CN105713158B - A kind of ABA type and ABCBA types block copolymer and preparation and application - Google Patents
A kind of ABA type and ABCBA types block copolymer and preparation and application Download PDFInfo
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- 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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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- 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
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- 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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- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
A kind of ABA type and ABCBA types block copolymer and preparation and application, are related to technical field of polymer materials.By using bifunctionality RAFT reagents, acrylic acid carries out emulsifier-free emulsion polymerization, two-step method synthesis triblock polymer or three-step approach synthesize five block polymers as hydrophilic section A, acrylic ester monomer as hydrophobic section B or C for the ABA type and ABCBA types polymer.Wherein, B or C sections of monomer is the block polymer or copolymer of styrene, acrylic acid trifluoro ethyl ester, ethyl acrylate, butyl acrylate or hexafluorobutyl acrylate.The ABA type and ABCBA type block polymers are elastomers.It is transparent membrane after its lotion room temperature film-forming, forms hydrophobic surface after heat-treated, surface contact angle reaches as high as 120 degree.
Description
Technical field
The present invention relates to technical field of polymer materials, further say, RAFT emulsion polymerizations are used the present invention relates to a kind of
Acrylic acid-b- polyacrylate-b- acrylic acid three block ABA types and ABCBA types co-polymer and preparation side prepared by method
Method and application.
Background technology
Elastomer is the elasticity for having under room temperature rubber, has the molding a kind of elastomer of plasticization under high temperature.It is common
Elastomer is triblock copolymer, and by being connected chemically, resin section forms physics crosslinking points, rubber segments contribution for resin section and rubber segments
Elasticity.The physical crosslinking variation with temperature of plastics section and in reversible change, ensure that the plastic processing characteristic of elastomer.Cause
This, elastomer has the physical mechanical property of vulcanization rubber and the processing performance of plastics.Since Bayer companies in 1958 make for the first time
It is standby go out polyurethane (TPU) since, elastomer is just rapidly developed, especially styrenic elastomer in 1963 come out with
Afterwards, elastomer application field further expands, and related industry is quickly grown.
Since RIZZARDO in 1998 invents RAFT polymerizations, which obtains
The extensive concern of academia all over the world.In the industry it is believed that Controlled Living Radical Polymerization is it is possible that substitute anion and sun
Ionic polymerization becomes the new method of the structural polymers such as the more blocks of more easy-to-use synthesis, star-like, tree-shaped.
Aqueous emulsion polymerization process receives much attention as being easiest to carry out industrialized polymerization.And RAFT emulsion polymerizations
Method has the characteristics that the raising reaction rate on the premise of ensureing that polymer architecture activity is controllable, and more friendly to environment
Good, prepared product emulsion can directly be processed application.
The content of the invention
The object of the present invention is to provide a kind of hydrophobic ABA type and ABCBA type elastomer block copolymers, wherein A is poly- third
Olefin(e) acid, B, C are that the block of styrene, acrylic acid trifluoro ethyl ester, ethyl acrylate, butyl acrylate or hexafluorobutyl acrylate gathers
Close object or copolymer.It is a further object to provide a kind of hydrophobic ABA type and ABCBA type triblock copolymer elastomers
(A is polyacrylic acid, and B, C are styrene, acrylic acid trifluoro ethyl ester, ethyl acrylate, butyl acrylate or hexafluorobutyl acrylate
Block polymer or copolymer) preparation method, including using bifunctionality RAFT reagents two-step method prepare with by lotion into
The sample of type carries out high-temperature process etc.；It is a further object to provide the ABA type and ABCBA type triblock copolymers
Elastomer application field.
The preparation of ABA type or ABCBA type elastomer block copolymers, which is characterized in that by ABA type three block or ABCBA
Five block RAFT polymerized emulsions of type, direct machine-shaping are surface hydrophilic type product；Or by ABA type three block or ABCBA types five
Block RAFT polymerized emulsions, direct machine-shaping are surface hydrophilic type product, then carry out being thermally treated resulting in surface hydrophobicity type system
Product；Or will heat after ABA type three block or the drying of five block RAFT polymerized emulsions of ABCBA types, it is prepared into surface and dredges
Water type product.
The present invention is prepared for acrylic acid-polyacrylate-acrylic acid three block ABA type using RAFT emulsion polymerisation process
And the lotion and its product of ABCBA type copolymer elastomers.
Bifunctionality RAFT reagents of the present invention include：S-S'- bis- (α, α ' dimethyl, α "-acetic acid) three is thio
Carbonic ester (2,2 '-(thiocarbonylbis (sulfanediyl)) bis (2-methylpropanoic acid)).
Five block RAFT polymerized emulsions of ABA type three block or ABCBA types of the present invention carry out two using bifunctional RAFT reagents
Footwork emulsion polymerization obtains；Synthetic method is as follows：In reaction vessel add in A corresponding to monomeric acrylic, RAFT reagents,
Initiator and reaction dissolvent react 1-2h, the rear monomer being added dropwise corresponding to B or B and C, drop at 60-80 DEG C after removing oxygen
It is 3-6h between added-time, cooling discharging.Initiator be V-501 or KPS, RAFT reagent for two-tube energy degree RAFT reagents S-S'- bis- (α,
α ' dimethyl, α "-acetic acid) trithiocarbonate.
Above-mentioned ABA and the tri- embedding degree of polymerization of ABCBA can be adjusted as needed, and RAFT reagents, initiator amount can also
It adjusts as needed.The corresponding monomers of B and C are different, and preferably and during three block the corresponding monomers of B are not styrene.
If B, C is block, substep adds in respectively for B and monomer corresponding to C, such as B sections of corresponding lists of addition after A section polymerizations
Body or A sections polymerization after add in B sections of corresponding monomer reactions after continuously add C sections of corresponding monomers, be respectively synthesized ABA type or
ABCBA type block polymers；If B, C is copolymer, B and the monomer mixing corresponding to C add in.
Reaction dissolvent is water or the mixed solvent of water and organic solvent, and organic solvent is：Ethyl alcohol, acetone, tetrahydrofuran, two
Six ring of oxygen etc., the ratio of water and organic solvent is adjusted as needed, and the volume of common organic solvents is not more than 40%.
With polyacrylic acid-b- butyl polyacrylate-b- polyacrylic acid block polymers, polyacrylic acid-b- polyacrylic acid six
Exemplified by fluorine butyl ester-b- polyacrylic acid and polyacrylic acid-b- polyethyl acrylate-b- polyacrylic acid block polymers, using double officials
Energy RAFT reagents carry out what two-step method emulsion polymerization obtained；Synthetic method is as follows：400 mol propylenes acid, 0.5-2 moles of RAFT examination
Agent, 0.1-0.5 mole initiators and deionized water are added in reaction kettle, and 1-2h is reacted at 60-80 DEG C after removing oxygen, rear to be added dropwise
400-4000 molar parts Butyl Acrylate Monomer or one of hexafluorobutyl acrylate or ethyl acrylate, time for adding 3-6h,
Cooling discharging.Initiator is one of V-501, KPS, RAFT reagents for two-tube energy degree RAFT reagents S-S'- bis- (α, α ' dimethyl,
α "-acetic acid) trithiocarbonate.
Heat treatment temperature of the present invention is：80-150 DEG C, preferably 100-130 DEG C, more preferable 110-120 DEG C
The present invention prepares poly acrylic acid-poly butyl acrylate-polyacrylic acid triblock copolymer elastomer and polypropylene
Acid-polyethyl acrylate-polyacrylic acid triblock copolymer lotion and poly acrylic acid-poly acrylic acid trifluoro ethyl ester-polyacrylic acid
Butyl ester-polyacrylic acid trifluoro ethyl ester-polyacrylic acid, poly acrylic acid-poly acrylic acid trifluoro ethyl ester-polyethyl acrylate-polypropylene
Sour trifluoro ethyl ester-polyacrylic acid, poly acrylic acid-poly acrylic acid trifluoro ethyl ester-polyacrylic acid hexafluoro butyl ester-polyacrylic acid trifluoro second
Ester-polyacrylic acid and hydrophobic product.
Prepared copolymer can be applied directly by lotion machine-shaping, including elastic coating, transparent elastic latex
Hose and sheath etc.；Also applied after can drying by being processed into product, including injection-molded item, pressing, blow-molded article and
Extruded product etc..
The surface contact angle of hydrophobic copolymer is more than or equal to 95 °, preferably greater than or equal to 105 °, is more preferably greater than equal to
115°。
The tensile set of copolymer is less than or equal to 10%, preferably smaller than equal to 6%, more preferably less than or equal to 3%.
Film prepared by present copolymer is transparent.Vermiform Microphase Structure is mutually formed including acrylic acid after film forming
Film etc..
The two-step method, which prepares ABA type and ABCBA type RAFT emulsion polymerisation process, also has following features：
1) emulsion polymerization is carried out using two function RAFT reagents, two-step method forms ABA type and the polymerization of ABCBA types three block
Object.
2) RAFT polymerisation in solutions are carried out in aqueous solution using hydrophilic monomer, then the phase adds in hydrophobic monomer after the reaction,
Emulsion particle is self-assembly of by polymerisation induced.
3) glass transition temperature for the polymer that the hydrophobic monomer of B sections used in is formed is necessarily less than polymerisation temperature
Degree.
4) water solubility of hydrophobic monomer can be increased by increasing temperature, so as to its favourable migration in system, increased
The stability of reaction system.
5) water solubility of hydrophobic monomer can be increased by adding in organic solvent (such as ethyl alcohol), so that favorably it is in system
In migration, increase the stability of reaction system.
6) emulsion intercalation method can be improved by controlling the rate of addition of hydrophobic monomer.
ABA triblock polymer emulsion process prepared by this method is relatively easy, selects low in raw material price, and step is compared
Traditional chain extension formula emulsion polymerization is more simplified, and obtained material has the property of elastomer.The present invention uses difunctionality RAFT examinations
Agent, it is possible to reduce the step of block polymerization, synthetic method is simple.The bifunctional RAFT polymerisation induceds self assembly shape that the present invention uses
Method into lotion is suitble to prepare elastomer, raw because intermediate B or B and C block polymers must have low Tg
The raw material that the monomer of production high glass transition temperature polymer is not suitable as this method uses.Poly acrylic acid-poly prepared by the present invention
Butyl acrylate-polyacrylic acid triblock copolymer, poly acrylic acid-poly hexafluorobutyl acrylate-polyacrylic acid and polyacrylic acid-
B- polyethyl acrylate-b- polyacrylic acid triblock copolymer is hydrophilic by room temperature emulsion direct formation of film at surface rear surface, and contact angle can
Up to 30 degree；By forming hydrophobic surface after high-temperature heating, surface contact angle is up to 120 degree.
Figure of description
Fig. 1：The synthesis step of ABA type poly acrylic acid-poly esters of acrylic acid-polyacrylate emulsion.
Fig. 2：The stress-strain diagram of poly acrylic acid-poly butyl acrylate-polyacrylic acid of different component content.
Fig. 3：The stress-strain diagram of poly acrylic acid-poly hexafluorobutyl acrylate-polyacrylic acid of different component content.
The WAC of (a) and (b) after heat treatment before being heat-treated after Fig. 4 poly acrylic acid-polies esters of acrylic acid-polyacrylic acid film forming
Photo
Contact angle variation diagram before and after Fig. 5 heat treatments；
Example 24 (a), example 25 (b), example 26 (c) and example 27 (d).
Fig. 6：Before being heat-treated after poly acrylic acid-poly esters of acrylic acid-polyacrylic acid film forming (left side) afterwards (right side) AFM as a result,
Film has emulsion particle and vermiform acrylic acid Microphase Structure.
Fig. 7：The synthesis step of ABCBA types poly acrylic acid-poly esters of acrylic acid-polyacrylate emulsion.
Fig. 8：Synthesis GPC and the solid content tracking of ABCBA poly acrylic acid-polies esters of acrylic acid-polyacrylic acid
Fig. 9：The synthesis FTIR tracking of ABCBA poly acrylic acid-polies esters of acrylic acid-polyacrylic acid.
Figure 10：The synthesis NMR tracking of ABCBA poly acrylic acid-polies esters of acrylic acid-polyacrylic acid.
Wherein a is corresponded to
B is corresponded to
C is corresponded to
D is corresponded to
Figure 11：The stress-strain diagram of different component content ABCBA types.
Figure 12：The GPC spectrograms of different component content ABA type.
Figure 13：The GPC spectrograms of different component content ABCBA types.
Specific embodiment
The present invention is further described with reference to embodiment.The scope of the present invention is not restricted by the embodiments, this hair
Bright protection domain proposes in detail in the claims.
Monomer and raw material of the present invention include：Azo dicyano valeric acid (this Co., Ltd of Shanghai Adama,
ACVA, V501,99%), dioxane (Beijing Chemical Plant, analysis pure), acrylic acid (AA, Beijing Chemical Plant, analysis are pure), propylene
Sour trifluoro ethyl ester (TFEMA, Harbin Xue Jiafu chemistry of silicones Co., Ltd, 98%), hexafluorobutyl acrylate (HFBA, Harbin
Xue Jiafu chemistry of silicones Co., Ltd, 98%), butyl acrylate (BA, Beijing Chemical Plant, vacuum distillation purification), ethyl acrylate
(EA, Beijing Chemical Plant, analysis are pure), styrene (St, Beijing Chemical Plant, vacuum distillation purification), deionized water.
Example used test method and standard：
Emulsion solid content and monomer conversion：1-2mL reaction system solution is injected in the bottle of 8mL, is placed in 80 DEG C
Rear weight method calculates its solid content and monomer conversion to oven drying for 24 hours.
1HNMR and13CNMR is tested：Sample size about 10mg is taken, is dissolved in DMSO, instrument is total to for the nuclear-magnetism of Brooker company
Vibration wave spectrometer AV600, carries out respectively1HNMR and13CNMR is tested.
Examination of infrared spectrum：Instrument model is tested for the Fourier infrared spectrograph of Brooker company of the U.S..Respectively
KBr (potassium bromide) pressed disc method sample preparations are employed to carry out transmiting infrared (TR) test and directly carry out in total reflection Fu film-forming products
Leaf infrared (ATR) is tested.
Molecular weight (Mn) and its molecular weight distribution PDI (Mw/Mn)：It is measured using the gel chromatography of 515 model of Waters companies
The molecular weight and its molecular weight distribution of polymer, wherein, mobile phase THF, rate of outflow 1mLmin-1, calibration sample is
PS, test temperature are 30 DEG C, and the chemical modification that methylates must be carried out to-the COOH in polymer poly acrylic acid section before GPC is surveyed.
The dried polymer powders of 4-7mg is taken to be dissolved in the mixed solution (v of water and tetrahydrofuran:V=1:1) the inside, is added dropwise dropwise
For methylating reagent trimethyl silane diazomethane until solution bubble-free generates, system, which is faded, becomes light yellow.System is stirred in room temperature
After mixing 6h, methylate completion.Methylated polymer object is placed in 80 DEG C of oven dryings and send GPC afterwards for 24 hours.
Emulsion particle diameter and particle diameter distribution：It is equal that its number is measured using the laser dynamics instrument of the Nano-ZS models of MALVERN companies
Grain size and particle diameter distribution.
The contact angle test of emulsion film forming：By the lotion stoste of synthesis, it is added dropwise on glass slide, room temperature film-forming.In room temperature
The OCA20 contact angle measurements produced after vacuum drying oven drying to constant weight with DATAPHGSICS colloid chemistry company are contacted
The test at angle.
The water resistance test of emulsion film forming：Sample after forming a film is taken, is submerged into after weighing in deionized water, stands 72 hours
After take out, weigh, calculate water absorption rate.
The media-resistant alkalescence test of emulsion film forming：Take film forming after sample, weigh be submerged into respectively 5% sodium carbonate, hydrochloric acid,
In sodium hydroxide solution, stand 72 it is small when after take out, weigh, calculate water absorption rate.
Tensile property is tested:Using the CMT4204 type universal tensile testing machines of SANS companies, testing standard according to
GB16421-1996。
Atomic force microscope (AFM)：Using the NanoScopeIIIA atomic force microscope of Veeco companies in Tapping moulds
It is tested under formula.
Embodiment 1
Acrylic acid (200mol), bifunctionality RAFT reagents S- are added in the container equipped with reflux condensate device and stirring
S'- bis- (α, α ' dimethyl, α "-acetic acid) trithiocarbonate (1mol), V-501 (0.2mol), and add in deionized water and be adjusted to
System solid content is 20%, is passed through nitrogen, reacts 1.5h at 75 DEG C.The deionized water for adding in deoxygenation afterwards keeps solid content
20%, the Butyl Acrylate Monomer (400mol) for removing oxygen is added dropwise, reacts 5h, cooling discharging prepares polyacrylic acid-b-
Butyl polyacrylate-b- polyacrylic acid triblock copolymers.Front and rear contact angle test is heat-treated after film forming to provide in Fig. 4.
Embodiment 2
It is other same as Example 1 in addition to polymerization temperature changes into 60 DEG C.
Embodiment 3
It is other same as Example 1 in addition to polymerization temperature changes into 80 DEG C.
Embodiment 4
In addition to polymerization initiator V501 is changed to 14mg, other are same as Example 1.
Embodiment 5
In addition to polymerization initiator V501 is changed to 56mg, other are same as Example 1.
Embodiment 6
In addition to RAFT reagents are changed to 35.25mg, other are same as Example 1.
Embodiment 7
In addition to RAFT reagents are changed to 70.5mg, other are same as Example 1.
Embodiment 8
In addition to RAFT reagents are changed to 282mg, other are same as Example 1.
Embodiment 9
It is 10% except bifunctional RAFT reagents and solid content is used, other are same as Example 1.
Embodiment 10
It is 20% except bifunctional RAFT reagents and solid content is used, other are same as Example 1.
Embodiment 11
It is 25% except bifunctional RAFT reagents and solid content is used, other are same as Example 1.
Embodiment 12
Except being changed to water/ethyl alcohol volume ratio (9 using bifunctional RAFT reagents and reaction medium：1) outside, other and embodiment 1
It is identical.
Embodiment 13
Except reaction medium is that water/ethyl alcohol is changed to 8：Outside 2, other are identical with embodiment 12.
Embodiment 14
Except reaction medium is that water/ethyl alcohol is changed to 7：Outside 3, other are identical with embodiment 12.
Embodiment 15
Except reaction medium is changed to water/tetrahydrofuran volume ratio (9：1) outside, other are same as Example 1.
Embodiment 16
Except reaction medium is changed to water/acetone volume ratio (9：1) outside, other are same as Example 1.
Embodiment 17
Except reaction medium is changed to water/dioxane volume ratio (9：1) outside, other are same as Example 1.
Embodiment 18
Except reaction ABA block polymerization degree ratios change into 1：2：Outside 1, other are same as Example 1.
Embodiment 19
Except reaction ABA block polymerization degree ratios change into 1：4：Outside 1, other are same as Example 1.GPC is tested in annex
Table 1 is listed.Extension test result is provided in Fig. 2 and table 2.
Embodiment 20
Except reaction ABA block polymerization degree ratios change into 1：6：Outside 1, other are same as Example 1.GPC is tested in annex
Table 1 is listed.
Embodiment 21
Except reaction ABA block polymerization degree ratios change into 1：8：Outside 1, other are same as Example 1.GPC is tested in annex
Table 1 is listed.Extension test result is provided in Fig. 2 and table 2.
Embodiment 22
Except reaction ABA block polymerization degree ratios change into 1：10：Outside 1, other are same as Example 1.
Embodiment 23
Except reaction ABA block polymerization degree ratios change into 1：12：Outside 1, other are same as Example 1.GPC is tested in annex
Table 1 is listed.Extension test result is provided in Fig. 2 and table 2.Media-resistant test result is listed in table 3.
Embodiment 24
It is 1 except butyl polyacrylate is replaced by polyacrylic acid hexafluoro butyl ester and block polymerization degree ratio：3：Outside 1, other with
Embodiment 1 is identical.GPC tests are listed in annex table 1.After film forming, contact angle changes and is provided in Fig. 5 before and after heat treatment.
Embodiment 25
It is 1 except butyl polyacrylate is replaced by polyacrylic acid hexafluoro butyl ester and block polymerization degree ratio：4：Outside 1, other with
Embodiment 1 is identical.GPC tests are listed in annex table 1.GPC tests are listed in annex table 1.Extension test result is in Fig. 3 and table 2
It provides.After film forming, contact angle changes and is provided in Fig. 5 before and after heat treatment.
Embodiment 26
It is 1 except butyl polyacrylate is replaced by polyacrylic acid hexafluoro butyl ester and block polymerization degree ratio：6：Outside 1, other with
Embodiment 1 is identical.GPC tests are listed in annex table 1.Extension test result is provided in Fig. 3 and table 2.After film forming, before and after heat treatment
Contact angle variation is provided in Fig. 5.
Embodiment 27
It is 1 except butyl polyacrylate is replaced by polyacrylic acid hexafluoro butyl ester and block polymerization degree ratio：8：Outside 1, other with
Embodiment 1 is identical.Extension test result is provided in Fig. 3 and table 2.After film forming, contact angle changes and is provided in Fig. 5 before and after heat treatment.
Front and rear surface A FM phasors are heat-treated after film forming to provide in Fig. 6.Media-resistant test result is listed in table 3.
Embodiment 28
It is 1 except butyl polyacrylate is replaced by polyethyl acrylate and block polymerization degree ratio：4：Outside 1, other and implementation
Example 1 is identical.GPC tests are listed in annex table 1.
Embodiment 29
It is 1 except butyl polyacrylate is replaced by polyethyl acrylate and block polymerization degree ratio：8：Outside 1, other and implementation
Example 1 is identical.GPC tests are listed in annex table 1.
Embodiment 30
It is 1 except butyl polyacrylate is replaced by polyethyl acrylate and block polymerization degree ratio：10：Outside 1, other and implementation
Example 1 is identical.GPC tests are listed in annex table 1.
Embodiment 31
It is 1 except butyl polyacrylate is replaced by polyethyl acrylate and block polymerization degree ratio：12：Outside 1, other and implementation
Example 1 is identical.GPC tests are listed in annex table 1.Media-resistant test result is listed in table 3.
Embodiment 32
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter butyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：4：1：1.
Embodiment 33
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, add
Butyl acrylate is polymerize.ABCBA blocks ratio is 1：1：8：1：1.
Embodiment 34
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter butyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：12：1：1.
Embodiment 35
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, add
Butyl acrylate is polymerize.ABCBA blocks ratio is 1：2：8：2：1.
Embodiment 36
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, add
Butyl acrylate is polymerize.ABCBA blocks ratio is 1：3：8：3：1.
Embodiment 37
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter ethyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：4：1：1.
Embodiment 38
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter ethyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：8：1：1.
Embodiment 39
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter ethyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：12：1：1.
Embodiment 40
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter hexafluorobutyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：4：1：1.
Embodiment 41
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter hexafluorobutyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：8：1：1.
Embodiment 42
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter hexafluorobutyl acrylate to be polymerize.ABCBA blocks ratio is 1：1：12：1：1.
Embodiment 43
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter hexafluorobutyl acrylate to be polymerize.ABCBA blocks ratio is 1：2：8：2：1.
Embodiment 44
Except butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester.After acrylic acid trifluoro ethyl ester polymerize, then add
Enter hexafluorobutyl acrylate to be polymerize.ABCBA blocks ratio is 1：3：8：3：1.
Embodiment 45
In addition to butyl polyacrylate is replaced by polystyrene, other are same as Example 1.
Embodiment 46
In addition to butyl polyacrylate is replaced by polyacrylic acid trifluoro ethyl ester, other are same as Example 1.
Table 1：The GPC of poly acrylic acid-poly esters of acrylic acid-polyacrylic acid triblock polymer containing different component ratio
Data
| Example | Molecular formula | Molecular weight | PDI |
| Example 19 | AA100-BA400-AA100 | 36111 | 1.44 |
| Example 20 | AA100-BA600-AA100 | 99073 | 1.76 |
| Example 22 | AA100-BA1000-AA100 | 144308 | 2.4 |
| Example 23 | AA100-BA1200-AA100 | 181861 | 2.75 |
| Example 24 | PAA100-PHFBA300-PAA100 | 87990 | 1.33 |
| Example 25 | PAA100-PHFBA400-PAA100 | 113374 | 1.45 |
| Example 26 | PAA100-PHFBA600-PAA100 | 140080 | 1.44 |
| Example 28 | AA100-EA400-AA100 | 51084 | 1.51 |
| Example 29 | AA100-EA800-AA100 | 95291 | 1.87 |
| Example 30 | AA100-EA1000-AA100 | 77762 | 1.9 |
| Example 31 | AA100-EA1200-AA100 | 163826 | 2.23 |
Table 2：The mechanical performance data of poly acrylic acid-poly esters of acrylic acid-polyacrylic acid example.
| Example | Sample | Fracture strength (MPa) | Elongation at break (%) | Permanent deformation (%) |
| Example 19 | AA100-BA400-AA100 | 6.33 | 504.37 | 73.2 |
| Example 21 | AA100-BA800-AA100 | 2.89 | 564.49 | 50.4 |
| Example 23 | AA100-BA1200-AA100 | 4.57 | 2376.84 | 5.3 |
| Example 24 | PAA100-PHFBA300-PAA100 | 5.92 | 468.91 | 140.5 |
| Example 25 | PAA100-PHFBA400-PAA100 | 5.72 | 694.11 | 112.3 |
| Example 26 | PAA100-PHFBA600-PAA100 | 3.21 | 1311.64 | 23.1 |
Table 3:Different poly acrylic acid-poly esters of acrylic acid-water absorption rate of the polyacrylic acid example in different medium.
Table 4:Different poly acrylic acid-poly esters of acrylic acid-water absorption rate of the polyacrylic acid example in different medium.
| water | 5%NaOH | 5%HCl | 5%NaCl | |
| Embodiment 40 | solved | solved | 5.21% | 3.40% |
| Embodiment 41 | solved | solved | 2.49% | 7.98% |
| Embodiment 42 | 3.35% | partly solved | 1.37% | 4.73% |
| Embodiment 43 | 7.83% | solved | 7.18% | partly solved |
| Embodiment 44 | 8.96% | solved | 5.23% | 6.71% |
Table 5：The GPC of poly acrylic acid-poly esters of acrylic acid-polyacrylic acid triblock polymer containing different component ratio
Data
| Design | Design molecular weight | Actual molecular weight | PDI | |
| Embodiment 32 | PAA50-PTFEMA50-PBA200-PTFEMA50-PAA50 | 56200 | 50584 | 2.09 |
| Embodiment 33 | PAA50-PTFEMA50-PBA400-PTFEMA50-PAA50 | 81800 | 85561 | 2.27 |
| Embodiment 34 | PAA50-PTFEMA50-PBA600-PTFEMA50-PAA50 | 107400 | 115297 | 2.47 |
| Embodiment 35 | PAA50-PTFEMA100-PBA200-PTFEMA100-PAA50 | 71800 | 58120 | 2.07 |
| Embodiment 36 | PAA50-PTFEMA150-PBA200-PTFEMA150-PAA50 | 87400 | 56419 | 2.21 |
| Embodiment 37 | PAA50-PTFEMA50-PEA200-PTFEMA50-PAA50 | 66200 | 21565 | 2.4 |
| Embodiment 38 | PAA50-PTFEMA50-PEA400-PTFEMA50-PAA50 | 86200 | 65988 | 2.2 |
| Embodiment 39 | PAA50-PTFEMA50-PEA600-PTFEMA50-PAA50 | 106200 | 87288 | 1.96 |
| Embodiment 40 | PAA50-PTFEMA50-PHFBA200-PTFEMA50-PAA50 | 81800 | 78874 | 1.21 |
| Embodiment 41 | PAA50-PTFEMA50-PHFBA400-PTFEMA50-PAA50 | 133000 | 99909 | 1.3 |
| Embodiment 42 | PAA50-PTFEMA50-PHFBA600-PTFEMA50-PAA50 | 184200 | 104463 | 1.42 |
| Embodiment 43 | PAA50-PTFEMA100-PHFBA400-PTFEMA100-PAA50 | 148600 | 108216 | 1.26 |
| Embodiment 44 | PAA50-PTFEMA150-PHFBA400-PTFEMA150-PAA50 | 164200 | 110659 | 1.34 |
Claims (15)
1. the preparation method of a kind of ABA type or ABCBA type inlay section thermal plastic elastic bodies, which is characterized in that by ABA type or ABCBA
Type block RAFT polymerized emulsions, direct machine-shaping are surface hydrophilic type product；Or ABA type or ABCBA type blocks RAFT are gathered
Lotion is closed, direct machine-shaping is surface hydrophilic type product, then carries out being thermally treated resulting in surface hydrophobicity type product；Or by ABA
Heated after type or the drying of ABCBA type block RAFT polymerized emulsions, be prepared into surface hydrophobicity type product；
The ABA type or ABCBA type block RAFT polymerized emulsions carry out two-step method emulsion polymerization using bifunctional RAFT reagents and obtain
It arrives；Synthetic method is as follows：Monomer, RAFT reagents, initiator and the reaction dissolvent corresponding to A, removal are added in reaction vessel
1-2h is reacted at 60-80 DEG C after oxygen, the monomer corresponding to B or B and C, time for adding 3-6h, cooling discharging is then added dropwise；
The A is polyacrylic acid, and B, C are styrene, acrylic acid trifluoro ethyl ester, ethyl acrylate, butyl acrylate or acrylic acid
The block polymer or copolymer of hexafluoro butyl ester, during ABCBA five inlay section thermal plastic elastic bodies of type, the corresponding monomers of B and C are different.
2. the preparation method of a kind of ABA type according to claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
Be the initiator be V-501 or KPS, RAFT reagent be bifunctionality RAFT reagents S-S'- bis- (α, α ' dimethyl, α "-second
Acid) trithiocarbonate.
3. the preparation method of a kind of ABA type according to claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
It is, ABA type or ABCBA types inlay section thermal plastic elastic body are poly acrylic acid-poly butyl acrylate-polyacrylic acid, polyacrylic acid-
Polyethyl acrylate-polyacrylic acid, poly acrylic acid-poly acrylic acid trifluoro ethyl ester-butyl polyacrylate-polyacrylic acid trifluoro second
Ester-polyacrylic acid, poly acrylic acid-poly acrylic acid trifluoro ethyl ester-polyethyl acrylate-polyacrylic acid trifluoro ethyl ester-polyacrylic acid
Or poly acrylic acid-poly acrylic acid trifluoro ethyl ester-polyacrylic acid hexafluoro butyl ester-polyacrylic acid trifluoro ethyl ester-polyacrylic acid.
4. the preparation method of a kind of ABA type described in accordance with the claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
It is, if B, C are block, substep adds in respectively for B and monomer corresponding to C；If B, C is copolymer, corresponding to B and C
Monomer mixing adds in.
5. according to a kind of ABA type described in claim 4 or the preparation method of ABCBA type inlay section thermal plastic elastic bodies, feature
Be, if B, C are block, substep adds in respectively for B and monomer corresponding to C, i.e. A section polymerize after B sections of corresponding monomers of addition
Or C sections of corresponding monomers are continuously added after B sections of corresponding monomer reactions of addition after A sections of polymerizations, it is respectively synthesized ABA type or ABCBA
Type block polymer.
6. the preparation method of a kind of ABA type described in accordance with the claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
It is, reaction dissolvent is water or the mixed solvent of water and organic solvent, and organic solvent is：Ethyl alcohol, acetone, tetrahydrofuran, dioxy
The ratio of six rings, water and organic solvent is adjusted as needed, and the volume of organic solvent is not more than 40%.
7. the preparation method of a kind of ABA type described in accordance with the claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
It is, increases the water solubility of hydrophobic monomer by increasing temperature, so as to its favourable migration in system, increase reaction system
Stability；Increase the water solubility of hydrophobic monomer by adding in organic solvent, so as to its favourable migration in system, increase reaction
The stability of system；By controlling the rate of addition of the corresponding monomers of B or the corresponding monomers of B and C, emulsion intercalation method is improved.
8. the preparation method of a kind of ABA type described in accordance with the claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
It is, heat treatment temperature is：80-150℃.
9. according to a kind of ABA type described in claim 8 or the preparation method of ABCBA type inlay section thermal plastic elastic bodies, feature
It is, heat treatment temperature is 100-130 DEG C.
10. according to a kind of ABA type described in claim 9 or the preparation method of ABCBA type inlay section thermal plastic elastic bodies, feature
It is, heat treatment temperature is 110-120 DEG C.
11. the preparation method of a kind of ABA type described in accordance with the claim 1 or ABCBA type inlay section thermal plastic elastic bodies, feature
It is, the surface contact angle of hydrophobic surface product is more than or equal to 95 °.
It is 12. special according to a kind of ABA type described in claim 11 or the preparation method of ABCBA type inlay section thermal plastic elastic bodies
Sign is that the surface contact angle is more than or equal to 105 °.
It is 13. special according to a kind of ABA type described in claim 12 or the preparation method of ABCBA type inlay section thermal plastic elastic bodies
Sign is that the surface contact angle is more than or equal to 115 °.
14. a kind of ABA type or ABCBA type inlay section thermal plastic elastic bodies, by claim 1-13 any one of them preparation side
Method obtains.
15. ABA type or ABCBA type inlay section thermal plastic elastic bodies described in claim 14, which is characterized in that the A corresponds to single
Body is acrylic acid, and B, C correspond to block polymer or block copolymerization of the monomer for acrylic acid trifluoro ethyl ester or hexafluorobutyl acrylate
Object, during ABCBA five elastomer block copolymers of type, the corresponding monomers of B and C are different.
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