CN103910820B - A kind of hexahedron silsesquioxane-based dissaving polymer and the application in supercritical carbon dioxide foaming thereof - Google Patents
A kind of hexahedron silsesquioxane-based dissaving polymer and the application in supercritical carbon dioxide foaming thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- 238000005187 foaming Methods 0.000 title claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 title description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title description 4
- 239000001569 carbon dioxide Substances 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000002608 ionic liquid Substances 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 206010000269 abscess Diseases 0.000 claims abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 230000007704 transition Effects 0.000 claims abstract description 4
- -1 tetrafluoroborate Chemical compound 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 20
- 238000010926 purge Methods 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- 239000004626 polylactic acid Substances 0.000 claims description 10
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 8
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 229940046149 ferrous bromide Drugs 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 230000036772 blood pressure Effects 0.000 claims description 3
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920005553 polystyrene-acrylate Polymers 0.000 claims 1
- 230000006911 nucleation Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000013019 agitation Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000010791 quenching Methods 0.000 description 13
- 230000000171 quenching effect Effects 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 244000117499 Colubrina elliptica Species 0.000 description 3
- 101100075837 Drosophila melanogaster Mabi gene Proteins 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- JZLFUUHOTZKEFU-UHFFFAOYSA-N methyl 4-azidobenzenecarboximidate Chemical compound COC(=N)C1=CC=C(N=[N+]=[N-])C=C1 JZLFUUHOTZKEFU-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 150000001412 amines Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The preparation method that the invention discloses a kind of hexahedron silsesquioxane-based dissaving polymer (POSS base dissaving polymer): POSS base initiator, ionic liquid monomer, catalyst, catalyst ligand or POSS base initiator, ionic liquid monomer, catalyst, catalyst ligand, the second reaction monomers are carried out atom transition free radical polymerization reaction in a solvent, prepares hexahedron silsesquioxane-based dissaving polymer. POSS base dissaving polymer provided by the invention can be applied to the foaming of polymer supercritical CO 2 as nucleator, prepares polymeric foamable material, and the abscess-size of gained expanded material can be reduced to less than 2 μm, and cell nucleation rate can improve an order of magnitude.
Description
(1) technical field
The present invention relates to the synthesis of a kind of hexahedron silsesquioxane-based dissaving polymer and at supercritical CO2Application in foaming.
(2) background technology
Polymer micro expanded material refers to have the diameter abscess less than 10um and cell density 109～1015Individual/cm3A kind of Novel foam material. Compare unfoamed polymeric material, microcellular foam material has light weight, with low cost, specific stiffness is high, impact strength is high, dielectric constant and the advantage such as heat conductivity is low, it is widely used in packaging, aircraft and auto parts and components, sports equipment, insulation insulant and bio-medical material etc., is a key areas of polymeric material application.
The method preparing polymer micro expanded material is a lot, but all follow a ultimate principle: make gas be dissolved in polymer first under an increased pressure and obtain homogeneous system, then pass through and be rapidly heated or the mode of blood pressure lowering makes gas reach hypersaturated state, at a suitable temperature, gas karyomorphism becomes and grows up, and finally sizing obtains microcellular foam material. In numerous foamed gas, supercritical CO2Having most application prospect, its critical temperature (Tc=31.1 DEG C) is relatively low, easily realizes operation near room temperature, and critical pressure is only 7.37Mpa, low for equipment requirements. Further, supercritical CO2Also have colourless, odorless, nontoxic, inexpensive, non-combustible, consume ozone latent energy value (ODP) and be zero, environmental friendliness, there is the advantages such as good chemical stability, it is expected to substitute the physical blowing agent of currently used more hydrochlorofluorocarsolvent (HCFCs) and poisonous CBA, is real " green foaming agent ".
Ionic liquid (IonicLiquid writes a Chinese character in simplified form IL) is the salt being in a liquid state under low temperature (< 100 DEG C), and it has good heat stability, major part ionic liquid can remain stable at 300～400 DEG C, and the close friend to environment, its application prospect is extensive, thus one of becomes the accumulation point of research in the present age.Substantial amounts of bibliographical information shows (first National Chemical engineering with biochemical industry nd Annual Meeting summary collection (on) .2004.11) (J.Phys.Chem.B, 2005,109:6366-6374) (J.Phys.Chem.B, 2002,106:7315-7320) (Chinese patent: CN200510073345.0,2005.12) CO2There is stronger interaction with partial ion liquid, it has significantly high dissolubility in ionic liquid. At present, ionic liquid CO absorption2And carry out polymer micro foaming research and be still in the experimentation stage, but it embodies excellent adsorptivity in foaming process and becomes nuclearity, and various novel ionic liquids are also constantly used for the research that polymer micro foams.
(3) summary of the invention
The present invention seeks to synthesize a kind of hexahedron silsesquioxane (being called for short POSS) base dissaving polymer as CO2Adsorbent, Nucleating Agent, it is achieved polymer supercritical CO2Microporous foam formation. The prepared feature that expanded material has uniform foam cell, cell diameter is little, cell density is high.
The technical solution used in the present invention is:
The preparation method that a kind of hexahedron silsesquioxane-based dissaving polymer (is called for short POSS base dissaving polymer), described method is with next:
(1) POSS base initiator, ionic liquid monomer, catalyst, catalyst ligand are carried out in a solvent atom transfer radical polymerization (ATRP) reaction, at 80～120 DEG C of temperature, stirring reaction is cooled to 0～5 DEG C of termination reaction after 12～24 hours, reaction pours reactant in alcoholic solvent precipitation product after terminating, and prepares hexahedron silsesquioxane-based dissaving polymer after gained mixed liquor sucking filtration, filtration cakes torrefaction;
(2) POSS base initiator, ionic liquid monomer, catalyst, catalyst ligand, the second reaction monomers are carried out atom transition free radical polymerization reaction in a solvent, at 80～120 DEG C of temperature, stirring reaction is cooled to 0～5 DEG C of termination reaction after 12～24 hours, reaction pours reactant in alcoholic solvent precipitation product after terminating, and prepares hexahedron silsesquioxane-based dissaving polymer after gained mixed liquor sucking filtration, filtration cakes torrefaction;
In described method () or (two), the formula of described POSS base structure of initiator is such as shown in formula A:
In formula A, R group is shown in one of following formula I Formulas I V, and in formula A chemical formula, the R of diverse location represents identical group:
In described method () or (two), the formula of described ionic liquid monomer is A+B-, wherein B-For tetrafluoroborate (BF4 -), hexafluoro-phosphate radical (PF6 -) or double; two (fluoroform sulphonyl) imines root ((CF3SO2)2N-, write a Chinese character in simplified form TF2N-), wherein A+Shown in one of following formula a formula d:
In formula a formula d, R1、R3、R5、R7Each stand alone as the C containing one or more double bond thiazolinyl2～C8Fatty thiazolinyl or C8～C10Aromatic alkenyl, R2、R4、R6Each stand alone as C1～C8Aliphatic group or and C6～C8Aryl radical; In formula a, the R of diverse location2Represent identical group, in formula c, the R of diverse location6Represent identical group.
As preferably, R1、R3、R5、R7Each stand alone as vinyl, pi-allyl, vinyl benzyl or methylacryoyloxyethyl, more preferably vinyl benzyl or methylacryoyloxyethyl.
As preferably, R2、R4、R6Each stand alone as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, n-octyl or phenyl.
The ratio of described POSS base initiator and the amount of substance of ionic liquid monomer is 1:200～1800, it is preferable that 1:400～1600, more preferably 1:700～1400.
In described method () or (two), described catalyst is cuprous bromide (CuBr), Cu-lyt. (CuCl), cuprous acetate (CuAc), ferrous bromide (Fe2Br), ferrous chloride (Fe2Cl) one in, it is preferred to cuprous bromide or ferrous bromide.
In described method () or (two), described catalyst ligand is double; two (2,2 '-bipyridyl) (bpy), N, N, N', N, ' N''-five methyl diethylentriamine (PMDTA), 1,1, one in 4,7,10,10-hexamethyl triens (HMTETA).
In described method (two), the second described reaction monomers is styrene (St), methyl methacrylate (MMA), acrylonitrile (AN), acrylic acid methyl ester. (MA) or ethyl acrylate (EA).
In described method (two), the ratio of the amount of substance of described ionic liquid monomer and the second reaction monomers is 1:0～4, and 0 representative therein is infinitely close to 0 but is not 0, it is preferred to 1:0.5～2, more preferably 1:1.
In described method () or (two), described POSS base initiator, catalyst, catalyst ligand the ratio of amount of substance be 1:8～16:24～48, it is preferred to 1:8～10:24～30.
In described method () or (two), described solvent is N, N dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).
In described method (), described solvent quality consumption is ionic liquid monomer quality 0.5～4 times, in described method (two), described solvent quality consumption is 0.5～4 times of ionic liquid monomer and the second reaction monomers gross mass.
Described alcoholic solvent is methanol or dehydrated alcohol. The quality consumption of described alcoholic solvent is generally 10～20 times of ionic liquid monomer quality.
POSS base initiator of the present invention is published compound, can prepare by the following method:
In A, formula A, R group is the POSS base initiator of formula I, it is called for short POSS-Cl initiator, its synthetic route is: add γ-chloropropyl triethoxysilane, dehydrated alcohol and distilled water in there-necked flask successively, then adding concentrated hydrochloric acid adjustment pH value is 2～3, after at 60 DEG C, magnetic agitation is reacted 3～5 days, reacting liquid filtering obtains white crystal, is drying to obtain POSS-Cl initiator with absolute ethanol washing final vacuum for several times.
In B, formula A, R group is the POSS base initiator of Formula II, III or IV, is called for short POSS-Br initiator, and its synthetic route is: add eight hydroxyl POSS, eight aminopropyl POSS or eight aminophenyl POSS, N in three mouthfuls of beakers2Add oxolane (THF) under protection to dissolve, the bath of gained solution cryosel is cooled to 0～5 DEG C, triethylamine is instilled under magnetic agitation, after stirring reaction 5～10 minutes, it is slowly dropped into 2-bromine isobutyl acylbromide (BIBB) and THF mixed solution again, system neutrality is carved with pink precipitate and produces, reaction 2h is continued under ice bath, rise to room temperature and react 20h again, filter out triethylamine salt precipitation, filtrate rotary evaporation removes THF, residue dichloromethane dissolves, again with deionized water wash for several times, dichloromethane solution containing product is dripped to normal hexane is settled out product, 50 DEG C of vacuum dryings, the corresponding R group for preparing is Formula II, the POSS-Br initiator of III or IV, the ratio of described eight hydroxyl POSS, eight aminopropyl POSS or eight aminophenyl POSS and triethylamine, the amount of substance of 2-bromine isobutyl acylbromide is 1:8～16:8～16.
This is all well known to a person skilled in the art preparation method.
The present invention also provides for described POSS base dissaving polymer and is applied to polymer supercritical CO as nucleator2Foaming, prepares polymeric foamable material.Described polymer can be polylactic acid (being called for short PLA), polystyrene (being called for short GPPS), polymethyl methacrylate (being called for short PMMA) etc.
Comparatively concrete, the foaming method of described application is one of following:
(1) intensification foaming: POSS base dissaving polymer, polymer raw material are melt extruded with extruder under 180～220 DEG C of conditions, producing foamed sample; Foamed sample is put into autoclave, uses CO2Purge 2-3 minute, remove the air in autoclave, in still, inject supercritical CO2Fluid, control pressure is 10～15Mpa, at room temperature seals maintenance 2～15 hours, makes CO2Let out after reaching dissolution equilibrium in the material to atmospheric pressure, then the sample taken out is immersed the oil bath pan constant temperature 1 hour of 80～140 DEG C, be then quickly cooled to 0～5 DEG C, make abscess sizing namely prepare polymeric foamable material. Described polymer raw material is GPPS, PLA or PMMA; The mass ratio of described POSS base dissaving polymer and polymer raw material is 2～45:100, it is preferable that 5～25:100.
(2) blood pressure lowering foaming: POSS base dissaving polymer, polymer raw material are melt extruded with extruder under 180～220 DEG C of conditions, producing foamed sample; Foamed sample is put into autoclave, uses CO2Purge 2～3 minutes, remove the air in autoclave, then autoclave is warmed up to 80～140 DEG C, in still, inject supercritical CO2Fluid, control pressure is 10～15Mpa, keeps 2～15 hours at constant temperature and pressure lower seal, makes CO2Reach dissolution equilibrium in the sample, then quickly let out to atmospheric pressure, and be quickly cooled to 0～5 DEG C, namely prepare polymeric foamable material. Described polymer raw material is GPPS, PLA or PMMA; The mass ratio of described POSS base dissaving polymer and polymer raw material is 2～45:100, it is preferable that 5～25:100.
The beneficial effects of the present invention is:
(1) the POSS base dissaving polymer that prepared by the present invention is the polymer of a kind of green, reusable edible, it and CO2There is good affinity, it is possible to CO in significant increase system2Dissolubility, add the polymer prepared by 10% present invention and can improve the CO of 2.89%2Adsorbance;
(2) polymer prepared by the present invention has higher fusing point, nucleation energy can well be reduced, improve nucleation efficiencies, reduce polymeric foamable material abscess-size, improve cell density, adding the polymer prepared by 10% present invention, the abscess-size of gained expanded material can be reduced to less than 2 μm, and cell nucleation rate can improve an order of magnitude;
(3) dissaving polymer prepared by the present invention can as the additive supercritical CO for each base polymer2The research of foaming and industrial circle, easy and simple to handle, it is easy to control.
(4) accompanying drawing explanation
The SEM picture (13.8MPa, 100 DEG C, 2000 ×) of pure GPPS foamed sample in Fig. 1 comparative example 1
POSS-Cl in Fig. 2 embodiment 11HNMR spectrogram.
The infrared spectrogram of POSS-Cl in Fig. 3 embodiment 1.
POSS-g-[VBTMA] [BF in Fig. 4 embodiment 14] infrared spectrogram.
GPPS/POSS-g-[VBTMA] [BF in Fig. 5 embodiment 14] foamed sample SEM figure (13.8MPa, 100 DEG C, 2000 ×).
POSS-g-{ [VBTMA] [BF in Fig. 6 embodiment 44] infrared spectrogram of-co-St}.
GPPS/POSS-g-{ [VBTMA] [BF in Fig. 7 embodiment 44]-co-St} foamed sample SEM figure (13.8MPa, 100 DEG C, 2000 ×).
The infrared spectrogram of POSS-Br in Fig. 8 embodiment 5.
(5) detailed description of the invention
Example below is further illustrating the present invention, rather than restriction the scope of the present invention.
Comparative example 1:
Take 30 grams of GPPS icroextrusion machines after 200 DEG C are extruded sample preparation, load sealing in autoclave, with a small amount of CO2Purging 2min, is warmed up to 100 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa, and constant temperature and pressure is after 12 hours, and then quick pressure releasing, in frozen water, quenching prepares polymeric foamable material. The expanded material liquid nitrogen freezing brittle failure prepared, is scanned electronic microscope photos and sees shown in accompanying drawing 1. Embodiment 1:
150mL there-necked flask is sequentially added into 20mL γ-chloropropyl triethoxysilane, 40mL dehydrated alcohol and 10mL distilled water, then adding concentrated hydrochloric acid adjustment pH value is 3, after at 60 DEG C, magnetic agitation is reacted 5 days, it is filtrated to get white crystal, drying with absolute ethanol washing final vacuum for several times and obtain 5.832 grams of POSS-Cl initiators, productivity is 29.1%, obtained POSS-Cl's1HNMR spectrogram is shown in that, shown in accompanying drawing 2, infrared spectrogram is shown in shown in accompanying drawing 3.
Take 0.05 gram of POSS-Cl initiator, 10.11 grams of (4-vinyl benzyl) QAE tetrafluoroborate ([VBTMA] [BF4]), 0.06 gram of cuprous bromide (CuBr), 0.2 gram of N, N, N', N, ' N''-five methyl diethylentriamine (PMDETA), 30mlN, dinethylformamide (DMF) adds in the reaction bulb of 100ml, in frozen water, magnetic agitation is warmed up to 90 DEG C of reactions 24 hours after 10 minutes, pour in 150ml methanol after being placed in mixed liquor in frozen water to terminate reaction and precipitate, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 8.02 grams of polymer, be designated as POSS-g-[VBTMA] [BF4], productivity is 79%. Prepared product infrared spectrogram is shown in shown in accompanying drawing 4.
Take 3 grams of POSS-g-[VBTMA] [BF4], 27 grams of GPPS, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 100 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material. The expanded material liquid nitrogen freezing brittle failure prepared, is scanned electronic microscope photos and sees shown in accompanying drawing 5.
Embodiment 2:
Take 0.05 gram of POSS-Cl initiator, 15.32 grams of 1-(4-vinyl benzyl)-3-1-Butyl-1H-imidazole hexafluorophosphate ([VBBI] [PF6]), 0.06 gram of cuprous bromide (CuBr), 0.2 gram of N, N, N', N, ' N''-five methyl diethylentriamine (PMDETA), 30mlN, dinethylformamide (DMF) adds in the reaction bulb of 100ml, and in frozen water, magnetic agitation is warmed up to 80 DEG C of reactions 24 hours after 10 minutes, mixed liquor is placed in frozen water terminate reaction after pour into 150ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 11.39 grams of POSS-g-[VBBI] [PF6], productivity is 74.1%.
Take 1.5 grams of POSS-g-[VBBI] [PF6], 28.5 grams of GPPS, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 100 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Embodiment 3:
Take 0.025 gram of POSS-Cl initiator, 13.97 grams of (4-vinyl benzyl) triethyl quaternary amine hexafluorophosphate ([VBTEA] [PF6]), 0.03 gram of cuprous bromide (CuBr), 0.1 gram of N, N, N', N, ' N''-five methyl diethylentriamine (PMDETA), 30mlN, dinethylformamide (DMF) adds in the reaction bulb of 100ml, and in frozen water, magnetic agitation is warmed up to 90 DEG C of reactions 24 hours after 10 minutes, mixed liquor is placed in frozen water terminate reaction after pour into 150ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 10.84 grams of POSS-g-[VBTEA] [PF6], productivity is 77.6%.
Take 4.5 grams of POSS-g-[VBTEA] [PF6], 25.5 grams of GPPS, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 100 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Embodiment 4:
Take 0.05 gram of POSS-Cl initiator, 10.11 grams of (4-vinyl benzyl) QAE tetrafluoroborate ([VBTMA] [BF4]), 4.02 grams of styrene (St), 0.06 gram of cuprous bromide (CuBr), 0.2 gram of N, N, N', N, ' N''-five methyl diethylentriamine (PMDETA), 30mlN, dinethylformamide (DMF) adds in the reaction bulb of 100ml, in frozen water magnetic agitation be warmed up to after 10 minutes 90 DEG C react 24 hours, mixed liquor is placed in frozen water terminate reaction after pour into 150ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 10.74 grams of POSS-g-{ [VBTMA] [BF4]-co-St}, productivity is 76%. Prepared product infrared spectrogram is shown in shown in accompanying drawing 6.
Take 3 grams of POSS-g-{ [VBTMA] [BF4]-co-St}, 27 grams of GPPS, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 100 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material. The expanded material liquid nitrogen freezing brittle failure prepared, is scanned electronic microscope photos and sees shown in accompanying drawing 7.
Table 1
Comparative example 2:
Take 30 grams of PMMA icroextrusion machines after 220 DEG C are extruded sample preparation, load sealing in autoclave, with a small amount of CO2Purging 2min, is warmed up to 120 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa, and constant temperature and pressure is after 12 hours, and then quick pressure releasing, in frozen water, quenching prepares polymeric foamable material.
Embodiment 5:
Tri-mouthfuls of beakers of 500ml add 3 grams of aminophenyls POSS(AM0280, HybridPlasticsINC), N2Protection is lower adds 200ml oxolane (THF) dissolving. Solution cryosel bath cooling, magnetic agitation, instill 6ml triethylamine, after stirring 5min, then be slowly dropped into 6ml2-bromine isobutyl acylbromide (BIBB) and 30mlTHF mixed solution, system neutrality is carved with pink precipitate and produces. Continue reaction 2h under ice bath, rise to room temperature and react 20h again. Filtering out triethylamine salt precipitation, filtrate rotary evaporation removes THF, dissolves products therefrom with dichloromethane, then with deionized water wash for several times. Being dripped to by above-mentioned dichloromethane solution and be settled out product in normal hexane, 50 DEG C of vacuum dryings obtain 1.27 grams of POSS-Br initiators, and productivity is 23.9%, and the infrared spectrogram of obtained POSS-Br is as shown in Figure 8.
Take 0.05 gram of POSS-Br initiator, 12.2 grams of (2-methylacryoyloxyethyl) QAE hexafluorophosphate ([MATMA] [PF6]), 0.03 gram of cuprous bromide (CuBr), 0.1 gram of N, N, N', N, ' N''-five methyl diethylentriamine (PMDETA), 30mlN, dinethylformamide (DMF) adds in the reaction bulb of 100ml, and in frozen water, magnetic agitation is warmed up to 90 DEG C of reactions 24 hours after 10 minutes, mixed liquor is placed in frozen water terminate reaction after pour into 150ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 9.47 grams of POSS-g-[MATMA] [PF6], productivity is 77.3%.
Take 3 grams of POSS-g-[MATMA] [PF6], 27 grams of PMMA, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 120 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Embodiment 6:
Take 0.05 gram of POSS-Br initiator, 10.1 grams of (4-vinyl benzyl) triphenyl phosphorus hexafluorophosphate ([VBTPP] [PF6]), 1.93 grams of methyl methacrylates (MMA), 0.05 gram of ferrous bromide (FeBr2), 0.1 gram of N, N, N', N, ' N''-five methyl diethylentriamine (PMDTA), 30ml dimethyl sulfoxide (DMSO) adds in the reaction bulb of 100ml, and in frozen water, magnetic agitation is warmed up to 100 DEG C of reactions 24 hours after 10 minutes, mixed liquor is placed in frozen water terminate reaction after pour into 150ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 8.38 grams of POSS-g-{ [VBTPP] [PF6]-co-MMA}, productivity is 69.4%.
Take 6 grams of POSS-g-{ [VBTPP] [PF6]-co-MMA}, 24 grams of PMMA, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 120 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Embodiment 7:
Take 0.1 gram of POSS-Br initiator, 12.39 grams of 1-[2-(methylacryoyloxyethyl)]-3-1-Butyl-1H-imidazole tetrafluoroborate ([MABI] [BF4]), 3.86 grams of ethyl acrylate (EA), 0.06 gram of cuprous bromide (CuBr), 0.3 gram 1,1,4,7,10,10-hexamethyl triens (HMTETA), 60ml dimethyl sulfoxide (DMSO) adds in the reaction bulb of 150ml, in frozen water magnetic agitation be warmed up to after 10 minutes 120 DEG C react 20 hours, mixed liquor is placed in frozen water terminate reaction after pour in 200ml ethanol solution precipitate, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 10.45 grams of POSS-g-{ [MABI] [BF4]-co-EA}, productivity is 63.9%.
Take 6 grams of POSS-g-{ [MABI] [BF4]-co-EA}, 24 grams of PMMA, load in autoclave after 220 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 120 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Embodiment 8:
Take 0.1 gram of POSS-Br initiator, 13.17 grams of 1-(4-vinyl benzyl) pyridine hexafluorophosphate ([VBP] [PF6]), 3.32 grams of acrylic acid methyl ester .s (MA), 0.06 gram of cuprous bromide (CuBr), 0.3 gram 1,1,4,7,10,10-hexamethyl triens (HMTETA), 60ml dimethyl sulfoxide (DMSO) adds in the reaction bulb of 150ml, in frozen water magnetic agitation be warmed up to after 10 minutes 120 DEG C react 20 hours, mixed liquor is placed in frozen water terminate reaction after pour into 200ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 11.4 grams of POSS-g-{ [VBP] [PF6]-co-MA}, productivity is 68.7%.
Take 6 grams of POSS-g-{ [VBP] [PF6]-co-MA}, 24 grams of PMMA, load in autoclave after 220 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 120 DEG C by autoclave, injects CO in autoclave2, control pressure is 13.8Mpa. After saturated 12 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Table 2
Comparative example 3:
Take 30 grams of PLA icroextrusion machines after 220 DEG C are extruded sample preparation, load sealing in autoclave, with a small amount of CO2Purging 2min, is warmed up to 130 DEG C by autoclave, injects CO in autoclave2, control pressure is 10Mpa, and constant temperature and pressure is after 2 hours, and then quick pressure releasing, in frozen water, quenching prepares polymeric foamable material.
Embodiment 9:
Take 0.1 gram of POSS-Br initiator, 10.65 grams of 1-[2-(methacryloxy) ethyl] pyridinium tetrafluoroborate salt ([MAP] [BF4]), 0.06 gram of cuprous bromide (CuBr), 0.3 gram 1, Isosorbide-5-Nitrae, 7,10,10-hexamethyl triens (HMTETA), 30mlN, dinethylformamide (DMF) adds in the reaction bulb of 100ml, in frozen water magnetic agitation be warmed up to after 10 minutes 80 DEG C react 24 hours, mixed liquor is placed in frozen water terminate reaction after pour into 150ml ethanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 7.75 grams of POSS-g-[MAP] [BF4], productivity is 72.1%.
Take 3 grams of POSS-g-[MAP] [BF4], 27 grams of PLA, load in autoclave after 180 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 130 DEG C by autoclave, injects CO in autoclave2, control pressure is 10Mpa. After saturated 2 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Embodiment 10:
Take 0.1 gram of POSS-Br initiator, 8.81 grams of double; two (fluoroform sulphonyl) inferior amine salt ([VBTMA] [Tf of (4-vinyl benzyl) QAE2N]), 0.06 gram of cuprous bromide (CuBr), 0.2 gram double; two (2,2 '-bipyridyl) (bpy), 30ml dimethyl sulfoxide (DMSO) adds in the reaction bulb of 100ml, and in frozen water, magnetic agitation is warmed up to 120 DEG C of reactions 18 hours after 10 minutes, mixed liquor is placed in frozen water terminate reaction after pour into 150ml methanol solution precipitation, after filtering and washing, by much filtrate 80 DEG C of vacuum dryings 24 hours, obtain 7.33 grams of POSS-g-[VBTMA] [Tf2N], productivity is 82.3%.
Take 3 grams of POSS-g-[VBTMA] [Tf2N], 27 grams of PLA, load in autoclave after 200 DEG C are extruded sample preparation with icroextrusion machine and seal, with a small amount of CO2Purging 2min, is warmed up to 130 DEG C by autoclave, injects CO in autoclave2, control pressure is 10Mpa. After saturated 2 hours of constant temperature and pressure, then quick pressure releasing, in frozen water, namely quenching prepares polymeric foamable material.
Table 3
Claims (9)
1. the preparation method of a hexahedron silsesquioxane-based dissaving polymer, it is characterised in that described method is one below:
(1) POSS base initiator, ionic liquid monomer, catalyst, catalyst ligand are carried out atom transition free radical polymerization reaction in a solvent, at 80～120 DEG C of temperature, stirring reaction is cooled to 0～5 DEG C of termination reaction after 12～24 hours, reaction pours reactant in alcoholic solvent precipitation product after terminating, and prepares hexahedron silsesquioxane-based dissaving polymer after gained mixed liquor sucking filtration, filtration cakes torrefaction;
(2) POSS base initiator, ionic liquid monomer, catalyst, catalyst ligand, the second reaction monomers are carried out atom transition free radical polymerization reaction in a solvent, at 80～120 DEG C of temperature, stirring reaction is cooled to 0～5 DEG C of termination reaction after 12～24 hours, reaction pours reactant in alcoholic solvent precipitation product after terminating, and prepares hexahedron silsesquioxane-based dissaving polymer after gained mixed liquor sucking filtration, filtration cakes torrefaction;
In described method () or (two), described POSS base initiator, catalyst, catalyst ligand the ratio of amount of substance be 1:8～16:24～48;
In described method () or (two), the formula of described POSS base structure of initiator is such as shown in formula A:
In formula A, R group is shown in one of following formula I Formulas I V, and in formula A chemical formula, the R of diverse location represents identical group:
In described method () or (two), the formula of described ionic liquid monomer is A+B-, wherein B-For tetrafluoroborate, hexafluoro-phosphate radical or double; two (fluoroform sulphonyl) imines root, wherein A+Shown in one of following formula a formula d:
In formula a～formula d, R1、R3、R5、R7Each stand alone as the C containing one or more double bond thiazolinyl2～C8Fatty thiazolinyl or C8～C10Aromatic alkenyl, R2、R4、R6Each stand alone as C1～C8Aliphatic group or and C6～C8Aryl radical; In formula a, the R of diverse location2Represent identical group, in formula c, the R of diverse location6Represent identical group;
The ratio of described POSS base initiator and the amount of substance of ionic liquid monomer is 1:200～1800;
In described method () or (two), described catalyst is the one in cuprous bromide, Cu-lyt., cuprous acetate, ferrous bromide, ferrous chloride;
In described method () or (two), described catalyst ligand is double; two (2,2 '-bipyridyl), N, N, N', N, ' N "-five methyl diethylentriamine, 1, Isosorbide-5-Nitrae, the one in 7,10,10-hexamethyl triens;
In described method (two), the second described reaction monomers is styrene, methyl methacrylate, acrylonitrile, acrylic acid methyl ester. or ethyl acrylate.
2. the method for claim 1, it is characterised in that in described formula a～formula d, R1、R3、R5、R7Each stand alone as vinyl, pi-allyl, vinyl benzyl or methylacryoyloxyethyl; R2、R4、R6Each stand alone as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, n-octyl or phenyl.
3. the method for claim 1, it is characterised in that in described method (two), the ratio of the amount of substance of described ionic liquid monomer and the second reaction monomers is 1:0～4, and 0 representative therein is infinitely close to 0 but is not 0.
4. method as claimed in claim 3, it is characterised in that in described method (two), the ratio of the amount of substance of described ionic liquid monomer and the second reaction monomers is 1:1.
5. the method for claim 1, it is characterised in that in described method () or (two), described solvent is N, N dimethylformamide or dimethyl sulfoxide.
6. the hexahedron silsesquioxane-based dissaving polymer that the method as described in one of Claims 1 to 5 prepares.
7. hexahedron silsesquioxane-based dissaving polymer as claimed in claim 6 is at polymer supercritical CO2Application in foaming.
8. apply as claimed in claim 7, it is characterised in that described polymer is polylactic acid, polystyrene or polymethyl methacrylate.
9. apply as claimed in claim 8, it is characterised in that the method for described application is one of following:
(1) intensification foaming: hexahedron silsesquioxane-based dissaving polymer, polymer raw material are melt extruded with extruder under 180～220 DEG C of conditions, producing foamed sample;Foamed sample is put into autoclave, uses CO2Purge 2～3 minutes, remove the air in autoclave, in still, inject supercritical CO2Fluid, control pressure is 10～15Mpa, at room temperature seals maintenance 2～15 hours, makes CO2Let out after reaching dissolution equilibrium in the material to atmospheric pressure, then the sample taken out is immersed the oil bath pan constant temperature 1 hour of 80～140 DEG C, be then quickly cooled to 0～5 DEG C, make abscess sizing namely prepare polymeric foamable material; Described polymer raw material is GPPS, PLA or PMMA; The mass ratio of described hexahedron silsesquioxane-based dissaving polymer and polymer raw material is 2～45:100;
(2) blood pressure lowering foaming: hexahedron silsesquioxane-based dissaving polymer, polymer raw material are melt extruded with extruder under 180～220 DEG C of conditions, producing foamed sample; Foamed sample is put into autoclave, uses CO2Purge 2～3 minutes, remove the air in autoclave, then autoclave is warmed up to 80～140 DEG C, in still, inject supercritical CO2Fluid, control pressure is 10～15Mpa, keeps 2～15 hours at constant temperature and pressure lower seal, makes CO2Reach dissolution equilibrium in the sample, then quickly let out to atmospheric pressure, and be quickly cooled to 0～5 DEG C, namely prepare polymeric foamable material; Described polymer raw material is GPPS, PLA or PMMA; The mass ratio of described hexahedron silsesquioxane-based dissaving polymer and polymer raw material is 2～45:100.
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