CN102492145A - Preparation method for high molecular weight raw rubber of methyl phenyl siloxane rubber - Google Patents
Preparation method for high molecular weight raw rubber of methyl phenyl siloxane rubber Download PDFInfo
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- CN102492145A CN102492145A CN2011104037730A CN201110403773A CN102492145A CN 102492145 A CN102492145 A CN 102492145A CN 2011104037730 A CN2011104037730 A CN 2011104037730A CN 201110403773 A CN201110403773 A CN 201110403773A CN 102492145 A CN102492145 A CN 102492145A
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Abstract
The invention relates to the field of rubber preparation, in particular to a preparation method for high molecular weight raw rubber of methyl phenyl siloxane rubber, which is characterized by including: adding siloxane, an end socket agent and an additive into a dehydration kettle to dehydrate, pressing the siloxane, the end socket agent and the additive into a polymerizer after dehydration, adding silanol lithium as a catalyst to polymerize, adding phosphoric acid to neutralize materials in the polymerizer to reach a pH ranging from 6 to 7 after polymerization, and finally desorbing low molecular weight raw rubber of the methyl phenyl siloxane rubber to obtain the high molecular weight raw rubber of the methyl phenyl siloxane rubber under the vacuum condition. The obtained product is high in molecular weight, reaches the molecular weight of higher than 1million, and is low in volatile matter and transparent in product appearance.
Description
Technical field
The present invention relates to the preparation field of rubber, be specifically related to a kind of preparation method of HMW methyl phenyl silicone rubber.
Background technology
Methyl silicone rubber has advantages such as good thermostability, electrical insulating property, weathering resistance, ozone resistance, ventilation property, very high transparency, good thermal diffusivity and excellent cohesiveness, flowability; And phenyl siloxane rubber is because the introducing of bulky group is damaged the regularity of polymer chain; Changed the reactive force between polymer molecule simultaneously; It is had than methyl polysilicon rubber have better resistance to low temperature, resistance to elevated temperatures, damping capacity, anti-ablation and radiation resistance.
The preparation of methyl phenyl silicone rubber rubber generally adopts the silicon alkoxide of Pottasium Hydroxide, sodium hydroxide or quaternary ammonium hydroxide as catalyzer; Adopt such catalyzer can cause rubber polymeric molecular weight chain link on the low side or low-molecular-weight more, cause MWD uneven.Adopt that traditional prepared methyl phenyl silicone rubber exists generally that phenyl content is lower, MWD is uneven, reaction process is difficult to control and the unstable situation of products production.
Summary of the invention
The objective of the invention is the problem to the prior art existence, a kind of preparation method of HMW methyl phenyl silicone rubber rubber is provided, this method technology is simple, and polyreaction is controlled, the product homogeneous.
The present invention mainly realizes through following technical scheme, specifically comprises:
Siloxanes is added dehydration with closure agent to dewater in the still; Be pressed in the polymeric kettle after the dehydration; Add the silanol lithium and carry out polymerization as catalyzer; After polymerization was accomplished, adding phosphoric acid, the material in the polymeric kettle is neutralized to pH was 6～7, under vacuum condition, removed the secure satisfactory grades methyl phenyl silicone rubber rubber of son amount of low molecule in the material at last.Said siloxanes is benzyl ring trisiloxanes (being called for short A3), or the mixture of benzyl ring trisiloxanes and octamethylcyclotetrasiloxane (being called for short D4), or benzyl ring trisiloxanes and methyl cyclosiloxane (being called for short DMC) mixture.
Be that in the said mixture of siloxanes, the weight ratio of benzyl ring trisiloxanes and octamethylcyclotetrasiloxane or methyl cyclosiloxane is: 5～100: 95～0 wherein when selecting mixture of siloxanes.
Wherein dehydration conditions is preferably: vacuum tightness-0.01～-0.095Mpa, 60～80 ℃ of temperature of reaction, dewatering time 2～4 hours.
Polymerization temperature is preferably: 130～190 ℃, polymerization time is preferably: 4～6 hours, preferably perhaps lead to nitrogen bubble with micro-vacuum during polymerization.
The condition optimization that removes low minute substep in the material is: temperature is 160～200 ℃, 2～4 hours time.
Closure agent is preferably from vinyl double-seal head agent (being tetramethyl divinyl disiloxane), hydroxy silicon oil or low viscous methyl-silicone oil (preferred 5-10cs).
Wherein the add-on of closure agent is preferably 0.1～1wt% of siloxanes weight.
Also preferred auxiliary agent, the preferred tetramethyl-tetrem of the auxiliary agent thiazolinyl cyclotetrasiloxane of adding when siloxanes and closure agent reaction.
The add-on of auxiliary agent is preferably 0.05～5wt% of siloxanes weight.
The add-on of catalyzer silanol lithium is preferably 0.25～5wt% of siloxanes.
The invention has the advantages that: the molecular weight of products obtained therefrom is high, and molecular weight reaches more than 1,000,000, and fugitive constituent is low, and product appearance is transparent.It molecular weight polymerizedly is not more than 600,000 to adopt sodium silanolate to make catalyzer, and in polymerization process, occurs unsuitable polymerization or cracking situation more easily, causes molecular weight less.
Embodiment
Embodiment 1
150kgA3,850kgD4 and 2kg vinyl double-seal head are joined the dehydration still, at 70 ℃, vacuum tightness is-0.02～-0.095Mpa dehydration 2hr down; Material after the dehydration is pressed into polymeric kettle, adds 2.5kg silanol lithium catalyst, the drying nitrogen bubbling; Be warming up to 175 ℃, reactive polymeric 5hr.Add among the phosphoric acid 2kg and stir 1hr, survey pH=6, after reaction is accomplished, stop logical nitrogen with material, vacuumize (133～1330Pa), be warming up to 180 ℃, remove low molecule 2hr, be chilled to 90 ℃, through the forcing machine extruded material.
Embodiment 2
Repeat embodiment 1 said step, the vinyl double-seal head in the mixture is changed into to add the 2kg hydroxyl value be 6% hydroxy silicon oil.
Embodiment 3
Repeat embodiment 1 said step, the vinyl double-seal head in the mixture is changed into to add the 2kg hydroxyl value be 6% hydroxy silicon oil and 2kg second ring.
Embodiment 4
Repeat embodiment 1 said step, change the vinyl double-seal head in the mixture into adding 2kg methyl-silicone oil and 2kg second ring.
Embodiment 5
Repeat embodiment 1 said step, change the polymerization temperature of material into 135 ℃.
Embodiment 6
Repeat embodiment 1 said step, the D4 in the mixture changes DMC into.
Embodiment 7
1000kgA3 and 2kg vinyl double-seal head are joined the dehydration still, at 70 ℃, vacuum tightness is-0.02～-0.095Mpa dehydration 2hr down; Material after the dehydration is pressed into polymeric kettle, adds 2.5kg silanol lithium catalyst, the drying nitrogen bubbling; Be warming up to 175 ℃, reactive polymeric 5hr.Add among the phosphoric acid 2kg and stir 1hr, survey pH=6, after reaction is accomplished, stop logical nitrogen with material, vacuumize (133～1330Pa), be warming up to 180 ℃, remove low molecule 2hr, be chilled to 90 ℃, through the forcing machine extruded material.The product performance test
1, the molecular weight of test methyl phenyl silicone rubber rubber
Adopt the Ubbelohde viscosimetry to measure the limiting viscosity of aminomethyl phenyl rubber, obtain corresponding molecular weight.The solvent that adopts is toluene (AR), and probe temperature is 25 ℃.
2, the contents of ethylene of test methyl phenyl silicone rubber
Adopt the chemical titration test according to the contents of ethylene in the methyl phenyl silicone rubber rubber.The solvent that adopts is toluene (AR), and probe temperature is 25 ℃.
3, the mensuration of methyl phenyl silicone rubber volatile matter
Adopt thermogravimetry to measure volatile content.Probe temperature is 150 ℃.
Wherein comparative example 1 is: repeat embodiment 1 described step, the catalyzer that polymerization is adopted changes sodium silanolate into, and the silanol lithium is identical among its alkali content and the embodiment 1.
Embodiment result sees table 1:
Table 1
Visible from table 1, it is high that the present invention uses the silanol lithium to make behind the catalyzer molecular weight of synthesis of methyl phenyl raw-silastic continuously, can reach more than 1,000,000, and the volatile matter of rubber is few.
Claims (10)
1. the preparation method of a HMW methyl phenyl silicone rubber rubber; Comprise: with dewatering in siloxanes and the closure agent adding dehydration still; Be pressed into after the dehydration in the polymeric kettle, add catalyzer and carry out polymerization, after polymerization is accomplished; It is 6～7 that adding phosphoric acid is neutralized to pH with the material in the polymeric kettle; The secure satisfactory grades methyl phenyl silicone rubber rubber of son amount of the last low molecule that under vacuum condition, removes in the material, said siloxanes is benzyl ring trisiloxanes, benzyl ring trisiloxanes and octamethylcyclotetrasiloxane mixture or benzyl ring trisiloxanes and methyl ring siloxane mixture, it is characterized in that: said catalyzer is the silanol lithium.
2. the preparation method of claim 1, wherein dehydration conditions be vacuum tightness-0.01～-0.095Mpa, 60～80 ℃ of temperature of reaction, dewatering time 2～4 hours.
3. the preparation method of claim 1, wherein polymerization temperature is 130～190 ℃, polymerization time is 4～6 hours, is micro-vacuum or logical nitrogen bubble during polymerization.
4. the preparation method of claim 1, wherein remove the condition of low minute substep in the material: temperature is 160～200 ℃, 2～4 hours time.
5. the preparation method of claim 1, wherein closure agent is selected from tetramethyl divinyl disiloxane, hydroxy silicon oil or low viscous methyl-silicone oil.
6. the preparation method of claim 1, wherein the add-on of closure agent is 0.1～1wt% of siloxanes.
7. the preparation method of claim 1 also adds auxiliary agent when wherein siloxanes and closure agent react, and auxiliary agent is a tetramethyl-tetrem thiazolinyl cyclotetrasiloxane.
8. the preparation method of claim 1, wherein the add-on of auxiliary agent is 0.05～5wt% of siloxanes.
9. the preparation method of claim 1, wherein the add-on of silanol lithium is 0.25～5wt% of siloxanes.
10. the preparation method of claim 1, benzyl ring trisiloxanes in the wherein said mixture of siloxanes: the weight ratio of octamethylcyclotetrasiloxane or methyl cyclosiloxane is: 5～100: 95～0.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011104037730A CN102492145A (en) | 2011-12-07 | 2011-12-07 | Preparation method for high molecular weight raw rubber of methyl phenyl siloxane rubber |
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| CN2011104037730A CN102492145A (en) | 2011-12-07 | 2011-12-07 | Preparation method for high molecular weight raw rubber of methyl phenyl siloxane rubber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976422A (en) * | 2018-06-15 | 2018-12-11 | 北京石油化工学院 | A kind of high viscosity bumper and absorbing shock phenyl siloxane rubber and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4551515A (en) * | 1984-02-27 | 1985-11-05 | General Electric Company | Process for the continuous manufacture of silicone gums |
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2011
- 2011-12-07 CN CN2011104037730A patent/CN102492145A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4551515A (en) * | 1984-02-27 | 1985-11-05 | General Electric Company | Process for the continuous manufacture of silicone gums |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976422A (en) * | 2018-06-15 | 2018-12-11 | 北京石油化工学院 | A kind of high viscosity bumper and absorbing shock phenyl siloxane rubber and preparation method thereof |
| CN108976422B (en) * | 2018-06-15 | 2021-03-16 | 北京石油化工学院 | High-viscosity buffering and damping phenyl silicone rubber and preparation method thereof |
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Application publication date: 20120613 |