CN106433146A - Room-temperature vulcanization heat-resistant silicon rubber with active hydrogen based cage structure and preparation method thereof - Google Patents

Room-temperature vulcanization heat-resistant silicon rubber with active hydrogen based cage structure and preparation method thereof Download PDF

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Publication number
CN106433146A
CN106433146A CN201610809804.5A CN201610809804A CN106433146A CN 106433146 A CN106433146 A CN 106433146A CN 201610809804 A CN201610809804 A CN 201610809804A CN 106433146 A CN106433146 A CN 106433146A
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rubber
silicon rubber
solvent
room temperature
catalyst
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葛铁军
张瑾
肖尚雄
张煜新
赵越
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/549Silicon-containing compounds containing silicon in a ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/21Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04Polysiloxanes
    • C08J2383/07Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses room-temperature vulcanization heat-resistant silicon rubber with an active hydrogen based cage structure and a preparation method thereof, and in particular relates to silicon rubber and a preparation method thereof. The silicon rubber is prepared from the raw materials of vinylsiloxane rubber, a crosslinking agent, a solvent, a Pt catalyst, and PC610 with the following percentages by weight: 60-70% of the vinylsiloxane rubber, 2-4% of the crosslinking agent,30-40% of cyclohexane, 0.3-0.5% of the Pt catalyst, and 0.01-0.02% of an inhibitor. Polyhedral oligomeric silsesquioxane (POSS) is added into a vinylsiloxane rubber system in a mode of chemical bonding, and under the action of the catalyst, the polyhedral oligomeric silsesquioxane and vinylsiloxane rubber are subjected to an addition reaction, so that the crosslinking density of the silicon rubber is improved, and POSS reinforced novel room-temperature vulcanization silicon rubber with good thermal stability and mechanical properties is prepared.

Description

A kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure and its preparation Method
Technical field
The present invention relates to a kind of silicone rubber and preparation method thereof, more particularly to a kind of with active hydrogen-based cage structure Room temperature vulcanization heat-resistant silicon rubber and preparation method thereof.
Background technology
Silicone rubber is due to the characteristic such as its excellent resistant of high or low temperature, weatherability, ozone resistance and electric property, and adds phase The filler that answers can make the conductive rubber of various uses, heat conductive rubber, thus in aerospace field, be mainly used as spacecraft table Facestock material binders for coatings etc., it turns out that, severe spatial environmentss can destroy polymeric material, therefore improve the resistance to of silicone rubber Hot have very important significance.
Silastic elastomer is typically to adopt containing hydrogen silicone oil as cross-linking agent at present, but the silicon rubber heat-resisting temperature after solidification Tend not to meet operation requirement, heat stability and mechanical property are poor.
Cage-type silsesquioxane (POSS), its general molecular formula is(RSiO3/2n.It is that the organic-inorganic that latest development is got up is received Nano composite material, with excellent thermal stability and mechanical property, is added in the middle of silicone rubber not only as cross-linking agent The heat stability that silicone rubber can be improved can also improve its mechanical property.
Content of the invention
It is an object of the invention to provide a kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure and its Preparation method, the octahydro base cage-type silsesquioxane for preparing is reacted with silicone rubber by the present invention as cross-linking agent, improves silicone rubber Crosslink density, improve silicon rubber heat-resisting temperature while, improve silicone rubber heat stability and its mechanical property.
The purpose of the present invention is achieved through the following technical solutions:
A kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure, octahydro base cage-type silsesquioxane selected by raw material (T8H8), it is by trichlorosilane, solvent, catalyst, and concentrated hydrochloric acid is obtained by hydrolysis-condensation reaction, and proportioning is as follows(Mass fraction):Three Chlorosilane 7%-8%, solvent 75%-80%, catalyst 10%-15%, concentrated hydrochloric acid 4%-6%, react as follows:
A kind of described described room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure, solvent is methanol, toluene, Normal hexane, two or three of combination in petroleum ether.
A kind of described room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cagelike structure, catalyst is anhydrous tri-chlorination One kind in aluminum or ferric chloride.
A kind of described room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cagelike structure, vinyl silicon selected by raw material Rubber, cross-linking agent, solvent, Pt platinum catalyst, PC610, are prepared by following weight ratio (%):Vinylsiloxane rubber 60%- 70%, cross-linking agent 2%-4%, 0. 3%-0. 5% of hexamethylene 30%-40%, Pt catalyst, inhibitor 0.01%-0.02%, reactional equation Formula is as follows:
A kind of described room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure, described vinylsiloxane rubber, glues Spend for 20000MPa.s;
A kind of room temperature vulcanization heat-resistant silicon rubber preparation method with active hydrogen-based cage structure, comprises the following steps:
(1)The preparation of octahydro base cage-type silsesquioxane
Catalyst and concentrated hydrochloric acid being added in there-necked flask, is subsequently added and solvent is also added in there-necked flask, stirs 30 min By HSiCl3It is dissolved in solvent, is slowly dropped in 6h in flask, after completion of dropping, continues quick stirring 1h, course of reaction Not higher than 60 DEG C of middle control system temperature, reacts in N2Carry out under gas shield, after completion of the reaction separately normal hexane layer, will band The normal hexane layer for having a small amount of tan crystals is filtered, and filtrate adds anhydrous C aC l2And anhydrous K2CO3It is stirred overnight, filters;Will The distillation of gained liquid pressure-reducing is filtered, crystal precipitation has been concentrated into, products therefrom has been collected, then is washed with solvent 2 times, obtain product T8H8
(2)The preparation of addition type room temperature vulcanized silicone rubber
Weigh cage modle octahydro base silsesquioxane(POSS)In beaker, hexamethylene is used as solvent so as to dissolve, and adds vinyl Silicone rubber, makes its mixing with Glass rod stirring;Evacuation de-bubble in vacuum drying oven is put into, then, PC610 inhibitor is added, Platinum catalyst is added after Glass rod stirring and evenly mixing, put into after stirring evenly under room temperature environment, until silicone rubber becomes to have the bullet of hardness Gonosome.
Advantages of the present invention with effect is:
In the present invention, octahydro base cage-type silsesquioxane is added in vinylsiloxane rubber as cross-linking agent.Its heat resisting temperature can More than 400 DEG C are reached, the heat stability of silicone rubber compared with the cross-linking agent such as containing hydrogen silicone oil, is not only substantially increased, is also improved The combination properties such as its mechanical property, expand the range of application of cage-type silsesquioxane.
Specific embodiment
With reference to embodiment, the present invention is described in detail.
Do not do in following instance illustrate refer both to mass percent.
In embodiment, raw material removes specified otherwise, is commercial.
Implement raw materials used:
Vinylsiloxane rubber
Cross-linking agent is homemade octahydro base cage-type silsesquioxane
Catalyst is Pt platinum catalyst
Inhibitor is PC610
Solvent is hexamethylene
Embodiment 1
Weigh the cage modle octahydro base silsesquioxane that mass fraction is 2.5%(POSS)In beaker, 35% hexamethylene is used as molten Agent so as to dissolve.64.2% vinylsiloxane rubber is added, and its mixing is made with Glass rod stirring.It is put in vacuum drying oven and takes out very Empty de-bubble.Then, 0.02%PC610 inhibitor being added, 0.45% platinum catalyst is added after Glass rod stirring and evenly mixing, is put after stirring evenly Under entering to room temperature environment, a period of time is placed, until silicone rubber becomes the elastomer for having certain degree of hardness.
Embodiment 2
Weigh the cage modle octahydro base silsesquioxane that mass fraction is 3%(POSS)In beaker, 35% hexamethylene as solvent, Make its dissolving.64.2% vinylsiloxane rubber is added, and its mixing is made with Glass rod stirring.It is put into evacuation in vacuum drying oven De-bubble.Then, 0.02%PC610 inhibitor being added, 0.45% platinum catalyst is added after Glass rod stirring and evenly mixing, is put into after stirring evenly To under room temperature environment, a period of time is placed, until silicone rubber becomes the elastomer for having certain degree of hardness.
Embodiment 3
Weigh the cage modle octahydro base silsesquioxane that mass fraction is 4%(POSS)In beaker, 35% hexamethylene as solvent, Make its dissolving.64.2% vinylsiloxane rubber is added, and its mixing is made with Glass rod stirring.It is put into evacuation in vacuum drying oven De-bubble.Then, 0.02%PC610 inhibitor being added, 0.45% platinum catalyst is added after Glass rod stirring and evenly mixing, is put into after stirring evenly To under room temperature environment, a period of time is placed, until silicone rubber becomes the elastomer for having certain degree of hardness.
Comparative example
Weigh mass fraction be 3% containing hydrogen silicone oil in beaker, add 64.2% vinyl silicon 2%PC610 inhibitor, glass 0.45% platinum catalyst being added after rod stirring and evenly mixing, is put under room temperature environment after stirring evenly, places a period of time, until silicon rubber Glue becomes the elastomer for having certain degree of hardness.
.
Can be seen that in embodiment 1-3 by data in form adds octahydro base cage-type silsesquioxane to add as cross-linking agent Enter in the middle of vinylsiloxane rubber, due to eight summits of cage-type silsesquioxane be respectively connected with double in Si -- H bond and silicone rubber There is hydrosilylation in key, improve the crosslink density of silicone rubber, and then improve the heat stability of silicone rubber, cage model sesquialter Siloxane structure characteristic, can function as reinforcing agent, improve the mechanical property of silicone rubber.

Claims (6)

1. a kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure, it is characterised in that octahydro base cage selected by raw material Type silsesquioxane(T8H8), it is by trichlorosilane, solvent, catalyst, and concentrated hydrochloric acid is obtained by hydrolysis-condensation reaction, and proportioning is as follows (Mass fraction):Trichlorosilane 7%-8%, solvent 75%-80%, catalyst 10%-15%, concentrated hydrochloric acid 4%-6%, react as follows:
.
2. described a kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure according to claim 1, It is characterized in that solvent is methanol, toluene, and normal hexane, two or three of combination in petroleum ether.
3. a kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cagelike structure according to claim 1, its feature It is catalyst for the one kind in aluminum trichloride (anhydrous) or ferric chloride.
4. a kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cagelike structure according to claim 1, its feature It is that raw material, from vinylsiloxane rubber, cross-linking agent, solvent, Pt platinum catalyst, PC610, is joined by following weight ratio (%) System:Vinylsiloxane rubber 60%-70%, cross-linking agent 2%-4%, 0. 3%-0. 5% of hexamethylene 30%-40%, Pt catalyst, inhibitor 0.01%-0.02%, reaction equation is as follows:
.
5. a kind of room temperature vulcanization heat-resistant silicon rubber with active hydrogen-based cage structure according to claim 4, its feature It is described vinylsiloxane rubber, viscosity is 20000MPa.s.
6. a kind of room temperature vulcanization heat-resistant silicon rubber preparation method with active hydrogen-based cage structure, it is characterised in that including following Step:
The preparation of octahydro base cage-type silsesquioxane
Catalyst and concentrated hydrochloric acid being added in there-necked flask, is subsequently added and solvent is also added in there-necked flask, stirs 30 min By HSiCl3It is dissolved in solvent, is slowly dropped in 6h in flask, after completion of dropping, continues quick stirring 1h, course of reaction Not higher than 60 DEG C of middle control system temperature, reacts in N2Carry out under gas shield, after completion of the reaction separately normal hexane layer, will band The normal hexane layer for having a small amount of tan crystals is filtered, and filtrate adds anhydrous C aC l2And anhydrous K2CO3It is stirred overnight, filters;Will The distillation of gained liquid pressure-reducing is filtered, crystal precipitation has been concentrated into, products therefrom has been collected, then is washed with solvent 2 times, obtain product T8H8
The preparation of addition type room temperature vulcanized silicone rubber
Weigh cage modle octahydro base silsesquioxane(POSS)In beaker, hexamethylene is used as solvent so as to dissolve, and adds vinyl Silicone rubber, makes its mixing with Glass rod stirring;Evacuation de-bubble in vacuum drying oven is put into, then, PC610 inhibitor is added, Platinum catalyst is added after Glass rod stirring and evenly mixing, put into after stirring evenly under room temperature environment, until silicone rubber becomes to have the bullet of hardness Gonosome.
CN201610809804.5A 2016-09-08 2016-09-08 Room-temperature vulcanization heat-resistant silicon rubber with active hydrogen based cage structure and preparation method thereof Pending CN106433146A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109749083A (en) * 2018-12-10 2019-05-14 沈阳化工大学 Eight (trimethoxy silica ethyl) poss silicone rubber crosslinking agent
CN110016297A (en) * 2019-02-25 2019-07-16 陈琪峰 A kind of conductive adhesive film and preparation method thereof
CN111253860A (en) * 2020-02-09 2020-06-09 西北工业大学 Ablation-resistant organic silicon resin coating material and preparation method thereof
CN114437355A (en) * 2021-12-31 2022-05-06 山东省科学院新材料研究所 Polymer cross-linking agent based on cage-type silsesquioxane structure

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Publication number Priority date Publication date Assignee Title
CN102181159A (en) * 2011-03-15 2011-09-14 杭州师范大学 Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN102181159A (en) * 2011-03-15 2011-09-14 杭州师范大学 Polysilsesquioxane reinforced light emitting diode (LED) encapsulation organic silicon rubber and preparation method thereof

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109749083A (en) * 2018-12-10 2019-05-14 沈阳化工大学 Eight (trimethoxy silica ethyl) poss silicone rubber crosslinking agent
CN110016297A (en) * 2019-02-25 2019-07-16 陈琪峰 A kind of conductive adhesive film and preparation method thereof
CN111253860A (en) * 2020-02-09 2020-06-09 西北工业大学 Ablation-resistant organic silicon resin coating material and preparation method thereof
CN114437355A (en) * 2021-12-31 2022-05-06 山东省科学院新材料研究所 Polymer cross-linking agent based on cage-type silsesquioxane structure

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Application publication date: 20170222