CN107603157A - A kind of Janus bulking agents for rubber-toughened epoxy resin and preparation method thereof - Google Patents
A kind of Janus bulking agents for rubber-toughened epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Janus bulking agents for rubber-toughened epoxy resin and preparation method thereof, the preparation method is：1）Polydivinylbenezene/silica Janus materials and azo-bis-isobutyl cyanide are scattered in toluene, after the logical h of nitrogen 0.5, quick to instill lauryl mercaptan, centrifuge washing obtains lauryl mercaptan polydivinylbenezene/silica Janus materials after reacting a period of time；2）Lauryl mercaptan polydivinylbenezene/silica Janus materials and γ methacryloxypropyl trimethoxy silanes are scattered in toluene, centrifuge washing obtains lauryl mercaptan polydivinylbenezene/silica γ methacryloxypropyl trimethoxy silane Janus materials, i.e., described Janus bulking agents after reaction a period of time.Janus bulking agents prepared by the inventive method have anisotropic chemical constitution, possess abundant boundary behavior, strong to liquid isoprene rubber/epoxy resin composite material compatibilization.
Description
Technical field
The present invention relates to a kind of preparation method of bulking agent, and in particular to a kind of for rubber-toughened epoxy resin
Janus bulking agents and preparation method thereof.
Background technology
Contain active epoxide group in epoxy molecule structure, reaction can be crosslinked with polytype curing agent
And form the high polymer of insoluble tridimensional network.Epoxy resin cured product has excellent chemical resistance, shrinkage factor
It is low, adhesive strength is high, high mechanical strength, electrical insulating property are excellent, therefore be widely used in the fields such as coating, adhesive, ink.But
It is that epoxy resin fragility is larger, toughness and weatherability are poor, limit its application.The method of epoxy resin roughening has a variety of, rubber
Glue toughness reinforcing is a kind of conventional method.Because epoxy resin is a kind of polarity macromolecule, lead to for epoxy resin toughened rubber
It is often the nitrile rubber with polarized, neoprene etc., the compatibility of nonpolar natural rubber and epoxy resin is poor, limitation
It is as the application in terms of epoxy resin roughening.
Janus materials are that a kind of surface chemistry composition is different, anisotropic center asymmetric particle.Chinese patent CN
103204508 B disclose Janus materials with double properties and preparation method thereof, using polymeric colloid particle as template,
By seeded emulsion polymerization method, based on interface self assembly and phase separation mechanism, hybrid Janus particles are obtained, its
It is that the polymer containing double bond, the other ends such as polystyrene, polyacrylate are inorganic material to have generator terminal.Really as bulking agent
The Janus materials used form demand to its both ends by more rich, and the both ends of Janus materials are modified respectively, can be with
Regulate and control its chemical property, it is shown the boundary behavior of very abundant in Polymer Blending System, " riveting is played getting along
Nail " effect.2008, anisotropic single ball Janus particles were applied in PS/PMMA co-mixing systems by Walther etc. first,
It was found that under high temperature and the twin-screw immixture of high shear, Janus particles also can be orderly at polymer two-phase interface
Arrangement, and have strong suction-operated to the polymer of interface both sides, the size of dispersed phase is with Janus amount of particles
Increase and reduce, its compatibilization effect is better than block copolymer.At present, Janus materials are mainly concentrated as the research of bulking agent
In thermoplastic resin, the application of Janus materials is limited.Therefore, it is simple to find a kind of synthetic method, applied to thermosetting
The Janus materials of resin alloy polymer compatibilizer are very necessary.
The content of the invention
It is an object of the invention to provide a kind of for the Janus bulking agents of rubber-toughened epoxy resin and its preparation side
Method, this method is simple and feasible, has expanded the application of Janus materials.
To achieve these goals, the present invention uses following technical scheme：
A kind of preparation method of Janus bulking agents for rubber-toughened epoxy resin, comprises the following steps：
1）Polymerisation：Reacted with lauryl mercaptan at polydivinylbenezene end
By polydivinylbenezene/silica Janus materials（By document Macromolecules 2015,48： 2715−2722
Method prepare）It is placed in azo-bis-isobutyl cyanide in flask, adds toluene, be transferred to after ultrasonic disperse in 45 ~ 95 DEG C of water-bath, magnetic
Power stirs, and after being passed through nitrogen 0.5 ~ 1 hour, is slowly dropped into lauryl mercaptan, reacts 12 ~ 48 hours, product is through centrifuging, washing
Wash, obtain lauryl mercaptan-polydivinylbenezene/silica Janus materials,
Wherein, the quality of polydivinylbenezene/silica Janus materials, toluene, lauryl mercaptan and azo-bis-isobutyl cyanide
Than for 1：17：10~30：0.055~0.62；
2）Coupling reaction：Reacted with γ-methacryloxypropyl trimethoxy silane at silica end
By step 1）Obtained lauryl mercaptan-polydivinylbenezene/silica Janus materials and γ-methacryl
Epoxide propyl trimethoxy silicane is placed in flask, is added toluene, is transferred to after ultrasonic disperse in 45 ~ 95 DEG C of water-bath, magnetic force stirs
Mix, react 8 ~ 24 hours, product obtains lauryl mercaptan-polydivinylbenezene/silica-γ-first through centrifuging, washing
Base acryloxypropyl trimethoxy silane Janus materials, it is the Janus increase-volumes for being used for rubber-toughened epoxy resin
Agent,
Wherein, lauryl mercaptan-polydivinylbenezene/silica Janus materials, toluene and γ-methacryloxy
The ratio of propyl trimethoxy silicane is 1 g：17 g ：0.1~0.5 mL.
Further, the step 1) and 2）Mode of washing be：Product washs three with ethanol again after being washed three times with toluene
It is secondary.
Step 1 of the present invention）Described polydivinylbenezene/silica Janus materials are by document
Macromolecules 2015, 48：It is prepared by 2715 2722 method.
The present invention uses above technical scheme, is silica by one end, and the other end is the Janus particles of divinylbenzene
Both ends are modified, the bulking agent epoxy resin toughened as liquid isoprene rubber.Specific method is to pass sequentially through to two
Vinyl benzene termination branch lauryl mercaptan, silica termination branch γ-methacryloxypropyl trimethoxy silane, modified
To Janus materials can be embedded in liquid isoprene rubber as bulking agent, on epoxy resin boundary, reduce interface
Power, suppress to be separated.
The present invention can be made suitable for the epoxy resin toughened Janus increase-volumes of liquid isoprene rubber using the above method
Agent, there is advantages below：
1. Janus bead bulking agent preparation methods are simple and easy, it is adapted to industrialized production.
2. lauryl mercaptan-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silicon
Alkane Janus materials both ends are reacted respectively with composite two-phase, wherein, the vulcanization of lauryl mercaptan end participation rubber phase, γ-
Methacryloxypropyl trimethoxy silane participates in the crosslinking curing of epoxy resin.Modified Janus beads are used to increase
Hold liquid isoprene rubber/epoxy resin composite material, can be with phased array at two-phase interface.
3. Janus beads have anisotropic chemical constitution, possess abundant boundary behavior, to liquid isoamyl two
Alkene rubber/epoxy resin composite material compatibilization is strong.
Brief description of the drawings
Fig. 1 is Janus bulking agents made from embodiments of the invention 1（Product I）Infrared spectrum.
Fig. 2 is the scanning electron microscope (SEM) photograph of composite I made from the application examples 1 of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of composite II made from the application examples 1 of the present invention.
Embodiment
Below with reference to specific embodiment, the invention will be further described.
Embodiment 1
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
0.5 g polydivinylbenezene/silica Janus materials and 0.0281 g azo-bis-isobutyl cyanides are placed in a flask,
8.51 g toluene are added, are transferred to after ultrasonic disperse in 50 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
6.01g lauryl mercaptans, react 24 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain 12 three times
Alkyl hydrosulfide-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 0.46 and 0.05 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, adds toluene, and 50 DEG C of water is transferred to after ultrasonic disperse
In bath, magnetic agitation, react 12 hours, through centrifugation, toluene washs three times product, and ethanol washing obtains dodecyl sulphur three times
Alcohol-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials（Product I）.
Fig. 1 is Janus bulking agents made from embodiment 1（Product I）Infrared spectrum, it can be seen from Fig. 1 that 3080,3057 and
3025 cm-1C-H stretching vibration peak on phenyl ring, 1601 cm-1The skeletal vibration of phenyl ring, 1493 cm-1With 1450 cm-1Locate benzene
Stretching vibration and in-plane bending vibration peak, 757 and 701cm in the face of ring-1C-H out-of-plane bending vibration derives from two on phenyl ring
Vinyl benzene； 2925 cm-1With 2850 cm-1It is lauryl mercaptan and γ-methacryloxypropyl trimethoxy silicon
Alkane saturation-CH and-CH2Stretching vibration peak；1724 cm-1C=O stretching vibration peak is by γ-methacryloxypropyl three
Methoxy silane causes；The characteristic absorption of silica Si-O keys is in 473 cm-1Place.
Embodiment 2
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
0.48 g polydivinylbenezene/silica Janus materials and 0.2421 g azo-bis-isobutyl cyanides are placed in a flask,
8.20 g toluene are added, are transferred to after ultrasonic disperse in 70 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
9.64 g lauryl mercaptans, react 24 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 0.30 and 0.09 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, adds 5.15 g toluene, 70 are transferred to after ultrasonic disperse
DEG C water-bath in, magnetic agitation, react 24 hours, product after centrifugation, toluene wash three times, ethanol washing obtain 12 three times
Alkyl hydrosulfide-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials（Production
Thing II）.
Embodiment 3
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
0.48 g polydivinylbenezene/silica Janus materials and 0.1457 g azo-bis-isobutyl cyanides are placed in a flask,
8.23 g toluene are added, are transferred to after ultrasonic disperse in 90 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
14.50 g lauryl mercaptans, react 48 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 0.31 and 0.12 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, adds 5.20 g toluene, 90 are transferred to after ultrasonic disperse
DEG C water-bath in, magnetic agitation, react 12 hours, product after centrifugation, toluene wash three times, ethanol washing obtain 12 three times
Alkyl hydrosulfide-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials（Production
Thing III）.
Embodiment 4
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
0.51 g polydivinylbenezene/silica Janus materials and 0.1009 g azo-bis-isobutyl cyanides are placed in a flask,
8.69 g toluene are added, are transferred to after ultrasonic disperse in 70 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
10.21 g lauryl mercaptans, react 36 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 0.39 and 0.08 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, adds 6.63 g toluene, 70 are transferred to after ultrasonic disperse
DEG C water-bath in, magnetic agitation, react 8 hours, product after centrifugation, toluene wash three times, ethanol washing obtain 12 three times
Alkyl hydrosulfide-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials（Production
Thing IV）.
Embodiment 5
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
1.11g polydivinylbenezene/silica Janus materials and 0.0673 g azo-bis-isobutyl cyanides are placed in a flask,
18.92g toluene is added, is transferred to after ultrasonic disperse in 60 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
22.20 g lauryl mercaptans, react 24 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 0.82 and 0.25 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, is added 14.09 g toluene, is transferred to after ultrasonic disperse
In 90 DEG C of water-bath, magnetic agitation, react 24 hours, after centrifugation, toluene washs three times product, and ethanol washing obtains ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials
（Product V）.
Embodiment 6
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
2.56 g polydivinylbenezene/silica Janus materials and 1.0262 g azo-bis-isobutyl cyanides are placed in a flask,
43.50 g toluene are added, are transferred to after ultrasonic disperse in 70 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
25.67 g lauryl mercaptans, react 24 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 1.87 and 0.94 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, is added 31.84 g toluene, is transferred to after ultrasonic disperse
In 90 DEG C of water-bath, magnetic agitation, react 16 hours, after centrifugation, toluene washs three times product, and ethanol washing obtains ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials
（Product VI）.
Embodiment 7
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
3.01 g polydivinylbenezene/silica Janus materials and 0.2431 g azo-bis-isobutyl cyanides are placed in a flask,
50.98 g toluene are added, are transferred to after ultrasonic disperse in 90 DEG C of water-bath, magnetic agitation, leads to nitrogen after 0.5 hour, is slowly dropped into
45.11 g lauryl mercaptans, react 24 hours, product after centrifugation, with toluene wash three times, ethanol wash obtain ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica Janus materials.
2）Coupling reaction：
Take step 1）Obtained lauryl mercaptan-polydivinylbenezene/g of silica Janus materials 2.24 and 0.45 mL
γ-methacryloxypropyl trimethoxy silane is placed in a flask, is added 38.06 g toluene, is transferred to after ultrasonic disperse
In 70 DEG C of water-bath, magnetic agitation, react 18 hours, after centrifugation, toluene washs three times product, and ethanol washing obtains ten three times
Dialkyl group mercaptan-polydivinylbenezene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials
（Product VII）.
Embodiment 8
Preparation method for the Janus bulking agents of rubber-toughened epoxy resin：
1）Polymerisation：
Polydivinylbenezene/silica Janus materials and azo-bis-isobutyl cyanide are placed in flask, add toluene, ultrasound point
It is transferred to after dissipating in 45 DEG C of water-bath, magnetic agitation, after being passed through nitrogen 0.5 hour, is slowly dropped into lauryl mercaptan, reaction 12 is small
When, product is after centrifugation, and toluene washs three times, and ethanol washs three times, obtains lauryl mercaptan-polydivinylbenezene/dioxy
SiClx Janus materials,
Wherein, the quality of polydivinylbenezene/silica Janus materials, toluene, lauryl mercaptan and azo-bis-isobutyl cyanide
Than for 1：17：10：0.055；
2）Coupling reaction：
By step 1）Obtained lauryl mercaptan-polydivinylbenezene/silica Janus materials and γ-methacryl
Epoxide propyl trimethoxy silicane is placed in flask, is added toluene, is transferred to after ultrasonic disperse in 45 DEG C of water-bath, magnetic agitation,
Reaction 8 hours, product is after centrifugation, and toluene washs three times, and ethanol washs three times, obtains lauryl mercaptan-poly- divinyl
Benzene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials, it is as described to be used for rubber toughened ring
The Janus bulking agents of oxygen tree fat,
Wherein, lauryl mercaptan-polydivinylbenezene/silica Janus materials, toluene and γ-methacryloxy
The ratio of propyl trimethoxy silicane is 1 g：17 g ：0.1 mL.
Embodiment 9
A kind of preparation method of Janus bulking agents for rubber-toughened epoxy resin：
1）Polymerisation：
Polydivinylbenezene/silica Janus materials and azo-bis-isobutyl cyanide are placed in flask, add toluene, ultrasound point
It is transferred to after dissipating in 95 DEG C of water-bath, magnetic agitation, after being passed through nitrogen 1 hour, is slowly dropped into lauryl mercaptan, reaction 48 is small
When, product obtains lauryl mercaptan-polydivinylbenezene/silica Janus materials through centrifuging, wash,
Wherein, the quality of polydivinylbenezene/silica Janus materials, toluene, lauryl mercaptan and azo-bis-isobutyl cyanide
Than for 1：17：30： 0.62；
2）Coupling reaction：
By step 1）Obtained lauryl mercaptan-polydivinylbenezene/silica Janus materials and γ-methacryl
Epoxide propyl trimethoxy silicane is placed in flask, is added toluene, is transferred to after ultrasonic disperse in 95 DEG C of water-bath, magnetic agitation,
Reaction 24 hours, product is after centrifugation, and toluene washs three times, and ethanol washs three times, obtains lauryl mercaptan-poly- divinyl
Benzene/silica-γ-methacryloxypropyl trimethoxy silane Janus materials, it is as described to be used for rubber toughened ring
The Janus bulking agents of oxygen tree fat,
Wherein, lauryl mercaptan-polydivinylbenezene/silica Janus materials, toluene and γ-methacryloxy
The ratio of propyl trimethoxy silicane is 1 g：17 g ： 0.5 mL.
Application examples 1
Take 1.01 g liquid isoprene rubbers, 0.05 g cumyl peroxides, 0.06 g triallyl isocyanurates with
4.02g epoxy blends, stir 3h at 90 DEG C, then add 0.99 g 4,4-diaminodiphenyl-methane, stirring 5
Min, solidify 2 h at 120 DEG C, 160 DEG C of 2 h of solidification, obtain composite I.
Take 1.06 g liquid isoprene rubbers, 0.06 g cumyl peroxides, 0.06 g triallyl isocyanurates,
4.11 g epoxy blends, and add 0.18 g Janus bead bulking agents（The product II of embodiment 2）, stirred at 90 DEG C
3 h are mixed, 1.03 g 4 is then added, 4-diaminodiphenyl-methane, stirs 5 min, solidify 2 h at 120 DEG C, 160 DEG C solid
Change 2 h, obtain composite II.
Fig. 2 and Fig. 3 is respectively the scanning electron microscope (SEM) photograph of composite I and composite II, the ring without Janus bulking agents
Oxygen tree fat/isoprene rubber co-mixing system phase size is big, and boundary is clear, and isoprene rubber is mutually from asphalt mixtures modified by epoxy resin during brittle failure
Fat continuous phase comes off（Fig. 2）.And Janus bulking agents are amphipathic due to self structure, in epoxy resin/isoprene rubber
It can be distributed in order in co-mixing system（Fig. 3）, the interfacial adhesion of reinforced epoxy and isoprene rubber, reduce scattered different
The phase size of pentadiene rubber, epoxy resin/isoprene rubber composite of Janus particle increase-volumes are used in outer masterpiece
Under, isoprene rubber does not come off largely from continuous phase.
Claims (3)
- A kind of 1. preparation method of Janus bulking agents for rubber-toughened epoxy resin, it is characterised in that：It includes following step Suddenly：1）Polymerisation：Polydivinylbenezene/silica Janus materials and azo-bis-isobutyl cyanide are placed in flask, add toluene, ultrasound point It is transferred to after dissipating in 45 ~ 95 DEG C of water-bath, magnetic agitation, after being passed through nitrogen 0.5 ~ 1 hour, is slowly dropped into lauryl mercaptan, instead To answer 12 ~ 48 hours, product obtains lauryl mercaptan-polydivinylbenezene/silica Janus materials through centrifuging, wash,Wherein, the quality of polydivinylbenezene/silica Janus materials, toluene, lauryl mercaptan and azo-bis-isobutyl cyanide Than for 1：17：10~30：0.055~0.62；2）Coupling reaction：By step 1）Obtained lauryl mercaptan-polydivinylbenezene/silica Janus materials and γ-methacryl Epoxide propyl trimethoxy silicane is placed in flask, is added toluene, is transferred to after ultrasonic disperse in 45 ~ 95 DEG C of water-bath, magnetic force stirs Mix, react 8 ~ 24 hours, product obtains lauryl mercaptan-polydivinylbenezene/silica-γ-first through centrifuging, washing Base acryloxypropyl trimethoxy silane Janus materials, it is the Janus increase-volumes for being used for rubber-toughened epoxy resin Agent,Wherein, lauryl mercaptan-polydivinylbenezene/silica Janus materials, toluene and γ-methacryloxy The ratio of propyl trimethoxy silicane is 1 g：17 g ：0.1~0.5 mL.
- 2. a kind of preparation method of Janus bulking agents for rubber-toughened epoxy resin according to claim 1, it is special Sign is：The mode of washing is to be washed three times with ethanol again after being washed three times with toluene.
- 3. lauryl mercaptan-polydivinylbenezene/silica that preparation method according to claim 1 or 2 obtains- γ-methacryloxypropyl trimethoxy silane Janus materials.
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