CN106496566A - A kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto alkene reaction and preparation method and application - Google Patents
A kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto alkene reaction and preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto alkene reaction and preparation method and application, the compatilizer has the 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.The compatilizer compatibilization effect of the present invention is excellent, is remarkably improved the tensile strength and tearing strength of silicon rubber/unsaturated carbon chains rubber blending system, and, up to 2.63MPa, tearing strength raising amount is up to 2.98KN/m for tensile strength raising amount.
Description
Technical field
The present invention relates to a kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto-alkene reaction and preparation method thereof,
Belong to rubber chemicals technical field.
Background technology
At present, including the unsaturated carbon chains rubber such as butyl rubber, natural rubber, nitrile rubber be most widely used one
Class rubber.By taking butyl rubber (IIR) as an example, as pending methyl group is very intensive on its strand, vermicular texture is formed, thus is had
There is higher fissipation factor, and because secondary transition is there is near the glass transition temperature of butyl rubber, cause its in-fighting
Peak was not only high but also wide, thus there is excellent damping effect by butyl rubber, and the damping material prepared with which is in Aero-Space, automobile
The fields such as manufacture are widely used.But the temperature province that butyl rubber plays damping action is narrower, especially in low temperature
Under environment, it is difficult to meet use requirement.
Organosilicon polymer with silicon rubber as representative, with good resistant of high or low temperature, heat endurance, weatherability and resistance to
Aging, within the scope of very wide temperature, its performance quite stable, but its mechanical property is poor.
Blending is the effective way for improving 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 silicon rubber and the difference of unsaturated carbon chains butyl structures, cause their poor compatibility, altogether
Easily it is separated when mixed, makes the material of preparation not reach expected requirement, or even reduce performance.
Chinese patent document CN105418935A (application number：CN201510982704.8) a kind of graft polymers is disclosed
Compatilizer and preparation method and application, compatilizer are the SANs with Merlon (PC) as main chain
(SAN) it is the graft polymers of side chain, i.e. PC-g-SAN.The compatilizer can effectively reduce PC/ABS and PC/ASA system phase boundaries
Face tension force is so as to improving compatibility.But, the synthesis condition of the compatilizer is more harsh, and reaction temperature is high, system range of application
Narrow.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of silicon rubber/unsaturated carbon chains rubber based on mercapto-alkene reaction
Compatilizer and preparation method and application.Compatilizer applicability of the invention is extensive, cost of material is low, process is simple, compatilizer
Compatibilization effect is good.Prepare reaction efficiency height, react thorough, high conversion rate, purity height.Silicon rubber be can be widely applied to unsaturation
In the paralled system of carbochain rubber.
Technical scheme is as follows：
A kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto-alkene reaction, with the 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 of described alkyl for C1-C10, further preferred methyl, ethyl or propyl group；
Alkylene of the described alkylene for C2-C20, further preferred vinyl or pi-allyl.
, according to the invention it is preferred to, described 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, grafting thiol molecule formula used is CnH2n+1SH, 2≤n≤30, n are integer；Enter 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 is as follows including step：
It is dissolved in after mercaptan is mixed with vinyl silicone oil in solvent, adds initiator, stirring to be reacted under illumination；Instead
After should terminating, product is washed, then removes the small molecule low-boiling-point substance in material under reduced pressure, that is, obtain compatilizer.
Preparation in accordance with the present invention, it is preferred that the mixed proportion of mercaptan and vinyl silicone oil is with mercaptan and vinyl
Ratio calculate, the amount ratio of its material is 0.001-10：1.
Preparation in accordance with the present invention, it is preferred that the addition of initiator is mercaptan and vinyl silicone oil gross mass
0.5%-5%.
Preparation in accordance with the present invention, it is preferred that reaction temperature is 10 DEG C -90 DEG C.
Preferably, intensity of illumination is 5-500cd/m2, the illumination reaction time is 3min～60min.
Preparation in accordance with the present invention, it is preferred that described solvent be toluene, tetrahydrofuran, HMPA,
Dimethylformamide, hexamethylene or ethanol；Described initiator is 2,2- dihydromethyl propionic acids, 2- hydroxy-2-methyl -1- phenyl
Acetone or methyl benzoylformate.
Preparation in accordance with the present invention, it is preferred that described vinyl silicone oil has the structure shown in formula (II)：
Identical in y=l+m, x, l, m, R and formula (I).Preferably, the number-average molecular weight of vinyl silicone oil is 0.3～100,000,
Vinyl molar content 5%-50%.
Preparation in accordance with the present invention, it is preferred that described vinyl silicone oil is prepared as follows obtaining：
By D4(octamethylcy-clotetrasiloxane), D4 ViAfter (t etram-ethyltetravinylcyclotetrasiloxane) mixing, first reduced pressure
Dehydration, is warming up to polymeric reaction temperature after drying nitrogen displaced air, add end-capping reagent, catalyst, after polymerisation terminates, subtract
Small molecule low-boiling-point substance in pressure removing material, that is, obtain vinyl silicone oil.Vinyl silicone oil molecular weight is by catalyst and envelope
The consumption control of end agent.
According to the preparation method of vinyl silicone oil of the present invention, it is preferred that described D4With D4 ViMaterial amount ratio be 0.5-
20:1.
According to the preparation method of vinyl silicone oil of the present invention, it is preferred that 50-150 DEG C of polymeric reaction temperature, during polymerisation
Between be 0.5～5h, polymerisation be normal pressure under react.
According to the preparation method of vinyl silicone oil of the present invention, it is preferred that described catalyst is TMAH, hydrogen
Potassium oxide, solid acid or the concentrated sulfuric acid, the addition of catalyst is D4And D4 ViThe 0.5%-5% of gross mass；
It is further preferred that described solid acid is Emathlite, sulfonate resin or heteropoly acid, the matter of the described concentrated sulfuric acid
Amount concentration is 90%-98%.
According to the preparation method of vinyl silicone oil of the present invention, it is preferred that described end-capping reagent is water, HMDO
Or 1,3- divinyl-tetramethyl disiloxane, the addition 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, for the paralled system of silicon rubber/unsaturated carbon chains rubber, blending
Refining glue.
Application according to the present invention, the preparation of silicon rubber/unsaturated carbon chains rubber blending system can be in mill or close
Carry out in mill.Preferably, the preparation method of silicon rubber/unsaturated carbon chains rubber blending system raw material is as follows：
Compatilizer is added in silicon rubber and unsaturated carbon chains rubber, while adding white carbon, vulcanizing agent, sulfuration promotion
Agent, auxiliary agent, mixing are uniform, and in 140-180 DEG C, sulfuration molding 10-35min obtains final product silicon rubber/unsaturated carbon chains rubber blending body
System.
Application according to the present invention, it is preferred that described unsaturated carbon chains rubber is butyl rubber, natural rubber or butyronitrile
Rubber；
Preferably, the number-average molecular weight of described silicon rubber be 30～1,000,000, vinyl molar content be 0.05%～
5%；
Preferably, described white carbon is fume colloidal silica or precipitated silica；
Preferably, described auxiliary agent is the mixture of lubricant and reinforced additive；It is further preferred that described lubrication
Agent is stearic acid, and described reinforced additive is aluminum oxide or zinc oxide.
Application according to the present invention, it is preferred that described vulcanizing agent is double 2,5, cumyl peroxide (DCP), sulphur,
Two kinds in benzoyl peroxide, 2,4- dichlorobenzoperoxides, the perbenzoic acid tert-butyl group, di-t-butyl peroxide or
Two or more mixing；
Preferably, described vulcanization accelerator is 4,4 '-dithio morpholine (DTDM), dithiocar-bamate, Huang
Two kinds in ortho acid salt, thiazole and tetramethylthiuram disulfide (TMTD) press 0.1～10:The mixture of 1 mass ratio.
Application according to the present invention, it is preferred that silicon rubber, unsaturated carbon chains rubber, white carbon, vulcanizing agent, sulfuration promote
Agent, auxiliary agent, the mass ratio of compatilizer are 100：(10-1000)：(20-200)：(0.05-5)：(0.01-3)：(0.01-3)：
(0.5-5).
The principle and feature of the present invention is as follows：
The present invention makes vinyl silicone oil side chain graft mercaptan prepare compatilizer using mercapto-alkene reaction and prepares vinyl silicone oil,
Its number-average molecular weight is 0.3～100,000, the too big mechanical strength for affecting Blend rubber of molecular weight, and molecular weight is too little to cause compatilizer
Compatibilization effect is not obvious；In 5%-50%, contents of ethylene is from synthesis complexity and compatilizer increase-volume to contents of ethylene
The factors such as effect determine；Specified end group can make paralled system have specific performance, and such as end group can make compatible for vinyl
Agent " chain extension ", can increase paralled system mechanical property；End group can play physics compatibilization effect for alkyl, can strengthen and use body
The damping capacity of system；Hydroxyl can make compatilizer have certain polarity, it is adaptable to the paralled system of polarized group.
Be obtained compatilizer a certain amount of mercaptan being grafted by mercapto-alkene reaction, wherein the percent grafting of sulfydryl is in 10%-
100% is advisable, i.e., the mixed proportion of mercaptan and vinyl silicone oil is calculated with the ratio of mercaptan and vinyl, and the amount ratio of its material is
0.001-10：1.
Compatilizer should be advisable at 0.5 part -5 parts using number, in terms of 100 parts of silicon rubber, not have compatibilization effect very little, too
Paralled system mechanical strength how can be caused to reduce.
The present invention has the advantage that：
1st, in compatilizer preparation process of the invention, high using mercapto alkene reaction preparation efficiency, high conversion rate, purity are high, former
Material low cost, process is simple；
2nd, 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；
3rd, compatilizer compatibilization effect of the invention is excellent, is remarkably improved silicon rubber/unsaturated carbon chains rubber blending system
Tensile strength and tearing strength, up to 2.63MPa, tearing strength raising amount is up to 2.98KN/m for tensile strength raising amount.
Description of the drawings
Fig. 1 is the infrared spectrum of compatilizer obtained in the present invention.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, but not limited to this.
Number described in embodiment is weight portion.
Embodiment 1
(1) preparation of vinyl silicone oil
By 270g D4, 35g D4 ViAdd polymerization reaction kettle be dehydrated, dehydration conditions be -0.01～-0.02MPa, 60
～80 DEG C, 2h is warming up to 80～120 DEG C of polymerization temperature after drying nitrogen ventilation, adds HMDO end-capping reagent, hydrogen-oxygen
Change potassium catalyst, synthesis under normal pressure 4h, after polymerization terminates, is warming up to 150 DEG C, little point under 133～1330Pa in removing material
Sub- low-boiling-point substance, time obtain vinyl silicone oil for 2h, and its molecular weight is by HMDO end-capping reagent and potassium hydroxide catalysed
The consumption control of agent, 5 or so, contents of ethylene is 10% or so for number-average molecular weight.
The structural formula of obtained vinyl silicone oil is as follows：
(2) preparation of compatilizer
The vinyl silicone oil that 9.8g n- dodecyl mereaptans and 37g steps (1) are obtained is added in 50g toluene solvants, light-initiated
Agent 2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, stirring.
Product is washed 3～4 times, is warming up to 120 DEG C, and the small molecule in the lower removing material of 133～1330Pa decompressions is low
Boiling thing obtains 44g compatilizers, yield 96%, and number-average molecular weight is 60,000 or so.
The structural formula of obtained compatilizer is as follows：
(3) preparation of silicon rubber/unsaturated carbon chains rubber blending system raw material
By 100 parts of raw-silastic continuously, 10 parts of butyl rubber, 30 parts of white carbon, 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 are sequentially added two-roll mill
Upper mixing is uniform, carries out 160 DEG C with the material, 20min sulfuration moldings, that is, obtain 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 ViAdd polymerization reaction kettle be dehydrated, dehydration conditions be -0.01～-0.02MPa, 60
～80 DEG C, 2h is warming up to 80～120 DEG C of polymerization temperature after drying nitrogen ventilation, adds 1,3- divinyl-two silica of tetramethyl
Alkane end-capping reagent, TMAH catalyst, synthesis under normal pressure 4h, after polymerization terminates, are warming up to 150 DEG C, in 133～1330Pa
Small molecule low-boiling-point substance in lower removing material, time obtain vinyl silicone oil for 2h, and its molecular weight passes through 1,3- divinyl-tetramethyl
The consumption control of base disiloxane end-capping reagent and TMAH catalyst, 30,000 or so, vinyl contains number-average molecular weight
Measure 10% or so.
The structural formula of obtained vinyl silicone oil is as follows：
(2) preparation of compatilizer
The vinyl silicone oil that positive for 14g stearylmercaptan and 37g steps (1) are obtained is added in 60g tetrahydrofuran solvents, and light draws
Send out agent methyl benzoylformate 1.8g, 60 DEG C of reaction temperature, illumination 40min, stirring.
Product is washed 3～4 times, is warming up to 120 DEG C, and the small molecule in the lower removing material of 133～1330Pa decompressions is low
Boiling thing obtains 48g compatilizers, yield 95%, and number-average molecular weight is 40,000 or so.
The structural formula of obtained compatilizer is as follows：
(3) preparation of silicon rubber/unsaturated carbon chains rubber blending system raw material
By 30 parts of raw-silastic continuously, 70 parts of natural rubber, 30 parts of white carbon, 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 are sequentially added in two-roll mill and knead uniformly, carry out 160 with the material
DEG C, 20min sulfuration moldings 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 ViAdd polymerization reaction kettle be dehydrated, dehydration conditions be -0.01～-0.02MPa, 60
～80 DEG C, 2h is warming up to 80～120 DEG C of polymerization temperature after drying nitrogen ventilation, adds HMDO end-capping reagent, hydrogen-oxygen
Change potassium catalyst, synthesis under normal pressure 4h, after polymerization terminates, is warming up to 150 DEG C, little point under 133～1330Pa in removing material
Sub- low-boiling-point substance, time obtain vinyl silicone oil for 2h, and its molecular weight is by HMDO end-capping reagent and potassium hydroxide catalysed
The consumption control of agent, 30,000 or so, contents of ethylene is 5% or so for number-average molecular weight.
The structural formula of obtained vinyl silicone oil is as follows：
(2) preparation of compatilizer
The vinyl silicone oil that 5g n- dodecyl mereaptans and 37g steps (1) are obtained adds 50g HMPA solvents
In, light trigger 2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, stirring.
Product is washed 3～4 times, is warming up to 120 DEG C, and the small molecule in the lower removing material of 133～1330Pa decompressions is low
Boiling thing obtains 39g compatilizers, yield 93%, and number-average molecular weight is 3.4 ten thousand or so.
The structural formula of obtained compatilizer is as follows：
(3) preparation of silicon rubber/unsaturated carbon chains rubber blending system raw material
Concrete operations mode is same as Example 1.
Embodiment 4
(1) preparation of vinyl silicone oil
By 270g D4, 35g D4 ViAdd polymerization reaction kettle be dehydrated, dehydration conditions be -0.01～-0.02MPa, 60
～80 DEG C, 2h is warming up to 80～120 DEG C of polymerization temperature after drying nitrogen ventilation, adds HMDO end-capping reagent, hydrogen-oxygen
Change potassium catalyst, synthesis under normal pressure 4h, after polymerization terminates, is warming up to 150 DEG C, little point under 133～1330Pa in removing material
Sub- low-boiling-point substance, time obtain vinyl silicone oil for 2h, and its molecular weight is by HMDO end-capping reagent and potassium hydroxide catalysed
The consumption control of agent, 10,000 or so, contents of ethylene is 10% or so for number-average molecular weight.
The structural formula of obtained vinyl silicone oil is as follows：
(2) preparation of compatilizer
The vinyl silicone oil that 9.8g n- dodecyl mereaptans and 37g steps (1) are obtained is added in 60g toluene solvants, light-initiated
Agent 2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, stirring.
Product is washed 3～4 times, is warming up to 120 DEG C, and the small molecule in the lower removing material of 133～1330Pa decompressions is low
Boiling thing obtains 44g compatilizers, yield 94%, and number-average molecular weight is 1.2 ten thousand or so.
The structural formula of obtained compatilizer is as follows：
(3) preparation of silicon rubber/unsaturated carbon chains rubber blending system raw material
Concrete operations mode is same as Example 1.
Embodiment 5
(1) preparation of vinyl silicone oil
By 45g D4, 35g D4 ViAdd polymerization reaction kettle be dehydrated, dehydration conditions be -0.01～-0.02MPa, 60～
80 DEG C, 2h is warming up to 80～120 DEG C of polymerization temperature after drying nitrogen ventilation, adds HMDO end-capping reagent, solid acid
Catalyst, synthesis under normal pressure 4h, after polymerization terminates, are warming up to 150 DEG C, and the small molecule under 133～1330Pa in removing material is low
Boiling thing, time obtain vinyl silicone oil for 2h, and its molecular weight is by HMDO end-capping reagent and the use of solid acid catalyst
Amount control, 30,000 or so, contents of ethylene is 40% or so for number-average molecular weight.
The structural formula of obtained vinyl silicone oil is as follows：
(2) preparation of compatilizer
The vinyl silicone oil that 33g n- dodecyl mereaptans and 37g steps (1) are obtained is added in 80g alcohol solvents, light trigger
2,2- dihydromethyl propionic acid 2g, 50 DEG C of reaction temperature, illumination 40min, stirring.
Product is washed 3～4 times, is warming up to 120 DEG C, and the small molecule in the lower removing material of 133～1330Pa decompressions is low
Boiling thing obtains 64g compatilizers, yield 91%, and number-average molecular weight is 60,000 or so.
The structural formula of obtained compatilizer is as follows：
(3) preparation of silicon rubber/unsaturated carbon chains rubber blending system raw material
Concrete operations mode is same as Example 1.
Embodiment 6
(1) preparation of vinyl silicone oil
By 270g D4, 35g D4 ViAdd polymerization reaction kettle be dehydrated, dehydration conditions be -0.01～-0.02MPa, 60
～80 DEG C, 2h is warming up to 80～120 DEG C of polymerization temperature after drying nitrogen ventilation, adds a certain amount of water, concentrated sulfuric acid catalyst,
Synthesis under normal pressure 4h, after polymerization terminates, is warming up to 150 DEG C, the small molecule low-boiling-point substance under 133～1330Pa in removing material, when
Between obtain vinyl silicone oil for 2h, consumption control of its molecular weight by water and the concentrated sulfuric acid, number-average molecular weight 30,000 or so, ethene
Base content is 10% or so.
The structural formula of obtained vinyl silicone oil is as follows：
(2) preparation of compatilizer
The vinyl silicone oil that 9.8g n- dodecyl mereaptans and 37g steps (1) are obtained is added in 50g cyclohexane solvents, and light draws
Send out agent 2- hydroxy-2-methyl -1- phenylacetone 1.5g, 50 DEG C of reaction temperature, illumination 40min, stirring.
Product is washed 3～4 times, is warming up to 120 DEG C, and the small molecule in the lower removing material of 133～1330Pa decompressions is low
Boiling thing obtains 45g compatilizers, yield 97%, and number-average molecular weight is 3.5 ten thousand or so.
The structural formula of obtained compatilizer is as follows：
(3) preparation of silicon rubber/unsaturated carbon chains rubber blending system raw material
Concrete operations mode is same as Example 1.
Comparative example 1
Concrete operations mode is same as Example 1, and difference is that step (3) compatilizer addition is 0 part.
Comparative example 2
Concrete operations mode is same as Example 2, and difference is that step (3) compatilizer addition is 0 part.
Comparative example 3
Concrete operations mode is same as Example 1, and difference is that step (3) compatilizer addition is 1 part.
Comparative example 4
Concrete operations mode is same as Example 1, and difference is that step (3) compatilizer addition is 10 parts.
Comparative example 5
Concrete operations mode is same as Example 1, and difference is that the compatilizer molecular weight that step (2) is obtained is
2000.
Comparative example 6
Concrete operations mode is same as Example 1, and difference is that the compatilizer molecular weight that step (2) is obtained 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 proportioning embodiment (parts by weight)
2 silicon rubber of table/unsaturated carbon chains rubber vulcanization system proportioning 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 understand that at identical conditions, the compatilizer of the addition present invention can be significantly improved
The tensile strength and tearing strength of silicon rubber/unsaturated carbon chains rubber (butyl rubber) paralled system, tensile strength raising amount reach
2.63MPa, tearing strength raising amount reach 2.98KN/m.
Comparative example 2 and comparative example 2 understand that at identical conditions, the compatilizer of the addition present invention can be significantly improved
The tensile strength and tearing strength of silicon rubber/unsaturated carbon chains rubber (natural rubber) paralled system, tensile strength raising amount reach
1.08MPa, tearing strength raising amount reach 1.30KN/m.
Knowable to comparative example 1 and comparative example 3, comparative example 1 and comparative example 3, at identical conditions, add the present invention's
Compatilizer is crossed that I haven't seen you for ages and causes the compatibilization effect of silicon rubber/unsaturated carbon chains rubber blending system unobvious.
Knowable to comparative example 1 and comparative example 4, comparative example 1 and comparative example 4, at identical conditions, add the present invention's
Compatilizer excessively can cause the compatibilization effect of silicon rubber/unsaturated carbon chains rubber blending system to decline on the contrary.
Knowable to comparative example 1 and comparative example 5, comparative example 1 and comparative example 5, at identical conditions, add the present invention's
The too small meeting of compatilizer molecular weight causes the compatibilization effect of silicon rubber/unsaturated carbon chains rubber blending system unobvious.
Knowable to comparative example 1 and comparative example 6, comparative example 1 and comparative example 6, at identical conditions, add the present invention's
Compatilizer molecular weight is crossed conference and causes the compatibilization effect of silicon rubber/unsaturated carbon chains rubber blending system unobvious.
Knowable to comparative example 3 and embodiment 4, at identical conditions, silicone oil used by the compatilizer of the present invention is added
The too small meeting of contents of ethylene causes the compatibilization effect of silicon rubber/unsaturated carbon chains rubber blending system unobvious.
Knowable to comparative example 3 and embodiment 5, at identical conditions, silicone oil used by the compatilizer of the present invention is added
Contents of ethylene can excessively cause the compatibilization effect of silicon rubber/unsaturated carbon chains rubber blending system unobvious.
Knowable to comparative example 1, embodiment 4 and embodiment 6, at identical conditions, the compatilizer end of the present invention is added
Base difference can cause the compatibilization effect difference of silicon rubber/unsaturated carbon chains rubber blending system, and compatibilization effect is with compatilizer end group
Successively decrease for alkylene, alkyl, hydroxyl successively.
Claims (10)
1. a kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto-alkene reaction, with the 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.
2. silicon rubber/unsaturated carbon chains rubber the compatilizer based on mercapto-alkene reaction according to claim 1, its feature exist
In described alkyl is the alkyl of C1-C10, preferably methyl, ethyl or propyl group；
Alkylene of the described alkylene for C2-C20, preferred vinyl or pi-allyl.
3. silicon rubber/unsaturated carbon chains rubber the compatilizer based on mercapto-alkene reaction according to claim 1, its feature exist
In described compatilizer number-average molecular weight is 0.5-15 ten thousand.
4. the preparation of the silicon rubber based on mercapto-alkene reaction described in any one of claim 1-3/unsaturated carbon chains rubber compatilizer
Method is as follows including step：
It is dissolved in after mercaptan is mixed with vinyl silicone oil in solvent, adds initiator, stirring to be reacted under illumination；Reaction knot
Shu Hou, product are washed, then remove the small molecule low-boiling-point substance in material under reduced pressure, that is, obtain compatilizer.
5. preparation method according to claim 4, it is characterised in that the mixed proportion of mercaptan and vinyl silicone oil is with mercaptan
Calculate with the ratio of vinyl, the amount ratio of its material is 0.001-10：1；
Preferably, described thiol molecule formula is CnH2n+1SH, 2≤n≤30, n are integer；
The addition of initiator is the 0.5%-5% of mercaptan and vinyl silicone oil gross mass.
6. preparation method according to claim 4, it is characterised in that reaction temperature is 10 DEG C -90 DEG C, and intensity of illumination is 5-
500cd/m2, the illumination reaction time is 3min～60min；
Preferably, described solvent is toluene, tetrahydrofuran, HMPA, dimethylformamide, hexamethylene or second
Alcohol；Described initiator is 2,2- dihydromethyl propionic acids, 2- hydroxy-2-methyl -1- phenylacetones or methyl benzoylformate.
Preferably, described vinyl silicone oil has the structure shown in formula (II)：
Identical in y=l+m, x, l, m, R and formula (I).
7. preparation method according to claim 4, it is characterised in that described vinyl silicone oil is prepared as follows
Arrive：
By D4(octamethylcy-clotetrasiloxane), D4 ViAfter (t etram-ethyltetravinylcyclotetrasiloxane) mixing, decompression dehydration is carried out first,
Polymeric reaction temperature is warming up to after drying nitrogen displaced air, adds end-capping reagent, catalyst, after polymerisation terminates, under decompression
Small molecule low-boiling-point substance in removing material, that is, obtain vinyl silicone oil；
Described D4With D4 ViMaterial amount ratio be 0.5-20:1,50-150 DEG C of polymeric reaction temperature, polymerization reaction time are 0.5
～5h, polymerisation are to react under normal pressure；
Described catalyst is TMAH, potassium hydroxide, solid acid or the concentrated sulfuric acid, and the addition of catalyst is D4With
D4 ViThe 0.5%-5% of gross mass；
Described end-capping reagent be water, HMDO or 1,3- divinyl-tetramethyl disiloxane, the addition of end-capping reagent
Measure as D4And D4 ViThe 0.05-5% of gross mass.
8. the silicon rubber based on mercapto-alkene reaction described in any one of claim 1-3/unsaturated carbon chains rubber compatilizer should
With for the paralled system of silicon rubber/unsaturated carbon chains rubber, blending refining glue.
9. application according to claim 8, it is characterised in that silicon rubber/unsaturated carbon chains rubber blending system raw material
Preparation method is as follows：
Compatilizer is added in silicon rubber and unsaturated carbon chains rubber, at the same add white carbon, vulcanizing agent, vulcanization accelerator,
Auxiliary agent, mixing are uniform, and in 140-180 DEG C, sulfuration molding 10-35min obtains final product silicon rubber/unsaturated carbon chains rubber blending system.
10. application according to claim 8, it is characterised in that described unsaturated carbon chains rubber is butyl rubber, natural
Rubber or nitrile rubber；
The number-average molecular weight of described silicon rubber is 30～1,000,000, and vinyl molar content is 0.05%～0.5%；
Described white carbon is fume colloidal silica or precipitated silica；
Described auxiliary agent is the mixture of lubricant and reinforced additive；
Described vulcanizing agent is double 2,5, cumyl peroxide (DCP), sulphur, benzoyl peroxide, 2,4- dichloro peroxidating
Two or more mixing in benzoyl, the perbenzoic acid tert-butyl group, di-t-butyl peroxide；
Described vulcanization accelerator is 4,4 '-dithio morpholine (DTDM), dithiocar-bamate, xanthates, thiazole
0.1～10 is pressed with two kinds in tetramethylthiuram disulfide (TMTD):The mixture of 1 mass ratio；
Silicon rubber, unsaturated carbon chains rubber, white carbon, vulcanizing agent, vulcanization accelerator, auxiliary agent, the mass ratio of compatilizer are 100：
(10-1000)：(20-200)：(0.05-5)：(0.01-3)：(0.01-3)：(0.5-5).
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| CN112062966A (en) * | 2020-06-23 | 2020-12-11 | 西南科技大学 | Preparation method of high-electrostriction silicone rubber dielectric elastomer |
| WO2022121328A1 (en) * | 2020-12-09 | 2022-06-16 | 山东大学 | Hydrophilic silicone rubber serving as medical catheter, preparation method therefor and application thereof |
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| CN115028928A (en) * | 2022-06-13 | 2022-09-09 | 浙江大学 | High-performance ethylene propylene diene monomer/silicone rubber blend and preparation method thereof |
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