CN102775567A - POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof - Google Patents
POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a POSS (polyhedral oligomeric silsesquioxane) contained polyacrylate-polysiloxane block copolymer and a preparation method thereof. The preparation method includes subjecting hydrogen-terminated polysiloxane and vinylcarbinol to reaction to obtain hydroxy-terminated polysiloxane; subjecting the hydroxy-terminated polysiloxane and carboxyl thiocarbonic acid ester to reaction to obtain polysiloxane macromolecular RAFT (reversible addition-fragmentation chain transfer polymerization) reagent; polymerizing the polysiloxane macromolecular RAFT reagent, acrylate monomer and POSS monomer with initiator to prepare the POSS contained polyacrylate-polysiloxane block copolymer. The method has the advantages of simple operation and mild reaction conditions, reaction products have better surface performance and bonding performance with substrates, and further, the reaction products can be used in low-surface-energy lyophobic coating materials and used for preparing ice and snow preventive and antifouling coatings.
Description
Technical field
The present invention relates to polyacrylic ester-polysiloxane block copolymers of a kind of POSS of containing and preparation method thereof, belong to the organic silicon modified propenoic ester copolymer technical field.
Background technology
Organosilicon polymer has excellent hydrophobic nature, lower surface energy, and better chemical stability is a kind of extraordinary surfacecti proteon material.The sticking power of organosilicon material and substrate surface is relatively poor.Vinyl resin and substrate surface then have extraordinary adhesion property.Through the method for copolymerization or blend, organosilicon material is incorporated in the vinyl resin, vinyl resin is carried out modification, the comprehensive advantage of the two obtains the new copolymer of excellent performance.Through active controllable free-radical polymerisation, organosilicon material and propenoate are carried out copolymerization, be a good solution route.
Active controllable free-radical polymerisation is because the molecular weight and the MWD of controlling polymers effectively; Reaction conditions is relatively gentleer; Can be used to prepare grafting, block, the special multipolymer of structure such as star-like or hyperbranched, become a focus of polymer research in recent years.Reversible addition-fracture chain transfer (RAFT) radical polymerization is a kind of of active controllable free-radical polymerisation, owing to have the good molecular weight and the controllability of MWD, thus people's attention extremely.It is macromole RAFT reagent with the YSR 3286 that Chinese patent CN101983976A has reported a kind of, carries out the method that RAFT radical polymerization prepares fluorosilicic block copolymer with vinylformic acid fluoroalkyl esters monomer.Chinese patent CN101205260A, CN101200526A adopt the method for RAFT radical polymerization; Cause temperature sensitive monomer polymerization with initiator and chain-transfer agent; Form macromole RAFT reagent; Cause photosensitive monomer and the polymerization of pH value sensitive monomer with initiator and macromole RAFT reagent again, prepare a kind of novel multiple environment-responsive segmented copolymer.
Cage modle polysilsesquioxane (POSS) is one type of material that contains the hybrid structure itself; It is incorporated in the polymkeric substance, can improves the performance such as use temperature, oxidation-resistance, surface hardness, mechanical property, thermotolerance, flame retardant resistance of polymkeric substance effectively.At present, the method for preparing the multipolymer that contains the POSS group adopts atom transferred free radical (ATRP) polymerization more.Have report to contain acrylate block copolymer and the star copolymer of POSS through ATRP polymerization method preparation, the MWD of these multipolymers narrower (Pyun J, Matyjaszewski K. Macromolecules, 2000,33:217-220).There is research to prepare with the ATRP polymerization method that POSS is end capped to be gathered
N-NSC 11448; The amphiphilic cpds of this hybrid can be in the aqueous solution self-assembly form aggregate (Zheng YC, Wang L, the Zheng SX. European Polymer Journal of micella class; 2012,48:945-955).Though the ATRP polymerization is a kind of extraordinary method for preparing multipolymer, the ATRP polymerization requires relatively harsher to reaction conditions, also can introduce the heavy metal salt, increases the operation easier of product purification process.It is feedstock production macromole RAFT reagent with POSS that report is also arranged, and carry out RAFT radical polymerization with propenoate and obtain segmented copolymer, but this copolymer chain is harder; Second-order transition temperature is higher, restricted application (Mya KY, Lin EMJ; Gudipati CS, Shen L, He CB. Journal of Physical Chemistry B; 2010,114:9119-9127).Use polyacrylic ester-polysiloxane block thing that the preparation of RAFT free radical polymerisation process contains the POSS group to rarely have report at present.
Summary of the invention
The purpose of this invention is to provide polyacrylic ester-polysiloxane block copolymers of a kind of POSS of containing and preparation method thereof.This method is simple to operate, and reaction conditions is gentle, and prepared multipolymer is mainly used in the low surface energy hydrophobic coating material, is used to prepare anti-ice and snow, antifouling paint.
The present invention realizes through following technical scheme, a kind of preparation method who contains polyacrylic ester-polysiloxane block copolymers of POSS, and the repeat unit structure of the described polyacrylic ester-polysiloxane block copolymers that contains POSS is following:
Formula 1
In the formula 1, m, n are respectively independently 1 ~ 1000 integer; I, j are respectively independently 0 ~ 18 integer; X is 10 ~ 300 integer;
R
1Be CH
3Or OH;
R
2For
, wherein R is C
1-C
8Alkane or fluor alkaline;
R
3, R
4Independently be H or CH separately
3R
5Be CH
3Or CH
2CH
2CF
3
It is characterized in that comprising following process:
1) preparation of hydroxy-end capped ZGK 5
With hydrogen terminated polysiloxane and vinylcarbinol in molar ratio 1: (1 ~ 2) joins in the Virahol; Obtain the aqueous isopropanol of 50 ~ 60wt%, under the protection of nitrogen or argon gas, in the mol ratio 1 of si-h bond in platinum catalyst and the hydrogen terminated polysiloxane: the ratio of (0.0001 ~ 0.0002) adds platinum catalyst; Behind reaction 0.5 ~ 1.5h under 20 ~ 30 ℃; Be warmed up to 60 ~ 100 ℃, use Rotary Evaporators to remove reaction solvent, vacuum-drying behind reaction 0.5 ~ 1.5h; Thoroughly remove and desolvate, obtain hydroxy-end capped ZGK 5;
The preparation of 2) the reversible addition of ZGK 5 macromole-fracture chain transfer (RAFT) reagent
Hydroxy-end capped ZGK 5 that step 1) is made and catalyzer NSC 57182 (DCC) in molar ratio 1: (1 ~ 2) joins in the anhydrous methylene chloride, obtains containing the hydroxy-end capped dichloromethane solution that gathers radical siloxane 5 ~ 7wt%, and again in the mol ratio 1 of hydroxy-end capped ZGK 5 and carboxyl thiocarbonic ester: the ratio of (1 ~ 5) adds the carboxyl thiocarbonic ester; After stirring 48 ~ 72h under the room temperature, clean the filtering insolubles with normal hexane; Use Rotary Evaporators to remove reaction solvent; Supernatant liquid is got in centrifugal layering, with washed with methanol 3 ~ 5 times; After the vacuum-drying, obtain number-average molecular weight at the ZGK 5 macromole RAFT of 1000 ~ 20000g/mol reagent;
3) contain the preparation of polyacrylic ester-polysiloxane block copolymers of POSS
With step 2) the reversible addition of ZGK 5 macromole-fracture chain transfer (RAFT) reagent, acrylic ester monomer, cage modle polysilsesquioxane (POSS) monomer and the initiator that make be in mass ratio 1: (1 ~ 5): (0.05 ~ 0.50): the ratio of (0.05 ~ 0.1) joins in an amount of solvent dissolves; Obtain containing the solution of ZGK 5 macromole RAFT reagent 15 ~ 30wt%; Behind reaction 10 ~ 15h under 65 ~ 85 ℃; With the frozen water cooling, the THF dilution repeatedly precipitates with methyl alcohol; After throw out carried out vacuum-drying, obtain containing polyacrylic ester-polysiloxane block copolymers of POSS.
Above-mentioned hydrogen terminated polysiloxane comprises single-ended hydrogen base terminated polysiloxane and both-end hydrogen base terminated polysiloxane, and number-average molecular weight is between 2000 ~ 20000 g/mol;
Above-mentioned carboxyl thiocarbonic ester is S-dodecyl-S '-(2-methyl-2-vinylformic acid) trithiocarbonate (DDMAT);
Above-mentioned acrylic ester monomer is one or more in TEB 3K, Rocryl 400, n-butyl acrylate and the tert-butyl acrylate; Above-mentioned initiator is Diisopropyl azodicarboxylate or BPO; Above-mentioned solvent is a hexone, the mixed solvent of one or more in ETHYLE ACETATE and the YLENE;
The multipolymer that makes with aforesaid method is used for low surface energy hydrophobic coating material, as the resin matrix in the coated material.
Advantage of the present invention is simple to operate, and reaction conditions is gentle; After forming coating; ZGK 5 partly can be in the coatingsurface enrichment in the multipolymer; Reduce the surface energy of coating, the ROHM ester moiety then can improve the cohesive force between coating and the base material, thus improve coating surface property and and base material between adhesion property; And can regulate and control the second-order transition temperature of polymkeric substance through the feed ratio of regulating acrylic ester monomer; Enlarge the use range of polymkeric substance, the YSR 3286 segmental is introduced the soft durometer that can improve main chain, and the introducing of POSS can improve the hydrophobic properties of the surface of coating.
Embodiment
Through case study on implementation technical scheme of the present invention is done further to describe below, following case study on implementation is to further specify of the present invention, does not limit use range of the present invention.
Embodiment 1
(a) take by weighing 30g both-end hydrogen end-blocking YSR 3286 (molecular weight is 1000), 28.6g Virahol, 1.74g vinylcarbinol; Join in the 250mL there-necked flask, add 68 μ L platinum catalysts again, magnetic agitation; At 20 ℃ of reaction 1h, be warmed up to 6 ℃ of reaction 1.5h then.The liquid that obtains removed on Rotary Evaporators desolvate, vacuum-drying obtains molecular weight and is 2000 hydroxyl endblocked polydimethylsiloxane;
(b) be that 1000 hydroxyl endblocked polydimethylsiloxane, 1.1g catalyzer NSC 57182 (DCC), 100mL anhydrous methylene chloride join in the 250mL single port flask together with the 10g molecular weight, add 4.55g trithiocarbonate (DDMAT) then.After adding, stirring at room 72h.Add the normal hexane dilution, the filtering insolubles uses Rotary Evaporators to remove and desolvates; Centrifugal 5min under the rotating speed of 5000r/min gets the yellow clear liquid in upper strata, with washed with methanol 2 ~ 3 times; Obtain yellow oily liquid, obtain molecular weight and be 2000 ZGK 5 macromole RAFT reagent A;
(c) with there-necked flask, sealings such as prolong, vacuum outgas three times is full of nitrogen.With 2.5g ZGK 5 macromole RAFT reagent A, 2.5g TEB 3K (MMA), 1.8g n-butyl acrylate (
nBA), after 0.5g TEB 3K (HEMA), 0.13g methylacrylic acid isobutyl-POSS, 0.16gAIBN, 10mL ETHYLE ACETATE mix, join in the reaction vessel, at 70 ℃ of reaction 15h down with syringe.After reaction finished, behind methanol extraction, vacuum-drying 12h under the room temperature obtained containing polyacrylic ester-polysiloxane block copolymers of POSS, and number-average molecular weight is 9.2 ten thousand, and molecular weight distributing index is 1.16.
Embodiment 2
(a) take by weighing 30g both-end hydrogen end-blocking trifluompropyl methyl polysiloxane (molecular weight is 2000), 18.6g Virahol, 0.87g vinylcarbinol; Join in the 250mL there-necked flask, add 34 μ L platinum catalysts again, magnetic agitation; At 30 ℃ of reaction 0.5h, be warmed up to 100 ℃ of reaction 0.5h then.The liquid that obtains removed on Rotary Evaporators desolvate, vacuum-drying obtains molecular weight and is 2000 the hydroxy-end capped trifluoropropyl siloxane that gathers;
(b) be that 2000 hydroxy-end capped trifluompropyl methyl polysiloxane, 2.0g catalyzer NSC 57182 (DCC), 150mL anhydrous methylene chloride join in the 250mL single port flask together with the 10g molecular weight, add 4.55g trithiocarbonate (DDMAT) then.After adding, stirring at room 72h.Add the normal hexane dilution, the filtering insolubles uses Rotary Evaporators to remove and desolvates; Centrifugal 5min under the rotating speed of 5000r/min gets the yellow clear liquid in upper strata, with washed with methanol 2 ~ 3 times; Obtain yellow oily liquid, obtain molecular weight and be 2000 ZGK 5 macromole RAFT reagent B;
(c) with there-necked flask, sealings such as prolong, vacuum outgas three times is full of nitrogen.With 2.5g ZGK 5 macromole RAFT reagent B, 2.5g TEB 3K (MMA), 2.5g n-butyl acrylate (
nBA), after 0.5g TEB 3K (HEMA), 0.13g methylacrylic acid isobutyl-POSS, 0.16gAIBN, 10mL ETHYLE ACETATE mix, join in the reaction vessel, at 70 ℃ of reaction 15h down with syringe.After reaction finished, behind methanol extraction, vacuum-drying 12h under the room temperature obtained containing polyacrylic ester-polysiloxane block copolymers of POSS, and number-average molecular weight is 8.9 ten thousand, and molecular weight distributing index is 1.12.
Embodiment 3
(a) take by weighing the single-ended hydrogen end-blocking of 30g YSR 3286 (molecular weight is 5000), 30g Virahol, 0.70g vinylcarbinol; Join in the 250mL there-necked flask, add 21 μ L platinum catalysts again, magnetic agitation; At 25 ℃ of reaction 1h, be warmed up to 65 ℃ of reaction 1h then.The liquid that obtains removed on Rotary Evaporators desolvate, vacuum-drying obtains molecular weight and is 5000 hydroxyl endblocked polydimethylsiloxane;
(b) be that 5000 hydroxyl endblocked polydimethylsiloxane, 1.8g catalyzer NSC 57182 (DCC), 120mL anhydrous methylene chloride join in the 250mL single port flask together with the 10g molecular weight, add 4.55g trithiocarbonate (DDMAT) then.After adding, stirring at room 72h.Add the normal hexane dilution, the filtering insolubles uses Rotary Evaporators to remove and desolvates; Centrifugal 5min under the rotating speed of 5000r/min gets the yellow clear liquid in upper strata, with washed with methanol 2 ~ 3 times; Obtain yellow oily liquid, obtain molecular weight and be 5000 ZGK 5 macromole RAFT reagent C;
(c) with there-necked flask, sealings such as prolong, vacuum outgas three times is full of argon gas.With 3.0g ZGK 5 macromole RAFT reagent C, 2.0g TEB 3K (MMA), 6.0g n-butyl acrylate (
nBA), after 1.0g Rocryl 400 (HEMA), 0.75g methacryloyl ethyl POSS, 0.20gAIBN, 10mL hexone mix, join in the reaction vessel, at 75 ℃ of reaction 12h down with syringe.After reaction finished, behind methanol extraction, vacuum-drying 12h under the room temperature obtained containing polyacrylic ester-polysiloxane block copolymers of POSS, and number-average molecular weight is 9.3 ten thousand, and molecular weight distributing index is 1.18.
Embodiment 4
(a) take by weighing 30g both-end hydrogen end-blocking YSR 3286 (molecular weight is 20000), 21g Virahol, 1.4g vinylcarbinol; Join in the 250mL there-necked flask, add 6.0 μ L platinum catalysts again, magnetic agitation; At 25 ℃ of reaction 1h, be warmed up to 65 ℃ of reaction 1h then.The liquid that obtains removed on Rotary Evaporators desolvate, vacuum-drying obtains molecular weight and is 20000 hydroxyl endblocked polydimethylsiloxane;
(b) be that 20000 hydroxyl endblocked polydimethylsiloxane, 1.8g catalyzer NSC 57182 (DCC), 120mL anhydrous methylene chloride join in the 250mL single port flask together with the 10g molecular weight, add 4.55g trithiocarbonate (DDMAT) then.After adding, stirring at room 72h.Add the normal hexane dilution, the filtering insolubles uses Rotary Evaporators to remove and desolvates; Centrifugal 5min under the rotating speed of 5000r/min gets the yellow clear liquid in upper strata, with washed with methanol 2 ~ 3 times; Obtain yellow oily liquid, obtain molecular weight and be 10000 ZGK 5 macromole RAFT reagent D;
(c) with there-necked flask, sealings such as prolong, vacuum outgas three times is full of nitrogen.With 2.0g ZGK 5 macromole RAFT reagent D, 4.0g TEB 3K (MMA), 4.0g tert-butyl acrylate (
tBA), after 2.0g Rocryl 400 (HEMA), 1.0g methylacrylic acid cyclohexyl POSS, 0.16gBPO, 10mL YLENE mix, join in the reaction vessel, at 80 ℃ of reaction 10h down with syringe.After reaction finished, behind methanol extraction, vacuum-drying 12h under the room temperature obtained containing polyacrylic ester-polysiloxane block copolymers of POSS, and number-average molecular weight is 8.2 ten thousand, and molecular weight distributing index is 1.15.
Claims (7)
1. preparation method who contains the polyacrylic ester-polysiloxane block copolymers of cage modle polysilsesquioxane, the repeat unit structure of the described ZGK 5-ROHM ester block copolymer that contains the cage modle polysilsesquioxane is following:
Formula 1
In the formula 1, m, n are respectively independently 1 ~ 1000 integer; I, j are respectively independently 0 ~ 18 integer; X is 10 ~ 300 integer;
R
1Be CH
3Or OH;
R
2For
Wherein: R is C
1-C
8Alkane or fluor alkaline;
R
3, R
4Independently be H or CH separately
3
R
5Be CH
3Or CH
2CH
2CF
3,
It is characterized in that comprising following process:
1) preparation of hydroxy-end capped ZGK 5
With hydrogen terminated polysiloxane and vinylcarbinol in molar ratio 1: (1 ~ 2) joins in the Virahol; Obtain the aqueous isopropanol of 50 ~ 60wt%, under the protection of nitrogen or argon gas, in the mol ratio 1 of si-h bond in platinum catalyst and the hydrogen end-blocking YSR 3286: the ratio of (0.0001 ~ 0.0002) adds platinum catalyst; Behind reaction 0.5 ~ 1.5h under 20 ~ 30 ℃; Be warmed up to 60 ~ 100 ℃, use Rotary Evaporators to remove reaction solvent, vacuum-drying behind reaction 0.5 ~ 1.5h; Thoroughly remove and desolvate, obtain hydroxy-end capped ZGK 5;
The preparation of 2) the reversible addition of ZGK 5 macromole-fracture chain transfer agents
Hydroxy-end capped ZGK 5 that step 1) is made and catalyzer NSC 57182 in molar ratio 1: (1 ~ 2) joins in the anhydrous methylene chloride; Obtain containing the hydroxy-end capped dichloromethane solution that gathers radical siloxane 5 ~ 7wt%, again in the mol ratio 1 of hydroxy-end capped ZGK 5 and carboxyl thiocarbonic ester: the ratio of (1 ~ 5) adds the carboxyl thiocarbonic ester, stir 48 ~ 72h under the room temperature after; Clean with normal hexane; The filtering insolubles uses Rotary Evaporators to remove reaction solvent, centrifugal layering; Get supernatant liquid; With washed with methanol 3 ~ 5 times, after the vacuum-drying, obtain number-average molecular weight in the reversible addition of the ZGK 5 macromole of 1000 ~ 20000g/mol-fracture chain transfer agents;
3) contain the preparation of the polyacrylic ester-polysiloxane block copolymers of cage modle polysilsesquioxane
With step 2) the reversible addition of the ZGK 5 macromole-fracture chain transfer agents, acrylic ester monomer, cage modle polysilsesquioxane monomer and the initiator that make be in mass ratio 1: (1 ~ 5): (0.05 ~ 0.50): the ratio of (0.05 ~ 0.1) joins in the reaction solvent dissolves; Obtain containing the solution of ZGK 5 macromole RAFT reagent 15 ~ 30wt%; Behind reaction 10 ~ 15h under 65 ~ 85 ℃; With the frozen water cooling, the THF dilution repeatedly precipitates with methyl alcohol; After throw out carried out vacuum-drying, obtain containing the polyacrylic ester-polysiloxane block copolymers of cage modle polysilsesquioxane.
2. preparation method according to claim 1 is characterized in that, said hydrogen terminated polysiloxane comprises single-ended hydrogen terminated polysiloxane and both-end hydrogen terminated polysiloxane, and number-average molecular weight is between 1000 ~ 20000 g/mol.
3. preparation method according to claim 1 is characterized in that, the carboxyl thiocarbonic ester is S-dodecyl-S '-(2-methyl-2-vinylformic acid) trithiocarbonate.
4. preparation method according to claim 1 is characterized in that, acrylic ester monomer is one or more in TEB 3K, Rocryl 400, n-butyl acrylate and the tert-butyl acrylate.
5. preparation method according to claim 1 is characterized in that, initiator is Diisopropyl azodicarboxylate or BPO.
6. preparation method according to claim 1 is characterized in that, reaction solvent is a hexone, the mixed solvent of one or more in ETHYLE ACETATE and the YLENE.
7. the application of the polyacrylic ester-polysiloxane block copolymers that contains the cage model sesquialter ZGK 5 that makes of a method according to claim 1, this multipolymer is used for low surface energy hydrophobic coating material, as the resin matrix in the coated material.
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