-resisting silicon rubber sizing material of the present invention:

Add the silicon-nitrogen polymer C that 3-7 divides in 100 parts of above-mentioned sizing materials, mix well back degassing 5-10 minute, the potting compound or the tackiness agent that promptly can be used as self cure high-temperature resistant silicon rubber use.The surface sulfuration needs 12-24 hour, and complete cure needs 3-7 days, as the need accelerated cure, can add 0.01～0.1 part dibutyl tin laurate, and the surface just can be vulcanized in 1～8 hour, and little to the silicon rubber performance impact after the sulfuration.

Since the silicon-nitrogen polymer linking agent can be quickly with silicon rubber in hydroxyl reaction, it is cross-linking vulcanized to make this class glue carry out on-catalytic, the consumption of silicon-nitrogen polymer linking agent C is again excessive simultaneously, so can remove planar water in the sizing material and the hydroxyl in the filler again, so the main chain with silicon-nitrogen polymer linking agent C sulfurized silicon rubber is very stable, can be anti-350 ℃, shown in Fig. 1 and table 1, the silicon-nitrogen polymer linking agent is again the chain propagation agent of silicon rubber simultaneously, so than having better mechanical property with the crosslinked cross-linked rubber of orthosilicic acid second fat, as shown in table 1, its cohesive strength can improve 2-10 doubly, and is as shown in table 2.

* TS-tensile strength (kg/cm ²)

* E-elongation (%)

* * H-hardness (Shao Shi)

Added 0.05 part of dibutyl tin laurate in the * * * sizing material.

Pressing GB531-83 and GB528 method measures

* pressing the HGA-851-81 method measures.

Example 1

In beaker, be weighed into the silicon-nitrogen polymer linking agent C of 100 part of 107 raw-silastic continuously (Beijing chemical industry two factories) and 5 parts, mixing well the back outgased 3-5 minute under vacuum, pour into then in the tetrafluoroethylene mould and vulcanize, after room temperature is placed 7 days, cross-linked rubber is carried out thermal weight loss measures, the result as shown in Figure 1:

Example 2

With 1.8g hexamethyldisilazane (MM ^N) be added in 100 grams, 107 glue that (chemical industry two factories in Beijing produce, and add 15g SiO again after viscosity～5400CP) is mixed well ₂(vapor phase process 2 ^#), 30g CaCO ₃With 20g TiO ₂Kneading is 1.5 hours in kneader, takes out the back on three roller rubber mixing machines mixing for 2 times, and the sizing material that obtains dried by the fire 3 hours in 135 ℃ baking oven, after the cooling again on three roller rubber mixing machines freshening arrive for 3 times silicone rubber compounds A.

In beaker, be weighed into 100 parts of silicone rubber compounds A and 3 parts of silicon-nitrogen polymer linking agent C, mixing well the back outgased 5-10 minute under vacuum, pour into then in the mould of tetrafluoroethylene, obtain the thick sulfide film of about 2mm after the sulfuration, be cut into the test piece of inferior bell shape then, after in the test tube of 5 test pieces under 350 ℃ sealing nitrogen aging 24 hours, measure its mechanical property such as table 3.

Example 3:

Be weighed into 100 parts of silicone rubber compounds A of example 2 and 7 parts silicon-nitrogen polymer linking agent C in beaker, then by the operational condition sulfuration of example 2 with carry out thermal ageing, the result is as shown in table 4:

It is as shown in table 2 that this glue is made the binding agent result.

Example 4:

Be weighed into 100 parts SDL-1-41 sizing material (morning twilight chemical research institute two subsidiary factory's products) and 5 parts silicon-nitrogen polymer linking agent C in beaker, then by the sulfuration of the operational condition of example 2 with carry out thermal ageing, the result is as shown in table 5.

Example 5

In beaker, be weighed into 100 parts SDL-1-41, the dibutyl tin laurate of 5 parts of silicon-nitrogen polymer linking agent C and 0.05 part, then by the operational condition sulfuration of example 2 with carry out thermal ageing, the result is as shown in table 6.

Example 6

Be weighed into 100 parts SDL-1-41 sizing material in beaker, 5 parts of silicon-nitrogen polymer linking agent C and 0.1 part of dibutyl tin laurate vulcanize and carry out thermal ageing by the operational condition of example 2 then.Its result is as shown in table 7.

Description of drawings:

Fig. 1, cross-linked rubber sample thermogravimetric curve

△ 250℃ Si（OEt） ₄

■ 200℃ Si（OEt） ₄

● 350 ℃ of silicon nitrogen superpolymer C

▲ 380 ℃ of silicon nitrogen superpolymer C

Claims

1, a kind of self cure high-temperature resistant silicon rubber, it is characterized in that adopting silicon-nitrogen polymer C is that linking agent is realized, the component of described silicon rubber (weight) is:

100 parts of silicone rubber compounds

Silicon-nitrogen polymer C 3-7 part

The structural formula of described silicon-nitrogen polymer C is

n=1～2 m=100～200

Described silicone rubber compounds can be hydroxy silicon oil (107 or 108, any in viscosity 2000～10000CP) or silicone rubber compounds A or 106 glue or the SDL series sizing material.

Described silicon rubber material A contains following component (weight)

Hydroxy silicon oil (2000～10000CP) 100 parts of 107 or 108 viscosity

SiO ₂(vapor phase process 2#) 12-30 part

GaCO ₃0-50 part

TiO ₂0-25 part

ZnO ₂0-25 part

Fe ₂O ₃0-5 part

MM ^NOr D ^N ₃1.5-3 part.

2, self cure high-temperature-resisting silicon rubber according to claim 1 is characterized in that can adding in the component 0.01～0.1 two bay glue dibutyl tins.