CN106366217A - Polymer functional micro-spheres capable of removing stabilizing agent and preparation method of polymer functional micro-spheres - Google Patents
Polymer functional micro-spheres capable of removing stabilizing agent and preparation method of polymer functional micro-spheres Download PDFInfo
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- CN106366217A CN106366217A CN201610751262.0A CN201610751262A CN106366217A CN 106366217 A CN106366217 A CN 106366217A CN 201610751262 A CN201610751262 A CN 201610751262A CN 106366217 A CN106366217 A CN 106366217A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003381 stabilizer Substances 0.000 title claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 41
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
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- 238000010790 dilution Methods 0.000 claims description 2
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- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims 1
- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 claims 1
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- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims 1
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- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 description 1
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
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Abstract
The invention discloses polymer functional micro-spheres capable of removing a stabilizing agent and a preparation method of the eurotium cristatum brick tea. The preparation method comprises the following steps: first, performing esterification reaction on a terminal hydroxyl of polyethylene glycol and a reversible addition-fragmentation chain transfer agent (RAFT) of which a non-leaving group contains a carboxyl group to synthesize a Z-type macromolecular RAFT reagent of which the two ends contain RAFT active groups; then, using the Z-type macromolecular RAFT reagent of which the two ends contain the RAFT active groups in light dispersion polymerization as a stable dispersant; particularly, mixing the stable dispersant and polymeric monomers, a photoinitiator and functional monomers; introducing nitrogen; taking ethyl alcohol/water as a dispersing medium; irradiating for 0.5 to 5 hours to obtain a stable white emulsion dispersing liquid; diluting the stable white emulsion dispersing liquid by using water, and adding excessive heat initiator; introducing the nitrogen, heating for about 24 hours in an oil bath; removing the dispersing medium to obtain clean polymer functional micro-spheres of which the surfaces do not contain the stable dispersing agent. In the process of the method, the stable dispersing agent can be removed to obtain the polymer functional micro-spheres of which the surfaces are clean quickly; the problem that functional groups are influenced by the stable dispersing agent on the surfaces is solved.
Description
Technical field
The invention belongs to technical field of polymer preparation.More particularly, to a kind of polymer work(excising stabilizer
Energy microsphere and preparation method thereof.
Background technology
Dispersion copolymerization method is to prepare micrograde polymer microsphere most common method at present, this method have simple to operate, Gu
The features such as content height and microspherulite diameter are evenly distributed.Carry out copolymerization by adding the monomer containing functional group, can be easily
Obtain various functions copolymerization microsphere.
But, a shortcoming of dispersion copolymerization method is to need to use stable dispersant in microsphere preparation process, and these are steady
Determine dispersant and be anchored at microsphere surface generally by chemical bonding it is difficult to remove, the microsphere surface obtained by leading to covers
One layer of stable dispersant.When needing the functional group using microsphere body, this layer of stable dispersant will play iris action, impact
The using effect of functional group.
At present, solving one of method of this problem is to reduce the consumption of stable dispersant as far as possible, reduces it to microsphere
Cover, but so will affect nucleation and the propagation process of microsphere, when stabilizing agent dosage is too low, be generally difficult to
To mono-dispersion microballoon.Another method is the mechanism using charge stable, adds charge-carrying monomers to replace macromolecular stabilizer dispersant
(macromolecular chemistry and physics, 2010,211 (7): 744-751), the microsphere surface so obtaining
Except containing a small amount of charged group, without other stable dispersants.But this using a small amount of electric charge, microsphere is carried out stable
Method be restricted when preparing some function copolymerization microspheres because function comonomer addition interference nucleation process, and
It is possible to affect charge stable effect.From document report, in order to introduce functional group on microsphere, need to close in microsphere
Carry out the further functionalization of chemical modification after one-tenth.And the method is belonging to the dispersin polymerization of thermal initiation, need longer reaction
Time.
Content of the invention
The technical problem to be solved in the present invention is to overcome microsphere surface in prior art to cover stable dispersant, makes microsphere originally
The problem that the application of body function group is somewhat limited, has synthesized a kind of special, two ends and has contained reversible addition-fracture
The straight chain living polymer of chain-transferring agent (raft), as stable dispersant, carries out light dispersin polymerization one step under ultraviolet light
Then the stabilizer of microsphere surface is excised, is prepared surface " clean " (not by stable dispersant by complex functionality copolymerization microsphere again
Cover) single dispersing functional polymer microsphere.
It is an object of the invention to provide a kind of z- type macromole raft reagent.
The present invention another object is that provides a kind of preparation method of the polymer microballoon excising stabilizer.
Another object of the present invention is the polymer microballoon of the stabilizer excised providing methods described to prepare.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of z- type macromole raft reagent, its structural formula is as follows:
Wherein, n=25～500.
As one kind preferably can embodiment, described z- type macromole raft reagent is the z in small molecule raft reagent
Macromolecular chain is connected on group obtain.
Specifically, described z- type macromole raft preparation method of reagent thereof is: using Polyethylene Glycol (peg) and z group upper band
The raft reagent having carboxyl carries out esterification and obtains.Carboxylic on the terminal hydroxy group of Polyethylene Glycol (peg) and the z group of raft reagent
Base carries out the z- type macromole raft reagent that the two ends that esterification obtains contain raft group.
Preferably, the raft reagent described z group carrying carboxyl is (but not limited to) benzyl dihydrogen thiocarbonate. ester group third
Sour (abbreviation btpa), the esterification reaction product abbreviation btpa-peg-btpa with peg.
Preferably, the molecular weight of described Polyethylene Glycol is 1000～20000.
Except peg, all two ends hydroxyl in principle and the polymer that is dissolved in reaction medium are adapted to preparation and contain
Polyethylene Glycol (peg) z- type macromole raft reagent, and it is used for light dispersin polymerization.
In addition, a kind of preparation method of the polymer microballoon excising stabilizer, it is with above-mentioned z- type macromole raft examination
Agent, as stable dispersant, using ethanol/water mixed liquor as disperse medium, carries out light dispersin polymerization, and synthesis obtains stable white
Color emulsion；Then add excessive thermal initiator, logical nitrogen oil bath heating 20～28h (preferably 24h) after dilute with water, remove and divide
The clean polymers function microsphere that surface does not contain stable dispersant is obtained after dispersion media.
Specifically, as one kind preferably can embodiment, the preparation side of the described polymer microballoon excising stabilizer
Method, comprises the steps:
S1. the polymer microballoon dispersion liquid that light raft dispersin polymerization obtains:
Z- type macromole raft reagent and function monomer described in polymerized monomer, light trigger, claim 1 are dissolved in second
In alcohol/water mixed solvent, seal after logical nitrogen, with causing light source light to shine, obtain stable white polymer microsphere dispersion liquid；
S2. polymer microballoon surface raft active group is decomposed, thus the stable dispersant strand excision surface.
Wherein it is preferred to, polymerized monomer described in step s1 is methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid isobornyl thiocyanoacetate, butyl methacrylate, lauryl methacrylate, isobutyl methacrylate, isodecyl
Ester, 2-Propenoic acid, 2-methyl-, isooctyl ester, acrylic acid methyl ester., ethyl acrylate, isobornyl acrylate, butyl acrylate, the acrylic acid moon
Osmanthus ester, Isobutyl 2-propenoate, isodecyl acrylate or Isooctyl acrylate monomer any one or a few.
Preferably, light trigger described in step s1 is 2,4,6- trimethylbenzoyl diphenyl phosphine oxides, 2- hydroxyl -2- first
Base -1- phenylacetone -1,1- hydroxy-cyciohexyl benzophenone, bis(benzoylphenyl) phosphine oxide, 2- methyl isophthalic acid-[4- first sulfydryl benzene
Base] any one in -2- morpholine acetone -1 or 2- phenyl -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone -1.
Preferably, function monomer described in step s1 be acrylic acid, methacrylic acid, itaconic acid, glycidyl acrylate,
Any one of glycidyl methacrylate, acrylic acid -2- hydroxyl ethyl ester or 2-hydroxyethyl methacry-late.
Preferably, the consumption of polymerized monomer described in step s1 is 5～20wt%.
Preferably, the consumption of z- type macromole raft reagent described in step s1 is 0.1～15wt% of polymerized monomer.
Preferably, the consumption of light trigger described in step s1 is 1～10wt% of polymerized monomer.
Preferably, the consumption of function monomer described in step s1 is 1～10wt% of polymerized monomer.
Preferably, light source is caused to be uv-led point source described in step s1.
Preferably, the light intensity causing light source described in step s1 is 0.2～20mw/cm2.
Preferably, the radiation wavelength causing light source described in step s1 is 365nm.
Preferably, the time of illumination described in step s1 is 0.5～5h.
Preferably, described initiation light source irradiates from the top of reactor.
Preferably, in ethanol/water mixed solvent described in step s1, the weight of ethanol and water is than for 20:80～80:20.
It is highly preferred that in ethanol/water mixed solvent described in step s1, the weight of ethanol and water is than for 40:60.
Preferably, described in step s1, the time of logical nitrogen is 10～20min (preferably 15min).
As one kind preferably can embodiment, decompose excision polymer microballoon surface raft active group described in step s2
Concrete grammar be: the polymer microballoon dispersion liquid of s1 is added water dilution, is subsequently adding excessive thermal initiator, logical nitrogen
Afterwards, the oil bath reaction of 60～80 DEG C (preferably 70 DEG C), centrifugation, and with washing with alcohol for several times, obtain clean polymers function micro-
Ball.
Preferably, described thermal initiator is potassium peroxydisulfate (kps) or azodiisobutyronitrile (aibn).
Preferably, the consumption of described thermal initiator is 10～200 times of the molal quantity of polymers function microsphere.
In addition, the polymer microballoon of the stabilizer excised being prepared by said method and its application, also all at this
Within bright protection domain.
The key problem in technology of the present invention is that design has synthesized a kind of special z- type macromole raft reagent, and as stable point
Powder is used for light dispersin polymerization.
Raft reagent is generally the compound that dithioesters and three thioesters etc. have high chain transfer constant, the structure of raft reagent
Formula is as follows:
When carrying out raft polymerization, by reversible addition-fracture, chain tra nsfer process, monomer constantly inserts between s and r, shape
Become macromolecular chain, its chain end remains with raft active group.The macromolecular chain that this end contains raft group is referred to as macromole
Raft reagent.When macromole raft reagent is used for dispersin polymerization, partial monosomy is polymerized on macromole raft reagent, existing
Field forms block copolymer, and newly-generated macromolecular chain is attached in microsphere body, and original parent on macromole raft reagent
Medium macromolecular chain stretches in media as well, polymer microballoon is produced with stable dispersion effect, thus it is micro- to obtain monodisperse polymer
Ball.But it is typically used for the macromole raft reagent of stable dispersant, its macromolecular chain is located at the position of r group, form block
After copolymer, two block molecule chains firmly connect, and raft group is always positioned at macromolecular chain least significant end, are embedded in microsphere body
Face.Therefore it is difficult to the macromolecular chain of close medium to remove from microsphere surface.
Macromole raft reagent prepared by the present invention, then be the z that macromolecular chain close medium is connected to raft reagent
Group end, we term it z- type macromole raft reagent.When forming block copolymer, new strand is in raft reagent
R group end grows.The block copolymer so being formed, raft group is between two strands, all the time with close medium molecule chain
It is joined directly together, thus when stablizing polymer microballoon, raft reagent is in microsphere surface (as shown in Figure 1).Then pass through one
Simple method a bit, raft radical decomposition, just can excise the stable dispersant strand on surface.One is given in the present invention
The scheme of kind, adds appropriate thermal initiator after forming microsphere, in the free radical meeting and polymer microballoon that heat resolve produces
Raft reagent in three thioesters c=s key reaction formed transition state free radical, then the free radical of these transition states may proceed to
The free radical producing with initiator reacts, thus the three thioester groups related stable dispersant parent's medium molecule chain by surface
Excision, that is, obtain the polymers function microsphere that surface does not contain stabilizer.
The method have the advantages that
The present invention utilizes carboxylic reversible addion-fragmentation chain transfer agent on the terminal hydroxy group of Polyethylene Glycol and non-leaving group
(raft) carry out esterification synthesis obtain two ends contain raft active group z- type macromole raft reagent, then as
Stable dispersant is used in light dispersin polymerization, prepares polymers function microsphere, can stablizing by simple method removal surface
Dispersant, quickly obtains the polymers function microsphere on surface " clean ", and solving surface-stable dispersant affects functional group
Problem.
Brief description
Fig. 1 is to carry out light dispersin polymerization thus obtained microsphere structural representation using z- type macromole raft reagent.
Fig. 2 is the scanning electron microscope (SEM) photograph (sem) of the polymers function microsphere of embodiment 2～4 preparation.
Fig. 3 is the scanning electron microscope (SEM) photograph (sem) of the polymers function microsphere of embodiment 5～7 preparation.
Fig. 4 is the scanning electron microscope (SEM) photograph (sem) of the polymers function microsphere of embodiment 8～10 preparation.
Fig. 5 is the x-ray XPS Analysis (xps) before polymers function microsphere product excises stabilizer.
Fig. 6 is to excise the x-ray XPS Analysis (xps) after stabilizer with kps for thermal initiator.
Fig. 7 is to excise the x-ray XPS Analysis (xps) after stabilizer with aibn for thermal initiator.
Specific embodiment
To further illustrate the present invention below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
Limit in any form.Unless stated otherwise, the reagent that the present invention adopts, method and apparatus are the conventional examination of the art
Agent, method and apparatus.
Unless stated otherwise, following examples agents useful for same and material be commercial.
Embodiment 1 prepares z- type macromole raft reagent
Addition ho-peg (20000)-oh (30.0g, 1.5mmol) in the single-necked flask of 500ml, btpa (1.65g,
6mmol), dmap (73.7mg, 0.6mmol) and anhydrous ch2cl2(120ml), stirring and dissolving in ice-water bath.Treat that temperature drops to 0
DEG C about when, the dropwise ch of Deca dcc (1.24g, 6mmol)2cl2Solution (30ml) more than 30min, and continue in ice-water bath
Reaction 1h.After room temperature reaction 48h, reacting liquid filtering removes the insoluble matter dcu generating, revolving, and with ice ether and ice normal hexane
Mixed liquor (v/v=1:1) precipitation, obtain the crude product of yellow powder.Then purified further with silica gel column chromatography, own
Mobile phase is chloroform and methanol (v/v=95:5), finally gives btpa-peg (20000)-btpa macromole raft reagent.
The synthesis of other macromole raft reagent btpa-peg (6000)-btpa and btpa-peg (10000)-btpa with
Btpa-peg455-btpa is similar to, and reaction equation is as follows:
The formula of polymers function microsphere is prepared respectively as shown in table 1 in example 2 below～10:
The polymers function microsphere of table 1 different formulations
* aa refers to acrylic acid, and gma refers to glycidyl methacrylate, and hema refers to hydroxyethyl methylacrylate.Its
Middle macromole raft reagent and light trigger consumption are with respect to monomer concentration.
Embodiment 2 prepares polymers function microsphere
1st, in glass reaction bottle, methyl methacrylate monomer (mma, 2.0g, 10% solid content), light trigger are added
D1173 (0.06g, 3% with respect to mma monomer), z- type macromole raft reagent (6% with respect to mma monomer), function monomer aa
(3% with respect to mma monomer) is dissolved in ethanol/water (7.2g/10.8g, 40/60, w/w) mixed solvent, after logical nitrogen 15min
With the sealing of quartz glass plug.Then with the uv-led point source of 365nm, (light intensity is 2.4mw/cm2) from the top illumination of reactor
1h.After illumination terminates, obtain stable white " milky " dispersion liquid, and with 10000 turns of centrifuge, and use ethanol/water
(40/60, w/w) mixed solution cleans three times, obtains final product the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 2.
Embodiment 3 prepares polymers function microsphere
1st, in this embodiment, function monomer acrylic acid aa consumption is changed to 5% (with respect to polymerized monomer mma), remaining reagent
Species and consumption and implementation steps are in the same manner as in Example 2, obtain the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 2.
Embodiment 4 prepares polymers function microsphere
1st, in this embodiment, function monomer acrylic acid aa consumption is changed to 10% (with respect to polymerized monomer mma), remaining reagent
Species and consumption and implementation steps are in the same manner as in Example 2, obtain the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 2.
Embodiment 5 prepares polymers function microsphere
1st, in this embodiment, macromole raft reagent dosage is changed to 10% (with respect to polymerized monomer mma), remaining reagent kind
Class and consumption and implementation steps are in the same manner as in Example 4, obtain the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 3.
Embodiment 6 prepares polymers function microsphere
1st, in this embodiment, macromole raft reagent dosage is changed to 15% (with respect to polymerized monomer mma), remaining reagent kind
Class and consumption and implementation steps are in the same manner as in Example 4, obtain the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 3.
Embodiment 7 prepares polymers function microsphere
1st, in this embodiment, by macromole raft reagent btpa-peg (20000)-btpa be changed to btpa-peg (6000)-
Btpa, consumption is 15% (with respect to polymerized monomer mma), in remaining reagent type and consumption and implementation steps and embodiment 6
Identical, obtain the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 3.
Embodiment 8 prepares polymers function microsphere
1st, in this embodiment, by macromole raft reagent btpa-peg (20000)-btpa be changed to btpa-peg (10000)-
Btpa, consumption is 15% (with respect to polymerized monomer mma), in remaining reagent type and consumption and implementation steps and embodiment 6
Identical, obtain the polymers function microsphere of surface band carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 4.
Embodiment 9 prepares polymers function microsphere
1st, in this embodiment, function monomer acrylic acid aa is changed to glycidyl methacrylate gma, consumption is 10%
(with respect to polymerized monomer mma), remaining reagent type and consumption and implementation steps are in the same manner as in Example 6, obtain surface band
The polymers function microsphere of epoxy radicals.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 4.
Embodiment 10 prepares polymers function microsphere
1st, in this embodiment, function monomer acrylic acid aa is changed to hydroxyethyl methylacrylate hema, consumption is 10% (phase
For polymerized monomer mma), remaining reagent type and consumption and implementation steps in the same manner as in Example 6, obtain surface hydroxyl
Polymers function microsphere.
2nd, products therefrom scanning electron microscope (SEM) photograph (sem) is shown in Fig. 4.
Embodiment 11 excises the stabilizer of polymers function microsphere surface
1st, being based on macromole raft reagent btpa-peg (20000)-btpa (10wt% of monomer mass) is stabilizer
Light raft dispersin polymerization obtains the polymers function microsphere dispersion liquid of surface band carboxyl, adds 10.0g water to be diluted to 10% and admittedly contains
Amount.It is subsequently adding more than 100 times of thermal initiator potassium peroxydisulfate kps.Reactant mixture is led to after nitrogen 30min, is placed in 70 DEG C
Oil bath pan in reaction 24h after, centrifugation and with washing with alcohol several times, be dried, obtain the clean polymer work(with carboxyl in surface
Can microsphere.
2nd, the x-ray XPS Analysis (xps) before and after product excises stabilizer are respectively as shown in Figure 5 and Figure 6.
Embodiment 12 excises the stabilizer of polymers function microsphere surface
In this embodiment, thermal initiator aibn is replaced kps, remaining reagent type and consumption and the reality in embodiment 11
Apply step identical with embodiment 12.
X-ray XPS Analysis (xps) after product excises stabilizer are as shown in Figure 7.
Claims (10)
1. a kind of z- type macromole raft reagent is it is characterised in that its structural formula is as follows:
Wherein, n=25～500.
2. a kind of preparation method of the polymer microballoon excising stabilizer is it is characterised in that big with z- type described in claim 1
Molecule raft reagent, as stable dispersant, using ethanol/water mixed liquor as disperse medium, carries out light dispersin polymerization, synthesizes
To stable white " milky " dispersion liquid；Then the excessive thermal initiator of addition after dilute with water, logical nitrogen oil bath heating 20～28h,
The clean polymers function microsphere that surface does not contain stable dispersant is obtained after removing disperse medium.
3. preparation method according to claim 2 is it is characterised in that comprise the steps:
S1. the polymer microballoon dispersion liquid that light raft dispersin polymerization obtains:
By z- type macromole raft reagent described in polymerized monomer, light trigger, claim 1 and function monomer be dissolved in ethanol/
In water mixed solvent, seal after logical nitrogen, with causing light source light to shine, obtain stable white polymer microsphere dispersion liquid；
S2. polymer microballoon surface raft active group is decomposed, thus the stable dispersant strand excision surface.
4. preparation method according to claim 3 is it is characterised in that polymerized monomer described in step s1 is methyl methacrylate
Ester, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, metering system
Sour isobutyl ester, isodecyl methacrylate, 2-Propenoic acid, 2-methyl-, isooctyl ester, acrylic acid methyl ester., ethyl acrylate, isobomyl acrylate
Ester, butyl acrylate, lauryl acrylate, Isobutyl 2-propenoate, isodecyl acrylate or Isooctyl acrylate monomer any one
Or it is several.
5. preparation method according to claim 3 is it is characterised in that light trigger described in step s1 is 2,4,6- trimethyls
Benzoyl diphenyl phosphine oxide, 2- hydroxy-2-methyl -1- phenylacetone -1,1- hydroxy-cyciohexyl benzophenone, double Benzoylbenzene
Base phosphine oxide, 2- methyl isophthalic acid-[4- first mercaptophenyl] -2- morpholine acetone -1 or 2- phenyl -2- dimethylamino -1-(4- morpholine benzene
Base) any one in-butanone -1.
6. preparation method according to claim 3 is it is characterised in that function monomer described in step s1 is acrylic acid, methyl
Acrylic acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate, acrylic acid -2- hydroxyl ethyl ester or metering system
Any one of acid -2- hydroxyl ethyl ester.
7. preparation method according to claim 3 it is characterised in that polymerized monomer described in step s1 consumption be 5～
20wt%；The consumption of z- type macromole raft reagent described in step s1 is 0.1～15wt% of polymerized monomer；Described in step s1, light draws
The consumption sending out agent is 1～10wt% of polymerized monomer；The consumption of function monomer described in step s1 is 1～10wt% of polymerized monomer.
8. preparation method according to claim 3 is it is characterised in that cause light source to be medium pressure mercury lamp, purple described in step s1
Outer smooth Non-polarized lamp, metal halid lamp or uv-led light source；The light intensity causing light source described in step s1 is 0.2～20mw/cm2.
9. preparation method according to claim 3 is it is characterised in that the concrete grammar of step s2 is: by the polymer of s1
Microsphere dispersion liquid adds water dilution, is subsequently adding excessive thermal initiator, after logical nitrogen, 60～80 DEG C of oil bath reaction, from
The heart, and with washing with alcohol for several times, obtain clean polymers function microsphere.
10. the polymer microballoon of the stabilizer excised that the arbitrary methods described of claim 2～9 prepares.
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| CN109134737B (en) * | 2018-07-02 | 2021-01-22 | 中山大学 | Rare earth ion-loaded cross-linked polymer microsphere and preparation method thereof |
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