CN106496566B - It is a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof - Google Patents
It is a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof Download PDFInfo
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- 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
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
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- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- 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
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- 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
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- 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
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- 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 based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer and the preparation method and application thereof, which has structure shown in formula (I): in formula (I), R is alkyl, alkylene or hydroxyl；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 and application of above-mentioned compatilizer.Compatilizer compatibilization 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 2.63MPa, and tearing strength raising amount is up to 2.98KN/m.
Description
Technical field
The present invention relates to a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer and preparation method thereof,
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 silicon rubber as the organosilicon polymer of representative, there is good resistant of high or low temperature, thermal stability, weatherability and resistance to
Aging, 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 CN105418935A (application number: CN201510982704.8) discloses a kind of graft polymers
Compatilizer and the preparation method and application thereof, compatilizer are with polycarbonate (PC) for main chain, styrene-acrylonitrile copolymer
It (SAN) is the graft polymers of side chain, i.e. PC-g-SAN.The compatilizer can effectively reduce PC/ABS and PC/ASA system phase boundary
Face tension is to improve compatibility.But the synthesis condition of the compatilizer is more harsh, reaction temperature is high, system application range
It is narrow.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber
Compatilizer and the preparation method and application thereof.Compatilizer applicability of the invention is extensive, cost of material is low, simple process, compatilizer
Compatibilization effect is good.It prepares reaction efficiency height, react thorough, high conversion rate, purity is high.It can be widely applied to silicon rubber and unsaturation
In the paralled system of carbochain rubber.
Technical scheme is as follows:
It is a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer, there is structure shown in formula (I):
In formula (I), R is alkyl, alkylene or hydroxyl；
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 methyl, ethyl or propyl；
The alkylene is the alkylene of C2-C20, further preferred vinyl or allyl.
, according to the invention it is preferred to, the compatilizer number-average molecular weight is 0.5-15 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, being grafted thiol molecule formula used is CnH2n+1SH, 2≤n≤30, n are integer；Into one
Walk preferred n- dodecyl mereaptan, tert-dodecylmercaotan, secondary lauryl mercaptan or positive stearylmercaptan.
According to the present invention, the preparation method of above-mentioned compatilizer, comprises the following steps that
It is dissolved in solvent after mercaptan is mixed with vinyl silicone oil, initiator is added, stirring is reacted under illumination；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 mixed proportion of mercaptan and vinyl silicone oil is with mercaptan and vinyl
Ratio calculate, the mass ratio of the material 0.001-10:1.
Preparation method according to the present invention, it is preferred that the additional amount of initiator is mercaptan and vinyl silicone oil gross mass
0.5%-5%.
Preparation method according to the present invention, it is preferred that reaction temperature is 10 DEG C -90 DEG C.
Preferably, intensity of illumination 5-500cd/m2, the illumination reaction time is 3min~60min.
Preparation method according to the present invention, it is preferred that the solvent be toluene, tetrahydrofuran, hexamethylphosphoramide,
Dimethylformamide, hexamethylene or ethyl alcohol；The initiator is 2,2- dihydromethyl propionic acid, 2- hydroxy-2-methyl -1- phenyl
Acetone or methyl benzoylformate.
Preparation method according to the present invention, it is preferred that the vinyl 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 vinyl silicone oil is 0.3~100,000,
Vinyl molar content 5%-50%.
Preparation method according to the present invention, it is preferred that the vinyl silicone oil is prepared as follows to obtain:
By D4(octamethylcy-clotetrasiloxane), D4 ViAfter (t etram-ethyltetravinylcyclotetrasiloxane) mixing, first depressurized
Dehydration is warming up to polymeric reaction temperature after drying nitrogen displaced air, is added end-capping reagent, catalyst, after polymerization reaction, subtracts
Pressure removes the small molecule low-boiling-point substance in material to get vinyl silicone oil is arrived.Vinyl silicone oil molecular weight passes through catalyst and envelope
Hold the dosage control of agent.
The preparation method of vinyl silicone oil according to the present invention, it is preferred that the D4With D4 ViThe mass ratio of the material be 0.5-
20:1。
The preparation method of vinyl silicone oil according to the present invention, it is preferred that 50-150 DEG C of polymeric reaction temperature, when polymerization reaction
Between be 0.5~5h, polymerization reaction be normal pressure under react.
The preparation method of vinyl silicone oil according to the present invention, it is preferred that the catalyst is tetramethylammonium hydroxide, hydrogen
Potassium oxide, solid acid or the concentrated sulfuric acid, the additional amount of catalyst are D4And D4 ViThe 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 vinyl silicone oil according to the present invention, it is preferred that the end-capping reagent is water, hexamethyldisiloxane
Or 1,3- divinyl-tetramethyl disiloxane, the additional amount of end-capping reagent is D4And D4 ViThe 0.05-5% of gross mass.
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%~
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 mercapto-alkene reaction that vinyl silicone oil side chain graft mercaptan is made to prepare compatilizer and prepares vinyl silicone oil,
Its number-average molecular weight is 0.3~100,000, and the too big mechanical strength for influencing Blend rubber of molecular weight, molecular weight is too small to will lead to compatilizer
Compatibilization effect is unobvious；For contents of ethylene in 5%-50%, contents of ethylene is from synthesis complexity and compatilizer increase-volume
What the factors such as effect determined；Specified end group can make paralled system have specific performance, as end group be vinyl can make it is compatible
Agent " chain extension ", can increase paralled system mechanical property；End group is that alkyl can play physics compatibilization effect, can enhance and use body
The damping capacity of system；Hydroxyl can make compatilizer have certain polarity, the paralled system suitable for polarized group.
Compatilizer is made being grafted a certain amount of mercaptan by mercapto-alkene reaction, wherein the grafting rate of sulfydryl is in 10%-
100% is advisable, i.e., the mixed proportion of mercaptan and vinyl silicone oil is with the calculating of the ratio of mercaptan and vinyl, 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, not have compatibilization effect very little, too
The reduction of paralled system mechanical strength can mostly be made.
Present invention has the advantage that
1, high using mercapto alkene reaction preparation efficiency in compatilizer preparation process of the invention, high conversion rate, purity is high, original
Expect at low cost, 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 compatibilization 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 2.63MPa, and tearing strength raising amount is up to 2.98KN/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 vinyl silicone oil
By 270g D4, 35g D4 ViBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 60
~80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, hydrogen-oxygen is added
Change potassium catalyst, synthesis under normal pressure 4h after polymerization, is warming up to 150 DEG C, and small point in material is removed at 133~1330Pa
Sub- low-boiling-point substance, time are that 2h obtains vinyl silicone oil, and molecular weight passes through hexamethyldisiloxane end-capping reagent and potassium hydroxide catalysed
The dosage of agent controls, and number-average molecular weight is 5 or so, and contents of ethylene is 10% or so.
The structural formula of vinyl silicone oil obtained is as follows:
(2) preparation of compatilizer
The vinyl silicone oil that 9.8g n- dodecyl mereaptan and 37g step (1) are obtained is added in 50g toluene solvant, light-initiated
Agent 2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, 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 44g compatilizer, and yield 96%, number-average molecular weight is 60,000 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 vinyl silicone oil
By 270g D4, 35g D4 ViBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 60
~80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, 1,3- divinyl-tetramethyl, two silicon oxygen is added
Alkane end-capping reagent, tetramethylammonium hydroxide catalyst, synthesis under normal pressure 4h after polymerization, are warming up to 150 DEG C, in 133~1330Pa
Small molecule low-boiling-point substance in lower removing material, time are that 2h obtains vinyl silicone oil, and molecular weight passes through 1,3- divinyl-tetramethyl
The control of the dosage of base disiloxane end-capping reagent and tetramethylammonium hydroxide catalyst, 30,000 or so, vinyl contains number-average molecular weight
Amount is 10% or so.
The structural formula of vinyl silicone oil obtained is as follows:
(2) preparation of compatilizer
The vinyl silicone oil that the positive stearylmercaptan of 14g and 37g step (1) are obtained is added in 60g tetrahydrofuran solvent, and light draws
Agent methyl benzoylformate 1.8g is sent out, 60 DEG C of reaction temperature, illumination 40min, is stirred.
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 48g compatilizer, and yield 95%, 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
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 vinyl silicone oil
By 570g D4, 35g D4 ViBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 60
~80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, hydrogen-oxygen is added
Change potassium catalyst, synthesis under normal pressure 4h after polymerization, is warming up to 150 DEG C, and small point in material is removed at 133~1330Pa
Sub- low-boiling-point substance, time are that 2h obtains vinyl silicone oil, and molecular weight passes through hexamethyldisiloxane end-capping reagent and potassium hydroxide catalysed
The dosage of agent controls, and number-average molecular weight is 30,000 or so, and contents of ethylene is 5% or so.
The structural formula of vinyl silicone oil obtained is as follows:
(2) preparation of compatilizer
50g hexamethylphosphoramide solvent is added in the vinyl silicone oil that 5g n- dodecyl mereaptan and 37g step (1) are obtained
In, photoinitiator 2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, 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 39g compatilizer, and yield 93%, number-average molecular weight is 3.4 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
Concrete operations mode is same as Example 1.
Embodiment 4
(1) preparation of vinyl silicone oil
By 270g D4, 35g D4 ViBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 60
~80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, hexamethyldisiloxane end-capping reagent, hydrogen-oxygen is added
Change potassium catalyst, synthesis under normal pressure 4h after polymerization, is warming up to 150 DEG C, and small point in material is removed at 133~1330Pa
Sub- low-boiling-point substance, time are that 2h obtains vinyl silicone oil, and molecular weight passes through hexamethyldisiloxane end-capping reagent and potassium hydroxide catalysed
The dosage of agent controls, and number-average molecular weight is 10,000 or so, and contents of ethylene is 10% or so.
The structural formula of vinyl silicone oil obtained is as follows:
(2) preparation of compatilizer
The vinyl silicone oil that 9.8g n- dodecyl mereaptan and 37g step (1) are obtained is added in 60g toluene solvant, light-initiated
Agent 2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, 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 44g compatilizer, and yield 94%, number-average molecular weight is 1.2 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
Concrete operations mode is same as Example 1.
Embodiment 5
(1) preparation of vinyl silicone oil
By 45g D4, 35g D4 ViBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 60~
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 4h 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 2h obtains vinyl silicone oil, the use that molecular weight passes through hexamethyldisiloxane end-capping reagent and solid acid catalyst
Amount control, number-average molecular weight is 30,000 or so, and contents of ethylene is 40% or so.
The structural formula of vinyl silicone oil obtained is as follows:
(2) preparation of compatilizer
The vinyl silicone oil that 33g n- dodecyl mereaptan and 37g step (1) are obtained is added in 80g alcohol solvent, photoinitiator
2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, 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 64g compatilizer, and yield 91%, number-average molecular weight is 60,000 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 6
(1) preparation of vinyl silicone oil
By 270g D4, 35g D4 ViBe added polymerization reaction kettle be dehydrated, dehydration conditions be -0.01~-0.02MPa, 60
~80 DEG C, 2h, 80~120 DEG C of polymerization temperature are warming up to after drying nitrogen ventilation, a certain amount of water, concentrated sulfuric acid catalyst is added,
Synthesis under normal pressure 4h after polymerization, is warming up to 150 DEG C, and the small molecule low-boiling-point substance in material is removed at 133~1330Pa, when
Between for 2h obtain vinyl silicone oil, molecular weight is by the control of the dosage of water and the concentrated sulfuric acid, and number-average molecular weight is 30,000 or so, ethylene
Base content is 10% or so.
The structural formula of vinyl silicone oil obtained is as follows:
(2) preparation of compatilizer
The vinyl silicone oil that 9.8g n- dodecyl mereaptan and 37g step (1) are obtained is added in 50g cyclohexane solvent, and light draws
Agent 2- hydroxy-2-methyl -1- phenylacetone 1.5g is sent out, 50 DEG C of reaction temperature, illumination 40min, is stirred.
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 45g compatilizer, and yield 97%, number-average molecular weight is 3.5 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
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 1 part.
Comparative example 4
Concrete operations mode is same as Example 1, the difference is that step (3) compatilizer additional amount is 10 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
2000。
Comparative example 6
Concrete operations mode is same as Example 1, the difference is that the compatilizer molecular weight that step (2) obtains is 20
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
2.63MPa, tearing strength raising amount reach 2.98KN/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
1.08MPa, tearing strength raising amount reach 1.30KN/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 contents of ethylene 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
Contents of ethylene 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
Successively successively decrease for alkylene, alkyl, hydroxyl.
Claims (10)
1. it is a kind of based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer, there is structure shown in formula (I):
(I)
In formula (I), R is alkyl, alkylene or hydroxyl；
10≤x+l+m≤3000, x/(l+m)>0,0<l/(l+m)≤1,2≤n≤30, x, l, m, n is integer；
The compatilizer number-average molecular weight is 0.5-15 ten thousand.
2. according to claim 1 based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer, feature exists
In the alkyl is the alkyl of C1-C10, and the alkylene is the alkylene of C2-C20.
3. according to claim 2 based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer, feature exists
In the alkyl of the C1-C10 is methyl, ethyl or propyl, and the alkylene of the C2-C20 is vinyl or allyl.
4. claim 1-3 is described in any item based on the preparation of mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer
Method comprises the following steps that
It is dissolved in solvent after mercaptan is mixed with vinyl silicone oil, initiator is added, stirring is reacted under illumination；Reaction knot
Shu Hou, product are washed, then remove 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 mixed proportion of mercaptan and vinyl silicone oil is with mercaptan
It is calculated with the ratio of vinyl, the mass ratio of the material 0.001-10:1；
The thiol molecule formula is CnH2n+1SH, 2≤n≤30, n are integer；
The additional amount of initiator is the 0.5%-5% of mercaptan and vinyl silicone oil gross mass.
6. the preparation method according to claim 4, which is characterized in that reaction temperature is 10 DEG C -90 DEG C, and intensity of illumination is
5-500 cd/m2, the illumination reaction time is the min of 3 min ~ 60；
The solvent is toluene, tetrahydrofuran, hexamethylphosphoramide, dimethylformamide, hexamethylene or ethyl alcohol；
The initiator is 2,2- dihydromethyl propionic acid, 2- hydroxy-2-methyl -1- phenylacetone or methyl benzoylformate；
The vinyl silicone oil has structure shown in formula (II):
(II)
Y=l+m, x, l, m, R are identical with formula (I).
7. the preparation method according to claim 4, which is characterized in that the vinyl silicone oil is prepared as follows
It arrives:
By D4(octamethylcy-clotetrasiloxane), D4 ViAfter (t etram-ethyltetravinylcyclotetrasiloxane) mixing, decompression dehydration is first carried out,
It is warming up to polymeric reaction temperature after drying nitrogen displaced air, is added end-capping reagent, catalyst, after polymerization reaction, under decompression
The small molecule low-boiling-point substance in material is removed to get vinyl silicone oil is arrived；
The D4With D4 ViThe mass ratio of the material be 0.5-20:1,50-150 DEG C of polymeric reaction temperature, polymerization reaction time 0.5
~ 5h, polymerization reaction are to react under normal pressure；
The catalyst is tetramethylammonium hydroxide, potassium hydroxide, solid acid or the concentrated sulfuric acid, and the additional amount of catalyst is D4With
D4 ViThe 0.5%-5% of gross mass；
The end-capping reagent is water, hexamethyldisiloxane or 1,3- divinyl-tetramethyl disiloxane, the addition of end-capping reagent
Amount is D4And D4 ViThe 0.05-5% of gross mass.
It is answered 8. claim 1-3 is described in any item based on mercapto-alkene reaction silicon rubber/unsaturated carbon chains rubber compatilizer
With for silicon rubber/unsaturated carbon chains rubber paralled system, blending refining glue.
9. 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 8, 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).
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| CN111188183B (en) * | 2020-02-17 | 2022-06-21 | 南通纺织丝绸产业技术研究院 | Method for preparing super-hydrophobic cotton textile by utilizing thiol-ene click chemical modification |
| CN112062966A (en) * | 2020-06-23 | 2020-12-11 | 西南科技大学 | Preparation method of high-electrostriction silicone rubber dielectric elastomer |
| CN112538271A (en) * | 2020-12-09 | 2021-03-23 | 山东大学 | Hydrophilic silicone rubber capable of being used as medical catheter and preparation method and application thereof |
| CN113087905B (en) * | 2021-04-30 | 2022-09-16 | 郑州中原思蓝德高科股份有限公司 | Thiol-terminated polymer, preparation method thereof and polysulfide sealant |
| CN115028928B (en) * | 2022-06-13 | 2023-08-18 | 浙江大学 | High-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber and preparation method thereof |
| CN115785575B (en) * | 2022-12-06 | 2024-03-29 | 浙江大学 | High-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber and preparation method thereof |
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