CN106046379A - Hydrophobic sulfydryl-modified silicone rubber and preparation method thereof - Google Patents
Hydrophobic sulfydryl-modified silicone rubber and preparation method thereof Download PDFInfo
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- CN106046379A CN106046379A CN201610475405.XA CN201610475405A CN106046379A CN 106046379 A CN106046379 A CN 106046379A CN 201610475405 A CN201610475405 A CN 201610475405A CN 106046379 A CN106046379 A CN 106046379A
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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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- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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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
- 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
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention relates to surface-modified vulcanized silicone rubber and a preparation method thereof, belonging to the field of preparation of a new material. The preparation method can be used for preparing a series of silicone rubber containing carboxyl and ester group by controlling reaction conditions and material proportions. The prepared sulfydryl-modified silicone rubber has relatively high molecular weight, and the number average molecular weight is more than 200000. By adding the carboxyl and ester group, the hydrophilicity of the surface of the silicone rubber can be well increased, so that the silicone rubber can be widely applied to the field of biomedical materials with relatively high hydrophilicity requirements. In addition, the molar fraction of the carboxyl or ester group on the molecular chain of the silicone rubber can be controlled by adjusting the content of double bonds in methyl vinyl silicone rubber. The carboxyl and ester group of the lateral chain of the sulfydryl-modified silicone rubber have certain reaction activity, and the application prospect of utilizing the carboxyl and ester group for modification so as to further improve the performance of the silicone rubber is excellent.
Description
Technical field
The present invention relates to a kind of surface modification sulphurated siliastic and the method for preparation thereof, belong to the preparation field of new material.
Background technology
Silicone rubber has nontoxic, the performance of resistance to ag(e)ing, and chemical stability is splendid, still is able to keep under high temperature and low temperature
Original mechanical strength and caoutchouc elasticity, human body and silicone rubber are without obvious rejection simultaneously, and therefore silicone rubber is widely used
In medical product, can be as impression material, complete denture restoration material, injection silicon rubber filling prosthese, nose prosthesis, air bag
Shape silicone rubber lung prosthese, stomach tube, incidence vascular specimen pouring material etc. use.This will ask medical material to have good biology
The compatibility and anticoagulation function.But, silastic surface free energy is low, and material surface is hydrophobic, therefore, it is necessary to carry out silicone rubber
Hydrophilically modified, just can be applied more broadly in medical material field.
The hydrophilically modified method of silicone rubber has two kinds: this modifies and surface modification.The advantage of surface modification is to improve
The anticoagulant property of material and biocompatibility, the most do not change the excellent properties of material itself simultaneously.Surface modification is broadly divided into
Gas ions hydrophilic modifying, face coat hydrophilic modifying and surface grafting hydrophilic modifying.The present invention considers to make full use of high-vinyl
Double bond functional group on the methyl vinyl silicone rubber molecular backbone of content, carries out molecular chain structure design.Utilize sulfydryl-double bond
The principle of click chemistry, success grafted polar group on the strand of silastic surface, improve the hydrophilic of goods, improve
Its biocompatibility, have also been introduced active group simultaneously, provides reaction site for its next step chemical modification.
Summary of the invention
The present invention proposes a kind of surface modification sulphurated siliastic and the method for preparation thereof, uses sulfydryl acids, sulfydryl esters
By the reaction mechanism of click chemistry, being grafted on silicone rubber side chain, the structure of described hydrophilic silicone rubber is as follows:
R is alkyl.
Preparation method is as follows:
(1) octamethylcy-clotetrasiloxane (D in parts by weight, is taken4) 50～95 parts, t etram-ethyltetravinylcyclotetrasiloxane
(V4) 5～50 parts, catalyst 0.01～1 part, end-capping reagent 0.05～0.2 part.
(2) by octamethylcy-clotetrasiloxane (D before polymerization4), t etram-ethyltetravinylcyclotetrasiloxane (V4) and end-capping reagent exist
40～60 DEG C, under vacuum condition, it is dehydrated 2～3h, then passes to nitrogen and be also warmed up to 110～130 DEG C to normal pressure, addition catalyst,
Reaction 2～3h.
(3) after reaction terminates, being warming up to 160～170 DEG C, under vacuum conditions the little molecule in removing product, the time is 2
～3h, then pass to nitrogen to normal pressure, be cooled to room temperature, obtain methyl vinyl silicone rubber.
(4) remember with weight portion, take the methyl vinyl silicone rubber 100 parts obtained in step (2), white carbon 20～40 parts,
Hydroxy silicon oil 1～5 parts, 2,5-dimethyl-2, double (tert-butyl peroxide) hexane 0.05 of 5-～0.1 part, mixing, then 150
～180 DEG C of sulfurations, the response time is 10～40min.
(5) take the sulphurated siliastic in step (4), by washing with alcohol, put into the second equipped with sulfhydryl reagent and light trigger
In alcoholic solution, UV cure lamp (intensity 100mw/cm2) irradiation 0.5～1h, reaction temperature is 20～40 DEG C, and reaction terminates
After, by washing with alcohol, it is dried to obtain the sulfhydryl modified silicone rubber in surface.
Described catalyst is potassium hydroxide, Lithium hydrate, Tetramethylammonium hydroxide, or silicon alkoxide.
Described end-capping reagent is hexamethyl disiloxane, decamethyl tetrasiloxane or tetradecamethylhexasiloxane.
Step (5) described sulfhydryl reagent is sulfydryl acids, the TGAs such as TGA, mercaptopropionic acid, mercaptoethanol acid
The sulfydryl esters such as ethyl ester, methyl thioglycolate, mercapto-propionate, isooctyl mercaptopropionate.Light trigger described in step (4)
For dimethoxybenzoin (DMPA), methyl o-benzoylbenzoate (OMBB), (2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine
Benzyl phenyl) ultraviolet initiator such as butanone (light trigger 369).Light trigger with the mass ratio of methyl vinyl silicone rubber is
0.01～0.2.
The present invention, by controlling reaction condition and material proportion, can prepare a series of containing carboxyl, the silicone rubber of ester group.
The sulfhydryl modified silicone rubber of preparation has higher molecular weight, and its number-average molecular weight is more than 200,000.Carboxyl and the introducing of ester group
The hydrophilic of silastic surface can be improved very well.Furthermore, it is possible to by the content of double bond in regulation methyl vinyl silicone rubber
Control carboxyl or the molar fraction of ester group on silicone rubber strand.
The present invention, by the sulfhydryl modified method that technique is simple, reaction condition is gentle, is prepared for sulfhydryl modified silicon first
Rubber.The sulfhydryl modified silicone rubber of preparation has high hydrophilic, can be widely applied to bio-medical material requirement hydrophilic
Higher field.Additionally, the carboxyl of sulfhydryl modified silicone rubber side chain, ester group have certain reactivity, utilizing carboxyl, ester
Base is modified the aspects such as the performance improving silicone rubber further and also has good application prospect.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum that the silicone rubber of different contents of ethylene is modified
Fig. 2 is the DSC spectrogram that the silicone rubber of different contents of ethylene is modified
Detailed description of the invention
Embodiment 1
Taking 0.8g Tetramethylammonium hydroxide and 20g octamethylcy-clotetrasiloxane, at 50 DEG C, vacuum dehydration 1h, then heats up
To 80 DEG C of reaction 1h, prepare Tetramethylammonium hydroxide silicon alkoxide (catalyst alkali glue).Then 80g prestox ring four silica is taken
Alkane (D4), 20g t etram-ethyltetravinylcyclotetrasiloxane (V4) and 0.1g tetradecamethylhexasiloxane, 40 DEG C, under vacuum condition
Dehydration 3h, then passes to nitrogen, adds 0.6g Tetramethylammonium hydroxide silicon alkoxide (alkali glue), is warming up to 110 DEG C, reacts under normal pressure
3h.After reaction terminates, being warming up to 160 DEG C, under vacuum conditions the little molecule in removing product, the time is 3h, is then cooled to
Room temperature, obtains the methyl vinyl silicone rubber that contents of ethylene is 20%.Take 40g methyl vinyl silicone rubber, 16g white carbon,
2g hydroxy silicon oil, 0.04g 2,5-dimethyl-2, double (tert-butyl peroxide) hexane of 5-is mixing, takes 10g elastomeric compound at 160 DEG C
Sulfuration 20min.Vulcanizate is cut into the sheet rubber of 1cm*1cm, washs 10min with EtOH Sonicate.5g mercapto is added in conical flask
Guanidine-acetic acid, 0.05g dimethoxybenzoin, 50ml ethanol, configure mercaptoacetic acid solution.Sheet rubber is put in the solution prepared,
UV cure lamp (intensity 100mw/cm under stirring2) irradiation 30min, after reaction terminates, silicone rubber ethanol is washed
Wash, be dried.Silica Surface vinyl conversion rate is 100%, and recording contact angle is 80 °.
Embodiment 2
Take 70g octamethylcy-clotetrasiloxane (D4), 30g t etram-ethyltetravinylcyclotetrasiloxane (V4), in 40 DEG C, vacuum
Under the conditions of be dehydrated 2h, then pass to nitrogen to normal pressure, add 0.6g Tetramethylammonium hydroxide silicon alkoxide (alkali glue) and 0.1g 14
Methyl six siloxanes, is warming up to 120 DEG C, reacts 2h under normal pressure.After reaction terminates, it is warming up to 170 DEG C, removes under vacuum conditions
Little molecule in product, the time is 3h, is then cooled to room temperature, obtains the methyl ethylene silicon rubber that contents of ethylene is 30%
Glue.Take 20g methyl vinyl silicone rubber, 8g white carbon, 1g hydroxy silicon oil, 0.02g 2,5-dimethyl-2, double (the peroxidating uncle of 5-
Butyl) hexane is mixing, and take 10g elastomeric compound at 160 DEG C, vulcanize 20min.Vulcanizate is cut into the sheet rubber of 1cm*1cm, uses second
Alcohol supersound washing 10min.In conical flask, add 5g mercaptopropionic acid, 0.05g dimethoxybenzoin, 50ml ethanol, configure sulfydryl
Propionic acid solution.Sheet rubber is put in the solution prepared, UV cure lamp (intensity 100mw/cm under stirring2) irradiation
30min, after reaction terminates, by silicone rubber washing with alcohol, is dried.Silica Surface 30% vinyl conversion rate is 100%, records
Contact angle is 69 °.
Embodiment 3
Take 50g octamethylcy-clotetrasiloxane (D4), 50g t etram-ethyltetravinylcyclotetrasiloxane (V4), in 45 DEG C, vacuum
Under the conditions of be dehydrated 2h, then pass to nitrogen to normal pressure, add 0.6g Tetramethylammonium hydroxide silicon alkoxide (alkali glue) and 0.1g 14
Methyl six siloxanes, is warming up to 130 DEG C, reacts 3h under normal pressure.After reaction terminates, it is warming up to 160 DEG C, removes under vacuum conditions
Little molecule in product, the time is 3h, is then cooled to room temperature, obtains the methyl ethylene silicon rubber that contents of ethylene is 50%
Glue.Take 20g methyl vinyl silicone rubber, 8g white carbon, 1g hydroxy silicon oil, 0.02g 2,5-dimethyl-2, double (the peroxidating uncle of 5-
Butyl) hexane is mixing, and take 10g elastomeric compound at 160 DEG C, vulcanize 20min.Vulcanizate is cut into the sheet rubber of 1cm*1cm, uses second
Alcohol supersound washing 10min.In conical flask, add 5g mercaptopropionic acid, 0.05g dimethoxybenzoin, 50ml ethanol, configure sulfydryl
Propionic acid solution.Sheet rubber is put in the solution prepared, UV cure lamp (intensity 100mw/cm under stirring2) irradiation
30min, after reaction terminates, by silicone rubber washing with alcohol, is dried.Silica Surface 50% vinyl conversion rate is 100%, records
Contact angle is 51 °.
Embodiment 4
Take 50g octamethylcy-clotetrasiloxane (D4), 50g t etram-ethyltetravinylcyclotetrasiloxane (V4) and 0.1g hexamethyl
Disiloxane, 50 DEG C, be dehydrated 1h under vacuum condition, then pass to nitrogen, add 0.1g Lithium hydrate (LiOH), be warming up to
110 DEG C, under normal pressure, react 2h.After reaction terminates, it is warming up to 170 DEG C, under vacuum conditions the little molecule in removing product, time
For 2h, then it is cooled to room temperature, obtains the methyl vinyl silicone rubber that contents of ethylene is 50%.Take 40g methyl ethylene silicon
Rubber, 16g white carbon, 2g hydroxy silicon oil, 0.04g 2,5-dimethyl-2, double (tert-butyl peroxide) hexane of 5-is mixing, takes 10g
Elastomeric compound vulcanizes 20min under 160 degrees Celsius.Vulcanizate is cut into the sheet rubber of 1cm*1cm, washs 10min with EtOH Sonicate.
In conical flask, add 5g methyl thioglycolate, 0.05g dimethoxybenzoin, 50ml ethanol, configure mercaptopropionic acid.By rubber
Film is put in the solution prepared, UV cure lamp (intensity 100mw/cm under stirring2) irradiation 1h, reaction terminates
After, by silicone rubber washing with alcohol, it is dried.Silica Surface 50% vinyl conversion rate is 100%, and recording contact angle is 56 °.
Claims (8)
1. the sulfhydryl modified silicone rubber of hydrophilic, structure is as follows:
R is alkyl.
2. a kind of sulfhydryl modified silicone rubber of hydrophilic of preparation, it is characterised in that step is as follows:
(1) in parts by weight, octamethylcy-clotetrasiloxane 50～95 parts are taken, t etram-ethyltetravinylcyclotetrasiloxane 5～50 parts,
Catalyst 0.01～1 part, end-capping reagent 0.05～0.2 part.
(2) by octamethylcy-clotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane and end-capping reagent at 40～60 DEG C before being polymerized, very
It is dehydrated 2～3h under empty condition, then passes to nitrogen and be also warmed up to 110～130 DEG C to normal pressure, addition catalyst, react 2～3h.
(3) reaction terminate after, be warming up to 160～170 DEG C, under vacuum conditions removing product in little molecule, the time be 2～
3h, then passes to nitrogen to normal pressure, is cooled to room temperature, obtains methyl vinyl silicone rubber.
(4) remember with weight portion, take the methyl vinyl silicone rubber 100 parts obtained in step (3), white carbon 20～40 parts, hydroxyl
Silicone oil 1～5 parts, 2,5-dimethyl-2, double (tert-butyl peroxide) hexane 0.05 of 5-～0.1 part, mixing, then 150～180
DEG C sulfuration obtains sulphurated siliastic, and the response time is 10～40min.
(5) take the sulphurated siliastic in step (4), by washing with alcohol, put into the ethanol equipped with sulfhydryl reagent and light trigger molten
In liquid, UV cure lamp irradiation 0.5～1h, reaction temperature is 20～40 DEG C, after reaction terminates, by washing with alcohol, is dried
The sulfhydryl modified silicone rubber to surface.
Method the most according to claim 1, it is characterised in that: UV cure lamp intensity 100mw/cm2-150mw/cm2)
Method the most according to claim 1, it is characterised in that: described catalyst is potassium hydroxide, Lithium hydrate, tetramethyl
Ammonium hydroxide, or silicon alkoxide.
Method the most according to claim 1, it is characterised in that: described end-capping reagent is hexamethyl disiloxane, decamethyl four
Siloxanes or tetradecamethylhexasiloxane.
Method the most according to claim 1, it is characterised in that: step (5) described sulfhydryl reagent is TGA, sulfydryl third
Acid, mercaptoethanol acid, ethyl thioglycolate, methyl thioglycolate, mercapto-propionate or isooctyl mercaptopropionate.
Method the most according to claim 1, it is characterised in that: the light trigger described in step (4) be dimethoxybenzoin,
Methyl o-benzoylbenzoate or the (ultraviolet initiator such as 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone.
Method the most according to claim 1, it is characterised in that: light trigger with the mass ratio of methyl vinyl silicone rubber is
0.01～0.2.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496567A (en) * | 2016-12-05 | 2017-03-15 | 山东大学 | A kind of three thioesters of organosilicon for reversible addition-fragmentation chain transfer free radical polymerization and preparation method and application |
| CN107759820A (en) * | 2017-11-21 | 2018-03-06 | 海昌隐形眼镜有限公司 | A kind of method and application process of silastic surface hydrophilic modifying |
| CN109810252A (en) * | 2018-12-26 | 2019-05-28 | 福建拓烯新材料科技有限公司 | A kind of preparation method of organic siliconresin microemulsion |
| 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 |
| CN115785575A (en) * | 2022-12-06 | 2023-03-14 | 浙江大学 | High-strength anti-aging ethylene propylene diene monomer/silicone rubber blended rubber and preparation method thereof |
| CN117379605A (en) * | 2023-12-12 | 2024-01-12 | 湖南精涂医疗科技有限公司 | Medical silica gel surface hydrophilic modified coating and preparation method and application thereof |
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| CN102731789A (en) * | 2012-07-11 | 2012-10-17 | 常州大学 | Preparation method of surface hydrophilic silicon rubber |
| CN105237769A (en) * | 2015-11-13 | 2016-01-13 | 浙江中天氟硅材料有限公司 | Preparation method for methyl vinyl silicone rubber |
| CN105601928A (en) * | 2016-02-27 | 2016-05-25 | 北京化工大学 | Hydrophilic sulfydryl modified silicone rubber and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496567A (en) * | 2016-12-05 | 2017-03-15 | 山东大学 | A kind of three thioesters of organosilicon for reversible addition-fragmentation chain transfer free radical polymerization and preparation method and application |
| CN106496567B (en) * | 2016-12-05 | 2019-05-03 | 山东大学 | A kind of three thioesters of organosilicon and the preparation method and application thereof for reversible addion-fragmentation chain transfer free radical polymerization |
| CN107759820A (en) * | 2017-11-21 | 2018-03-06 | 海昌隐形眼镜有限公司 | A kind of method and application process of silastic surface hydrophilic modifying |
| CN109810252A (en) * | 2018-12-26 | 2019-05-28 | 福建拓烯新材料科技有限公司 | A kind of preparation method of organic siliconresin microemulsion |
| CN109810252B (en) * | 2018-12-26 | 2021-05-04 | 福建拓烯新材料科技有限公司 | Preparation method of organic silicon resin microemulsion |
| 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 |
| CN115785575A (en) * | 2022-12-06 | 2023-03-14 | 浙江大学 | High-strength anti-aging ethylene propylene diene monomer/silicone rubber blended 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 |
| CN117379605A (en) * | 2023-12-12 | 2024-01-12 | 湖南精涂医疗科技有限公司 | Medical silica gel surface hydrophilic modified coating and preparation method and application thereof |
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Application publication date: 20161026 |