CN112759934A - Deoximation type room temperature vulcanized silicone rubber and preparation method thereof - Google Patents
Deoximation type room temperature vulcanized silicone rubber and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种脱肟型室温硫化硅橡胶及其制备方法，涉及高分子聚合物的技术领域。以重量份计，所述脱肟型室温硫化硅橡胶的制备原料包括：有机聚硅氧烷聚合物80‑100份；增塑剂0‑20份；填料5‑30份；交联剂5‑15份；偶联剂1‑5份；所述交联剂的制备方法包括以下步骤：混合硅酸酯、丁酮肟和溶剂，加热回流反应。通过对交联剂的处理，改善了交联剂的活性，可省略添加有机锡类或金属盐类催化剂，达到基本相似的力学性能，同时，也避免出现返原现象，在受热密闭环境中，可保持较好的力学强度和硬度。The invention relates to a deoxime-type room temperature vulcanized silicone rubber and a preparation method thereof, and relates to the technical field of high molecular polymers. In parts by weight, the raw materials for preparing the deoxime-type RTV silicone rubber include: 80-100 parts of organopolysiloxane polymer; 0-20 parts of plasticizer; 5-30 parts of filler; 15 parts; 1-5 parts of coupling agent; the preparation method of the cross-linking agent comprises the following steps: mixing silicate, butanone oxime and solvent, heating and refluxing reaction. Through the treatment of the cross-linking agent, the activity of the cross-linking agent is improved, and the addition of organotin or metal salt catalysts can be omitted to achieve basically similar mechanical properties. At the same time, the phenomenon of reversion is also avoided. It can maintain good mechanical strength and hardness.
Description
Technical Field
The invention relates to the technical field of high molecular polymers, in particular to deoximation type room temperature vulcanized silicone rubber and a preparation method thereof.
Background
The oxime-removing RTV silicon rubber (oxime-removing room temperature vulcanized silicon rubber) is one of the fastest-developing products in the current domestic organic silicon market, and is mainly characterized in that: at room temperature, the curing speed of the sealant is better than that of the alcohol-type silicone sealant, and the construction is convenient. Therefore, the oxime-removing RTV silicone rubber is widely applied to the fields of civil construction, electronic and electric appliances, vehicle transportation, airplanes and ships, machinery, chemical engineering, light industry and the like.
Although great developments have been made in deoximation type RTV silicone rubbers, there are still some problems of defects to be solved, such as: in order to ensure that the oxime-removing type silicon rubber can effectively and timely perform good crosslinking curing at room temperature so as to achieve the mechanical property required by application, an organic tin catalyst or a metal salt catalyst is usually required to be added into the oxime-removing type RTV silicon rubber in the market, however, the addition of the catalyst can cause the breakage and degradation of a polymer Si-O chain segment in the silicon rubber under a heated closed environment, so that the silicon rubber is softened and even becomes liquid, namely, the phenomenon of thermal reversion occurs, and the mechanical strength and hardness of the silicon rubber are obviously reduced due to the reversion, so that the further application of the oxime-removing type RTV silicon rubber is limited.
Disclosure of Invention
Based on the above, the invention provides the deoximation type room temperature vulcanized silicone rubber, through the treatment of the cross-linking agent, the activity of the cross-linking agent is improved, the addition of an organic tin catalyst or a metal salt catalyst can be omitted, the basically similar mechanical properties are achieved, meanwhile, the reversion phenomenon is avoided, and the better mechanical strength and hardness can be maintained in a heated closed environment.
The preparation raw materials of the deoximation type room temperature vulcanized silicone rubber comprise the following components in parts by weight:
the preparation method of the cross-linking agent comprises the following steps:
mixing silicate ester, butanone oxime and solvent, heating and refluxing for reaction.
In one preferred embodiment, the reaction temperature of the heating reflux reaction is 140-180 ℃, and the reaction time is 15-25 h.
In one preferred embodiment, the weight ratio of silicate ester to butanone oxime is 50: (110-150).
In one of the preferred embodiments, the silicate is selected from methyl silicate and/or ethyl silicate.
In one preferred embodiment, the solvent is toluene.
In one preferred embodiment, the organopolysiloxane polymer is a hydroxyl terminated polydimethylsiloxane.
In one preferred embodiment, the plasticizer is a silicone oil.
In one preferred embodiment, the filler is selected from nano calcium carbonate and/or fumed silica.
In one preferred embodiment, the coupling agent is selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, epoxycyclohexylmethyltrimethoxysilane, epoxycyclohexylmethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, phenylaminomethyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropyltriethoxysilane, gamma-glycidylmethyltrimethoxysilane, gamma-, At least two of phenylaminomethyltriethoxysilane, divinyltriaminopropyltrimethoxysilane and divinyltriaminopropyltriethoxysilane.
In one preferred embodiment, the preparation raw material of the deoximation type room temperature vulcanized silicone rubber further comprises a flame retardant.
In one preferred embodiment, the preparation raw materials of the deoximation type room temperature vulcanized silicone rubber comprise the following components in parts by weight:
in one preferred embodiment, the flame retardant is selected from antimony trioxide and/or aluminum hydroxide.
The invention also provides a preparation method of the deoximation type room temperature vulcanized silicone rubber.
The preparation method of the deoximation type room temperature vulcanized silicone rubber comprises the following steps:
mixing an organopolysiloxane polymer and a plasticizer, and kneading to prepare a base;
mixing the base material, the filler, the cross-linking agent and the coupling agent, and stirring.
Compared with the prior art, the invention has the following beneficial effects:
the mixture obtained after the heating reflux reaction of the silicate ester and the butanone oxime is used as the cross-linking agent, the cross-linking activity is higher, the addition of an organic tin catalyst or a metal salt catalyst can be omitted, the mechanical property basically similar to that of the added catalyst is achieved, and the silicon rubber is prevented from being broken and degraded in a polymer Si-O chain segment under the action of the catalyst in a heated closed environment, so that the silicon rubber is softened, even liquefied, and the reversion phenomenon is caused. The obtained deoximation type room temperature vulcanized silicone rubber has good reversion resistance, and can avoid the phenomena of softening and mechanical property reduction of the silicone rubber in the application of buildings, automobiles, electronic and electric appliances and the like in a heated closed environment.
Furthermore, the deoximation type room temperature vulcanized silicone rubber can be added with a flame retardant to prepare flame-retardant type room temperature vulcanized silicone rubber, and the cross-linking agent also has higher activity.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The deoximation type room temperature vulcanized silicone rubber comprises the following preparation raw materials in parts by weight:
the preparation method of the cross-linking agent comprises the following steps:
mixing silicate ester, butanone oxime and solvent, heating and refluxing for reaction.
The mixture obtained after the heating reflux reaction of the silicate ester and the butanone oxime is used as the cross-linking agent, the cross-linking activity is higher, the addition of an organic tin catalyst or a metal salt catalyst can be omitted, the mechanical property basically similar to that of the added catalyst is achieved, and the silicon rubber is prevented from being broken and degraded in a polymer Si-O chain segment under the action of the catalyst in a heated closed environment, so that the silicon rubber is softened, even liquefied, and the reversion phenomenon is caused. The obtained deoximation type room temperature vulcanized silicone rubber has good reversion resistance, and can avoid the phenomena of softening and mechanical property reduction of the silicone rubber in the application of buildings, automobiles, electronic and electric appliances and the like in a heated closed environment.
Preferably, the reaction temperature of the heating reflux reaction is 140-180 ℃, and the reaction time is 15-25 h.
More preferably, the reaction temperature of the heating reflux reaction is 150-170 ℃, and the reaction time is 18-22 h.
It is understood that at 90 deg.C, vacuum is applied to 5-10mmHg, no distillate is regarded as the reaction is stopped, and the mixture after the reaction is finished is collected, i.e. the cross-linking agent.
Preferably, the weight ratio of the silicate ester to the butanone oxime is 50: (110-150).
More preferably, the weight ratio of the silicate ester to the butanone oxime is 50: (110-130).
Preferably, the silicate is selected from methyl silicate and/or ethyl silicate.
It is understood that methyl silicate refers to tetramethoxysilane and ethyl silicate refers to tetraethoxysilane.
Silicate ester and butanone oxime are mixed in a solvent, and the solvent is toluene.
Compared with the ketoxime silane cross-linking agent with three or four functional groups commonly used in the market, the cross-linking agent prepared by the method has higher cross-linking activity.
In a preferred embodiment, the organopolysiloxane polymer is a hydroxyl-terminated polydimethylsiloxane.
Further preferably, the hydroxy-terminated polydimethylsiloxane is an α, ω -dihydroxy polydimethylsiloxane.
In a preferred embodiment, the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is in the range of 20000 to 80000 mPas at 25 ℃.
In a preferred embodiment, the plasticizer is a silicone oil.
In a preferred embodiment, the silicone oil has a viscosity of 350 mPas at 25 ℃.
In a preferred embodiment, the filler is selected from nano calcium carbonate and/or fumed silica.
In a preferred embodiment, the coupling agent is selected from the group consisting of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, epoxycyclohexylmethyltrimethoxysilane, epoxycyclohexylmethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidylmethyltriethoxysilane, gamma-glycidylmethyltrimethoxysilane, gamma-glycid, At least two of divinyltriaminopropyltrimethoxysilane and divinyltriaminopropyltriethoxysilane.
In a preferred embodiment, the preparation raw material of the deoximation type room temperature vulcanized silicone rubber further comprises a flame retardant. After the flame retardant is added into the deoximation type room temperature vulcanized silicone rubber system, the cross-linking agent can also exert higher cross-linking activity, the addition of organic tin or metal salt catalysts can be omitted, and the mechanical property basically similar to that of the added catalysts can be achieved. The flame retardant is added, and on the basis of the effects, the flame retardant property of the room temperature vulcanized silicone rubber is also endowed, so that the application range of the room temperature vulcanized silicone rubber is wider.
In a preferred embodiment, the preparation raw materials of the deoximation type room temperature vulcanized silicone rubber comprise the following components in parts by weight:
in a preferred embodiment, the flame retardant is selected from antimony trioxide and/or aluminum hydroxide.
A preparation method of deoximation type room temperature vulcanized silicone rubber comprises the following steps:
mixing an organopolysiloxane polymer and a plasticizer, and kneading to prepare a base;
mixing the base material, the filler, the cross-linking agent and the coupling agent, and stirring.
It will be appreciated that the kneading step may be carried out in a kneader, and the organopolysiloxane polymer and plasticizer may be added to the kneader, preferably arranged: the temperature is 100 ℃ to 130 ℃, the vacuum degree is-0.06 MPa to-0.099 MPa, the mixture is dehydrated and blended for 60 minutes to 180 minutes, and the base material is obtained after cooling.
In a preferred embodiment, the preparation raw material of the deoximation type room temperature vulcanized silicone rubber further comprises a flame retardant, and during preparation, the organic polysiloxane polymer, the plasticizer and the flame retardant are mixed and kneaded to prepare the base material. That is, the organopolysiloxane polymer, plasticizer, and flame retardant are added to the kneader, preferably setting: the temperature is 100 ℃ to 130 ℃, the vacuum degree is-0.06 MPa to-0.099 MPa, the mixture is dehydrated and blended for 60 minutes to 180 minutes, and the base material is obtained after cooling.
It will be appreciated that the agitation step may be carried out in a planetary mixer, to which the above-mentioned binders, fillers, crosslinking agents and coupling agents may be added, preferably arranged: the vacuum degree is-0.08 MPa to-0.099 MPa, the rotating speed is 300rpm to 800rpm, and the stirring time is 30 minutes to 120 minutes, so that the deoximation type room temperature vulcanized silicone rubber is obtained.
The following examples and comparative examples are further described below, and the starting materials used in the following examples can be commercially available, unless otherwise specified, and the equipment used therein can be commercially available, unless otherwise specified. The parts of the related raw materials are calculated by weight parts except for special description.
Example 1
The embodiment provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of the crosslinking agent
Mixing 50 parts of methyl silicate, 120 parts of butanone oxime and 200 parts of toluene, heating and refluxing for 20 hours at 160 ℃, then vacuumizing to 5-10mmHg at 90 ℃, considering no distillate as the reaction stop, and collecting the mixture after the reaction is finished, namely the cross-linking agent.
(2) Preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 20000 mPas at 25 ℃ and 80 parts of antimony trioxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 180min under the conditions that the vacuum degree is 0.095MPa and the temperature is 100 ℃, cooled and discharged to obtain the base material.
(3) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 30 parts of nano calcium carbonate, 15 parts of the cross-linking agent, 1 part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 4 parts of gamma-aminopropyl trimethoxy silane are added into a planetary stirrer with the base material and stirred for 90 minutes at the vacuum degree of 0.095Mpa and the rotating speed of 500rpm, so as to prepare the oxime-removing room temperature vulcanized silicone rubber.
Comparative example 1
The comparative example provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, which are basically the same as the example 1, mainly have the difference that the crosslinking agent is different, and the specific steps are as follows:
(1) preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 20000 mPas at 25 ℃ and 80 parts of antimony trioxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 180min under the conditions that the vacuum degree is 0.095MPa and the temperature is 100 ℃, cooled and discharged to obtain the base material.
(2) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 30 parts of nano calcium carbonate, 15 parts of a cross-linking agent, 10 parts of methyl tributyl ketoxime silane, 5 parts of vinyl tributyroxime silane, 1 part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 4 parts of gamma-aminopropyl trimethoxy silane and 0.5 part of dibutyltin diacetate are added into a planetary stirrer with the base material and stirred for 90 minutes at the vacuum degree of 0.095Mpa and the rotating speed of 500rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Example 2
The embodiment provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of the crosslinking agent
Mixing 50 parts of methyl silicate, 120 parts of butanone oxime and 200 parts of toluene, heating and refluxing for 20 hours at 160 ℃, then vacuumizing to 5-10mmHg at 90 ℃, considering no distillate as the reaction stop, and collecting the mixture after the reaction is finished, namely the cross-linking agent.
(2) Preparation of the base stock
90 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 50000 mPas at 25 ℃, 60 parts of aluminum hydroxide and 10 parts of silicone oil are added into a kneader, and the mixture is blended, dehydrated and kneaded for 60min under the conditions that the vacuum degree is 0.06MPa and the temperature is 130 ℃, cooled and discharged to obtain the base material.
(3) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 15 parts of white carbon black, 10 parts of the cross-linking agent, 2 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1 part of gamma-aminopropyl trimethoxy silane are added into a planetary stirrer filled with the base material and stirred for 120 minutes at the vacuum degree of 0.08Mpa and the rotating speed of 300rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Comparative example 2
The comparative example provides a deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, which are basically the same as the example 2, mainly have the difference that the cross-linking agent is different, and the specific steps are as follows:
(1) preparation of the base stock
90 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 50000 mPas at 25 ℃, 60 parts of aluminum hydroxide and 10 parts of silicone oil are added into a kneader, and the mixture is blended, dehydrated and kneaded for 60min under the conditions that the vacuum degree is 0.06MPa and the temperature is 130 ℃, cooled and discharged to obtain the base material.
(2) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 15 parts of white carbon black, 5 parts of methyl tributyl ketoxime silane, 5 parts of vinyl tributyrinoxime silane, 2 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 1 part of gamma-aminopropyl trimethoxy silane and 2 parts of dibutyltin diacetate are added into a planetary stirrer with the base material and stirred for 120 minutes at the vacuum degree of 0.08Mpa and the rotating speed of 300rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Example 3
The embodiment provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of the crosslinking agent
Mixing 50 parts of ethyl silicate, 150 parts of butanone oxime and 200 parts of toluene, heating and refluxing for 15 hours at 180 ℃, then vacuumizing to 5-10mmHg at 90 ℃, considering no distillate as the reaction stop, and collecting the mixture after the reaction is finished, namely the cross-linking agent.
(2) Preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 30000 mPas at 25 ℃ and 80 parts of aluminum hydroxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 120min under the conditions that the vacuum degree is 0.09MPa and the temperature is 110 ℃, cooled and discharged to obtain the base material.
(3) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, adding 10 parts of nano calcium carbonate, 10 parts of the cross-linking agent, 1 part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1 part of gamma-aminopropyl trimethoxy silane into a planetary stirrer filled with the base material, and stirring for 30 minutes at the vacuum degree of 0.08Mpa and the rotating speed of 800rpm to prepare the oxime-removed room temperature vulcanized silicone rubber.
Comparative example 3
The comparative example provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, which are basically the same as the example 1, mainly have the difference that the crosslinking agent is different, and the specific steps are as follows:
(1) preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 30000 mPas at 25 ℃ and 80 parts of aluminum hydroxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 120min under the conditions that the vacuum degree is 0.09MPa and the temperature is 110 ℃, cooled and discharged to obtain the base material.
(2) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 10 parts of nano calcium carbonate, 5 parts of methyl tributyrinoxime silane, 5 parts of vinyl tributyrinoxime silane, 1 part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 1 part of gamma-aminopropyl trimethoxy silane and 1 part of dibutyl tin dilaurate are added into a planetary stirrer with the base material, and stirred for 30 minutes at the vacuum degree of 0.08Mpa and the rotating speed of 800rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Example 4
The embodiment provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of the crosslinking agent
Mixing 50 parts of ethyl silicate, 110 parts of butanone oxime and 200 parts of toluene, heating and refluxing for 24 hours at 140 ℃, then vacuumizing to 5-10mmHg at 90 ℃, considering no distillate as the reaction stop, and collecting the mixture after the reaction is finished, namely the cross-linking agent.
(2) Preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 80000 mPas at 25 ℃, 20 parts of silicone oil and 40 parts of antimony trioxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 150min under the conditions that the vacuum degree is 0.08MPa and the temperature is 120 ℃, cooled and discharged to obtain the base material.
(3) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 5 parts of white carbon black, 5 parts of the cross-linking agent, 2 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 1 part of gamma-aminopropyl trimethoxy silane are added into a planetary stirrer filled with the base material and stirred for 90 minutes at the vacuum degree of 0.09Mpa and the rotating speed of 600rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Comparative example 4
The comparative example provides deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, which are basically the same as the example 1, mainly have the difference that the crosslinking agent is different, and the specific steps are as follows:
(1) preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 80000 mPas at 25 ℃, 20 parts of silicone oil and 40 parts of antimony trioxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 150min under the conditions that the vacuum degree is 0.08MPa and the temperature is 120 ℃, cooled and discharged to obtain the base material.
(2) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 5 parts of white carbon black, 4 parts of methyl tributyl ketoxime silane, 1 part of vinyl tributanoximosilane, 2 parts of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 1 part of gamma-aminopropyl trimethoxy silane and 3 parts of dibutyl tin dilaurate are added into a planetary stirrer with the base materials, and stirred for 90 minutes at the vacuum degree of 0.09Mpa and the rotating speed of 600rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Comparative example 5
The comparative example provides a deoximation type room temperature vulcanized silicone rubber and a preparation method thereof, which are basically the same as the comparative example 1, and mainly have the difference that a catalyst of dibutyltin diacetate is not added, and the specific steps are as follows:
(1) preparation of the base stock
100 parts of alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 20000 mPas at 25 ℃ and 80 parts of antimony trioxide are added into a kneader, and the mixture is blended, dehydrated and kneaded for 180min under the conditions that the vacuum degree is 0.095MPa and the temperature is 100 ℃, cooled and discharged to obtain the base material.
(2) Preparation of deoximation type room temperature vulcanized silicone rubber
At room temperature, 30 parts of nano calcium carbonate, 15 parts of a cross-linking agent, 10 parts of methyl tributyrinoxime silane, 5 parts of vinyl tributyrinoxime silane, 1 part of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 4 parts of gamma-aminopropyl trimethoxy silane are added into a planetary stirrer with the base material and stirred for 90 minutes at the vacuum degree of 0.095Mpa and the rotating speed of 500rpm to prepare the deoximation type room temperature vulcanized silicone rubber.
Performance testing
Testing tensile strength and hardness according to GB/T16776 sample preparation, curing for 7 days under standard conditions after all test pieces are prepared, wherein one group is directly tested, and the other group is placed in a closed container and dried at 250 ℃ for 3 days and then tested; the flame retardancy was tested according to the corresponding specification GB/T24267. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the organic tin catalyst is not added in any of examples 1 to 4, and the prepared silicone rubber has mechanical properties basically similar to those of the silicone rubber prepared by adding the organic tin catalyst in comparative examples 1 to 4, so that the reversion phenomenon is avoided, and the silicone rubber can keep better mechanical strength and hardness in a heated closed environment.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The deoximation type room temperature vulcanized silicone rubber is characterized by comprising the following preparation raw materials in parts by weight:
the preparation method of the cross-linking agent comprises the following steps:
mixing silicate ester, butanone oxime and solvent, heating and refluxing for reaction.
2. The deoximation type room temperature silicon sulfide rubber according to claim 1, wherein the reaction temperature of the heating reflux reaction is 140 ℃ to 180 ℃, and the reaction time is 15h to 25 h.
3. The deoximation type room temperature silicon sulfide rubber according to claim 2, wherein the weight ratio of the silicate ester to the butanone oxime is 50: (110-150).
4. The deoximation type room temperature silicon sulfide rubber according to claim 3, wherein the silicate is selected from methyl silicate and/or ethyl silicate.
5. The deoximation type room temperature silicon sulfide rubber according to claim 1, wherein the solvent is toluene.
6. The deoximation type room temperature silicon sulfide rubber according to any one of claims 1 to 5, wherein the organopolysiloxane polymer is a hydroxyl-terminated polydimethylsiloxane; and/or the presence of a gas in the gas,
the plasticizer is silicone oil; and/or the presence of a gas in the gas,
the filler is selected from nano calcium carbonate and/or fumed silica; and/or the presence of a gas in the gas,
the coupling agent is selected from gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, epoxycyclohexylmethyltrimethoxysilane, epoxycyclohexylmethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, phenylaminomethyltrimethoxysilane, phenylaminomethyltriethoxysilane, and mixtures thereof, At least two of divinyltriaminopropyltrimethoxysilane and divinyltriaminopropyltriethoxysilane.
7. The deoximation type room temperature silicon sulfide rubber according to any one of claims 1 to 5, wherein a preparation raw material of the deoximation type room temperature silicon sulfide rubber further comprises a flame retardant.
8. The deoximation type room temperature silicon sulfide rubber according to claim 7, which is prepared from the following raw materials in parts by weight:
9. the deoximation type room temperature silicon sulfide rubber according to claim 8, wherein the flame retardant is selected from antimony trioxide and/or aluminum hydroxide.
10. A method for producing the deoximation type room temperature vulcanizing silicone rubber according to any one of claims 1 to 9, comprising the steps of:
mixing an organopolysiloxane polymer and a plasticizer, and kneading to prepare a base;
mixing the base material, the filler, the cross-linking agent and the coupling agent, and stirring.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605961A (en) * | 2022-03-02 | 2022-06-10 | 广州集泰化工股份有限公司 | Two-component sealant and preparation method and application thereof |
| CN115785527A (en) * | 2022-12-28 | 2023-03-14 | 佛山市普力达科技有限公司 | Coupling agent for accelerating deep curing, preparation method and transparent RTV (room temperature vulcanized) applied by coupling agent |
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| US4657967A (en) * | 1986-04-07 | 1987-04-14 | Dow Corning Corporation | Room temperature curing compositions containing tetrafunctional ethoxy-ketoximo silane crosslinkers |
| US4973623A (en) * | 1989-05-26 | 1990-11-27 | Dow Corning Corporation | Fast curing oximo-ethoxy functional siloxane sealants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4657967A (en) * | 1986-04-07 | 1987-04-14 | Dow Corning Corporation | Room temperature curing compositions containing tetrafunctional ethoxy-ketoximo silane crosslinkers |
| US4973623A (en) * | 1989-05-26 | 1990-11-27 | Dow Corning Corporation | Fast curing oximo-ethoxy functional siloxane sealants |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605961A (en) * | 2022-03-02 | 2022-06-10 | 广州集泰化工股份有限公司 | Two-component sealant and preparation method and application thereof |
| CN115785527A (en) * | 2022-12-28 | 2023-03-14 | 佛山市普力达科技有限公司 | Coupling agent for accelerating deep curing, preparation method and transparent RTV (room temperature vulcanized) applied by coupling agent |
| CN115785527B (en) * | 2022-12-28 | 2023-09-12 | 佛山市普力达科技有限公司 | Accelerated deep curing coupling agent, preparation method and transparent RTV (real time kinematic) applied to same |
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