CN106496563B - A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof - Google Patents
A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof Download PDFInfo
- Publication number
- CN106496563B CN106496563B CN201610946162.3A CN201610946162A CN106496563B CN 106496563 B CN106496563 B CN 106496563B CN 201610946162 A CN201610946162 A CN 201610946162A CN 106496563 B CN106496563 B CN 106496563B
- Authority
- CN
- China
- Prior art keywords
- rubber
- compatilizer
- carbon chains
- silicon rubber
- unsaturated carbon
- 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.)
- Active
Links
Classifications
-
- 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
-
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The present invention relates to a kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof, the compatilizer has structure shown in formula (I): in formula (I), R is alkyl or hydroxyl, and M is unsaturated alkyl.10≤x+l+m≤3000, x/ (l+m)>0,0<l/ (l+m)≤1,2≤n≤30, x, y, l, m, n are integer.The present invention also provides the preparation method of the compatilizer and applications.Compatilizer com-patibilising effect of the invention is excellent, is remarkably improved silicon rubber/unsaturated carbon chains rubber blending system tensile strength and tearing strength, tensile strength raising amount is up to 3.81MPa, and tearing strength raising amount is up to 2.45KN/m.
Description
Technical field
The present invention relates to a kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and its preparation side
Method and application, belong to rubber chemicals technical field.
Background technique
Currently, being one be most widely used including unsaturated carbon chains rubber such as butyl rubber, natural rubber, nitrile rubbers
Class rubber.By taking butyl rubber (IIR) as an example, since pending methyl group is very intensive on its strand, vermicular texture is formed, thus is had
There is higher fissipation factor, and because the glass transition temperature of butyl rubber leads to its in-fighting nearby there is secondary transition
Peak was not only high but also wide, thus had excellent damping effect by butyl rubber, with the damping material of its preparation in aerospace, automobile
The fields such as manufacture are widely used.But the temperature region that butyl rubber plays damping action is relatively narrow, especially in low temperature
Under environment, it is difficult to meet requirement.
Using polysiloxanes as the organosilicon polymer of representative, have good resistant of high or low temperature, thermal stability, weatherability and
Resistance to ag(e)ing, within the scope of very wide temperature, performance is quite stable, but its mechanical property is poor.
Blending is to improve the effective way of material property, exploitation new material and balancing material price.Therefore, silicon rubber with
Unsaturated carbon chains rubber blending can both widen the use temperature range of unsaturated carbon chains rubber, can also improve the mechanics of silicon rubber
Performance.
But due to the difference of silicon rubber and unsaturated carbon chains butyl structures, lead to their poor compatibility, altogether
Easily occur mutually to separate when mixed, makes the material of preparation that expected requirement be not achieved, or even make reduced performance.
Chinese patent document CN 105906950A (application number: 201610377516.7) discloses a kind of second resistant to high temperature
Third rubber/silicon rubber blend compounds and preparation method thereof, EP rubbers, silicon rubber, compatilizer and white carbon black, coupling agent etc. is mixed
Anti-aging agent and vulcanizing agent etc. are added after refining to be vulcanized to obtain product；The compatilizer used is that side chain contains unsaturated carbon-carbon double bond
Polysiloxane grafted polymer, one of polysiloxane block polymers on main chain or side chain containing unsaturated carbon-carbon double bond
Or it is a variety of.The patent document joined in EP rubbers, silicon rubber mixed process reacts the phase being prepared through MOLECULE DESIGN
Hold agent, due to, with unsaturated carbon-carbon double bond, the third rubber of second can be achieved in rubber compound preparation and sulfidation on design polymer
The physics of glue and silicon rubber, chemical increase-volume, further improve the heat resistance of blend compounds, can be used as needs Prolonged exposure in high temperature
Under environment and there is the materials'use of some strength requirement.
But compatilizer used in the patent document will consume a certain amount of unsaturated bond, this requires the third rubbers of second
Glue and silicon rubber have higher contents of ethylene, and it is very high that this will lead to Blend rubber hardness, so that paralled system elasticity reduces, and
The performances such as system damping can be sacrificed.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of silicon rubber/unsaturated carbon chains based on hydrosilylation
Rubber compatilizer and the preparation method and application thereof.Compatilizer applicability of the invention is extensive, cost of material is low, simple process, phase
It is good to hold agent compatibilization effect.It prepares reaction efficiency height, react thorough, high conversion rate, purity is high.Can be widely applied to silicon rubber with not
In the paralled system of saturated carbon chains rubber.
Technical scheme is as follows:
A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer has and ties shown in formula (I)
Structure:
In formula (I), R is alkyl or hydroxyl, and M is unsaturated alkyl.
10≤x+l+m≤3000, x/ (l+m)>0,0<l/ (l+m)≤1,2≤n≤30, x, y, l, m, n are integer.
, according to the invention it is preferred to, the alkyl that the alkyl is C1-C10, further preferred-CH3、-CH2CH3Or-
CH2CH2CH3。
, according to the invention it is preferred to, the compatilizer number-average molecular weight is 0.2-15 ten thousand.
, according to the invention it is preferred to, 20≤x+l+m≤2000,9≤x < 2000,1≤l < 1000,1≤m < 1000, x, l, m
It is integer.
, according to the invention it is preferred to, the alkylene that the unsaturated alkyl is C5-C20, further preferred 1- octene
Base, 1- nonenyl, 1- decene base, 1,7- octadienyl, 1,8- nonadiene base, 1,9- decadinene base, 7- methyl-1,6- octadiene
Base, dihydromyrcene base, myrcenyl or lemongrass alkenyl.
According to the present invention, the preparation of compatilizer is carried out by hydrosilylation.Preferably, the system of above-mentioned compatilizer
Preparation Method comprises the following steps that
It is dissolved in solvent after unsaturated hydrocarbons is mixed with containing hydrogen silicone oil, catalyst, co-catalyst is added, is stirred to react；Instead
After answering, product is washed, then removes the small molecule low-boiling-point substance in material under reduced pressure to get compatilizer is arrived.
Preparation method according to the present invention, it is preferred that the unsaturated hydrocarbons is 1- octene, 1- nonene, 1- decene, 1,7-
Octadiene, 1,8- nonadiene, 1,9- decadinene, 7- methyl-1,6- octadiene, dihydromyrcene, laurene or citronellene.
Preparation method according to the present invention, it is preferred that the mixed proportion of the unsaturated hydrocarbons and containing hydrogen silicone oil is with insatiable hunger
It is calculated with the ratio of hydrocarbon and Si-H, the mass ratio of the material 0.001-10:1.
Preparation method according to the present invention, it is preferred that the solvent be toluene, tetrahydrofuran, hexamethylphosphoramide,
Dimethylformamide, hexamethylene or ethyl alcohol.
Preparation method according to the present invention, it is preferred that the catalyst is the complex compound or chelate of metal, further
It is preferred that the complex compound or chelate of nickel, palladium, rhodium, platinum；Preferably, the additional amount of catalyst is unsaturated hydrocarbons and the total matter of containing hydrogen silicone oil
The 0.01%-2% of amount.
Preparation method according to the present invention, it is preferred that the co-catalyst is 4-dimethylaminopyridine, triphenyl chlorine silicon
Alkane, triphenylborane, triphenylphosphine, triphenylphosphine oxide, 1,3,5- triphenylbenzene, triphenylamine or triphenyl methane；Preferably,
The additional amount of co-catalyst is the 0.01%-2% of unsaturated hydrocarbons and containing hydrogen silicone oil gross mass.
Preparation method according to the present invention, it is preferred that be stirred to react temperature be 10 DEG C -150 DEG C, further preferred 60 DEG C -
120℃；Being stirred to react the time is 6~36h.
Preparation method according to the present invention, it is preferred that the containing hydrogen silicone oil has structure shown in formula (II):
Y=l+m, x, l, m, R are identical with formula (I).Preferably, the number-average molecular weight of containing hydrogen silicone oil is 0.1~100,000, is contained
Hydrogen molar content is 10~90% (molar contents).
Preparation method according to the present invention, it is preferred that the containing hydrogen silicone oil is prepared as follows to obtain:
By D4(octamethylcy-clotetrasiloxane), D4 H(tetramethyl-ring tetrasiloxane) mixing, is first dehydrated, drying nitrogen is set
It is warming up to polymerization temperature after ventilating, end-capping reagent, catalyst is added, polymerization under atmospheric pressure reacts, and after polymerization reaction, depressurizes lower de-
Except the small molecule low-boiling-point substance in material to get arrive containing hydrogen silicone oil.Containing hydrogen silicone oil molecular weight passes through the dosage of catalyst and end-capping reagent
Control.
The preparation method of containing hydrogen silicone oil according to the present invention, it is preferred that the D4With D4 HThe mass ratio of the material be 0.1-20:
1。
The preparation method of containing hydrogen silicone oil according to the present invention, it is preferred that the end-capping reagent be water or hexamethyldisiloxane,
The additional amount of end-capping reagent is D4And D4 HThe 0.01-5% of gross mass.
The preparation method of containing hydrogen silicone oil according to the present invention, it is preferred that the catalyst is tetramethylammonium hydroxide, hydrogen-oxygen
Change potassium, solid acid or the concentrated sulfuric acid, the additional amount of catalyst is D4And D4 HThe 0.5%-5% of gross mass；
It is further preferred that the solid acid is Emathlite, sulfonate resin or heteropoly acid, the matter of the concentrated sulfuric acid
Amount concentration is 90%-98%.
The preparation method of containing hydrogen silicone oil according to the present invention, it is preferred that dehydration conditions are as follows: -0.01~-0.02MPa, 40~90
DEG C, 0.5~5h.
The preparation method of containing hydrogen silicone oil according to the present invention, it is preferred that 50-150 DEG C of polymeric reaction temperature, polymerization reaction time
For 0.5-5h.Polymerization reaction is to react under normal pressure.
The preparation method of containing hydrogen silicone oil according to the present invention, it is preferred that after polymerization reaction, be warming up to 50~200 DEG C, In
The small molecule low-boiling-point substance in material is removed under 133~1330Pa, the time is 0.5~5h.
According to the present invention, the application of above-mentioned compatilizer is blended for silicon rubber/unsaturated carbon chains rubber paralled system
Refining glue.
Application according to the present invention, the preparation of silicon rubber/unsaturated carbon chains rubber blending system can be in open mills or close
It is carried out in mill.Preferably, silicon rubber/unsaturated carbon chains rubber blending system raw material the preparation method is as follows:
Compatilizer is added in silicon rubber and unsaturated carbon chains rubber, while adding white carbon black, vulcanizing agent, vulcanization promotion
Agent, auxiliary agent are kneaded uniformly, and in 140-180 DEG C, 10-35min is to get silicon rubber/unsaturated carbon chains rubber blending body for vulcanization molding
System.
Application according to the present invention, it is preferred that the unsaturated carbon chains rubber is butyl rubber, natural rubber or butyronitrile
Rubber；
Preferably, the number-average molecular weight of the silicon rubber be 30~1,000,000, vinyl molar content be 0.05%~
0.5%；
Preferably, the white carbon black is fume colloidal silica or precipitated silica；
Preferably, the auxiliary agent is the mixture of lubricant and reinforced additive；It is further preferred that the lubrication
Agent is stearic acid, and the reinforced additive is aluminium oxide or zinc oxide.
Application according to the present invention, it is preferred that the vulcanizing agent is double 2,5, cumyl peroxide (DCP), sulphur,
Benzoyl peroxide, 2,4- dichlorobenzoperoxide, perbenzoic acid tert-butyl, two kinds in di-t-butyl peroxide or
Two or more mixing；
Preferably, the vulcanization accelerator is 4,4 '-dithio morpholines (DTDM), dithiocar-bamate, Huang
Two kinds of mixtures by 0.1~10:1 mass ratio in ortho acid salt, thiazole and tetramethylthiuram disulfide (TMTD).
Application according to the present invention, it is preferred that silicon rubber, unsaturated carbon chains rubber, white carbon black, vulcanizing agent, vulcanization promote
Agent, auxiliary agent, compatilizer mass ratio be 100:(10-1000): (20-200): (0.05-5): (0.01-3): (0.01-3):
(0.5-5)。
The principle of the present invention and feature are as follows:
The present invention uses hydrosilylation that containing hydrogen silicone oil side chain graft unsaturated hydrocarbons is made to prepare compatilizer and prepares Silicon Containing Hydrogen
Oil, number-average molecular weight are 0.1~100,000, and the too big mechanical strength for influencing Blend rubber of molecular weight, molecular weight is too small to will lead to phase
It is unobvious to hold agent compatibilization effect；Hydrogen content in 10%~90% (molar content), is increased from synthesis complexity and compatilizer
Hold what the factors such as effect determined；Specified end group can make paralled system have specific performance, if end group is that alkyl can play object
Compatibilization effect is managed, the damping capacity of paralled system can be enhanced；Hydroxyl can make compatilizer have certain polarity, be suitable for polarized group
Paralled system.Compatilizer is made being grafted a certain amount of unsaturated hydrocarbons by hydrosilylation, wherein unsaturated alkyl
Grafting rate is advisable in 10%-100%, i.e., the mixed proportion of unsaturated hydrocarbons and containing hydrogen silicone oil is in terms of the ratio of unsaturated hydrocarbons and Si-H
It calculates, the mass ratio of the material 0.001-10:1.Compatilizer should be advisable using number at 0.5 part -5 parts, in terms of 100 parts of silicon rubber,
Compatibilization effect is not had very little, the reduction of paralled system mechanical strength can be made too much.
Present invention has the advantage that
1, high using hydrosilylation preparation efficiency in compatilizer preparation process of the invention, high conversion rate, purity
Height, cost of material is low, simple process；
2, in compatilizer application process of the invention, compatilizer compatibilization effect is good, can be widely applied to silicon rubber and insatiable hunger
In the paralled system of carbochain rubber；
3, compatilizer com-patibilising effect of the invention is excellent, is remarkably improved silicon rubber/unsaturated carbon chains rubber blending system
Tensile strength and tearing strength, tensile strength raising amount is up to 3.81MPa, and tearing strength raising amount is up to 2.45KN/m.
Detailed description of the invention
Fig. 1 is the infrared spectrum of compatilizer produced by the present invention.
Specific embodiment
The invention will be described in further detail With reference to embodiment, but not limited to this.
Number described in embodiment is parts by weight.
Embodiment 1
(1) preparation of containing hydrogen silicone oil
By 30g D4, 48g D4 HBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 40~
80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, hydroxide is added
Potassium catalyst, synthesis under normal pressure for 24 hours, after polymerization, are warming up to 150 DEG C, and the small molecule in material is removed at 133~1330Pa
Low-boiling-point substance, time are that 4h obtains containing hydrogen silicone oil, and molecular weight passes through hexamethyldisiloxane end-capping reagent and potassium hydroxide catalyst
Dosage control, number-average molecular weight is in 7000 or so, Si-H molar content 66% or so.
The structural formula of containing hydrogen silicone oil obtained is as follows:
(2) preparation of compatilizer
The containing hydrogen silicone oil that 48g 1- octene and 36g step (1) are obtained is added in 80g cyclohexane solvent, and 0.15mL is added
Chloroplatinic acid catalyst, the triphenyl methane co-catalyst of 0.05mL, 90 DEG C of temperature, stirring, react 12h.
Reaction product is washed 3~4 times, is warming up to 120 DEG C, the small molecule in the lower removing material of 133~1330Pa decompression is low
Boiling object obtains 76g compatilizer, and yield 95%, number-average molecular weight is 1.6 ten thousand or so.
The structural formula of compatilizer obtained is as follows:
(3) silicon rubber/unsaturated carbon chains rubber blending system raw material preparation
By 100 parts of raw-silastic continuously, 10 parts of butyl rubber, 30 parts of white carbon black, 1.5 parts of vulcanizing agent DCP, 0.1 part of sulphur,
0.14 part of stearic acid, 0.35 part of zinc oxide, 0.05 part of DTDM, 0.05 part of TMTD, 3 parts of compatilizer be sequentially added two-roll mill
It is upper to be kneaded uniformly, 160 DEG C are carried out with the material, 20min vulcanization is molded to arrive the good silicon rubber/unsaturation of compatibilization effect
Carbochain rubber blending system.
Embodiment 2
(1) preparation of containing hydrogen silicone oil
By 30g D4, 48g D4 HBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 40~
80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, tetramethyl is added
Ammonium hydroxide catalyst, synthesis under normal pressure for 24 hours, after polymerization, are warming up to 150 DEG C, remove in material at 133~1330Pa
Small molecule low-boiling-point substance, time are that 4h obtains containing hydrogen silicone oil, and molecular weight passes through hexamethyldisiloxane end-capping reagent and tetramethyl hydrogen-oxygen
Change the dosage control of ammonium catalyst, number-average molecular weight is in 5000 or so, Si-H molar content 66% or so.
The structural formula of containing hydrogen silicone oil obtained is as follows:
(2) preparation of compatilizer
The containing hydrogen silicone oil that 56g dihydromyrcene and 36g step (1) are obtained is added in 90g toluene solvant, and 0.15mL is added
Chloroplatinic acid catalyst, the triphenylphosphine oxide co-catalyst of 0.05mL, 80 DEG C of temperature, stirring, react 12h.
Reaction product is washed 3~4 times, is warming up to 120 DEG C, the small molecule in the lower removing material of 133~1330Pa decompression is low
Boiling object obtains 83g compatilizer, and yield 92%, number-average molecular weight is 1.1 ten thousand or so.
The structural formula of compatilizer obtained is as follows:
(3) silicon rubber/unsaturated carbon chains rubber blending system raw material preparation
By 30 parts of raw-silastic continuously, 70 parts of natural rubber, 30 parts of white carbon black, 1 part of sulphur, 2 parts of stearic acid, 5 parts of zinc oxide,
0.5 part of DTDM, 0.5 part of TMTD, 3 parts of compatilizer be sequentially added in two-roll mill be kneaded uniformly, carry out 160 with the material
DEG C, 20min vulcanization molding must arrive the good silicon rubber of compatibilization effect/unsaturated carbon chains rubber blending system.
Embodiment 3
(1) preparation of containing hydrogen silicone oil
By 30g D4, 24g D4 HBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 40~
80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, the concentrated sulfuric acid is added
Catalyst, synthesis under normal pressure for 24 hours, after polymerization, are warming up to 150 DEG C, and the small molecule removed in material at 133~1330Pa is low
Object is boiled, the time is that 4h obtains containing hydrogen silicone oil, the dosage that molecular weight passes through hexamethyldisiloxane end-capping reagent and concentrated sulfuric acid catalyst
Control, number-average molecular weight is in 5000 or so, Si-H molar content 50% or so.
The structural formula of containing hydrogen silicone oil obtained is as follows:
(2) preparation of compatilizer
The containing hydrogen silicone oil that 38g 1- decene and 36g step (1) are obtained is added in 90g tetrahydrofuran solvent, is added
The chloroplatinic acid catalyst of 0.15mL, the tri-phenyl chloride co-catalyst of 0.05mL, 90 DEG C of temperature, 12h is reacted in stirring.
Reaction product is washed 3~4 times, is warming up to 120 DEG C, the small molecule in the lower removing material of 133~1330Pa decompression is low
Boiling object obtains 69g compatilizer, and yield 94%, number-average molecular weight is 10,000 or so.
The structural formula of compatilizer obtained is as follows:
(3) silicon rubber/unsaturated carbon chains rubber blending system raw material preparation
Concrete operations mode is same as Example 1.
Embodiment 4
(1) preparation of containing hydrogen silicone oil
By 60g D4, 24g D4 HBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 40~
80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, solid acid is added
Catalyst, synthesis under normal pressure for 24 hours, after polymerization, are warming up to 150 DEG C, and the small molecule removed in material at 133~1330Pa is low
Object is boiled, the time is that 4h obtains containing hydrogen silicone oil, the dosage that molecular weight passes through hexamethyldisiloxane end-capping reagent and solid acid catalyst
Control, number-average molecular weight is in 20,000 or so, Si-H molar content 33% or so.
The structural formula of containing hydrogen silicone oil obtained is as follows:
(2) preparation of compatilizer
The containing hydrogen silicone oil that 22g 1,8- nonadiene and 36g step (1) obtain is added in 70g alcohol solvent, 0.15mL is added
Chloroplatinic acid catalyst, the 1 of 0.05mL, 3,5- triphenylbenzene co-catalysts, 90 DEG C of temperature, stirring, react 12h.
Reaction product is washed 3~4 times, is warming up to 120 DEG C, the small molecule in the lower removing material of 133~1330Pa decompression is low
Boiling object obtains 52g compatilizer, and yield 91%, number-average molecular weight is 40,000 or so.
The structural formula of compatilizer obtained is as follows:
(3) silicon rubber/unsaturated carbon chains rubber blending system raw material preparation
Concrete operations mode is same as Example 1.
Embodiment 5
(1) preparation of containing hydrogen silicone oil
By 30g D4, 24g D4 HBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 40~
80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, water end-capping reagent, potassium hydroxide catalyst is added, often
Pressure reaction for 24 hours, after polymerization, is warming up to 150 DEG C, and the small molecule low-boiling-point substance in material, time are removed at 133~1330Pa
Containing hydrogen silicone oil is obtained for 4h, molecular weight is existed by the control of the dosage of water end-capping reagent and potassium hydroxide catalyst, number-average molecular weight
1000 or so, Si-H molar content are 50% or so.
The structural formula of containing hydrogen silicone oil obtained is as follows:
(2) preparation of compatilizer
The containing hydrogen silicone oil that 35g 1- decene and 36g step (1) are obtained is added in 90g tetrahydrofuran solvent, is added
The chloroplatinic acid catalyst of 0.15mL, the triphenylphosphine co-catalyst of 0.05mL, 90 DEG C of temperature, 12h is reacted in stirring.
Reaction product is washed 3~4 times, is warming up to 120 DEG C, the small molecule in the lower removing material of 133~1330Pa decompression is low
Boiling object obtains 67g compatilizer, and yield 94%, number-average molecular weight is 2000 or so.
The structural formula of compatilizer obtained is as follows:
(3) silicon rubber/unsaturated carbon chains rubber blending system raw material preparation
Concrete operations mode is same as Example 1.
Embodiment 6
(1) preparation of containing hydrogen silicone oil
By 30g D4, 24g D4 HBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 40~
80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, water end-capping reagent, concentrated sulfuric acid catalyst, normal pressure is added
Reaction for 24 hours, after polymerization, is warming up to 150 DEG C, the small molecule low-boiling-point substance in material is removed at 133~1330Pa, the time is
4h obtains containing hydrogen silicone oil, and molecular weight is by the control of the dosage of water end-capping reagent and concentrated sulfuric acid catalyst, and number-average molecular weight is on 60,000 left sides
The right side, Si-H molar content is 50% or so.
The structural formula of containing hydrogen silicone oil obtained is as follows:
(2) preparation of compatilizer
90g hexamethylphosphoramide solvent is added in the containing hydrogen silicone oil that 40g 1,9- decadinene and 36g step (1) are obtained
In, the chloroplatinic acid catalyst of 0.15mL is added, the tri-phenyl chloride co-catalyst of 0.05mL 90 DEG C of temperature, stirs, reaction
12h。
Reaction product is washed 3~4 times, is warming up to 120 DEG C, the small molecule in the lower removing material of 133~1330Pa decompression is low
Boiling object obtains 68g compatilizer, and yield 90%, number-average molecular weight is 120,000 or so.
The structural formula of compatilizer obtained is as follows:
(3) silicon rubber/unsaturated carbon chains rubber blending system raw material preparation
Concrete operations mode is same as Example 1.
Comparative example 1
Concrete operations mode is same as Example 1, the difference is that step (3) compatilizer additional amount is 0 part.
Comparative example 2
Concrete operations mode is same as Example 2, the difference is that step (3) compatilizer additional amount is 0 part.
Comparative example 3
Concrete operations mode is same as Example 1, the difference is that step (3) compatilizer additional amount is 0.5 part.
Comparative example 4
Concrete operations mode is same as Example 1, the difference is that step (3) compatilizer additional amount is 5 parts.
Comparative example 5
Concrete operations mode is same as Example 1, the difference is that the compatilizer molecular weight that step (2) obtains is
1000。
Comparative example 6
Concrete operations mode is same as Example 1, the difference is that the compatilizer molecular weight that step (2) obtains is 21
Ten thousand.
Test example
The silicon rubber that embodiment 1-6 and comparative example 1-6 are obtained/unsaturated carbon chains rubber blending system carries out performance survey
Examination, as a result as shown in table 1,2,3.
Tensile strength and elongation are tested by GB/T 528-1998；Tearing strength is tested by GB/T 529-1999；Firmly
Degree is tested by GB/T 531-1999.
1 silicon rubber of table/unsaturated carbon chains rubber vulcanization system proportion embodiment (parts by weight)
2 silicon rubber of table/unsaturated carbon chains rubber vulcanization system proportion comparative example (parts by weight)
3 silicon rubber of table/unsaturated carbon chains rubber sulphur performance data
As shown in Table 3:
Comparative example 1 and comparative example 1 are it is found that at identical conditions, compatilizer of the invention, which is added, to be significantly improved
Silicon rubber/unsaturated carbon chains rubber (butyl rubber) paralled system tensile strength and tearing strength, tensile strength raising amount reach
1.93MPa, tearing strength raising amount reach 1.39KN/m.
Comparative example 2 and comparative example 2 are it is found that at identical conditions, compatilizer of the invention, which is added, to be significantly improved
Silicon rubber/unsaturated carbon chains rubber (natural rubber) paralled system tensile strength and tearing strength, tensile strength raising amount reach
3.81MPa, tearing strength raising amount reach 1.0KN/m.
Comparative example 1 and comparative example 3, comparative example 1 and comparative example 3 are it is found that at identical conditions, be added of the invention
The very few meeting of compatilizer is so that silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect is unobvious.
Comparative example 1 and comparative example 4, comparative example 1 and comparative example 4 are it is found that at identical conditions, be added of the invention
Compatilizer can excessively make silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect decline instead.
Comparative example 1 and comparative example 5, comparative example 1 and comparative example 5 are it is found that at identical conditions, be added of the invention
The too small meeting of compatilizer molecular weight is so that silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect is unobvious.
Comparative example 1 and comparative example 6, comparative example 1 and comparative example 6 are it is found that at identical conditions, be added of the invention
Compatilizer molecular weight crosses conference and makes silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect unobvious.
Comparative example 3 and embodiment 4 are it is found that at identical conditions, be added silicone oil used in compatilizer of the invention
The too small meeting of hydrogen content is so that silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect is unobvious.
Comparative example 3 and embodiment 5 are it is found that at identical conditions, be added silicone oil used in compatilizer of the invention
Hydrogen content can excessively make silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect unobvious.
Comparative example 1, embodiment 4 and embodiment 6 are it is found that at identical conditions, be added compatilizer end of the invention
The meeting of base difference is so that silicon rubber/unsaturated carbon chains rubber blending system compatibilization effect is different, and compatibilization effect is with compatilizer end group
It is greater than hydroxyl for alkyl.
Claims (10)
1. a kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer has structure shown in formula (I):
(I),
In formula (I), R is alkyl or hydroxyl, and M is 1- octenyl, 1- nonenyl, 1- decene base, dihydromyrcene base, myrcenyl
Or lemongrass alkenyl；
10≤x+l+m≤3000, x/(l+m)>0,0<l/(l+m)≤1,2≤m≤30, x, l, m are integer；
The compatilizer number-average molecular weight is 0.2-15 ten thousand.
2. the silicon rubber according to claim 1 based on hydrosilylation/unsaturated carbon chains rubber compatilizer, feature
It is, the alkyl is the alkyl of C1-C10.
3. the silicon rubber according to claim 2 based on hydrosilylation/unsaturated carbon chains rubber compatilizer, feature
It is, the alkyl of the C1-C10 is-CH3、-CH2CH3Or-CH2CH2CH3。
4. the described in any item silicon rubber based on hydrosilylation of claim 1-3/unsaturated carbon chains rubber compatilizer
Preparation method comprises the following steps that
It is dissolved in solvent after unsaturated hydrocarbons is mixed with containing hydrogen silicone oil, catalyst, co-catalyst is added, is stirred to react；Described
Unsaturated hydrocarbons is 1,7- octadiene, 1,8- nonadiene, 1,9- decadinene, dihydromyrcene, laurene or citronellene；
After reaction, product is washed, then removes the small molecule low-boiling-point substance in material under reduced pressure to get compatilizer is arrived.
5. the preparation method according to claim 4, which is characterized in that the mixing ratio of the unsaturated hydrocarbons and containing hydrogen silicone oil
Example is with the calculating of the ratio of unsaturated hydrocarbons and Si-H, the mass ratio of the material 0.001-10:1；
The solvent is toluene, tetrahydrofuran, hexamethylphosphoramide, dimethylformamide, hexamethylene or ethyl alcohol；
The catalyst is the complex compound or chelate of metal, and the additional amount of catalyst is unsaturated hydrocarbons and the total matter of containing hydrogen silicone oil
The 0.01%-2% of amount；
The co-catalyst is 4-dimethylaminopyridine, tri-phenyl chloride, triphenylborane, triphenylphosphine, triphenyl oxygen
Change phosphine, 1,3,5- triphenylbenzene, triphenylamine or triphenyl methane；The additional amount of co-catalyst is that unsaturated hydrocarbons and containing hydrogen silicone oil are total
The 0.01%-2% of quality.
6. the preparation method according to claim 4, which is characterized in that being stirred to react temperature is 10 DEG C -150 DEG C, and stirring is anti-
It is 6 ~ 36h between seasonable.
7. the preparation method according to claim 4, which is characterized in that the containing hydrogen silicone oil is prepared as follows
It arrives:
By D4(octamethylcy-clotetrasiloxane), D4 H(tetramethyl-ring tetrasiloxane) mixing, is first dehydrated, and drying nitrogen displacement is empty
It is warming up to polymerization temperature after gas, end-capping reagent, catalyst is added, polymerization under atmospheric pressure reacts, and after polymerization reaction, depressurizes lower removing object
Small molecule low-boiling-point substance in material is to get arriving containing hydrogen silicone oil；Containing hydrogen silicone oil molecular weight passes through the control of the dosage of catalyst and end-capping reagent；
The D4With D4 HThe mass ratio of the material be 0.1-20:1；
The end-capping reagent is water or hexamethyldisiloxane, and the additional amount of end-capping reagent is D4And D4 HThe 0.01-5% of gross mass；
The catalyst is tetramethylammonium hydroxide, potassium hydroxide, solid acid or the concentrated sulfuric acid, and the additional amount of catalyst is D4With
D4 HThe 0.5%-5% of gross mass；
50-150 DEG C of polymeric reaction temperature, polymerization reaction time 0.5-5h；Polymerization reaction is to react under normal pressure.
8. the described in any item silicon rubber based on hydrosilylation of claim 1-3/unsaturated carbon chains rubber compatilizer
Using for silicon rubber/unsaturated carbon chains rubber paralled system, blending refining glue.
9. the application according to claim 8, which is characterized in that silicon rubber/unsaturated carbon chains rubber blending system raw material
The preparation method is as follows:
Compatilizer is added in silicon rubber and unsaturated carbon chains rubber, at the same add white carbon black, vulcanizing agent, vulcanization accelerator,
Auxiliary agent is kneaded uniformly, and in 140-180 DEG C, 10-35min is to get silicon rubber/unsaturated carbon chains rubber blending system for vulcanization molding.
10. application according to claim 9, which is characterized in that the unsaturated carbon chains rubber is butyl rubber, naturally
Rubber or nitrile rubber；
The number-average molecular weight of the silicon rubber is 30 ~ 1,000,000, and vinyl molar content is 0.05% ~ 0.5%；
The white carbon black is fume colloidal silica or precipitated silica；
The auxiliary agent is the mixture of lubricant and reinforced additive；
The vulcanizing agent is double 2,5, cumyl peroxide (DCP), sulphur, benzoyl peroxide, 2,4- dichloro peroxidating
Benzoyl, perbenzoic acid tert-butyl, two or more mixing in di-t-butyl peroxide；
The vulcanization accelerator is 4,4 '-dithio morpholines (DTDM), dithiocar-bamate, xanthates, thiazole
The mixture of 0.1 ~ 10:1 mass ratio is pressed with two kinds in tetramethylthiuram disulfide (TMTD)；
Silicon rubber, unsaturated carbon chains rubber, white carbon black, vulcanizing agent, vulcanization accelerator, auxiliary agent, compatilizer mass ratio be
100:(10-1000): (20-200): (0.05-5): (0.01-3): (0.01-3): (0.5-5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610946162.3A CN106496563B (en) | 2016-11-02 | 2016-11-02 | A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610946162.3A CN106496563B (en) | 2016-11-02 | 2016-11-02 | A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106496563A CN106496563A (en) | 2017-03-15 |
| CN106496563B true CN106496563B (en) | 2019-11-08 |
Family
ID=58322092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610946162.3A Active CN106496563B (en) | 2016-11-02 | 2016-11-02 | A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106496563B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298803B (en) * | 2017-06-23 | 2020-04-21 | 成都硅宝科技股份有限公司 | Polysiloxane additive for improving aging resistance of ethylene propylene diene monomer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133054A (en) * | 1993-09-07 | 1996-10-09 | 罗纳布朗克化学公司 | Method for preparation of polyorganosiloxanes with insaturated functions by dehydrogenocondensation in presence of complexes of metals of group IV |
| CN101885846A (en) * | 2010-06-21 | 2010-11-17 | 陈俊光 | Fabricating method of silicon oil gelation preparation elastomer |
| CN103561929A (en) * | 2011-06-06 | 2014-02-05 | Abb研究有限公司 | Method of producing shaped articles from a uv-curable silicone rubber composition |
| CN105906950A (en) * | 2016-05-30 | 2016-08-31 | 成都硅宝科技股份有限公司 | High temperature resistant ethylene propylene rubber/silicon rubber blend and preparation method thereof |
-
2016
- 2016-11-02 CN CN201610946162.3A patent/CN106496563B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133054A (en) * | 1993-09-07 | 1996-10-09 | 罗纳布朗克化学公司 | Method for preparation of polyorganosiloxanes with insaturated functions by dehydrogenocondensation in presence of complexes of metals of group IV |
| CN101885846A (en) * | 2010-06-21 | 2010-11-17 | 陈俊光 | Fabricating method of silicon oil gelation preparation elastomer |
| CN103561929A (en) * | 2011-06-06 | 2014-02-05 | Abb研究有限公司 | Method of producing shaped articles from a uv-curable silicone rubber composition |
| CN105906950A (en) * | 2016-05-30 | 2016-08-31 | 成都硅宝科技股份有限公司 | High temperature resistant ethylene propylene rubber/silicon rubber blend and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106496563A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496566B (en) | It is a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof | |
| CN100537640C (en) | Polyester-modified polysiloxanes and their use as additives for thermoplastics, moulding compounds and coating materials | |
| JP5661600B2 (en) | Nitrile oxide compound, modified polymer material, method for producing the same, and molded article | |
| WO2013179651A1 (en) | Polymerization catalyst composition, method for producing synthetic polyisoprene, and synthetic polyisoprene | |
| 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 | |
| JP2013216850A (en) | Method for preparing synthetic polyisoprene, synthetic polyisoprene, rubber composition and tire | |
| CN112280309A (en) | Damping agent for silicon rubber, silicon rubber material and preparation method thereof | |
| CN106496563B (en) | A kind of silicon rubber based on hydrosilylation/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof | |
| 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 | |
| CN107446356B (en) | A kind of heat resistant transparent add-on type liquid silicon rubber and preparation method thereof | |
| 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 | |
| CN108707232B (en) | Preparation method of room-temperature condensation type nitrile silicone rubber | |
| CN114196215B (en) | MTQ silicone resin, preparation method thereof, fluorine-containing organic silicone rubber, preparation method thereof and application thereof | |
| CN1798773A (en) | Use of accelerators in free-radical polymerizations of styrene | |
| KR102151473B1 (en) | Aluminium chelate compound, and room-temperature-curable resin composition including same | |
| JP7208795B2 (en) | co-modified silicone | |
| JP6493268B2 (en) | Method for producing organopolysiloxane having arylene group in main chain | |
| JPH0312109B2 (en) | ||
| EP4339225A1 (en) | Fluorine-including organohydrosilane compound | |
| JP5171476B2 (en) | Organosilicon polymer and method for producing the same | |
| CN107746464A (en) | A kind of preparation method for chain PDMS g PE copolymers of drawing money on credit | |
| EP3581607B1 (en) | Novel mesogen-silicon compound (co)polymer and thermoplastic elastomer | |
| CN109312128A (en) | The application of rubber cross object | |
| CN117321114A (en) | Fluorine-containing organohydrogensilane compounds | |
| CN104448147B (en) | Preparation method of modified graft polyvinyl fluoride and the prepared modified graft polyvinyl fluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |