CN1927899A - Preparation method of micron monodisperse copolymerization microsphere - Google Patents
Preparation method of micron monodisperse copolymerization microsphere Download PDFInfo
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- CN1927899A CN1927899A CN 200610068709 CN200610068709A CN1927899A CN 1927899 A CN1927899 A CN 1927899A CN 200610068709 CN200610068709 CN 200610068709 CN 200610068709 A CN200610068709 A CN 200610068709A CN 1927899 A CN1927899 A CN 1927899A
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Abstract
The present invention is preparation process of micron level monodispersed copolymer microsphere. Polystyrene seed is first prepared through a dispersed polymerization process; and then secondarily swelled and polymerized together with the composite monomer of styrene (St), divinyl benzene (DVB and ethylene glycol dimethyl acrylate (EGDMA) to prepare micron level St/DVB/EGDMA copolymer microsphere. The microsphere is regular, solid, homogeneous in grain size, monodispersed and heat resistant, and has strength and toughness meeting the requirement for making ACF.
Description
Technical field
The present invention relates to a kind of preparation method of micron monodisperse copolymerization microsphere, belong to macromolecule material preparation area.Specifically, relate to dispersion polymerization processes and make polystyrene (PS) seed, adopt seed secondary swelling and polymerization technique to make the method that micron monodisperse copolymerization microsphere is the St/DVB/EGDMA copolymerization microsphere then, wherein St is a vinylbenzene, DVB is a Vinylstyrene, and EGDMA is an ethylene glycol dimethacrylate.
Technical background
Mono dispersed micrograde polymer microsphere not only is deep into the every aspect of daily life as functional material, and in recent ten years, has entered into high sophisticated technology field, as medical treatment and field of medicaments, and biochemical field, electronic information material field etc.Recent years, mono dispersed micrograde polymer microsphere has been opened up new Application Areas in the electronic information material field: the conductive micro-balloons that is used to make anisotropic conductive film.The panel that anisotropic conductive film is applied in the various flat-panel display devices is connected with conduction between the circuit, and making processes is at first to be the synthesizing monodisperse micron-level polymkeric substance, and microsphere surface chemical nickel plating then is at last by epoxy glue bonding film forming.Wherein the synthetic of mono dispersed micrograde polymer microsphere is the key point of this technology.It is particle diameter single dispersion between 1～10 μ m to the requirement of microballoon, solid ball, and anti-high temperature more than 180 ℃, compressible, elastic deformation is more than 50%.
The polymerization process that can prepare polymer microballoon has emulsion polymerization, suspension polymerization, dispersion polymerization usually.Though emulsion polymerization can be prepared dispersiveness microballoon preferably, can only prepare the microballoon of particle diameter less than 0.5 μ m; Polyalcohol microspherulite diameter 100 μ that suspension polymerization is made～1000 μ m, and be polymolecularity; Dispersion polymerization be the preparation monodisperse polymer microsphere in micro level than effective means, studying more is a cinnamic step dispersion polymerization polymerization process, the size of the microballoon that makes and monodispersity are all fine, but poor heat resistance, microballoon reaches 150 ℃ and will melt at once, can't satisfy the requirement as anisotropic conductive film conductive polymer microballoon; Carry out a step dispersion polymerization if add, just be difficult to obtain the good uniform microsphere of monodispersity as Vinylstyrene (DVB), ethylene glycol dimethacrylate linking agents such as (EGDMA).Therefore, satisfy by the preparation of these methods that to be used for anisotropic conductive film preparation that require, the mono dispersed micrograde polymer microsphere of particle diameter between 1～10 μ m be very difficult.The seed swelling polymerization is considered to prepare the effective means that satisfies size homogeneous, micron-level crosslinked polymer microballoon.The seed swelling method is to make small particle size seed microballoon with methods such as emulsifier-free emulsion polymerization, dispersion polymerizations earlier, carries out swelling with monomer then, particle is grown up, the re-initiation polymerization.Use identical seed and monomer component when changing seeding polymerization, it is identical to prepare diameter, and the microballoon that surface properties is different can also import microsphere surface in a large number with functional group.So can make the mono dispersed micrograde polymer microsphere of size homogeneous effectively with the seeding polymerization method.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of micron monodisperse copolymerization microsphere, technical problem to be solved is: make polystyrene (PS) seed with dispersion polymerization processes, adopt secondary swelling and polymerization technique to make uniform particle diameter, single dispersion, crosslinked micron order St/DVB/EGDMA copolymerization microsphere then.
Method comprises preparation and secondary swollen-state polymerization two portions of seed, and concrete steps are as follows:
(1), the preparation of seed
(1), vinylbenzene, initiator, solvent, dispersion agent, chain regulator are added in proportion reflux, whipping appts, temperature measuring equipment, N are housed
2In the four-hole reaction flask of protector and heating unit, mix;
(2), with N
2Inlet tube is inserted under the liquid phase, displaced air 30-90min, and then with N
2Inlet tube is mentioned and is continued logical N in the gas phase
2
(3), be rapidly heated to 50～90 ℃ stirring velocity 80～120 commentaries on classics/min, polymerization 15～24h;
(4), with the samples of latex ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon 3-5 time, the microballoon after washing is poured in the culture dish, dry 15-24h in 40-60 ℃ of loft drier promptly gets the polystyrene microsphere seed;
Wherein, vinylbenzene consumption: 8wt%～12wt%,
Initiator amount: 0.5wt%～1.5wt% (styrene-based),
Dispersant dosage: 10wt%～20wt% (styrene-based),
Chain regulator is dioctylis sulfosuccinas natricus consumption: 2wt%～4wt% (styrene-based),
Surplus is a solvent, and solvent is ethanol or ethylene glycol monomethyl ether or methyl alcohol, and perhaps they press the arbitrary proportion mixing;
(2), secondary swollen-state polymerization
The seed of preparation is gone on foot seed swellings, polymerization through two, obtain copolymer microsphere, detailed process is as follows:
(1), the first step swelling
With polystyrene seed, be put in the beaker with the lauryl sodium sulfate aqueous solution of the swelling agent of seed equal in quality, seed quality 200-1000 0.25wt% doubly, ultrasonic 5-10min in ultrasonic homogenizer, after finishing solution is transferred in the four-hole reaction flask, 25-40 ℃ of following swelling 8～10h, stirring velocity 100-200rpm;
(2), the second step swelling
With the St/DVB/EGDMA of following proportioning seed quality 200-1000 doubly lauryl sodium sulfate aqueous solution in behind the ultrasonic emulsification 5-10min, be transferred in the reaction flask, under 25-40 ℃, swelling 12～15h, wherein St, DVB, three kinds of monomeric total masses of EGDMA are 10～50 times of PS seed quality;
The mass ratio of St/DVB/EGDMA is: content 50wt%～90wt% of St; Content 5wt%～20wt% of DVB; Content 5wt%～30wt% of EGDMA;
Wherein St is a vinylbenzene, and DVB is a Vinylstyrene, and EGDMA is an ethylene glycol dimethacrylate;
(3), polymerization
After swelling is finished, in reaction flask, add seed quality 80-400 doubly, concentration is the aqueous solution of 5% dispersion agent, logical N
2Behind the 30-90min, under 60-90 ℃, polymerization 12～20h;
Then, water and ethanol repetitive scrubbing, drying is with the sample ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon, centrifugal again, washing again, so repeat 3-5 time, microballoon after the washing is poured in the culture dish, and dry 15-24h in 40-60 ℃ of loft drier promptly gets polymer microballoon.
In the preparation of seed, initiator is AIBN or BPO, preferred AIBN.
Dispersion agent is PVP-K30 or PVA or PVP-K90, preferred PVP-K30.
In the preparation of seed, solvent is preferably ethanol to be mixed by mass ratio with ethylene glycol monomethyl ether at 1: 1.
In the secondary swollen-state polymerization, swelling agent is a chlorododecane or toluene or n-Hexadecane, a preferred chlorododecane.
Positively effect of the present invention is: the present invention at first adopts dispersion polymerization processes to make polystyrene (PS) seed, adopts secondary swelling and polymerization technique to make micron order St/DVB/EGDMA copolymerization microsphere then.The microspherulite diameter that makes is between 1～10 μ m, and list disperses, the size homogeneous, and anti-high temperature more than 180 ℃, elastic deformation is satisfied the requirement of making anisotropic conductive film conducting polymer microballoon more than 50%.
Embodiment
Example 1
Vinylbenzene 15.0g, AIBN 0.15g, PVP-K30 2.7g, dioctylis sulfosuccinas natricus 0.5g, ethanol 60.0g, ethylene glycol monomethyl ether 60.0g join in the 250mL four-hole reaction flask, and reflux, whipping appts, temperature measuring equipment, N are housed on the reaction flask
2Protector is used heating in water bath.Earlier with N
2Inlet tube is inserted under the liquid phase, displaced air 1h, and then with N
2Inlet tube is mentioned and is continued logical N in the gas phase
2Be rapidly heated to 70 ℃, under the low whipping speed 80 commentaries on classics/min, polymerization 24h.After polymerization finishes,, discard supernatant liquid, use washing with alcohol lower floor microballoon 5 times the reactant ultracentrifugal sedimentation.In the microballoon culture dish of falling people after the washing, dry 24h in 60 ℃ of vacuum drying ovens promptly gets the polystyrene microsphere seed, mean diameter D=1.5 μ m.
Example 2
PS seed 0.3g, CD0.3g, 0.25% SLS aqueous solution 100g are put in the beaker ultrasonic 10min in ultrasonic homogenizer; After finishing solution is transferred in the four-hole reaction flask 30 ℃ of following swelling 10h, stirring velocity 200rpm.
With the aqueous solution 100g of prescription for St6g, DVB1g, EGDMA3g, 0.25% SLS, ultrasonic 5min in ultrasonic homogenizer is transferred in the reaction flask, under 30 ℃, and swelling 12h.
After swelling is finished, the aqueous solution 40g of the PVP of adding 5%; Add AIBN 0.1g; Logical N
2Behind the 1h, under 70 ℃, polymerization 16h.
After polymerization is finished, water and ethanol repetitive scrubbing, vacuum-drying.With the samples of latex ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon, so repeat 5 times.In the microballoon culture dish of falling people after the washing, dry 24h in 60 ℃ of vacuum drying ovens promptly gets polymer microballoon, mean diameter D=4.0 μ m.
Example 3
PS seed 0.3g, CD0.3g, 0.25% SLS aqueous solution 100g are put in the beaker ultrasonic 10min in ultrasonic homogenizer; After finishing solution is transferred in the four-hole reaction flask 30 ℃ of following swelling 10h, stirring velocity 200rpm.
With the aqueous solution 100g of prescription for St9g, DVB0.5g, EGDMA0.5g, 0.25% SLS, ultrasonic 5min in ultrasonic homogenizer is transferred in the reaction flask, under 30 ℃, and swelling 12h.
After swelling is finished, the aqueous solution 40g of the PVP of adding 5%; Add AIBN 0.1g; Logical N
2Behind the 1h, under 70 ℃, polymerization 16h.
After polymerization is finished, water and ethanol repetitive scrubbing, vacuum-drying.With the samples of latex ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon, so repeat 5 times.In the microballoon culture dish of falling people after the washing, dry 24h in 60 ℃ of vacuum drying ovens promptly gets polymer microballoon.Mean diameter D=4.2 μ m
Example 4
PS seed 0.2g, CD0.2g, 0.25% SLS aqueous solution 100g are put in the beaker ultrasonic 10min in ultrasonic homogenizer; After finishing solution is transferred in the four-hole reaction flask 30 ℃ of following swelling 10h, stirring velocity 200rpm.
With the aqueous solution 100g of prescription for St6g, DVB1g, EGDMA3g, 0.25% SLS, ultrasonic 5min in ultrasonic homogenizer is transferred in the reaction flask, under 30 ℃, and swelling 12h.
After swelling is finished, the aqueous solution 40g of the PVP of adding 5%; Add AIBN 0.1g; Logical N
2Behind the 1h, under 70 ℃, polymerization 16h.
After polymerization is finished, water and ethanol repetitive scrubbing, vacuum-drying.With the samples of latex ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon, so repeat 5 times.In the microballoon culture dish of falling people after the washing, dry 24h in 60 ℃ of vacuum drying ovens promptly gets polymer microballoon.Mean diameter D=5.0 μ m
Example 5
PS seed 0.2g, CD0.2g, 0.25% SLS aqueous solution 100g are put in the beaker ultrasonic 10min in ultrasonic homogenizer; After finishing solution is transferred in the four-hole reaction flask 30 ℃ of following swelling 10h, stirring velocity 200rpm.
With the aqueous solution 100g of prescription for St9g, DVB0.5g, EGDMA0.5g, 0.25% SLS, ultrasonic 5min in ultrasonic homogenizer is transferred in the reaction flask, under 30 ℃, and swelling 12h.
After swelling is finished, the aqueous solution 40g of the PVP of adding 5%; Add AIBN 0.1g; Logical N
2Behind the 1h, under 70 ℃, polymerization 16h.
After polymerization is finished, water and ethanol repetitive scrubbing, vacuum-drying.With the samples of latex ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon, so repeat 5 times.In the microballoon culture dish of falling people after the washing, dry 24h in 60 ℃ of vacuum drying ovens promptly gets polymer microballoon.Mean diameter D=5.5 μ m.
Claims (6)
1, a kind of preparation method of micron monodisperse copolymerization microsphere is characterized in that: comprise preparation and secondary swollen-state polymerization two portions of seed, concrete steps are as follows:
(1), the preparation of seed
(1), vinylbenzene, initiator, solvent, dispersion agent, chain regulator are added in proportion reflux, whipping appts, temperature measuring equipment, N are housed
2In the four-hole reaction flask of protector and heating unit, mix;
(2), with N
2Inlet tube is inserted under the liquid phase, displaced air 30-90min, and then with N
2Inlet tube is mentioned and is continued logical N in the gas phase
2
(3), be rapidly heated to 50～90 ℃ stirring velocity 80～120 commentaries on classics/min, polymerization 15～24h;
(4), with the samples of latex ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon 3-5 time, the microballoon after washing is poured in the culture dish, dry 15-24h in 40-60 ℃ of loft drier promptly gets the polystyrene microsphere seed;
Wherein, vinylbenzene consumption: 8wt%～12wt%,
Initiator amount: 0.5wt%～1.5wt% (styrene-based),
Dispersant dosage: 10wt%～20wt% (styrene-based),
Chain regulator is dioctylis sulfosuccinas natricus consumption: 2wt%～4wt% (styrene-based),
Surplus is a solvent, and solvent is ethanol or ethylene glycol monomethyl ether or methyl alcohol, and perhaps they press the arbitrary proportion mixing;
(2), secondary swollen-state polymerization
The seed of preparation is gone on foot seed swellings, polymerization through two, obtain copolymer microsphere, detailed process is as follows:
(1), the first step swelling
With polystyrene seed, be put in the beaker with the lauryl sodium sulfate aqueous solution of the swelling agent of seed equal in quality, seed quality 200-1000 0.25wt% doubly, ultrasonic 5-10min in ultrasonic homogenizer, after finishing solution is transferred in the four-hole reaction flask, 25-40 ℃ of following swelling 8～10h, stirring velocity 100-200rpm;
(2), the second step swelling
With the St/DVB/EGDMA of following proportioning seed quality 200-1000 doubly lauryl sodium sulfate aqueous solution in behind the ultrasonic emulsification 5-10min, be transferred in the reaction flask, under 25-40 ℃, swelling 12～15h, wherein St, DVB, three kinds of monomeric total masses of EGDMA are 10～50 times of PS seed quality;
The mass ratio of St/DVB/EGDMA is: content 50wt%～90wt% of St; Content 5wt%～20wt% of DVB; Content 5wt%～30wt% of EGDMA;
Wherein St is a vinylbenzene, and DVB is a Vinylstyrene, and EGDMA is an ethylene glycol dimethacrylate;
(3), polymerization
After swelling is finished, in reaction flask, add seed quality 80-400 doubly, concentration is the aqueous solution of 5% dispersion agent, logical N
2Behind the 30-90min, under 60-90 ℃, polymerization 12～20h;
Then, water and ethanol repetitive scrubbing, drying is with the sample ultracentrifugal sedimentation, discard supernatant liquid, with washing with alcohol lower floor microballoon, centrifugal again, washing again, so repeat 3-5 time, microballoon after the washing is poured in the culture dish, and dry 15-24h in 40-60 ℃ of loft drier promptly gets polymer microballoon.
2, the preparation method of micron monodisperse copolymerization microsphere as claimed in claim 1 is characterized in that: in the preparation of seed, initiator is AIBN or BPO, and dispersion agent is PVP-K30 or PVA or PVP-K90.
3, the preparation method of micron monodisperse copolymerization microsphere as claimed in claim 2 is characterized in that: in the preparation of seed, initiator is AIBN, and dispersion agent is PVP-K30.
4, the preparation method of micron monodisperse copolymerization microsphere as claimed in claim 1 is characterized in that: in the preparation of seed, solvent is that ethanol mixes by mass ratio with ethylene glycol monomethyl ether at 1: 1.
5, the preparation method of micron monodisperse copolymerization microsphere as claimed in claim 1 is characterized in that: in the secondary swollen-state polymerization, swelling agent is a chlorododecane or toluene or n-Hexadecane.
6, the preparation method of micron monodisperse copolymerization microsphere as claimed in claim 4 is characterized in that: in the secondary swollen-state polymerization, swelling agent is a chlorododecane.
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