CN108707232A - A kind of preparation method of room temperature condensed type nitrile silicone rubber - Google Patents
A kind of preparation method of room temperature condensed type nitrile silicone rubber Download PDFInfo
- Publication number
- CN108707232A CN108707232A CN201810632609.9A CN201810632609A CN108707232A CN 108707232 A CN108707232 A CN 108707232A CN 201810632609 A CN201810632609 A CN 201810632609A CN 108707232 A CN108707232 A CN 108707232A
- Authority
- CN
- China
- Prior art keywords
- siloxanes
- nitrile
- group
- room temperature
- silicone rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The present invention relates to a kind of preparation methods of room temperature condensed type nitrile silicone rubber, it is prepared for room temperature condensed type nitrile silicone rubber using the nitrile group-containing siloxanes of synthesis, nitrile group-containing siloxanes is by being prepared by the addition reaction of amino and double bond containing amino silicone and the nitrile group-containing compound containing unsaturated bond.Synthetic method of the present invention is simple, controllable, and combined coefficient is high, and the nitrile group-containing siloxanes of synthesis changes the polarity and solubility parameter of siloxanes due to containing nitrile group.The room temperature condensed type nitrile silicone rubber that the present invention is prepared using the siloxanes containing itrile group can be widely applied to various oil resistants, low temperature resistant place with the performance of solvent resistant oil.
Description
The application is the applying date application No. is 201610173484.9：The divisional application of 2016-03-24 applications
Technical field
The present invention relates to a kind of synthesis of nitrile group-containing siloxanes and the preparation methods of room temperature condensed type nitrile silicone rubber, and belonging to has
Machine polymeric silicon synthesizes field.
Background technology
Organosilicon macromolecule material has many superior functions, such as high-low temperature resistant, weather-proof, ageing-resistant, electric insulation etc.,
It is widely used in aerospace, electric, light industry, weaving, machinery, building, agricultural and communications and transportation etc., with people's
Daily life is in close relations, it has also become important high molecular material in national economy.Silicon rubber is important organosilicon macromolecule
Material, application products include mainly that pressing (press by such as various offset plates, washer, gasket, film, rubber roller, electronic apparatus
Key, the various die rubber products etc. for extraordinary occasion), squeeze (pressure) go out product (such as various sebific ducts, glue rope, proximate matter, electric wire electricity
Cable foreskin, adhesive tape etc.), spread goods (such as gasket, diaphragm, certainly glutinous cloth, isolation cloth).The main chain of silicon rubber is poly dimethyl
Siloxanes, introducing hetero-atoms or specific groups in its main chain can assign silicon rubber special performance, further expand it and answer
With.For example itrile group is introduced into silicon rubber main chain, prepared new type silicone rubber has preferable oil resistance, cold-resistant and satisfaction
Physical mechanical property, abbreviation nitrile silicone rubber in the market.
Nitrile silicone rubber is a kind of heat-resisting and oil resistant rubber, with good stability to conventional oil, fuel and solvent, can
It is used in -70 DEG C to+260 DEG C temperature ranges.Contain nitrile alkyl, mainly γ-nitrile propyl, gained rubber in nitrile silicone rubber molecule
Glue resistance to low temperature is close to phenyl siloxane rubber；Oil resistivity increases with the increase of γ-nitrile propyl content, when content is 33-50%
When, oil resistivity is similar to butyronitrile-26 rubber；Nitrile alkyl can also be β-nitrile ethyl, and gained rubber heat-resistant stability is good, be resistant to
250 DEG C of long-term hot air agings.
Solvent resistance and cold resistance are related to the nitrile alkyl content in elastomer.Russian document report, in polymer
The increase of nitrile group content, oil resistant, the fuel resistance of vulcanizate can significantly increase.The molar concentration of nitrile group increases from 20%
When to 50%, swellbility of the vulcanizate in 50 DEG C of isooctane reduces 4-5 times, and 1-2 times is reduced in 200 DEG C of fuel oil T-1.Contain
Without significant difference between the vulcanizate of γ-nitrile propyl group and β-nitrile ethyl group.The % nitrile alkyl molecule chains of gram molecule containing 33-50
The benzene resistance of nitrile silicon vulcanizate, under high temperature fuel-resistant T-1 performances no less than butyronitrile CKH-26 vulcanizates, and it is heat-resisting, cold-resistant then
It is more advantageous.Without linear relation between polymer cold resistance and nitrile alkyl concentration.When nitrile alkyl amount is few (7-10 gram molecule %), due to
Destroy polymer architecture regularity and cold resistance significantly improves.Nitrile chain element causes polymer glass to turn when continuing growing
Temperature increases, it is believed that is since the very strong CN bases of polarity increase caused by intermolecular force limits Chain Flexibility.
The most promising purposes of nitrile silicone rubber is, in airplane frame, automobile, railway traffic, electrical equipment and oil well rig
On be made for casing, connector, diaphragm, O-ring, gasket and washer.Its specific use may be close including being made for aircraft fuel tank
What big envelope, the sealing of powered pump, brake component and sliding were driven obturages.Aircraft industry by be this new material master
Want user.
Nitrile silicone rubber was produced by General Electric Co. Limited in 1958, and rubber compound (raw rubber is β-nitrile ethyl type) trade mark has NSR-
Tri- kinds of X5602, X4803 and X8701 estimate that its itrile group methylsiloxane segment is respectively 10,25 and 50 gram molecule %, hardness point
Not Wei 55 ± 5 (vulcanizations 1 hour) or 60 ± 5 (vulcanizations 3 hours), 70 ± 5 and 80 ± 5 totally four kinds.It is reported that novel butyronitrile silicon rubber
Glue volume expansion in jet fuel JP-4, ASTM standard fuel A (isooctane) and ASTM standard fuel B (isooctane and toluene)
It is small.At dibasic acid esters liquid (MiL-L7808), in ASTM No.3 oil and A type transmission fluids at 148.8 DEG C after aging 70 hours, body
Product expansion very little.It is said that these rubber make sealing element in industrial departments such as aviation, automobile and oil, the said firm, which still further developed, to be contained
The nitrile silicone rubber of phenyl has good heat-resisting, radiation resistance, intensity higher.In addition, Union Carbide Corporation is in 1959
Also begin to production nitrile silicone rubber year, also there is test manufacture (trade mark HCKT) in the Soviet Union.There is preproduction production in domestic Jilin chemical research institute,
Acetonitrile ethylsiloxane gram molecule content is 22% in its -25 model of nitrile silicon, and content is 40% in -50 model of nitrile silicon.Its sulphur
Change condition is 25 minutes at 155 DEG C.Shore hardness is 70 ± 5, and brittleness temperature is resistant to -66 DEG C.
It has been mentioned that preparing the silastic material with property, example using nitrile silicone rubber in domestic many patent documents
Such as, it is mentioned in Chinese patent document CN 104059242A and heat treatment foaming technique system is used using nitrile silicone rubber and other fillers
The standby tack silicon rubber foam material with superperformance；Chinese patent document CN 104109296A are using fluorubber, silicon nitrile
Rubber and other fillers, which are used in compounding, is prepared for a kind of rubber material with excellent Waterproofing/oilproofing performance；In addition Chinese patent
Be used in compounding neoprene in file CN 104312169A based on nitrile silicone rubber and other fillers be prepared for it is a kind of corrosion-resistant
Silicon rubber.But these domestic patent documents only reported the purposes using nitrile silicone rubber raw rubber, not report nitrile silicone rubber life
The preparation process of glue.
According to the literature, nitrile silicone rubber raw rubber is formed by acetonitrile alkyl dichlorosilane and dimethyldichlorosilane polycondensation
A kind of new polysiloxanes.Polymerization process reaction is violent, poor controllability.And prepared nitrile silicone rubber is in processing and property
Energy aspect haves the shortcomings that more serious, moisture absorption when being mainly kneaded, and increases with the increase of itrile group unit content, after water suction
Rubber compound be difficult to vulcanize, also vulcanization time length and the problems such as insufficient heat resistance thus limits its application and development.Nitrile
Silicon rubber has excellent performance in cold-resistant, oil resistant, solvent resistant, corrosion-resistant etc., has a extensive future, but recently about
Report in terms of nitrile silicone rubber preparation is few.
Invention content
For nitrile silicone rubber raw rubber in the prior art and being kneaded compose and processing in terms of deficiency, the present invention provides a kind of
The synthetic method of nitrile group-containing siloxanes, this method synthesis condition is simple, controllable, and combined coefficient is high；The present invention further uses conjunction
At nitrile group-containing siloxanes be prepared for room temperature condensed type nitrile silicone rubber.
Summary of the invention
The synthetic method of nitrile group-containing siloxanes provided by the invention by amino in siloxane molecule and contains itrile group
The addition reaction of double bond in unsaturated compound, prepares the siloxanes of nitrile group-containing；The siloxanes of prepared nitrile group-containing can be done
It is used alone or is used in compounding for extraordinary siloxanes, can also further prepare room temperature condensed type nitrile silicone rubber and other compound rubbers
Glue, for the places such as various oil resistants, low temperature resistant.
Detailed description of the invention
Technical scheme is as follows：
A kind of synthetic method of the siloxanes of nitrile group-containing, including steps are as follows：
Under conditions of using solvent or without using solvent, by the siloxanes containing amino and the unsaturationization containing itrile group
It closes object to mix, under conditions of using catalyst or without using any catalyst, by amino and unsaturated compound
The reaction occurred between double bond, itrile group is introduced into siloxane molecule, and the siloxanes containing itrile group is made.
The synthesis equation of nitrile group-containing siloxanes of the present invention is：
Wherein, R ' and R " is various organic groups.
, according to the invention it is preferred to, it reacts between the double bond in amino and unsaturated compound containing itrile group
Temperature is 25-100 DEG C, further preferred 40-60 DEG C；
Preferably, the reaction time is 3-5 hours.
, according to the invention it is preferred to, the molar ratio of the siloxanes containing amino and the unsaturated compound containing itrile group is
1：(1-2).
, according to the invention it is preferred to, the siloxanes containing amino is the chemical combination containing one or more silicon oxygen bonds
Object includes the following siloxanes containing amino：One alkyl silane of tri-alkoxy, dialkoxydialkyl silane, an alkoxy three
The copolymerization, siloxanes and other compounds of alkyl silane, disiloxane, polysiloxanes, siloxanes and other compounds
Graft compound, siloxanes and other compounds block compound；
It is further preferred that the siloxanes containing amino is one alkyl silane of tri-alkoxy containing amino, two
Alkoxy dialkyl silane, polysiloxanes.
, according to the invention it is preferred to, the unsaturated compound containing itrile group is to contain itrile group and other non-simultaneously
The compound of the unsaturated bond of itrile group, further preferably, the undersaturated aliphatic compound of nitrile group-containing, the aromatic series of nitrile group-containing
The unsaturated compound of compound, the unsaturated heterocyclic compound of nitrile group-containing, nitrile group-containing；
It is furthermore preferred that the unsaturated compound containing itrile group is acrylonitrile, butene nitrile, to cyanostyrene.
, according to the invention it is preferred to, the solvent can dissolve reactant and not chemically reacted with reactant
Various polarity or nonpolar solvent；Further preferably, toluene, tetrahydrofuran, chloroform, methanol, diphenyl ether, dimethyl sulfoxide, N, N-
Dimethylformamide；It is further preferred that toluene, tetrahydrofuran.
, according to the invention it is preferred to, the catalyst is each substance for capableing of catalytic amino and double bond addition, into one
Step is preferred, triethylamine, sodium acetate, pyridine, second bipyridine or melamine；It is further preferred that triethylamine, sodium acetate or pyridine.
A kind of preparation method of room temperature condensed type nitrile silicone rubber, including steps are as follows：
The siloxanes for the nitrile group-containing being prepared and crosslinking agent, crosslinking catalyst, filler and other auxiliary agents are answered
Match, prepares room temperature condensed type nitrile silicone vulcanizates.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that reactive component weight proportion is as follows：Contain
100 parts of the siloxanes of itrile group, 0.1-10 parts of crosslinking agent, 0.1-10 parts of catalyst of crosslinking, 0.1-400 parts of filler, other auxiliary agents
0-200 parts.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that reactive component weight proportion is as follows：Contain
100 parts of the siloxanes of itrile group, 0.5-5 parts of crosslinking agent, 0.5-3 parts of catalyst of crosslinking, 0.1-200 parts of filler, other auxiliary agent 0-
50 parts.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that the siloxanes of nitrile group-containing obtained is
Contain itrile group and hydroxyl (or can hydrolyze the group of generation hydroxyl), silicon that contain or not contain other groups in strand simultaneously
Oxygen alkane；
Preferably, the number-average molecular weight of the siloxanes of nitrile group-containing obtained is 3000-300000, further preferably hydroxyl
The nitrile group-containing silica that the nitrile group-containing siloxanes that the number-average molecular weight of sealing end is 5000 is 30000 with hydroxy-end capped number-average molecular weight
Alkane is used in compounding；
It is further preferred that nitrile group-containing siloxanes and hydroxy-end capped number-average molecular weight of the hydroxy-end capped number-average molecular weight for 5000
For 30000 nitrile group-containing siloxanes with 2:1 weight ratio is used in compounding.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that the crosslinking agent is in catalyst
Catalysis is lower or does not use any catalyst, and the compound of condensation reaction can occur with the hydroxyl in nitrile group-containing siloxanes, can be single
Using can also be used in compounding；
The crosslinking agent be more preferably ethyl orthosilicate, titanate esters, trialkoxy silane, α-silane coupling agent,
Silicones, Ketoxime Silane coupling agent；It is furthermore preferred that ethyl orthosilicate, is preferably 0.5-5 parts using number.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that the crosslinking is energy with catalyst
The compound that enough catalysis silicone hydroxyl is reacted with crosslinking agent, including organo-tin compound, organic acid, inorganic bronsted lowry acids and bases bronsted lowry；
The crosslinking is more preferably organo-tin compound with catalyst, the use of number is preferably 0.5-3 parts.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that the filler is that can improve room temperature
Various additives used in condensed type nitrile silicone rubber performance are further preferably, fume colloidal silica, precipitated silica, black
Carbon black, calcium carbonate, aluminium hydroxide or/and magnesium hydroxide and various specially treated above compounds, are more preferably precipitated
Method white carbon.Filler is 0.1-400 parts, preferably 10-30 parts using number.
According to the preparation method of room temperature condensed type nitrile silicone rubber of the present invention, it is preferred that other auxiliary agents are after being added
The various auxiliary agents of room temperature condensed type nitrile silicone rubber performance, further preferred thermal oxidation stabilizer, fire retardant, conduction are not significantly reduced
Agent, foaming agent, deeply-curing agent, pigment or plasticizer；Further preferably iron oxide red is preferably 1-10 parts using number.
What the present invention did not elaborated, press the prior art.
It the principle of the present invention and has the beneficial effect that：
The reaction route of the present invention has abandoned the reaction route using chlorosilane of prior document report, avoids and reacted
Corrosion of a large amount of hydrochloric acid that journey generates to equipment；After primary amino group is reacted with double bond in the present invention, keep primary amino group conversion Viability more
Low secondary amine improves the storage stability of siloxanes, reduces containing easy during amino silicones storage or use
The Yellowing of generation.The present invention is the addition reaction based on amino and double bond, and common amino exists with the needs that react of double bond
In the presence of catalyst, undergoing higher temperature and long period can just react.In the present invention, since itrile group is to double bond
Activation, which reacts more easy progress than common amino with double bond.In the present invention, if without using catalysis
Agent can react quickly, and reaction efficiency is high；If using catalyst, reaction is more rapid, and reaction efficiency carries significantly
It is high.Therefore significant effect is achieved.
The unsaturated compound containing itrile group of the present invention is the unsaturated bond simultaneously containing itrile group and other non-itrile groups
Compound, the substance can react in reaction condition of the present invention.When itrile group is connected with double bond, itrile group pair
The sensitization best results of double bond, so acrylonitrile can be easier to occur instead with amino under conditions of without using any catalyst
It answers；When double bond is not adjacent with any sensitizing group, which can also carry out, but need to use catalyst, reaction time
It is longer；
The addition reaction of amino according to the present invention and double bond, can not use any solvent can occur.Solvent
Use the raising for the blending and reaction efficiency that can aid in reaction mass, solvent-based polarity, boiling point, stability and safety
Property etc. consider, preferably toluene and tetrahydrofuran.
The siloxanes containing itrile group of the present invention changes the polarity of siloxanes due to containing this kind of polar group of itrile group
And solubility parameter, it is different from common dimethyl silicone polymer, enriches the type of siloxanes；It further uses containing itrile group
The room temperature condensed type nitrile silicone vulcanizates that prepare of siloxanes, can have the performances such as solvent resistant Oil-resistant cold-resistant.
It is according to the present invention to be vulcanized using the room temperature condensed type nitrile silicon prepared simultaneously containing the siloxanes of hydroxyl and itrile group
Rubber, cross-linked network are to be condensed structure by silicone hydroxyl, and the position of hydroxyl and quantity directly influence the room temperature contracting of preparation
The performance of mould assembly nitrile silicone vulcanizates.If hydroxy radical content is high, prepared vulcanized rubber crosslink density is big, hardness is high, still
Elongation at break is low；If hydroxy radical content is low, elongation at break is high, but crosslink density is small, hardness is small.Consider, preferably
Hydroxy-end capped nitrile group-containing siloxanes, and the scheme compounded via the nitrile group-containing siloxanes of different molecular weight, comprehensive raising are made
The mechanical mechanics property of standby vulcanized rubber.From laboratory experience, preferred number average molecular weight is 5000 hydroxy-end capped to contain
The hydroxy-end capped nitrile group-containing siloxanes that itrile group siloxanes is 30000 with number-average molecular weight is with 2:1 weight ratio is used in compounding.
Crosslinking agent according to the present invention and the basic phase of crosslinking agent in room temperature condensed type silicon rubber general formulation in the market
Together.Conventional crosslinking agent such as three fourth of first, three fourth of second, ethyl orthosilicate etc. can be directly used in the present invention in the market
In cross-linked formulation, and it is cheap and easily-available.It is tested via inventive formulation, preferably ethyl orthosilicate, the use of number is preferably 0.5-5
Part.
Crosslinking catalyst used in the present invention mainly can be catalyzed the compound that silicone hydroxyl is reacted with crosslinking agent, wrap
Include organo-tin compound, organic acid, inorganic bronsted lowry acids and bases bronsted lowry.From the aspect of test recipe and catalytic efficiency, preferred organotin chemical combination
Object is more preferably 0.5-3 parts using number.
Room temperature condensed type nitrile silicone vulcanizates prepared by the present invention also can if being added without any filler and auxiliary agent
Sulfidization molding, but intensity is not high.Using various fillers, especially reinforced filling, the machine of vulcanized rubber can be preferably improved
Tool mechanical property.Due to containing itrile group in base rubber used in the present invention, band polarized, therefore to various inorganic fillers and organic
Polar filler eats that powder is fast, compatibility is good, reinforcement is efficient.In order to further increase the mobility before nitrile silicone rubber vulcanization, this
It invents further preferred precipitated silica and reinforcement is carried out to nitrile silicone rubber, improve its mechanical mechanics property.
Room temperature condensed type nitrile silicone vulcanizates prepared by the present invention, are added various auxiliary agents in its formula, can be into one
Step improves its performance and simultaneously expands its application, for example, thermal oxidation stabilizer, fire retardant, conductive agent, foaming agent, deeply-curing agent, pigment,
Plasticizer etc..Certain auxiliary agents can play the role of a variety of, for example iron oxide red can play thermal oxidation stabilizer, pigment, reinforced filling simultaneously
Effect.The dosage and a variety of auxiliary agents for changing auxiliary agent are used in conjunction with, and can prepare the nitrile silicone rubber of a variety of excellent performances.
The nitrile group-containing polysiloxanes of the present invention can be used alone or be used in compounding as extraordinary polysiloxanes, can also make
It is standby to have a extensive future for various oil resistants, low temperature resistant place at nitrile silicone rubber and other compounded rubbers.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic spectrogram of the hydroxy-end capped nitrile group-containing siloxanes in the embodiment of the present invention 12.
Specific implementation mode
Below by specific embodiment, the present invention will be further described, but not limited to this.
It is raw materials used in embodiment to be regular market purchase raw material or synthesize to obtain according to bibliography method.
It is molar percentage to own " % " in embodiment.
Molecular weight described in embodiment is number-average molecular weight.
Number described in embodiment is parts by weight.
Embodiment 1
Ratio 1 is measured by mol:1.5 ratio by aminopropyl triethoxysilane and acrylonitrile in tetrahydrofuran solution into
Row is blended, and it is 40 DEG C to keep temperature, and mechanical agitation 4 hours obtains N- (β-itrile group)-gamma-aminopropyl-triethoxy-silane, reaction
Yield is 100%.
Embodiment 2
As described in Example 1, aminopropyl triethoxysilane is changed to two aminopropyl tetramethyl disiloxanes unlike,
Reaction temperature is 40 DEG C, and mechanical agitation 4 hours obtains N ,-two aminopropyl tetramethyl disiloxanes of N '-(two β-itrile groups)-γ, instead
Product yield is 100%.
Embodiment 3
It, will mole metering ratio 1 in tetrahydrofuran solution：The 2 hydroxy-end capped siloxanes containing aminopropyl (15%)
(molecular weight 5000) is blended with acrylonitrile, and it is 50 DEG C to keep reaction temperature, and mechanical agitation 4 hours obtains hydroxy-end capped contain
Itrile group siloxanes, reaction yield 100%.
Nitrile group-containing silicone oil obtained, molecular weight 5494, nitrile group content 15%.
Embodiment 4
As described in Example 3, unlike：The link content of aminopropyl becomes 5%.Reaction temperature is 50 DEG C, when reaction
Between be 4 hours, reaction yield is up to 100%.
Embodiment 5
As described in Example 3, the hydroxy-end capped siloxanes containing aminopropyl is changed to hydroxy-end capped contain unlike
There is the siloxanes of N- (β-aminoethyl)-γ-aminopropyls (chain link content 15%).Reaction temperature is 60 DEG C, 4 hours reaction time,
Reaction yield is 100%.
Embodiment 6
As described in Example 5, the chain link content of N- (β-aminoethyl)-γ-aminopropyls of polysiloxanes is changed unlike
It is 5%.60 DEG C of reaction temperature, 4 hours reaction time, reaction yield 100%.
Embodiment 7
As described in Example 3, the hydroxy-end capped siloxanes containing aminopropyl is changed to hydroxy-end capped side unlike
Chain contains the siloxanes of hydroxyl (chain link content 5%) and aminopropyl (chain link content 5%).40 DEG C of reaction temperature, the reaction time 4 is small
When, reaction yield 100%.
Embodiment 8
As described in Example 3, acrylonitrile is changed to butene nitrile unlike.Reaction temperature is 60 DEG C, and the reaction time 4 is small
When, reaction yield 96%.
Embodiment 9
As described in Example 3, acrylonitrile is changed to butene nitrile unlike, catalyst is pyridine, and reaction temperature is 60 DEG C,
4 hours reaction time, reaction yield 100%.
Embodiment 10
As described in Example 3, acrylonitrile is changed to cyanostyrene unlike, catalyst is sodium acetate, reaction temperature
Degree is 60 DEG C, 4 hours reaction time, reaction yield 100%.
Embodiment 11
By 100 parts of hydroxy-end capped nitrile group-containing siloxanes that molecular weight is 80000, molecular weight be 10000 it is hydroxy-end capped
200 parts of nitrile group-containing siloxanes, 5 parts of ethyl orthosilicate, 0.5 part of organotin catalysts, D4It is surface-treated precipitated silica 20
Part, 200 parts of aluminium hydroxide, 1 part of iron oxide red, N- 1 part of dimethoxysilanes of (β-aminoethyl)-γ-aminopropyltriethoxies (weight ratio) into
Row compounding prepares room temperature condensed type and vulcanizes nitrile silicone rubber.
Embodiment 12
By 100 parts of hydroxy-end capped nitrile group-containing siloxanes that molecular weight is 30000, molecular weight be 5000 it is hydroxy-end capped
200 parts of nitrile group-containing siloxanes, 5 parts of ethyl orthosilicate, 0.5 part of organotin catalysts, hexamethyldisilazane surface treatment precipitation
20 parts of method white carbon, calcium carbonate 200 parts (weight ratios), 1 part of iron oxide red, 1 part of three fourth of first are compounded, and the vulcanization of room temperature condensed type is prepared
Nitrile silicone rubber.
Embodiment 13
100 parts of the hydroxy-end capped nitrile group-containing siloxanes, 2 parts of triethoxy methyl silicane, organic for being 10000 by molecular weight
1 part of tin catalyst, 10 parts of siloxane treated precipitated silica, 200 parts of aluminium hydroxide, 1 part of iron oxide red, second three fourths, 1 part of (weight
Than) compounded, it prepares room temperature condensed type and vulcanizes nitrile silicone rubber.
Embodiment 14
100 parts of the hydroxy-end capped nitrile group-containing siloxanes, 2 parts of triethoxy methyl silicane, organic for being 30000 by molecular weight
1 part of tin catalyst, 20 parts of the fume colloidal silica of silazane processing, 200 parts of calcium carbonate, 20 parts of magnesium hydroxide, 1 part of iron oxide red (weight
Amount ratio) it is compounded, it prepares room temperature condensed type and vulcanizes nitrile silicone rubber.
Test example 1
Hydroxy-end capped nitrile group-containing siloxanes in embodiment 12 is analyzed and characterized, hydrogen nuclear magnetic spectrogram such as Fig. 1 institutes
Show, proton magnetic spectrum diagram data is 0.07 (s, SiCH3),0.50(t,2H,SiCH2),1.52(m,2H,SiCH2CH2),2.61(t,
2H,SiCH2CH2CH2),1.80(s,1H,NH),2.51(t,2H,CH2CH2CN),2.92(t,2H,CH2CN)。
Test example 2
The room temperature condensed type nitrile silicone rubber that embodiment 12,13 and 14 is prepared carries out mechanical test, as a result such as the following table 1
It is shown.
Table 1
| Index number | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| Hardness (continue that A) | 35 | 33 | 34 |
| Tensile strength (MPa) | 0.95 | 1.01 | 0.98 |
| Elongation rate of tensile failure % | 2.81 | 2.64 | 2.97 |
| Tearing strength KN/m | 5.28 | 5.64 | 5.62 |
As shown in Table 1, the tensile strength and tear strength properties of room temperature condensed type vulcanization nitrile silicone rubber produced by the present invention
It is excellent.Rubber hardness is not high, convenient for bending.By to the molecular weight of nitrile group-containing siloxanes, nitrile group content and crosslinking agent, crosslinking
It is further adjusted using number with catalyst, filler and other auxiliary agents, the more excellent nitrile of mechanical property can be obtained
Silicon rubber.
Claims (10)
1. a kind of preparation method of room temperature condensed type nitrile silicone rubber, including steps are as follows：
The siloxanes of nitrile group-containing and crosslinking agent, crosslinking catalyst, filler and other auxiliary agents are compounded, room temperature condensation is prepared
Type nitrile silicone vulcanizates；
The siloxanes of the nitrile group-containing is prepared as follows to obtain：
Under conditions of using solvent or without using solvent, by the siloxanes containing amino and contain the unsaturated compound of itrile group
It mixes, under conditions of using catalyst or without using any catalyst, passes through the double bond in amino and unsaturated compound
Between the reaction that occurs, itrile group is introduced into siloxane molecule, the siloxanes containing itrile group is made.
2. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that reactive component weight
Proportioning is as follows：100 parts of the siloxanes of nitrile group-containing, 0.1-10 parts of crosslinking agent, 0.1-10 parts of catalyst of crosslinking, filler 0.1-400
Part, other auxiliary agent 0-200 parts.
3. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the nitrile group-containing
Siloxanes be in strand simultaneously containing hydroxyl and itrile group, contain or not contain the siloxanes of other groups；
The molecular weight of the siloxanes of nitrile group-containing is 3000-300000, the nitrile group-containing that preferably hydroxy-end capped molecular weight is 5000
The nitrile group-containing siloxanes that siloxanes is 30000 with hydroxy-end capped molecular weight is used in compounding；It is further preferred that hydroxy-end capped molecular weight
The nitrile group-containing siloxanes that nitrile group-containing siloxanes for 5000 is 30000 with hydroxy-end capped molecular weight is with 2:1 weight ratio compounding makes
With.
4. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the crosslinking agent
For under catalyst or without using any catalyst, the chemical combination of condensation reaction can occur with hydroxy-end capped nitrile group-containing siloxanes
Object single use or can be used in compounding；
The crosslinking agent is ethyl orthosilicate, titanate esters, trialkoxy silane, α-silane coupling agent, silicones, Ketoxime Silane
Coupling agent；
The crosslinking catalyst is that can be catalyzed the compound that silicone hydroxyl is reacted with crosslinking agent；
The filler is black fume colloidal silica, precipitated silica, black wood charcoal, calcium carbonate, aluminium hydroxide or/and magnesium hydroxide
And various specially treated above compounds；
Other auxiliary agents are thermal oxidation stabilizer, fire retardant, conductive agent, foaming agent, deeply-curing agent, pigment or plasticizer.
5. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 4, which is characterized in that the crosslinking is used
Catalyst is organo-tin compound, organic acid, inorganic acid or alkali, and other auxiliary agents are iron oxide red.
6. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the silica of nitrile group-containing
In the preparation process of alkane, the temperature to react between the double bond in amino and unsaturated compound containing itrile group is 25-100
DEG C, preferably 40-60 DEG C；
Reaction time is 3-5 hours.
7. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the silica of nitrile group-containing
In the preparation process of alkane, the molar ratio of the siloxanes containing amino and the unsaturated compound containing itrile group is 1：(1-2)；It is preferred that
, the molar percentage of amino is 5-20% in the siloxanes containing amino.
8. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the silica of nitrile group-containing
In the preparation process of alkane, silicone hydroxyl or/and silicon-aerobic-carbon key are contained in the siloxanes containing amino；
Preferably, the siloxanes containing amino includes the following siloxanes containing amino：One alkyl silane of tri-alkoxy,
Dialkoxydialkyl silane, an alkoxy trialkylsilane, the copolymerization of siloxanes and other compounds, siloxanes with
The graft compound of other compounds, the block compound of siloxanes and other compounds.
9. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the silica of nitrile group-containing
In the preparation process of alkane, the unsaturated compound containing itrile group is the unsaturation containing itrile group and other non-itrile groups simultaneously
The compound of key；
Preferably, the undersaturated aliphatic compound of nitrile group-containing, the aromatic compound of nitrile group-containing, the unsaturation of nitrile group-containing are miscellaneous
Cycle compound；
It is furthermore preferred that the unsaturated compound containing itrile group is acrylonitrile, butene nitrile, to cyanostyrene.
10. the preparation method of room temperature condensed type nitrile silicone rubber according to claim 1, which is characterized in that the silicon of nitrile group-containing
In the preparation process of oxygen alkane, the solvent is toluene, tetrahydrofuran, chloroform, methanol, diphenyl ether, dimethyl sulfoxide or N, N- bis-
Methylformamide；
Preferably, the catalyst is triethylamine, sodium acetate, pyridine, second bipyridine or melamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810632609.9A CN108707232B (en) | 2016-03-24 | 2016-03-24 | Preparation method of room-temperature condensation type nitrile silicone rubber |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610173484.9A CN105646565B (en) | 2016-03-24 | 2016-03-24 | A kind of synthesis of nitrile group-containing siloxanes and the preparation method of room temperature condensed type nitrile silicone rubber |
| CN201810632609.9A CN108707232B (en) | 2016-03-24 | 2016-03-24 | Preparation method of room-temperature condensation type nitrile silicone rubber |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610173484.9A Division CN105646565B (en) | 2016-03-24 | 2016-03-24 | A kind of synthesis of nitrile group-containing siloxanes and the preparation method of room temperature condensed type nitrile silicone rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108707232A true CN108707232A (en) | 2018-10-26 |
| CN108707232B CN108707232B (en) | 2020-10-16 |
Family
ID=56494578
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610173484.9A Active CN105646565B (en) | 2016-03-24 | 2016-03-24 | A kind of synthesis of nitrile group-containing siloxanes and the preparation method of room temperature condensed type nitrile silicone rubber |
| CN201810632609.9A Active CN108707232B (en) | 2016-03-24 | 2016-03-24 | Preparation method of room-temperature condensation type nitrile silicone rubber |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610173484.9A Active CN105646565B (en) | 2016-03-24 | 2016-03-24 | A kind of synthesis of nitrile group-containing siloxanes and the preparation method of room temperature condensed type nitrile silicone rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN105646565B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439274A (en) * | 2018-11-02 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of preparation method of oil resistant sealant |
| CN114516960A (en) * | 2022-01-19 | 2022-05-20 | 山东共聚有机硅技术研究院有限公司 | Iron cyano silicone resin heat-resistant liquid filler and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698764B (en) * | 2017-10-21 | 2021-05-14 | 湖北三江航天江河化工科技有限公司 | Cyanoethyl grafted aminoalkyl silicone oil for composite solid propellant and synthetic method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584026A (en) * | 1968-07-17 | 1971-06-08 | Gen Electric | Cyanoalkoxyalkenyl and aminoalkoxyalkenylsilanes |
| CN101048448A (en) * | 2004-10-25 | 2007-10-03 | 南农股份公司 | Method of producing a silicone rubber item and the product obtainable by the method |
| CN101367943A (en) * | 2007-08-17 | 2009-02-18 | 赢创德固赛有限责任公司 | Silane-based, aqueous coating system, production and use thereof |
-
2016
- 2016-03-24 CN CN201610173484.9A patent/CN105646565B/en active Active
- 2016-03-24 CN CN201810632609.9A patent/CN108707232B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3584026A (en) * | 1968-07-17 | 1971-06-08 | Gen Electric | Cyanoalkoxyalkenyl and aminoalkoxyalkenylsilanes |
| CN101048448A (en) * | 2004-10-25 | 2007-10-03 | 南农股份公司 | Method of producing a silicone rubber item and the product obtainable by the method |
| CN101367943A (en) * | 2007-08-17 | 2009-02-18 | 赢创德固赛有限责任公司 | Silane-based, aqueous coating system, production and use thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439274A (en) * | 2018-11-02 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of preparation method of oil resistant sealant |
| CN109439274B (en) * | 2018-11-02 | 2020-11-10 | 烟台德邦科技有限公司 | Preparation method of oil-resistant sealant |
| CN114516960A (en) * | 2022-01-19 | 2022-05-20 | 山东共聚有机硅技术研究院有限公司 | Iron cyano silicone resin heat-resistant liquid filler and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646565A (en) | 2016-06-08 |
| CN105646565B (en) | 2019-01-29 |
| CN108707232B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4029629A (en) | Solvent resistant room temperature vulcanizable silicone rubber composition | |
| CN105622943B (en) | A kind of synthesis of the high molecular weight silicone of while nitrile group-containing and vinyl and the preparation method of additional hot vulcanized nitrile silicone rubber | |
| EP2368942B1 (en) | Fluorine-containing curable composition and rubber article | |
| JP5108092B2 (en) | Curable silicone elastomer composition, method for producing cured silicone elastomer, cured silicone elastomer, product containing the same, and method for improving thermal stability or heat resistance of silicone elastomer | |
| CN105778105B (en) | A kind of synthesis of the siloxanes of while nitrile group-containing and vinyl and the preparation method of room temperature add-on type nitrile silicone rubber | |
| KR101620882B1 (en) | Use of polyorganosiloxanes in the processing and vulcanization of rubber | |
| JP2001220509A (en) | Hardening composition | |
| CN105646565B (en) | A kind of synthesis of nitrile group-containing siloxanes and the preparation method of room temperature condensed type nitrile silicone rubber | |
| CN106432728B (en) | A kind of pheiiyldimetliyl siloxy cage-type silsesquioxane silicone rubber crosslinking agent and preparation method thereof | |
| CN101311238A (en) | Light-coloured high temperature resistant organic silicone adhesive/sealant | |
| BR112014012199B1 (en) | composition of olefinomically olefinically functionalized siloxanes based on alkoxysilanes, their preparation and use process | |
| WO2004050758A1 (en) | Fluorine-containing polymer composition and cured body | |
| CN109054734A (en) | It is a kind of based on the adhesive prepared containing amino silicone and its preparation and application | |
| JP2011529511A5 (en) | Rubber vulcanizing agent using polyorganosiloxane, masterbatch and mixture, and method for vulcanizing rubber | |
| CN105601845B (en) | A kind of synthesis of high molecular weight nitrile group-containing polysiloxanes and the preparation method of peroxide type heat cure nitrile silicone rubber | |
| CN104497579A (en) | One-component room temperature vulcanized organic silicon rubber with high adhesion and preparation method thereof | |
| KR20130037822A (en) | End-modified diene copolymer having a good compatibility with silica reinforcement, and process for preparing them | |
| JP5569720B2 (en) | Method for producing moisture curable composition | |
| US10428183B2 (en) | Room temperature-curable resin composition containing an aluminum chelate compound | |
| CN107383375A (en) | A kind of preparation method for the organosilicon modified polyester being modified for TPU | |
| US8735509B2 (en) | Use of polyorganosiloxanes in the processing and vulcanisation of rubber | |
| JPH0425563A (en) | Silicone rubber composition | |
| TWI525154B (en) | Method for producing silicone rubber compound and silicone rubber composition | |
| CN104817845A (en) | Liquid silicon rubber and preparation method thereof | |
| JP3858970B2 (en) | Curable fluoropolyether rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |