CN107739439A - A kind of preparation method of hyperbranched poly thioether - Google Patents
A kind of preparation method of hyperbranched poly thioether Download PDFInfo
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- CN107739439A CN107739439A CN201711045172.0A CN201711045172A CN107739439A CN 107739439 A CN107739439 A CN 107739439A CN 201711045172 A CN201711045172 A CN 201711045172A CN 107739439 A CN107739439 A CN 107739439A
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- hyperbranched poly
- poly thioether
- thioether
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- 229920006295 polythiol Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 238000005580 one pot reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000013049 sediment Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- DXRFZHILMCWCNG-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-2-amine Chemical compound C1=CC=NC2=NC(N(C)C)=CC=C21 DXRFZHILMCWCNG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 20
- -1 acryloxy Chemical group 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- IIMPKTUJEFLZNY-UHFFFAOYSA-N (3-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(O)OC(=O)C=C IIMPKTUJEFLZNY-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 description 2
- 235000019136 lipoic acid Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229960002663 thioctic acid Drugs 0.000 description 2
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of preparation method of hyperbranched poly thioether.The present invention utilizes the non-isoreactivity addition reaction of sulfydryl alkene, one pot process hyperbranched poly thioether using two degree of functionality asymmetry vinyl compounds and three-functionality-degree mercaptan as raw material.Raw material of the present invention is easy to get, step is simple, and the end group of the hyperbranched poly thioether of preparation is sulfydryl, can further carry out functional modification, so as to prepare the hyperbranched poly thioether with particular characteristic.
Description
【Technical field】
The present invention relates to a kind of preparation method of hyperbranched poly thioether, belong to organic polymer field.
【Background technology】
Hyperbranched polymer molecule has triaxial ellipsoid shape structure, and intramolecule has cavity, and there is substantial amounts of reaction end
Property group, it is and simple relative to dendritic, dissaving polymer synthesis step, before there are good industrial applications
Scape.
At present, hyperbranched poly thioether mainly has AB2And A2+B3Two kinds of preparation methods.Chinese patent
(CN2016105865276) AB containing sulfydryl and double bond simultaneously has been synthesized by multistep reaction using lipoic acid as raw material2It is single
Body, sulfydryl-alkene clicking chemistry reaction is recycled to be prepared for the hyperbranched poly thioether based on lipoic acid.But AB2The monomeric species of type
It is less, and the big organic synthesis process for being required for complexity；And A2+B3Polymerization system is during the course of the reaction due to poor, the pole of selectivity
Easily crosslink.
For the present invention using two degree of functionality asymmetry vinyl compounds as AA' monomers, three-functionality-degree mercaptan is B3Monomer, utilize mercapto
The non-isoreactivity addition reaction of base-alkene, the hyperbranched poly thioether of one pot process structure-controllable.The AA' monomer bags that the present invention uses
Include 3- (acryloxy)-Hydroxypropyl methacrylate and 2- (acryloxy) EMA, acrylic acid allyl
Ester, allyl methacrylate, A has very with the alkene of two kinds of different molecular structures of A' and the reactivity of sulfydryl in AA' monomers
Big difference, wherein acrylate>>Methacrylate>>Alkyl alkene, by controlling reaction condition, similar AB can be generated first2
The small molecule intermediates of type, further polymerization obtain hyperbranched poly thioether, and polymerization system is controllable and effectively avoids being crosslinked.The present invention
Raw material is easy to get, step is simple, and the end group of the hyperbranched poly thioether of preparation is sulfydryl, can further carry out functional modification.
The content of the invention：
The present invention relates to a kind of preparation method of hyperbranched poly thioether, can apply in all many-sides, such as in resin
There is potential application in the fields such as auxiliary agent, photocureable coating, biological medicine, packaging material for food, electronic package material.
A kind of hyperbranched poly thioether, it is characterised in that：Skeleton contains thioether, and end group is sulfydryl, and weight average molecular weight is 1.5~
50KDa, polydispersity index are 1.1~1.6, and polymer branching degree is 0.5~0.8；The structural formula of the dissaving polymer
It is as follows：
According to claim 1, one kettle way prepares hyperbranched poly thioether, comprises the following steps that：By 1.0~1.2 mole three
Degree of functionality mercaptan, 1.0 mole of two degree of functionality asymmetry vinyl monomer, 0~0.05 mol catalyst, 0~0.02 mole initiator
Reactor is added with solvent once, reacts 12~96h at a certain temperature；React reaction solution concentrated by rotary evaporation after terminating, use
Chloroform precipitates after dissolving again in absolute ether, repeats dissolving-precipitation operation 3 times, is overspend after sediment vacuum drying
Change polysulfide ether products.
According to claim 2, one kettle way prepares hyperbranched poly thioether, it is characterised in that described solvent is selected from tetrahydrochysene
One kind in furans, dioxane and N,N-dimethylformamide.
According to claim 2, one kettle way prepares hyperbranched poly thioether, it is characterised in that described catalyst is selected from three
Ethamine, dimethylamino naphthyridine, 1,5- diazabicyclos [4.3.0] -5- nonenes, the azabicyclics of 1,5,7- tri- [4.4.0] decyl- 5- alkene
In one kind.
According to claim 2, one kettle way prepares hyperbranched poly thioether, it is characterised in that described initiator is selected from even
One kind in nitrogen bis-isobutyronitrile, dibenzoyl peroxide.
Advantages of the present invention：
1. the present invention prepares the hyperbranched poly thioether with controllable active end group by one kettle way, A and A' in AA' monomers
The alkene of two kinds of different molecular structures and the reactivity of sulfydryl have very big difference, wherein acrylate>>Methacrylate>>
Alkyl alkene, by controlling reaction condition, similar AB can be generated first2Type small molecule intermediates, further polymerization are formed hyperbranched
Polythiaether.In whole course of reaction, there is not gelatin phenomenon, and synthesis material is cheap and easily-available, synthetic method is simple and yield
It is high.
2. the preparation of hyperbranched poly thioether is thioether with very high selection activity, in product skeleton in the present invention, end group
For sulfydryl, molecular weight and the degree of branching are higher and controllable；This method has the advantages of unique for conventional method,
Such as：Gel is not easy to, operation is simple, controllability height etc..
Brief description of the drawings：
Fig. 1 is the chemical constitution schematic diagram of hyperbranched poly thioether prepared by case study on implementation 1~10.
Fig. 2 is the Fourier infrared absorption spectrogram of hyperbranched poly thioether prepared by case study on implementation 1.
Fig. 3 is hyperbranched poly thioether prepared by case study on implementation 11H-NMR spectrum.
Fig. 4 is the gel permeation chromatography figure of hyperbranched poly thioether prepared by case study on implementation 1.
Specific implementation method：
Below in conjunction with specific implementation case, the invention will be further elaborated.It should be understood that the invention is not restricted to following reality
Case is applied, methods described is accordingly to be regarded as conventional method unless otherwise instructed.The material unless otherwise instructed can be from open business
Approach obtains.
Case 1~10 is the preparation case of hyperbranched poly thioether.
Case study on implementation 1：
By 9.965g (25mmol) 2- ethyl glycerine tri-thiol propionic esters, 75mL tetrahydrofurans and 5.355g (25mmol)
3- (acryloxy)-Hydroxypropyl methacrylate and 0.1265g (1.25mmol) triethylamine disposably add reactor
In, N at 40 DEG C2Protection reaction 48h；Reaction terminate after by reaction solution concentrated by rotary evaporation, in absolute ether after being dissolved again with chloroform
Middle precipitation, repeats dissolving-precipitation operation 3 times, and colorless viscous liquid product hyperbranched poly thioether is obtained after sediment vacuum drying
(12.68 g, yield 82.8%).
Fig. 2 is the infrared absorpting light spectra of hyperbranched poly thioether prepared by case study on implementation 1, for OH's wherein at 3505cm-1
Stretching vibration absworption peak, it is the characteristic absorption peak of sulfydryl at 2540cm-1, the double bond characteristic peak at 1600cm-1 is wholly absent,
Prove that hyperbranched poly thioether successfully synthesizes.
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of hyperbranched poly thioether prepared by case study on implementation 1, is terminal sulfhydryl group wherein at 1.64ppm
Proton signal peak, by characteristic peak integration calculate obtain the hyperbranched poly thioether the degree of branching be 0.65.
Fig. 4 be case study on implementation 1 prepare hyperbranched poly thioether gel permeation chromatography figure, the M of the hyperbranched poly thioetherwFor
7500 Da, polymer polydispersity PDI are 1.40.
Case study on implementation 2：
By 9.965g (25mmol) 2- ethyl glycerine tri-thiol propionic esters, 75mL dioxane and 5.355g (25mmol)
3- (acryloxy)-Hydroxypropyl methacrylate and 0.1265g (1.25mmol) triethylamine disposably add reactor
In, N at 40 DEG C2Protection reaction 48h；Reaction terminate after by reaction solution concentrated by rotary evaporation, in absolute ether after being dissolved again with chloroform
Middle precipitation, repeats dissolving-precipitation operation 3 times, and colorless viscous liquid product hyperbranched poly thioether is obtained after sediment vacuum drying
(12.44 g, yield 81.2%).
Case study on implementation 3：
By 10.961g (27.5mmol) 2- ethyl glycerine tri-thiol propionic esters, 75mL tetrahydrofurans and 5.355g
(25mmol) 3- (acryloxy)-Hydroxypropyl methacrylate and 0.1265g (1.25mmol) triethylamine disposably add
Enter in reactor, N at 40 DEG C2Protection reaction 24h；Reaction terminate after by reaction solution concentrated by rotary evaporation, after being dissolved again with chloroform
Precipitated in absolute ether, repeat dissolving-precipitation operation 3 times, colorless viscous liquid product over-expense is obtained after sediment vacuum drying
Change polythiaether (11.13g, yield 68.2%).
Case study on implementation 4：
By 9.965g (25mmol) 2- ethyl glycerine tri-thiol propionic esters, 75mL tetrahydrofurans and 5.355g (25mmol)
3- (acryloxy)-Hydroxypropyl methacrylate is disposably added in reactor, N at 40 DEG C2Protection reaction 96h；Instead
By reaction solution concentrated by rotary evaporation after should terminating, precipitated after being dissolved again with chloroform in absolute ether, repeat dissolving-precipitation operation 3
It is secondary, obtain colorless viscous liquid product hyperbranched poly thioether (12.91g, yield 84.3%) after sediment vacuum drying.
Case study on implementation 5：
By 9.965g (25mmol) 2- ethyl glycerine tri-thiol propionic esters, 75mL tetrahydrofurans and 5.355g (25mmol)
3- (acryloxy)-Hydroxypropyl methacrylate and the azabicyclics of 0.174g (1.25mmol) 1,5,7- tri--
[4.4.0]-decyl- 5- alkene is disposably added in reactor, N at 40 DEG C2Protection reaction 48h；Reaction rotates reaction solution after terminating
Concentration, is precipitated after being dissolved again with chloroform in absolute ether, repeats dissolving-precipitation operation 3 times, after sediment vacuum drying
To colorless viscous liquid product hyperbranched poly thioether (12.0g, yield 78.2%).
Case study on implementation 6：
By 9.965g (25mmol) 2- ethyl glycerine tri-thiol propionic esters, 75mL DMFs and
3.154g (25 mmol) allyl methacrylate, 0.1265g (1.25mmol) triethylamines and 0.082g (0.5mmol) azo
Bis-isobutyronitrile is disposably added in reactor, N at 80 DEG C2Protection reaction 48h；React reaction solution concentrated by rotary evaporation after terminating, use
Chloroform is precipitated after dissolving again in absolute ether, repeats dissolving-precipitation operation 3 times, and product is obtained after sediment vacuum drying
Hyperbranched poly thioether (colorless viscous liquid 9.50g, yield 72.4%).
Case study on implementation 7：
By 4.357g (25mmol) the mercaptan of benzene three, 75mL tetrahydrofurans and 5.355g (25mmol) 3- (acryloyl-oxies
Base)-Hydroxypropyl methacrylate and 0.1265g (1.25mol) triethylamine disposably added in reactor, N at 50 DEG C2Protect
Shield reaction 72h；React reaction solution concentrated by rotary evaporation after terminating, precipitated after being dissolved again with chloroform in absolute ether, repeated molten
Solution-precipitation operation 3 times, obtaining colorless viscous liquid product hyperbranched poly thioether after sediment vacuum drying, (7.05g, yield are
72.6%).Case study on implementation 8：
By 4.357g (25mmol) the mercaptan of benzene three, 75mL DMFs and 3.154g (25mmol) methyl
Allyl acrylate, 0.1265g (1.25mmol) triethylamines and 0.082g (0.5mmol) azodiisobutyronitrile disposably add anti-
Answer in device, N at 80 DEG C2Protection reaction 48h；Reaction terminate after by reaction solution concentrated by rotary evaporation, anhydrous after being dissolved again with chloroform
Precipitated in ether, repeat dissolving-precipitation operation 3 times, colorless viscous liquid product hyperbranched poly is obtained after sediment vacuum drying
Thioether (5.21g, yield 69.4%).
Case study on implementation 9：
By double (ethane -2,1- diyls) double (the 3- mercaptopropionic acids of 9.238g (25mmol) ((3- mercapto radical propionyl groups) dialkyl group)
Ester), 75mL tetrahydrofurans and 5.355g (25mmol) 3- (acryloxy)-Hydroxypropyl methacrylate and 0.1265g
(1.25 mol) triethylamine is disposably added in reactor, N at 40 DEG C2Protection reaction 48h；Reaction rotates reaction solution after terminating
Concentration, is precipitated after being dissolved again with chloroform in absolute ether, repeats dissolving-precipitation operation 3 times, after sediment vacuum drying
To colorless viscous liquid product hyperbranched poly thioether (10.74g, yield 73.6%).
Case study on implementation 10：
By double (ethane -2,1- diyls) double (the 3- mercaptopropionic acids of 9.238g (25mmol) ((3- mercapto radical propionyl groups) dialkyl group)
Ester), 75mL DMFs and 3.154g (25mmol) allyl methacrylate, 0.1265g (1.25mmol)
Triethylamine and 0.082g (0.5mmol) azodiisobutyronitrile are disposably added in reactor, N at 80 DEG C2Protection reaction 48h；Instead
By reaction solution concentrated by rotary evaporation after should terminating, precipitated after being dissolved again with chloroform in absolute ether, repeat dissolving-precipitation operation 3
It is secondary, obtain colorless viscous liquid product hyperbranched poly thioether (9.52g, yield 76.8%) after sediment vacuum drying.
Claims (5)
1. a kind of preparation method of hyperbranched poly thioether, the present invention is with two degree of functionality asymmetry vinyl compounds and three-functionality-degree sulphur
Alcohol is raw material, utilizes the non-isoreactivity addition reaction of sulfydryl-alkene, one pot process hyperbranched poly thioether；The hyperbranched poly thioether
It is characterised by：Skeleton contains thioether, and end group is sulfydryl, and weight average molecular weight is 1.5~50KDa, and polydispersity index is 1.1~
1.6, the degree of branching is 0.5~0.8；The structure of the hyperbranched poly thioether is as follows：
2. one kettle way prepares hyperbranched poly thioether according to claim 1, comprise the following steps that：By 1.0~1.2 mole of three official
Energy degree mercaptan, 1.0 mole of two degree of functionality asymmetry vinyl monomer, 0~0.05 mol catalyst, 0~0.02 mole initiator and
Solvent once adds reactor, reacts 12~96h at a certain temperature；React reaction solution concentrated by rotary evaporation after terminating, use chlorine
Precipitated after imitative dissolving again in absolute ether, repeat dissolving-precipitation operation 3 times, obtained after sediment vacuum drying hyperbranched
Polysulfide ether products.
3. one kettle way prepares hyperbranched poly thioether according to claim 2, it is characterised in that described solvent is selected from tetrahydrochysene furan
Mutter, one kind in dioxane and N,N-dimethylformamide.
4. one kettle way prepares hyperbranched poly thioether according to claim 2, it is characterised in that described catalyst is selected from three second
In amine, dimethylamino naphthyridine, 1,5- diazabicyclos [4.3.0] -5- nonenes, the azabicyclics of 1,5,7- tri- [4.4.0] decyl- 5- alkene
One kind.
5. one kettle way prepares hyperbranched poly thioether according to claim 2, it is characterised in that described initiator is selected from azo
One kind in bis-isobutyronitrile and dibenzoyl peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711045172.0A CN107739439B (en) | 2017-10-31 | 2017-10-31 | Preparation method of hyperbranched polythioether |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711045172.0A CN107739439B (en) | 2017-10-31 | 2017-10-31 | Preparation method of hyperbranched polythioether |
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| Publication Number | Publication Date |
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| CN107739439A true CN107739439A (en) | 2018-02-27 |
| CN107739439B CN107739439B (en) | 2020-02-21 |
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Cited By (11)
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| CN108912360A (en) * | 2018-07-02 | 2018-11-30 | 仲恺农业工程学院 | High-flexibility hemicellulose thin film and preparation method thereof |
| CN109370508A (en) * | 2018-10-08 | 2019-02-22 | 东莞市联灏新材料技术开发有限公司 | A kind of radiation-curable black shading Adhesive composition |
| CN110283314A (en) * | 2019-06-20 | 2019-09-27 | 江南大学 | A method of preparing hyperbranched poly thioether |
| CN110698672A (en) * | 2019-10-30 | 2020-01-17 | 贵州民族大学 | Multi-responsiveness dendritic polythioether polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN110760064A (en) * | 2019-10-30 | 2020-02-07 | 贵州民族大学 | Multi-responsiveness dendritic polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN111450307A (en) * | 2020-04-08 | 2020-07-28 | 江南大学 | Preparation method of double-component medical adhesive |
| CN111944392A (en) * | 2020-08-25 | 2020-11-17 | 江南大学 | Hyperbranched polythioether/epoxy acrylate resin composite photocureable coating and preparation method and application thereof |
| CN114031707A (en) * | 2020-07-20 | 2022-02-11 | 中国石油化工股份有限公司 | Cured material composition and application thereof, cured resin and preparation method and application thereof |
| CN115232311A (en) * | 2022-08-09 | 2022-10-25 | 河源然生新材料有限公司 | Synthesis method of hyperbranched methacrylate |
| CN116333314A (en) * | 2023-04-12 | 2023-06-27 | 华南理工大学 | Method for preparing degradable polyester based on solvent-free polymerization of 10-undecylenic acid |
| CN116622082A (en) * | 2023-05-26 | 2023-08-22 | 江苏可奥熙光学材料科技有限公司 | High-light-transmittance high-scratch-resistance polymeric resin, product and preparation process thereof |
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| CN108912360A (en) * | 2018-07-02 | 2018-11-30 | 仲恺农业工程学院 | High-flexibility hemicellulose thin film and preparation method thereof |
| CN109370508A (en) * | 2018-10-08 | 2019-02-22 | 东莞市联灏新材料技术开发有限公司 | A kind of radiation-curable black shading Adhesive composition |
| CN109370508B (en) * | 2018-10-08 | 2021-05-18 | 东莞市联灏新材料技术开发有限公司 | Radiation-curable black shading adhesive composition |
| WO2020252967A1 (en) * | 2019-06-20 | 2020-12-24 | 江南大学 | Method for preparing hyperbranched polysulfide |
| CN110283314A (en) * | 2019-06-20 | 2019-09-27 | 江南大学 | A method of preparing hyperbranched poly thioether |
| CN110760064A (en) * | 2019-10-30 | 2020-02-07 | 贵州民族大学 | Multi-responsiveness dendritic polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN110698672A (en) * | 2019-10-30 | 2020-01-17 | 贵州民族大学 | Multi-responsiveness dendritic polythioether polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN110760064B (en) * | 2019-10-30 | 2021-12-24 | 贵州民族大学 | Multi-responsiveness dendritic polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN111450307A (en) * | 2020-04-08 | 2020-07-28 | 江南大学 | Preparation method of double-component medical adhesive |
| CN114031707A (en) * | 2020-07-20 | 2022-02-11 | 中国石油化工股份有限公司 | Cured material composition and application thereof, cured resin and preparation method and application thereof |
| CN114031707B (en) * | 2020-07-20 | 2023-08-15 | 中国石油化工股份有限公司 | Cured material composition and application thereof, cured resin and preparation method and application thereof |
| CN111944392A (en) * | 2020-08-25 | 2020-11-17 | 江南大学 | Hyperbranched polythioether/epoxy acrylate resin composite photocureable coating and preparation method and application thereof |
| CN115232311A (en) * | 2022-08-09 | 2022-10-25 | 河源然生新材料有限公司 | Synthesis method of hyperbranched methacrylate |
| CN115232311B (en) * | 2022-08-09 | 2023-11-14 | 河源然生新材料有限公司 | Synthesis method of hyperbranched methacrylate |
| CN116333314A (en) * | 2023-04-12 | 2023-06-27 | 华南理工大学 | Method for preparing degradable polyester based on solvent-free polymerization of 10-undecylenic acid |
| CN116622082A (en) * | 2023-05-26 | 2023-08-22 | 江苏可奥熙光学材料科技有限公司 | High-light-transmittance high-scratch-resistance polymeric resin, product and preparation process thereof |
| CN116622082B (en) * | 2023-05-26 | 2024-08-13 | 江苏可奥熙光学材料科技有限公司 | High-light-transmittance high-scratch-resistance polymeric resin, product and preparation process thereof |
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