CN106009680B - A kind of silicon rubber/polylactic acid thermoplastic sulfurized rubber and preparation method thereof - Google Patents
A kind of silicon rubber/polylactic acid thermoplastic sulfurized rubber and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of silicon rubber/polylactic acid thermoplastic sulfurized rubbers and preparation method thereof, devise a kind of collaboration compatibilization system with good result, improve the interfacial interaction of polylactic acid and silicon rubber, tensile strength is obtained up to 25MPa, elongation at break is up to 200%, silicon rubber/polylactic acid thermoplastic sulfurized rubber with antistatic property, barrier properties for gases.So that the application extension of silicon rubber is to thermoplastic sulfurized rubber field, while further having widened the application range of polylactic acid, new material that is a kind of not only biodegradable but also can applying in field of biomedicine is provided.
Description
[technical field]
The present invention relates to a kind of silicon rubber (SR)/polylactic acid (PLA) thermoplastic sulfurized rubbers of dynamic vulcanization technology preparation, especially
It is related to a kind of mechanical strength height, the gas obtained using the method for functional graphene oxide and silane coupling agent collaboration increase-volume
Good, the antistatic and degradable part biological silicon rubber/polylactic acid thermoplastic sulfurized rubber of body barrier property belongs to new material preparation
Field.
[background technique]
Thermoplastic sulfurized rubber (TPV) is using the novel high polymer material of dynamic vulcanization technology preparation, and have both plastics can
The high resiliency of processability and rubber overcomes the deficiency of traditional rubber processing mode, in automobile component, sealing, medical treatment, packaging etc.
There is extensive and important application in field.
In recent years, based on the thermoplastic sulfurized rubber of PLA by extensive concern, and existing related patents occur, such as Patent No.
The Chinese invention patent of ZL 201310617651.0 discloses a kind of nitrile rubber/polylactic acid thermoplastic of dynamic vulcanization process preparation
Property vulcanizate, this thermoplastic sulfurized rubber can part biological degradation, while tensile strength reaches 15MPa, and elongation at break can
Up to 300%.The Chinese invention patent of Patent No. ZL201310618529.5 discloses a kind of polyurethane/polylactic acid thermoplasticity sulphur
Change glue and preparation method thereof, provides the novel elastomer material of a kind of not only biodegradable but also repeatable processing and utilization.It is worth
It is noted that the physical mechanical property that disclosed in foregoing invention although polylactic acid base TPV has been obtained, but due to elasticity used
Body component does not have biocompatibility, and in field of biomedicine, there is no too big practical values；Patent No.
The Chinese invention patent of ZL201210265636.X discloses a kind of degradable biological based thermoplastic vulcanizate, but made vulcanization
Glue intensity and elongation at break are relatively low, and polyester-type biology based elastomeric used is also in laboratory synthesis phase, difficult
To realize industrialization large-scale production.Additionally it has been disclosed that TPV technology of preparing in there has been no using functional graphene oxide with
The method of other components collaboration increase-volume.
Silicon rubber has good biocompatibility, high-low temperature resistant, electrical insulation capability, is widely used in biomedical neck
Domain.But the mechanical strength of silicon rubber is low, bad mechanical property, limits its extensive use.By silicon rubber in conjunction with polylactic acid, use
Dynamic vulcanization technology prepares vulcanizate, is expected to obtain with higher force intensity, good biological is compatible and part biological is degradable
The material of property, and be widely applied in biologic medical field.But due to the solubility parameter (21J of silicon rubber1/2·cm-3/2)
With polylactic acid solubility parameter (15.7J1/2·cm-3/2) differ too big, the poor compatibility of two kinds of polymer, it is prone to macroscopic view
It mutually separates, it is difficult to be blended.The present invention cooperates with increase-volume silicon rubber/polylactic acid using the graphene oxide and silane coupling agent of functionalization
Thermoplastic sulfurized rubber utilizes height possessed by functional graphene oxide while improving silicon rubber and polylactic acid compatibility
The performances such as elasticity modulus (≈ 1TPa), high-specific surface area, antistatic, make made TPV have both biocompatibility, super good physical machine
Tool performance, air-tightness and antistatic property.
[summary of the invention]
[technical problems to be solved]
The purpose of the present invention is to provide a kind of silicon rubber/polylactic acid thermoplastic sulfurized rubbers of dynamic vulcanization process preparation.
It is another object of the present invention to provide a kind of silicon rubber/polylactic acid thermoplastic sulfurized rubber preparation methods.
Increase-volume is cooperateed with silane coupling agent with functional graphene oxide it is another object of the present invention to provide a kind of
The method of thermoplastic sulfurized rubber.
[technical solution]
The invention discloses a kind of silicon rubber/polylactic acid thermoplastic sulfurized rubber (calling SR/PLATPV in the following text) and preparation method thereof,
The thermoplastic sulfurized rubber cooperates with increase-volume silicon rubber with silane coupling agent using the graphene oxide of silane coupling agent functionalization and gathers
Lactic acid assigns its good air-tightness and resists quiet while improving the two compatibility and made vulcanized mechanical
The characteristics such as electricity.
The present invention is achieved by the following technical solutions.
A kind of silicon rubber/polylactic acid thermoplastic sulfurized rubber, it is characterised in that: the raw material of the thermoplastic sulfurized rubber mainly includes
The component of following parts by weight:
The thermoplastic sulfurized rubber is that dynamic vulcanization is prepared in 150-230 DEG C of mixer.
According to another preferred method of implementation of the present invention, it is characterised in that: the expanding material includes the oxygen of functionalization
Graphite alkene and silane coupling agent, silane coupling agent used are 3- isocyanatopropyl trimethoxy silane, vinyl trimethoxy
Base silane, 3- glycidol ether oxygroup trimethoxy silane, γ-mercaptopropyl trimethoxysilane, gamma-aminopropyl-triethoxy silicon
One or more of alkane, γ-aminopropyltrimethoxysilane and 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane；
Functional graphene oxide and the weight ratio of silane coupling agent are 1:40-10:1 in expanding material.
According to another preferred method of implementation of the present invention, it is characterised in that: the functional graphene oxide be by
Silane coupling agent is grafted to be obtained on graphene oxide, can by silane coupling agent and graphene oxide in 60-80 DEG C of ethyl alcohol
Preparation is reacted in solution, and ball-milling method or other methods can also be used and prepare silane coupled be grafted on graphene oxide, function
Change in graphene oxide preparation process, the mass ratio of graphene oxide and silane coupling agent is 1:1-1:6.
According to another preferred method of implementation of the present invention, it is characterised in that: the polylactic acid is l-lactic acid, dextrorotation
Or mixtures thereof one of polylactic acid and racemic polylactic acid, content are preferably 20-100 parts by weight；The silicon rubber is two
One of methyl silicone rubber, methyl vinyl silicone rubber, phenyl siloxane rubber, fluorine silicone rubber or its blend.
According to another preferred method of implementation of the present invention, it is characterised in that: the peroxide is diphenyl peroxide first
One of acyl, 2,5- dimethyl -2,5 (di-t-butyl peroxide) hexane, the double lauroyl of cumyl peroxide and peroxidating or
Several, the dosage of peroxide is 1.0-3.0 parts by weight；The assistant crosslinking agent is N, penylene bismaleimide, sulphur between N'-
Or mixtures thereof one of sulphur, iso-cyanuric acid triallyl ester, zinc oxide, the preferred 1.5-3 parts by weight of dosage.
According to another preferred method of implementation of the present invention, it is characterised in that: the antioxidant is four [β-(3,5- bis-
Tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, or mixtures thereof one of 2,6-di-tert-butyl p-cresol.
The preparation method of the thermoplastic sulfurized rubber, it is characterised in that:
(1) graphene oxide for preparing functionalization, functional graphene oxide and peroxide are uniformly mixed；
(2) silicon rubber is put into mixer, antioxidant is added after plasticating, silicone master batch is made in mixing；
(3) polylactic acid is put into 150-230 DEG C of mixer, masterbatch, remaining silane coupled obtained by step (2) is added
Agent and assistant crosslinking agent are blended and rubber blend are made；
(4) it will be equipped with described in step (3) in 150-230 DEG C of mixer of rubber blend, the function of step (1) preparation be added
Graphene oxide and peroxide mixture can be changed, carry out dynamic vulcanization, silicon rubber/polylactic acid heat of dynamic vulcanization is thus made
Plasticity vulcanizate.
According to another preferred method of implementation of the present invention, it is characterised in that: the mixer is double screw extruder, close
Mill or open mill, dynamic vulcanization curing temperature are 150-200 DEG C, vulcanization time 5-15min.
According to another preferred method of implementation of the present invention, it is characterised in that: the functional graphene oxide be by
Silane coupling agent, which is grafted to, to be obtained on graphene oxide.
The expanding material of graphene oxide and silane coupling agent comprising functionalization is to improve silicon rubber/polylactic acid thermoplasticity
The purposes of mechanical property of vulcanized rubber, gas barrier property or antistatic property.
Wherein graphene oxide can use Hummer ' s method, improve Hummer ' s method or ultrasonic wave added Hummer ' s legal system
It is standby.
The preparation method of the thermoplastic sulfurized rubber can further describe are as follows:
It is according to the parts by weight that raw material preparation is good, polylactic acid is dried, then according to following sequences into
Row preparation:
(1) blend of functional graphene oxide and peroxide is prepared；
(2) silicon rubber is put into room temperature mixer, antioxidant is added after plasticating, continued mixing and silicon rubber masterbatching is made
Glue.
(3) polylactic acid is put into 150-230 DEG C of mixer, after its melting, masterbatch obtained by step (2) is added, remains
Rubber blend is made in remaining silane coupling agent and assistant crosslinking agent；
(4) it will be equipped with described in step (3) in 150-230 DEG C of mixer of rubber blend, the mistake of step (1) preparation be added
Oxide and functional graphene oxide blend carry out dynamic vulcanization, and silicon rubber/polylactic acid thermoplasticity of dynamic vulcanization is made
Vulcanizate.
Expanding material described in above scheme preferably includes 0.1-5 parts by weight functional graphene oxide and 1-5 parts by weight
Silane coupling agent, graphene oxide can use Hummer ' s method, improve Hummer ' s method or ultrasonic wave added Hummer ' s legal system
It is standby.By mass ratio be 1:1-1:6 silane coupling agent and graphene oxide in 60-80 DEG C of ethanol solution, stir 12-48h
Graft reaction is carried out, then freeze-drying obtains functional graphene oxide, ball-milling method or other methods can also be used silicon
Alkane coupling agent is grafted on graphene oxide.The dosage of functional graphene oxide is preferably 0.1-3 parts by weight, silane coupling agent
Dosage is preferably 2-5 parts by weight.Silane coupling agent used in the present invention and graphite can all pass through commercially available.
Polylactic acid described in above scheme is l-lactic acid (PLLA), dextrorotation polylactic acid (PDLA), racemic polylactic acid
One of (PDLLA) or mixtures thereof, glass transition temperature is between 50-80 DEG C, crystallization temperature 80-150 DEG C it
Between, melting temperature is between 150-230 DEG C.Polylactic acid used in the present invention can be commercially available, such as U.S. Nature
2002D, 2003D of works company production, 110, the 190 of Zhejiang Hisun Biomaterials Co., Ltd's production, Mitsui
The LACEA of Chemical Co., Ltd. production.The content of polylactic acid of the present invention is preferably 20-120 parts by weight.
Silicon rubber described in above scheme can be dimethyl silicone rubber, methyl vinyl silicone rubber, phenyl siloxane rubber, fluorine
One kind of silicon rubber or its blend, relative density 0.9-1.3 can be commercially available: as blue star organosilicon Shanghai has
It is limited that Sheng silicon industry is closed in the 110-2 silicon rubber of limit company, the methyl vinyl silicone rubber of Zhenjiang hongda Chemical Co., Ltd. and Zhejiang
110 methyl vinyl silicone rubbers of company, Shanghai Gui Shan high molecular material Co., Ltd silicon rubber.Its dosage is preferably 80-
160 parts by weight.
Peroxide described in above scheme can be bimonthly for dibenzoyl peroxide, oxidation diisopropylbenzene (DIPB) and peroxidating
Osmanthus acyl, preferential to select the other dibenzoyl peroxide of technical grade, dosage is 1-5 parts by weight, preferably 1-2 parts by weight.
Assistant crosslinking agent described in above scheme is N, the different melamine of penylene bismaleimide, sulphur, triallyl between N'-
Or mixtures thereof one of acid esters, zinc oxide, the preferred 1.5-3 parts by weight of dosage.
Antioxidant described in above scheme be four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters,
Or mixtures thereof one of 2,6-di-tert-butyl p-cresol, the preferred 1-10 parts by weight of dosage.
Above-mentioned peroxide, assistant crosslinking agent, compound is commercial products generally in the art described in antioxidant.
Made silicon rubber/PLA TPV material the tension test of the present invention is in the environment that temperature is 23 DEG C, relative humidity is 50%
Middle progress is tested using dumbbell shape sample by GB/T528-2009, and cupping machine is ZWICK/REOLL 2005, is drawn
Stretching speed is 500mm/min；Vulcanized rubber hardness is tested by GB/T531-2009；Vulcanizate resistance presses GB/T11210-2014
It is tested；Permeability is tested by GB/T19789-2005.
[beneficial effect]
The present invention take above scheme prepare SR/PLA TPV, have it is following the utility model has the advantages that
(1) it is plastics phase that the present invention, which selects environmentally-friendly polylactic acid, reduces the dependence to petroleum resources, meeting can
The demand of sustainable development strategy；Silicon rubber has good physiological inertia, and the thermoplastic sulfurized rubber that preparation is blended in the two can make up
The deficiency being individually present is expected to meet the needs of medical domain is to high performance material.Silicon rubber and polylactic acid blend are widened
Its application in terms of actual production life.
(2) present invention cooperates with increase-volume using functional graphene oxide and silane coupling agent, substantially increases made thermoplastic
The performance of property vulcanizate, makes the tensile strength of made TPV reach 15-28MPa, elongation at break 150-240%, hardness (shore)
30-60A, resistance 105-108Ω, permeability 8-11ccmm/m2Dayatm has good air-tightness and resists
Static characteristic；And prepared TPV, it is surfacing, smooth, have the elasticity of rubber and the mobility of plastics and good machine
Tool performance extends polylactic acid and silicon rubber in the application of field of biomedicine.
[specific embodiment]
Below with reference to embodiment, the present invention is described further, but protection scope of the present invention is not limited to that.
Embodiment 1
Graphene oxide is prepared first with ultrasonic wave added Hummer ' s method, then by 1g graphene oxide, tri- ammonia third of 2g
Ethyl triethoxy silicane alkane mixes in ethanol solution, and adjusting pH value is 5, and for 24 hours, functional graphene oxide dispersion is made in stirring
Liquid, then it is freeze-dried obtained functional graphene oxide；The SR that 100 parts by weight are put into room temperature open mill, plasticates, and adds
The antioxidant for entering 2 parts by weight continues to be kneaded, prepares silicone master batch；Then by 68 parts by weight PLA in 160 DEG C of mixers
Melting, is added silicone master batch, three aminopropyl triethoxysilanes of 3 parts by weight, and 1.5 parts by weight assistant crosslinking agents uniformly mix
Close the rubber blend that simple blend is made；The rubber blend of simple blend and pre- is added in 170 DEG C, 60rpm mixer
The functional graphene oxide of 0.1 parts by weight first mixed and the dibenzoyl peroxide of 1.5 parts by weight, dynamic vulcanization
6min obtains the rubber blend of dynamic vulcanization；The injection molding in injection molding machine, progressive by the rubber blend of dynamic vulcanization
It can test, the results are shown in Table 1.
Embodiment 2
Formulation Ingredients and dosage, process conditions and process flow with embodiment 1, unlike functional graphene oxide and
The dosage of dibenzoyl peroxide is respectively 0.3 parts by weight and 1.5 parts by weight, and the performance test results of gained SR/PLA TPV are shown in
Table 1.
Embodiment 3
Formulation Ingredients and dosage, process conditions and process flow with embodiment 1, unlike functional graphene oxide and
The dosage of dibenzoyl peroxide is respectively 0.3 parts by weight and 1.0 parts by weight, and the performance test results of gained SR/PLA TPV are shown in
Table 1.
Embodiment 4
Formulation Ingredients and dosage, process conditions and process flow with embodiment 1, unlike functional graphene oxide and
The dosage of dibenzoyl peroxide is respectively 1.0 parts by weight and 1.5 parts by weight, and the performance test results of gained SR/PLA TPV are shown in
Table 1.
Embodiment 5
Formulation Ingredients and dosage, process conditions and process flow with embodiment 1, unlike functional graphene oxide and
The dosage of dibenzoyl peroxide is respectively 3.0 parts by weight and 1.5 parts by weight, and the performance test results of gained SR/PLA TPV are shown in
Table 1.
Comparative example 1
The SR for putting into 100 parts by weight in room temperature open mill first, plasticates, and the antioxidant of 2 parts by weight is added, and continues
It is kneaded, prepares silicone master batch；Then 68 parts by weight PLA are melted in 160 DEG C of mixers, silicone master batch are added,
Uniformly it is mixed to prepare the rubber blend of simple blend；It by rubber blend injection molding, is tested for the property, performance test knot
Fruit is shown in Table 1.
Comparative example 2
The SR for putting into 100 parts by weight in room temperature open mill first, plasticates, and the antioxidant of 2 parts by weight is added, and continues
It is kneaded, prepares silicone master batch；Then 68 parts by weight PLA are melted in 160 DEG C of mixers, silicone master batch are added,
Uniformly it is mixed to prepare the rubber blend of simple blend；By rubber blend at 170 DEG C, 60rpm mixer and 1.5 parts by weight
Dibenzoyl peroxide, dynamic vulcanization 6min；By the rubber blend injection molding of dynamic vulcanization, it is tested for the property, performance
Test result is shown in Table 1.
Comparative example 3
The SR for putting into 100 parts by weight in room temperature open mill first, plasticates, and the antioxidant of 2 parts by weight is added, and continues
It is kneaded, prepares silicone master batch；Then 68 parts by weight PLA are melted in 160 DEG C of mixers, silicone master batch are added,
1.5 parts by weight assistant crosslinking agents, are uniformly mixed to prepare the rubber blend of simple blend；It is added in 170 DEG C, 60rpm mixer
The functional graphene oxide and 1.5 parts by weight of 0.3 parts by weight of the rubber blend of simple blend together with being pre-mixed
Dibenzoyl peroxide, dynamic vulcanization 6min obtains the rubber blend of dynamic vulcanization；By the rubber blend of dynamic vulcanization
The injection molding in injection molding machine, is tested for the property, and the performance test results are shown in Table 1.
Comparative example 4
Formula components and dosage and process conditions and process flow are with comparative example 2, the difference is that 68 parts by weight PLA are existed
It is melted in 160 DEG C of mixers, silicone master batch, 5 parts by weight, three aminopropyl triethoxysilane is added, 1.5 parts by weight help friendship
Join agent, is uniformly mixed to prepare the rubber blend of simple blend；The rubber and plastic of simple blend is added in 170 DEG C, 60rpm mixer
The dibenzoyl peroxide of blend and 1.5 parts by weight, the performance test results are shown in Table 1.
1 silicon rubber of table/PLA intermingling material performance
As can be seen from the table, functional graphene oxide and silane coupling agent collaboration increase-volume can be improved the stretching of material
Intensity, elongation at break, hardness, antistatic property reduce the permeability of material.Thermoplastic vulcanizates prepared by the present invention
Glue has good comprehensive mechanical property, antistatic property and barrier properties for gases, and silicon rubber is extended to thermoplastic sulfurized rubber neck
Domain, while further having widened the application range of polylactic acid.
Claims (9)
1. a kind of silicon rubber/polylactic acid thermoplastic sulfurized rubber, it is characterised in that: the raw material of the thermoplastic sulfurized rubber includes following heavy
Measure the component of part:
Polylactic acid 20-150 parts by weight；
Silicon rubber 100-160 parts by weight；
Expanding material 1-10 parts by weight；
Peroxide 1-5 parts by weight；
Assistant crosslinking agent 1-5 parts by weight；
Antioxidant 0.1-10 parts by weight；
The expanding material includes the graphene oxide and silane coupling agent of functionalization；
The thermoplastic sulfurized rubber is that dynamic vulcanization is prepared in 150-230 DEG C of mixer；
The functional graphene oxide is to be grafted to silane coupling agent on graphene oxide to obtain；
The silicon rubber be one of dimethyl silicone rubber, methyl vinyl silicone rubber, phenyl siloxane rubber, fluorine silicone rubber or its
Blend；
The silane coupling agent is 3- isocyanatopropyl trimethoxy silane, vinyltrimethoxysilane, 3- glycidol
Ether oxygen base trimethoxy silane, γ-mercaptopropyl trimethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-aminopropyl front three
One or more of oxysilane and 3- (2,3- the third oxygen of epoxy) hydroxypropyl methyl diethoxy silane；
The peroxide is that dibenzoyl peroxide, 2,5- dimethyl -2,5 (di-t-butyl peroxide) hexane, peroxidating two are different
Or mixtures thereof one of propyl benzene and the double lauroyl of peroxidating；
The assistant crosslinking agent is N, penylene bismaleimide, sulphur, iso-cyanuric acid triallyl ester, zinc oxide between N'-
Or mixtures thereof one of.
2. thermoplastic sulfurized rubber as described in claim 1, it is characterised in that: functional graphene oxide and silane in expanding material
The weight ratio of coupling agent is 1:40-10:1.
3. expanding material as claimed in claim 2, it is characterised in that: the functional graphene oxide preparation method can pass through
Silane coupling agent and graphene oxide react preparation in 60-80 DEG C of ethanol solution, and ball-milling method can also be used or other methods will
Silane coupling agent is grafted on graphene oxide and prepares；In functional graphene oxide preparation process, graphene oxide and silane
The mass ratio of coupling agent is 1:1-1:6.
4. thermoplastic sulfurized rubber as described in any one of claims 1-3, it is characterised in that: the polylactic acid is left-handed poly- cream
Or mixtures thereof one of acid, dextrorotation polylactic acid and racemic polylactic acid, content are 20-100 parts by weight.
5. thermoplastic sulfurized rubber as described in claim 1, it is characterised in that: the dosage of the peroxide is 1.0-3.0 weight
Measure part；The assistant crosslinking agent dosage is 1.5-3 parts by weight.
6. thermoplastic sulfurized rubber as described in claim 1, it is characterised in that: the antioxidant is four [β-(3,5- bis- tertiary fourths
Base -4- hydroxy phenyl) propionic acid] pentaerythritol ester, or mixtures thereof one of 2,6-di-tert-butyl p-cresol.
7. the preparation method of thermoplastic sulfurized rubber described in any one of claims 1-6, it is characterised in that:
(1) graphene oxide for preparing functionalization, functional graphene oxide and peroxide are uniformly mixed；
(2) silicon rubber is put into mixer, antioxidant is added after plasticating, silicone master batch is made in mixing；
(3) will polylactic acid put into 150-230 DEG C of mixer in, be added step (2) obtained by silicone master batch, silane coupling agent and
Assistant crosslinking agent is blended and rubber blend is made；
(4) it will be equipped with described in step (3) in 150-230 DEG C of mixer of rubber blend, the functionalization of step (1) preparation be added
Graphene oxide and peroxide mixture carry out dynamic vulcanization, and silicon rubber/polylactic acid thermoplasticity of dynamic vulcanization is thus made
Vulcanizate.
8. the preparation method of thermoplastic sulfurized rubber as claimed in claim 7, it is characterised in that: the mixer squeezes for twin-screw
Machine, mixer or open mill out, dynamic vulcanization temperature are 150-200 DEG C, vulcanization time 5-15min.
9. the preparation method of thermoplastic sulfurized rubber as claimed in claim 7, it is characterised in that: the functionalization oxygen in step (1)
Graphite alkene is to be grafted to silane coupling agent on graphene oxide to obtain.
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