CN108892763A - A kind of polyurethane binary mercaptan prepolymer, photosensitive resin composition and its preparation method and application - Google Patents
A kind of polyurethane binary mercaptan prepolymer, photosensitive resin composition and its preparation method and application Download PDFInfo
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- CN108892763A CN108892763A CN201810525101.9A CN201810525101A CN108892763A CN 108892763 A CN108892763 A CN 108892763A CN 201810525101 A CN201810525101 A CN 201810525101A CN 108892763 A CN108892763 A CN 108892763A
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- 0 CC(*)(C1)CC(C)(CCC#N)CC1N=C=O Chemical compound CC(*)(C1)CC(C)(CCC#N)CC1N=C=O 0.000 description 3
- MJCYFMBUETUVOR-UHFFFAOYSA-N O=C=Nc1cccc(CC2=CC(N=C=O)=CCCC2)c1 Chemical compound O=C=Nc1cccc(CC2=CC(N=C=O)=CCCC2)c1 MJCYFMBUETUVOR-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention relates to a kind of polyurethane binary mercaptan prepolymers, photosensitive resin composition and its preparation method and application.Shown in the prepolymer such as formula (I)：Wherein, R is2≤n1≤6；R1For 1≤n2≤ 100,1≤n3≤ 100,1≤n4≤ 100,1≤n5≤ 100,1≤n6≤100,1≤x≤3,1≤y≤3；R2For
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly, to a kind of polyurethane binary mercaptan prepolymer, light
Photosensitive resin composition and its preparation method and application.
Background technique
The advantages that low energy consumption due to it for Introduction To Stereolithography, precision is high and at low cost, is widely used in vapour
The fields such as vehicle manufacture, die casting, medical treatment, jewelry and art.1986, Charles doctor W.Hull in patent US 4,
The patent of this rapid shaping technique is disclosed in 575,330 first.Moulding material used in stereolithography is the photosensitive of liquid
Resin, photosensitive resin, can be according to computer 3D mathematical model curing moldings layer by layer under light radiation.
In early stage, the oligomer of main (methyl) acrylate or polyurethane (methyl) acrylate is used as stereolithography
Resin.Such as 1993, patent US 5,248,752 disclosed the light for being used as the molding of stereolithography with urethane oligomer
Quick resin.The shortcomings that (although methyl) acrylic resin has the advantages that photo-curing rate is fast, this resinoid also ten
It is clearly demarcated aobvious：On the one hand polymerization shrinkage is larger after its solidification, and formed precision is poor；On the other hand, it is easy to be made by the polymerization inhibitor of oxygen
With parts surface has a small amount of resin that cannot polymerize.The same year, Ciba-Geigy company release the light based on epoxies first
Quick resin is used for stereolithography, reduces the effect and polymerization shrinkage of the polymerization inhibitor of oxygen.But epoxylite rate of polymerization is too
Slow and toughness is poor.Therefore, people attempt for epoxy resin to be blended with acrylic acid, form with epoxy resin as main acrylate
Supplemented by radical-cation hybrid system, such as patent WO97/16482 and US2,001,046,642 discloses stereolithography
Resin be belong to epoxy resin and acrylate mix type photosensitive resin, this kind of resin is fast with rate of polymerization, polymerization
Relatively low advantage is shunk, commercialized stereolithography is mostly such with photosensitive resin at present, such as DMS company
The RenShapeSL of Somos series and Huntsman series.
But, this kind of resin for mixing type still has biggish polymerization shrinkage, and polymerization shrinkage is generally 5% or so；Separately
Outside, the functional group of (methyl) acrylate or epoxy resin conversion ratio when illumination polymerize is relatively low, these are uncured remaining
Monomer can have certain irritation to skin.In recent years, mercaptan-alkene class photosensitive resin is smaller due to its high reactivity
Polymerization shrinkage and shrinkage stress, high functional group conversions, which lead, to be obtained people with the preferable toughness of resin after polymerization and payes attention to, this
A little advantages make it have very big application potential in stereolithography.2004, patent EP 1477511, just make public for the first time by
Mercaptan-alkene photosensitive resin is used for stereolithography rapid shaping, and all polythiol monomers are commercialization small molecule polythiol monomer, or reference
The polyurethane mercaptan oligomer reported in patent US 5,744,514, although the polyurethane mercaptan oligomer that this patent provides is last
Oligomeric isocyanates are blocked using small molecule mercaptan, it is still unavoidable to remain small molecule mercaptan.
HolgerLeonards reports polyethylene glycol divinyl ether and four (3- mercaptopropionic acid) pentaerythritol esters are used separately as alkene
And polythiol monomer, mercaptan-alkene hydrocarbon photopolymer system is constructed, is had in tri- kinds of Stereolithographies of DLP, SLA and TPP/MPP
Applications well potentiality (Proc.SPIE 9353, Laser 3D Manufactring II, 2015).With urethane acrylate light
Quick resin is compared, and mercaptan-alkene hydrocarbon photopolymer system has good resistance to the oxygen inhibiting polymerization effect, lower polymerization shrinkage and good power
Learn performance (RapidPrototyping Journal, 22 (3):465-473,2016).Mercaptan-alkene hydrocarbon photosensitive resin described above
There is huge application value for photocureable rapid shaping, but above-mentioned patent or document report are mostly small molecule polythiol monomer,
The taste of small molecule polythiol monomer is unpleasant, hinders application of the mercaptan-alkene hydrocarbon photosensitive resin in photocureable rapid shaping.And US
The preparation method of the 5,744,514 polyurethane mercaptan oligomer provided is to be carried out using small molecule mercaptan to oligomeric isocyanates
Sealing end, it is possible to small molecule mercaptan can be remained by being difficult to avoid that, so as to cause there is remaining taste, still without solving mercaptan list
Body smell problem.
Therefore, developing a kind of scentless small molecule polythiol monomer or polyurethane mercaptan oligomer, there is important research to anticipate
Justice and application value.
Summary of the invention
It is an object of the invention to overcome small molecule polythiol monomer or polyurethane mercaptan oligomer smell in the prior art
Unpleasant defect and deficiency provides a kind of polyurethane binary mercaptan prepolymer.Prepolymer provided by the invention overcomes traditional sulphur
The unpleasant taste of alcohol-olefine resin, the photosensitive resin being prepared by it also odorlessness, and there is smaller volume contraction, faster
Rate of polymerization.
Another object of the present invention is to provide the preparation methods of above-mentioned polyurethane binary mercaptan pre-polymerization.
Another object of the present invention is to provide a kind of photocureable rapid shaping photosensitive resin compositions.
Another object of the present invention is to provide above-mentioned polyurethane binary mercaptan pre-polymerizations to prepare the application in photosensitive resin.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of polyurethane binary mercaptan prepolymer, shown in the prepolymer such as formula (I)：
Wherein, R is2≤n1≤6；
R1For 1≤n2≤ 100,1≤n3≤
100,1≤n4≤ 100,1≤n5≤ 100,1≤n6≤100,1≤x≤3,1≤y≤3；
R2For
It has been investigated that there are certain relevance between the length of the alkyl chain of mercaptan and its smell, mercaptan can be with
The increase of long alkyl chains, volatility weaken, and when there is 12 or more carbon atoms on chain, mercaptan is with regard to odorlessness, therefore,
The carbon atom number for increasing polythiol monomer is to reduce the effective means of thiol smell.Based on this, the present invention passes through to alkyl chain
The certain selected and chain length of group control to have obtained scentless polyurethane binary mercaptan prepolymer, are prepared by it photosensitive
Resin also odorlessness, and there is smaller volume contraction, faster rate of polymerization.
Preferably, the R1For
Preferably, the R2For
Preferably, describedMolecular weight be 200~2000 dalton；It is describedMolecular weight be 200~2000 dalton；It is describedMolecular weight
For 200~2000 dalton；It is describedMolecular weight be 200~2000
Er Dun；It is describedMolecular weight be 200~2000 dalton.
The present invention provides a kind of preparation method of above-mentioned polyurethane binary mercaptan prepolymer, and the method includes walking as follows
Suddenly：
S1：Bromo monohydric alcohol is added in the isocyanates of binary and the mixed solution of dibutyl tin dilaurate, in 20
6~12h is reacted at~50 DEG C；
The bromo monohydric alcohol is：
The binary isocyanates is：
The dibutyl tin dilaurate is：
S2：Poly-dihydric alcohol is added, 6~12h is reacted at 20~80 DEG C；The poly-dihydric alcohol is：
Wherein, 2≤n1≤ 6,1≤n2≤ 100,1≤n3≤ 100,1≤n4≤ 100,1≤n5≤ 100,1≤n6≤100,1
≤ x≤3 and 1≤y≤3.
S3：Thioacetic acid potassium or ehtyl potassium xanthate is added, is evaporated under reduced pressure, washed up to the pre-polymerization after 6~12h of reaction
Object.
The preparation process can be indicated with following reaction formula：
Preferably, the molar ratio of bromo monohydric alcohol described in S1 and the isocyanates of binary is 1:2.
Preferably, poly-dihydric alcohol described in S2 is 1 by the molar ratio of the molar equivalent of hydroxyl and the isocyanates of binary:1.
Preferably, S2 can track reaction using infrared spectroscopy to judge the degree of reaction progress, as isocyanates (- NCO)
When absorption peak is completed to disappear, reaction is completed.
Preferably, vacuum distillation described in S3, the process washed are：Vacuum distillation removes solvent and obtains head product；It will be described
It is evaporated under reduced pressure after head product dissolution, washing, drying；Be eventually adding n-butylamine reaction 6~be filtered, washed afterwards for 24 hours, be evaporated under reduced pressure to
To the prepolymer；The molar ratio of the n-butylamine and halogenated monohydric alcohol in S1 is 1~3:1.
Preferably, the poly-dihydric alcohol is polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, poly- tetrahydro
Furans glycol, polycaprolactone glycol or polyester diol.
It is further preferable that the poly- poly-dihydric alcohol is polyethylene glycol, polycaprolactone glycol or polyester diol.
Preferably, the diisocyanate of the binary be isophorone diisocyanate, methyl diphenylene diisocyanate,
Toluene di-isocyanate(TDI) (2,3- toluene di-isocyanate(TDI) and 2,4 toluene diisocyanate mixture), dicyclohexyl methyl hydride two are different
Cyanate, hexamethylene diisocyanate, 2,2,4- trimethyl cyclohexane -1,6- diisocyanate
It is further preferable that the diisocyanate of the binary is Toluene-2,4-diisocyanate, 4- diisocyanate or isophorone two are different
Cyanate.
A kind of photocureable rapid shaping photosensitive resin composition is also claimed in the present invention, and the composition includes as follows
The component of mass fraction：Above-mentioned polyurethane binary mercaptan oligomer 30~60%, vinyl monomer 30~60%, crosslinking agent 0~
10%, free radical photo-initiation 1~5%, stabilizer 1~5%.
Preferably, the composition includes the component of mass fraction：Polyurethane binary mercaptan oligomer 50%, vinyl monomer
40%, crosslinking agent 7%, free radical photo-initiation 1.5%, stabilizer 1.5%.
Preferably, the vinyl monomer is the first of the oligomer of the esters of acrylic acid containing 2 functional groups, 2 functional groups
The oligomer of base esters of acrylic acid, 2 functional groups norbornene oligomer or 2 functional groups vinyl ethers oligomer
One of or it is several.
The oligomer of esters of acrylic acid of the present invention containing 2 functional groups includes but is not limited to 1,3 butylene glycol dipropyl
Olefin(e) acid ester, 1,4-butanediol diacrylate, 1,6- hexanediyl ester, glycol diacrylate, 1,6- hexylene glycol
Ethoxy acid diacrylate, four (ethylene glycol) diacrylates, neopentylglycol diacrylate and its blend.
Preferably, the oligomer of the esters of acrylic acid containing 2 functional groups be 1,6- hexanediyl ester or
Four (ethylene glycol) diacrylates.
The oligomer of methyl acrylic ester of the present invention containing 2 functional groups includes but is not limited to bisphenol-A diformazan
Base acrylate, tetraethylene glycol dimethylacrylate, 1,3 butylene glycol dimethylacrylate, 1,4- butanediol dimethyl propylene
Olefin(e) acid ester, 1,6-Hexanediol dimethacrylate, ethylene glycol dimethacrylate, two urethane dimethylacrylates, four
Ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethacrylate and its blend.
Preferably, the oligomer containing 2 functional group's methyl acrylic esters is 1,6- hexylene glycol dimethyl allene
Acid esters, two urethane dimethylacrylates, tetraethylene glycol dimethylacrylate or triethylene glycol dimethacrylate.
The oligomer of norbornene of the present invention containing 2 functional groups includes but is not limited to that ice drops in 1,3 butylene glycol two
Piece alkene, two norbornene of 1,4- butanediol, 1,6-HD norbornene, two norbornene of ethylene glycol, 1,6-HD ethoxy
Sour two norbornene, four (ethylene glycol) two norbornene, two norbornene of neopentyl glycol and its blend.
Preferably, the oligomer of the norbornene containing 2 functional groups is sour two norborneols of 1,6- hexylene glycol ethoxy
Alkene or four (ethylene glycol) two norbornene.
The oligomer of vinyl ethers of the present invention containing 2 functional groups includes but is not limited to 1,4- butanediol divinyl
Base ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, four (ethylene glycol) divinyl ethers, 1,4- hexamethylene two
Methanol divinyl ether, 1,6-HD divinyl ether, two [4- (ethyleneoxy) butyl] adipic acids, two [4- (ethyleneoxy) fourths
Base] succinic acid and its blend.
Preferably, the oligomer of the vinyl ethers containing 2 functional groups be four (ethylene glycol) divinyl ethers or 1,
6- hexylene glycol divinyl ether.
Preferably, the crosslinking agent is acrylate, methacrylate, the vinyl ethers of 3 and 3 or more functional groups
Or one or more of thiol molecule；Or hyperbranched or dendrimer acrylate, methacrylate, vinyl ethers
Or mercaptan.
The acrylate of 3 and 3 or more functional groups' (i.e. polyfunctional group) includes but is not limited to tripropoxy glycerine
Triacrylate, triethoxy triacrylate, glycerol derivatives triacrylate, pentaerythritol tetraacrylate, ethoxyquin
Pentaerythritol tetraacrylate, 2- trimethylolpropane acrylates, the third oxidation pentaerythritol tetraacrylate, dipentaerythritol
Five acrylate.
Preferably, the acrylate of 3 and 3 or more functional groups is pentaerythritol tetraacrylate or pentaerythrite 4 third
Olefin(e) acid ester.
The methacrylate of 3 and 3 or more functional groups' (i.e. polyfunctional group) includes but is not limited to trimethylolpropane
Trimethyl acrylic ester, pentaerythritol tetramethylacrylate, triethoxy trimethyl acrylic ester, glycerol derivatives trimethyl
Acrylate, ethoxyquin pentaerythrite methacrylate, 2- trimethylolpropane methacrylate, the third oxidation pentaerythrite
Tetramethyl acrylate, dipentaerythritol pentamethacrylate,
Preferably, the methacrylate of described 3 and 3 or more functional groups is ethoxyquin pentaerythrite tetramethyl propylene
Acid esters or the third oxidation pentaerythritol tetramethylacrylate.
The norbornene of 3 and 3 or more functional groups' (i.e. polyfunctional group) mainly passes through more acrylate and ring penta 2
Obtained by alkene is reacted by Diels-Alder, including but not limited to tripropoxy glycerine trinorbornene alkene, triethoxy three
Norbornene, glycerol derivatives trinorbornene alkene, four norbornene of pentaerythrite, four norbornene of ethoxyquin pentaerythrite, 2-
Trimethylolpropane norbornene, the third oxidation four norbornene of pentaerythrite, five norbornene of dipentaerythritol.
Preferably, the norbornene of described 3 and 3 or more functional groups is four norbornene of pentaerythrite or two seasons penta 4
Five norbornene of alcohol.
The vinyl ethers (i.e. more vinyl ethers) of 3 and 3 or more functional groups can be etherified to obtain by polyalcohol, including
But it is not limited to triethoxy trivinyl ether, pentaerythrite tetravinyl ether, 2- trimethylolpropane vinyl ethers, the third oxidation season
Penta tetrol tetravinyl ether.
Preferably, the vinyl ethers of described 3 and 3 or more functional groups is triethoxy trivinyl ether or the third oxidation season
Penta tetrol tetravinyl ether.
The thiol molecule (i.e. multi-thiol molecule) of 3 and 3 or more functional groups includes but is not limited to four (3- sulfydryls third
Acid) pentaerythritol ester, trimethylolpropane tris (3-thiopropionate).
Preferably, the thiol molecule of described 3 and 3 or more functional groups is four (3- mercaptopropionic acid) pentaerythritol esters.
Hyperbranched or dendrimer acrylate, methacrylate, vinyl ethers and mercaptan, can or make
For crosslinking agent use.Such as Progress in Organic Coatings 56:252-255,2006 describes a kind of dendroid
Urethane acrylate preparation method；Journal of Mechanical Behavior of Biomedical
Materials 35:1-8 2014 describes a kind of more methyl methacrylates of dendroid；Macromolecular
Materials and Engineering 275:31-41,2000 describes a kind of dissaving vinyl ether；
Macromolecules,42(13):4596-4603 2009 describes a kind of hyperbranched norbornene polymer, above
As the crosslinking agent in the present invention.
The free radical photo-initiation is benzoin class, benzil class, acetophenones, benzoyl formic acid esters, acylphosphanes
One or more of oxide, including but not limited to diphenylhydroxyethanone, dibenzoyl, α, α-diethoxy acetophenone, 2- hydroxyl
- 2 methylphenyl acetone -1,1- hydroxy-cyciohexyl Benzophenone of base, 2- hydroxy-2-methyl-to ethoxy ether phenylacetone -1,
2- methyl-1-(4- first mercaptophenyl)-2- morpholine acetone-1,2- benzyl-2- dimethylamino-1- (4- morpholinyl phenyl) butanone-1,
Benzoyl formiate, 2,4,6- trimethylbenzoyls-ethyoxyl-phenyl phosphine oxide, 2,4,6- trimethylbenzoyls-hexichol
Base phosphine oxide, 4- is to toluene sulfydryl benzophenone, benzophenone, 2,4,6- tri-methyl benzophenones, thioxanthone, 2- ethyl anthracene
Quinone.
Preferably, the free radical photo-initiation is 2,4,6- trimethylbenzoy-dipheny phosphine oxides or 2,4,6-
Tri-methyl benzophenone.
The stabilizer is conventional stabilizer in the art.
Alkyl-substituted phenols class be the most common stabilizer, including but not limited to hydroquinone, 4- metoxyphenol, benzoquinones,
Naphthoquinones, 2,6-Di-tert-butyl-4-methylphenol or butylated hydroxy anisole, it can also be used in the present invention.
In addition patent US 5,459,173 disclose alkenyl substituted phenol and free radical scavenger, steric hindrance type phenols and hydroxyl
Amine composition can significantly improve mercaptan-alkene hydrocarbon light as mercaptan-alkene hydrocarbon or mercaptan-norbornene photosensitive resin stabilizer
The stability of quick resin system；Patent application WO2012/126695A1 also discloses a kind of for mercaptan-alkene hydrocarbon photosensitive resin
Stabilizer, this kind of stabilizer mainly by containing there are two and more than two hydroxyl phenols or naphthols and phosphonic acid material composition,
These two types of substances have synergistic effect, can effectively improve the stability of mercaptan-alkene photopolymer system.It can be used as this hair above
Stabilizer in bright.
Above-mentioned polyurethane binary mercaptan prepolymer prepare in photosensitive resin application it is also within the scope of the present invention.
Compared with prior art, the present invention has the advantages that：
The polyurethane binary mercaptan pre-polymerization that the present invention is obtained by increasing the substitution of mercaptan long alkyl chains and special groups
Object, mercaptan volatility weaken significantly, have no irritating odor, the photosensitive resin being prepared by it also odorlessness, and have more
Small volume contraction and faster rate of polymerization.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Embodiment 1
The present embodiment provides a kind of polyurethane binary mercaptan prepolymer (odorlessness polyurethane polythiol monomer T1) and by its system
Standby obtained photosensitive resin (photopolymer system S1).
The composition (mass fraction) of photopolymer system S1 is as follows：Poly- propylhomoserin binary polythiol monomer T160%, four (second two
Alcohol) diacrylate 38%, hydroquinone 1%, 2- hydroxy-2-methyl-is to ethoxy ether phenylacetone 1%.
Odorlessness polyurethane polythiol monomer T1 and photopolymer system S1 can be prepared via a method which to obtain：
(1) synthesis of odorlessness polyurethane polythiol monomer T1：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the 6- bromine hexanol of 181g, the di lauric dibutyl of isophorone diisocyanate (IPDI) and 0.97g of 147g
Tin is dissolved in the acetone of 200mL, is reacted 5 hours at 50 DEG C, then puts into the polyethylene glycol (molecular weight 200) of 21g, is warming up to
75 DEG C the reaction was continued 6 hours, is tracked and is reacted with infrared spectroscopy, until 2230cm-1Place's absorption peak completely disappears.After the reaction was completed,
60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thioacetic acid potassium, add the n-butylamine of 175g,
Continue stirring 12 hours, ether is added, is washed 3 times with dilute hydrochloric acid, vacuum distillation removes solvent, finally obtains odorlessness polyurethane
The oligomer T1 of mercaptan.
(2) preparation of photopolymer system S1：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 200g
Four (ethylene glycol) diacrylates of alcohol monomer T1,126.7g, hydroquinone 3.3g.At room temperature, after magnetic agitation is uniform.Again
Photoinitiator 2 is added, 2- dimethoxy-acetophenone 3.3g continues to stir evenly, and be kept in dark place.
Embodiment 2
The present embodiment provides a kind of polyurethane binary mercaptan prepolymer (odorlessness polyurethane polythiol monomer T2) and by its system
Standby obtained photosensitive resin (photopolymer system S2).
The composition (mass fraction) of photopolymer system S2 is as follows：Poly- propylhomoserin binary polythiol monomer T250%, four (second two
Alcohol) diacrylate 30%, tripropoxy glycerol triacrylate 10%, hydroquinone 5%, 2- hydroxy-2-methyl-right
Ethoxy ether phenylacetone 5%.
Odorlessness polyurethane polythiol monomer T2 and photopolymer system S2 can be prepared via a method which to obtain：
(1) synthesis of odorlessness polyurethane polythiol monomer T2：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 150g, the di lauric dibutyl of methyl diphenylene diisocyanate (MDI) and 0.97g of 300g
Tin is dissolved in the acetone of 200mL, is reacted 5 hours at 50 DEG C, then puts into the polyethylene glycol (molecular weight 2000) of 290g, heating
To 75 DEG C, the reaction was continued 6 hours, is tracked and is reacted with infrared spectroscopy, until 2230cm-1Place's absorption peak completely disappears.Reaction is completed
Afterwards, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thioacetic acid potassium, add the positive fourth of 175g
Amine continues stirring 12 hours, and ether is added, is washed 3 times with dilute hydrochloric acid, and vacuum distillation removes solvent, and it is poly- to finally obtain odorlessness
The oligomer T2 of urethane mercaptan.
(2) preparation of photopolymer system S2：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 200g
Four (ethylene glycol) diacrylates of alcohol monomer T2,120g, the pentaerythritol tetraacrylate of 40g, hydroquinone 20g.In room
Under temperature, after magnetic agitation is uniform.Photoinitiator 2- dimethoxy-acetophenone 20g is added, continues to stir evenly, and be protected from light guarantor
It deposits.
Embodiment 3
The present embodiment provides a kind of polyurethane binary mercaptan prepolymer (odorlessness polyurethane polythiol monomer T3) and by its system
Standby obtained photosensitive resin (photopolymer system S3).
Odorlessness polyurethane polythiol monomer T3 and photopolymer system S3 can be prepared via a method which to obtain：
The composition (mass fraction) of photopolymer system S3 is as follows：Poly- propylhomoserin binary polythiol monomer T360%, four (second two
Alcohol) diacrylate 30%, tripropoxy glycerol triacrylate 6%, hydroquinone 2%, 2- hydroxy-2-methyl-right
Ethoxy ether phenylacetone 2%.
(1) synthesis of odorlessness polyurethane polythiol monomer T3：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the 6- bromine hexanol of 120g, the dicyclohexyl methyl hydride diisocyanate (HMDI) of 147g and two fourth of tin dilaurate of 0.2g
Ji Xi is dissolved in the acetone of 200mL, is reacted 7 hours at 50 DEG C, then puts into the polyethylene glycol ethanedioic acid ester (molecular weight of 620g
200), the reaction was continued 7 hours.After the reaction was completed, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive
Thioacetic acid potassium adds the n-butylamine of 175g, continues stirring 12 hours, and ether is added and washs 3 times, vacuum distillation removes molten
Agent finally obtains the oligomer T3 of odorlessness polyurethane mercaptan.
(2) preparation of photopolymer system S3：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 200g
The triethylene glycol dimethacrylate of alcohol monomer T3,100g, hydroquinone 6.7g.At room temperature, after magnetic agitation is uniform.Again
Photoinitiator 2 is added, 2- dimethoxy-acetophenone 6.7g continues to stir evenly, and be kept in dark place.
Embodiment 4
The present embodiment provides a kind of polyurethane binary mercaptan prepolymer (odorlessness polyurethane polythiol monomer T4) and by its system
Standby obtained photosensitive resin (photopolymer system S4).
Odorlessness polyurethane polythiol monomer T4 and photopolymer system S4 can be prepared via a method which to obtain：
The composition (mass fraction) of photopolymer system S4 is as follows：Polyurethane binary polythiol monomer T430%, four (second two
Alcohol) diacrylate 60%, tripropoxy glycerol triacrylate 6%, hydroquinone 2%, 2- hydroxy-2-methyl-right
Ethoxy ether phenylacetone 2%.
(1) synthesis of odorlessness polyurethane polythiol monomer T4：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 80g, toluene di-isocyanate(TDI) (2,3- toluene di-isocyanate(TDI)s and 2, the 4- toluene diisocyanate of 111g
Acid ester mixtures) (TDI) and 0.2g dibutyl tin dilaurate, be dissolved in the acetone of 200mL, reacted 7 hours at 50 DEG C,
The polyadipate hexylene glycol ester (molecular weight 2000) of 480g is put into again, and the reaction was continued 7 hours.After the reaction was completed, investment 60g is thio
Potassium acetate is stirred at room temperature 12 hours, is filtered to remove excessive thioacetic acid potassium, add the n-butylamine of 175g, continues stirring 12
Hour, ether is added and washs 3 times, vacuum distillation removes solvent, finally obtains the oligomer T3 of odorlessness polyurethane mercaptan.
(2) preparation of photopolymer system S4：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 100g
The triethylene glycol dimethacrylate of alcohol monomer T4,200g, the Dipentaerythritol Pentaacrylate of 20g, hydroquinone 6.7g.
At room temperature, after magnetic agitation is uniform.Photoinitiator 2 is added, 2- dimethoxy-acetophenone 6.7g continues to stir evenly, and
It is kept in dark place.
Embodiment 5
The present embodiment provides a kind of polyurethane binary mercaptan prepolymer (odorlessness polyurethane polythiol monomer T5) and by its system
Standby obtained photosensitive resin (photopolymer system S5).
Odorlessness polyurethane polythiol monomer T5 and photopolymer system S5 can be prepared via a method which to obtain：
The composition (mass fraction) of photopolymer system S5 is as follows：Poly- propylhomoserin binary polythiol monomer T540%, four (second two
Alcohol) diacrylate 50%, tripropoxy glycerol triacrylate 6%, hydroquinone 2%, 2- hydroxy-2-methyl-right
Ethoxy ether phenylacetone 2%.
(1) synthesis of odorlessness polyurethane polythiol monomer T5：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 150g, the dibutyl tin dilaurate of hexamethylene diisocyanate (HDI) and 0.2g of 100g,
It is dissolved in the acetone of 200mL, is reacted 7 hours at 0 DEG C, then put into the polypropylene glycol 200 of 91g, the reaction was continued 7 hours.Reaction
After the completion, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thioacetic acid potassium, adds 175g's
N-butylamine continues stirring 12 hours, and ether is added and washs 3 times, and vacuum distillation removes solvent, finally obtains odorlessness polyurethane sulphur
The oligomer T5 of alcohol.
(2) preparation of photopolymer system S5：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 150g
The triethylene glycol dimethacrylate of alcohol monomer T5,300g, hydroquinone 5g.At room temperature, after magnetic agitation is uniform.Again plus
Enter photoinitiator 2,2- dimethoxy-acetophenone 5g continues to stir evenly, and be kept in dark place.
Embodiment 6
The present embodiment provides a kind of polyurethane binary mercaptan prepolymer (odorlessness polyurethane polythiol monomer T6) and by its system
Standby obtained photosensitive resin (photopolymer system S6).
Odorlessness polyurethane polythiol monomer T6 and photopolymer system S6 can be prepared via a method which to obtain：
The composition (mass fraction) of photopolymer system S6 is as follows：Poly- propylhomoserin binary polythiol monomer T640%, four (second two
Alcohol) diacrylate 50%, tripropoxy glycerol triacrylate 6%, hydroquinone 2%, 2- hydroxy-2-methyl-right
Ethoxy ether phenylacetone 2%.
(1) synthesis of odorlessness polyurethane polythiol monomer T6：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the 6- bromine hexanol of 120g, the February of the 2 of 69g, 2,4- trimethyl cyclohexane -1,6- diisocyanate (TMHDI) and 0.2g
Dilaurylate is dissolved in the acetone of 200mL, is reacted 7 hours at 0 DEG C, then put into the polypropylene glycol (molecular weight of 290g
2000), the reaction was continued 7 hours.After the reaction was completed, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excess
Thioacetic acid potassium, add the n-butylamine of 175g, continue stirring 12 hours, be added ether wash 3 times, vacuum distillation remove it is molten
Agent finally obtains the oligomer T5 of odorlessness polyurethane mercaptan.
(2) preparation of photopolymer system S6：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 150g
The triethylene glycol dimethacrylate of alcohol monomer T6,300g, hydroquinone 5g.At room temperature, after magnetic agitation is uniform.Again plus
Enter photoinitiator 2,2- dimethoxy-acetophenone 5g continues to stir evenly, and be kept in dark place.
Embodiment 7
The composition (mass fraction) of photopolymer system S7 is as follows：Polyurethane binary polythiol monomer T750%, 1,6- oneself two
Alcohol norbornene 40%, trimethylolpropane tris (3-thiopropionate) 3%, polymerization inhibitor 3.5%, 2- hydroxy-2-methyl-is to hydroxyl
Ethyl ether phenylacetone 3.5%.
(1) synthesis of odorlessness polyurethane polythiol monomer T7：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 100g, the dibutyl tin dilaurate of two cyclohexyl diisocyanate (HMDI) and 2g of 100g is molten
In the acetone of 200mL, react 12 hours at room temperature, then put into the polyethylene terephthalate (molecular weight 200) of 312g,
The reaction was continued 7 hours.After the reaction was completed, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thio
Potassium acetate adds the n-butylamine of 200g, continues stirring 12 hours, and ether is added and washs 3 times, vacuum distillation removes solvent, most
The oligomer T7 of odorlessness polyurethane mercaptan is obtained afterwards.
(2) preparation of photopolymer system S7：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 150g
1, the 6- hexylene glycol norbornene of alcohol monomer T7,120g, butylated hydroxy anisole 10.5g.At room temperature, magnetic agitation is uniform
Afterwards.Photoinitiator 2 is added, 4,6- trimethylbenzoyls-ethyoxyl-phenyl phosphine oxide 10.5g continues to stir evenly, and
It is kept in dark place.
Embodiment 8
The composition (mass fraction) of photopolymer system S8 is as follows：Polyurethane binary polythiol monomer T830%, two urethanes two
Methacrylate 60%, third aoxidizes pentaerythrite tetravinyl ether 10%, butylated hydroxy anisole 5%, 2- hydroxyl -2- first
Base-is to ethoxy ether phenylacetone 5%.
(1) synthesis of odorlessness polyurethane polythiol monomer T8：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by 100 6- bromine hexanol, the '-diphenylmethane diisocyanate of 46g and the dibutyl tin dilaurate of 0.2g, it is dissolved in
It in the acetone of 200mL, is reacted 12 hours at 0 DEG C, then puts into the polyethylene terephthalate (molecular weight 2000) of 290g,
The reaction was continued 12 hours.After the reaction was completed, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thio
Potassium acetate adds the n-butylamine of 200g, continues stirring 12 hours, and ether is added and dilute hydrochloric acid washs 3 times, vacuum distillation removes
Solvent is removed, the oligomer T8 of odorlessness polyurethane mercaptan is finally obtained.
(2) preparation of photopolymer system S8：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned synthesis 100g
The two urethane dimethylacrylates of alcohol monomer T8,200g, the third oxidation pentaerythrite tetravinyl ether 33.3g, butylhydroxy fennel
Fragrant ether 16.7g.At room temperature, after magnetic agitation is uniform.Add photoinitiator 2,4,6- trimethylbenzoyl-ethyoxyl-
Phenyl phosphine oxide 16.7g continues to stir evenly, and is kept in dark place.
Embodiment 9
The composition (mass fraction) of photopolymer system S9 is as follows：Polyurethane binary polythiol monomer T935%, (alkenes list
Body) the 50%, third oxidation pentaerythrite tetravinyl ether 8%, butylated hydroxy anisole 3.5%, 2- hydroxy-2-methyl-is to hydroxyl second
Base ether phenylacetone (photoinitiator) 3.5%.
(1) synthesis of odorlessness polyurethane polythiol monomer T9：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 100g, the dibutyl tin dilaurate of '-diphenylmethane diisocyanate (TDI) and 0.2g of 100g,
It is dissolved in the acetone of 200mL, is reacted 7 hours at 50 DEG C, then put into the polytetrahydrofuran 200 of 27g, the reaction was continued 7 hours.Instead
After the completion of answering, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thioacetic acid potassium, adds 100g
N-butylamine, continue stirring 12 hours, be added ether wash 3 times, vacuum distillation remove solvent, finally obtain odorlessness polyurethane
The oligomer T9 of mercaptan.
(2) preparation of photopolymer system S9：In the beaker of 1000mL, by the poly- of above-mentioned synthesis odorlessness mercaptan 120g
The third oxidation pentaerythrite tetravinyl ether of propylhomoserin binary polythiol monomer T9,214g, to butylated hydroxy anisole 12g.In room temperature
Under, after magnetic agitation is uniform.Add photoinitiator 2,4,6- trimethylbenzoyls-ethyoxyl-phenyl phosphine oxide 12g, after
It is continuous to stir evenly, and be kept in dark place.
Embodiment 10
The composition (mass fraction) of photopolymer system S10 is as follows：Polyurethane binary polythiol monomer T1045%, 1,6- oneself
Glycol norbornene 50%, glycerol derivatives trinorbornene alkene 3%, hydroquinone 1%, 2- hydroxy-2-methyl-is to hydroxyethyl ether
Base phenylacetone (photoinitiator) 1%.
(1) synthesis of odorlessness polyurethane polythiol monomer T10：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 150g, 4, the 4- hexylmethane of 126g and the di lauric dibutyl of 0.2g
Tin is dissolved in the acetone of 200mL, is reacted 12 hours at room temperature, then put into 573 polytetrahydrofurans (molecular weight 2000), in room
Temperature is lower, and the reaction was continued 12 hours.After the reaction was completed, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive
Thioacetic acid potassium adds the n-butylamine of 250g, continues stirring 12 hours, and ether is added, and dilute hydrochloric acid washs 3 times, vacuum distillation
Solvent is removed, the oligomer T10 of odorlessness polyurethane mercaptan is finally obtained.
(2) preparation of photopolymer system S10：In the beaker of 1000mL, by the poly- propylhomoserin binary of above-mentioned synthesis 180g
1, the 6- hexylene glycol norbornene of polythiol monomer T10,200g, the glycerol derivatives trinorbornene alkene of 18g, hydroquinone 4.5g,
At room temperature, after magnetic agitation is uniform.Photoinitiator 2- hydroxy-2-methyl-is added to ethoxy ether phenylacetone 4.5g,
Continue to stir evenly, and is kept in dark place.
Embodiment 11
The composition (mass fraction) of photopolymer system S11 is as follows：Polyurethane binary polythiol monomer T1150%, 1,6- oneself
Glycol norbornene 40%, glycerol derivatives trinorbornene alkene 7%, hydroquinone 1.5%, 2- hydroxy-2-methyl-is to ethoxy
Ether phenylacetone (photoinitiator) 1.5%.
(1) synthesis of odorlessness polyurethane polythiol monomer T11：In the three neck round bottom flask of 1000mL, in nitrogen protection
Under, first by the ethylene bromohyrin of 120g, the dibutyl tin dilaurate of 106g isophorone diisocyanate and 0.2g is dissolved in
It in the acetone of 200mL, is reacted 7 hours at 50 DEG C, then puts into the polytetrahydrofuran (molecular weight 650) of polypropylene glycol 875g, after
Continuous reaction 7 hours.After the reaction was completed, 60g thioacetic acid potassium is put into, is stirred at room temperature 12 hours, is filtered to remove excessive thio second
Sour potassium adds the n-butylamine of 150g, continues stirring 12 hours, and ether is added and washs 3 times, vacuum distillation removes solvent, finally
Obtain the oligomer T11 of odorlessness polyurethane mercaptan.
(2) preparation of photopolymer system S11：In the beaker of 1000mL, by the poly- propylhomoserin binary sulphur of above-mentioned conjunction 150g
The glycerol derivatives trinorbornene alkene of alcohol monomer T11,1,6- hexylene glycol norbornene 120g, 52.5g, hydroquinone 4.5g.?
At room temperature, after magnetic agitation is uniform.Photoinitiator 2- hydroxy-2-methyl-is added to ethoxy ether phenylacetone 4.5g, after
It is continuous to stir evenly, and be kept in dark place.
Reference examples 1
This control group provides the number of carbon less than 12 polythiol monomers and its obtained photosensitive resin (photosensitive resin of preparation
System C1)
Binary polythiol monomer used in this control group is dithioglycol, and chemical formula is as follows：
The composition (mass fraction) of photopolymer system C1 is as follows：Dithioglycol 45%, four (ethylene glycol) divinyl ethers
45%, triethoxy trivinyl ether 5%, hydroquinone 2.5%, 2,6-Di-tert-butyl-4-methylphenol 2.5%.
The preparation of photopolymer system C1：In the beaker of 1000mL, by the dithioglycol of above-mentioned synthesis 200g, 200g
Four (ethylene glycol) divinyl ethers, the triethoxy trivinyl ether of 22g, hydroquinone 11g.At room temperature, magnetic agitation is equal
After even.Photoinitiator 2,6-Di-tert-butyl-4-methylphenol 11g is added, continues to stir evenly, and be kept in dark place.
Reference examples 2
This control group provides the number of carbon less than 12 polythiol monomers and its obtained photosensitive resin (photosensitive resin of preparation
System C2)
Binary polythiol monomer used in this control group is ethanthiol, and chemical formula is as follows：
The composition (mass fraction) of photopolymer system C2 is as follows：Ethanthiol 50%, four (ethylene glycol) two norbornene
40%, triethoxy trinorbornene alkene 5%, hydroquinone 2.5%, 2,6-Di-tert-butyl-4-methylphenol 2.5%.
The preparation of photopolymer system C2：In the beaker of 1000mL, by the dithioglycol of above-mentioned synthesis 200g, 160g
Four (ethylene glycol) two norbornene, the triethoxy trivinyl ether of 22g, hydroquinone 11g.At room temperature, magnetic agitation is equal
After even.Photoinitiator 2,6-Di-tert-butyl-4-methylphenol 11g is added, continues to stir evenly, and be kept in dark place.
Performance test：
By taking resin S1~S11 provided by the invention as an example (sample), the performance of resin is tested, and and reference examples into
Row control.Meanwhile 5 or more Odor Evaluations persons being selected to evaluate the smell of each sample.
(1) viscosity measures
Using rotational viscometer, the viscosity of photopolymer system is measured at 25 DEG C, revolving speed is 60 turns/min, the use of sample
Amount is 250mL, each sample parallel testing 3 times.
(2) tensile property
According to standard ISO 527-1, dumb-bell shape batten is printed using 3D printer, is surveyed on universal testing machine
Examination, rate of extension 10mm/min, each sample are measured in parallel 5 times, remember average value.
(3) notch impact strength
According to standard ISO 179,5 battens (size) are printed using 3D printer, on radial-boom impact tester
It is tested, pendulum energy is selected as 2.75J, and each sample parallel testing 5 times, remembers average value.
(4) shore hardness
According to standard ISO 868, batten is printed using 3D printer, is tested using Shore durometer, each sample
Product are surveyed 5 times in parallel, remember average value.
(5) solidify polymerization shrinkage
(6) in each embodiment of table 1 photopolymer system performance
It can be seen from the above result that being compared to small-molecular-weight polythiol monomer, it is prepared by polyurethane binary mercaptan prepolymer
The photosensitive resin arrived is without obvious smell, and obtained polymerization shrinkage is smaller.
Claims (10)
1. a kind of polyurethane binary mercaptan prepolymer, which is characterized in that shown in the prepolymer such as formula (I)：
Wherein, R is2≤n1≤ 6,
R1For
1≤n2≤ 100,1≤n3≤ 100,1≤n4≤ 100,1≤n5≤ 100,1≤n6≤100,1≤x≤3,1≤y≤3；
R2For
2. polyurethane binary mercaptan prepolymer according to claim 1, which is characterized in that the R1For
3. polyurethane binary mercaptan prepolymer according to claim 1, which is characterized in that the R2For
4. polyurethane binary mercaptan prepolymer according to claim 1, which is characterized in that describedPoint
Son amount is 200~2000 dalton；It is describedMolecular weight be 200~2000 dalton；It is describedMolecular weight be 200~2000 dalton；It is describedMolecular weight be 200~2000 dalton；It is describedMolecular weight be 200~2000 dalton.
5. the preparation method of any polyurethane binary mercaptan prepolymer of Claims 1 to 4, which is characterized in that the method
Include the following steps：
S1：Bromo monohydric alcohol is added in the isocyanates of binary and the mixed solution of dibutyl tin dilaurate, in 20~50
6~12h is reacted at DEG C；
The bromo monohydric alcohol is：
The binary isocyanates is：
The dibutyl tin dilaurate is：
S2：Poly-dihydric alcohol is added, 6~12h is reacted at 20~80 DEG C；The poly-dihydric alcohol is：
Wherein, 2≤n1≤ 6,1≤n2≤ 100,1≤n3≤ 100,1≤n4≤ 100,1≤n5≤ 100,1≤n6≤100,1≤x≤
3 and 1≤y≤3.
S3：Thioacetic acid potassium or ehtyl potassium xanthate is added, is evaporated under reduced pressure, washed up to the prepolymer after 6~12h of reaction.
6. preparation method according to claim 4, which is characterized in that vacuum distillation described in S3, the process washed are：Decompression
Solvent is distilled off and obtains head product；It will be evaporated under reduced pressure after head product dissolution, washing, drying；It is eventually adding n-butylamine reaction 6
~be filtered, washed afterwards for 24 hours, vacuum distillation obtains the prepolymer；The molar ratio of the n-butylamine and halogenated monohydric alcohol in S1 is 1
~3:1.
7. a kind of photocureable rapid shaping photosensitive resin composition, which is characterized in that the composition includes following quality point
Several components：Any polyurethane binary mercaptan oligomer 30~60% of Claims 1 to 4, vinyl monomer 30~60% are handed over
Join agent 0~10%, free radical photo-initiation 1~5%, stabilizer 1~5%.
8. composition according to claim 7, which is characterized in that the composition includes the component of mass fraction：Polyurethane
Binary mercaptan oligomer 50%, vinyl monomer 40%, crosslinking agent 7%, free radical photo-initiation 1.5%, stabilizer 1.5%.
9. composition according to claim 7, which is characterized in that the olefinic monomer is the acrylic acid containing 2 functional groups
The oligomer of esters, the oligomer of the methyl acrylic ester of 2 functional groups, 2 functional groups norbornene oligomer or 2
One of oligomer of vinyl ethers of a functional group is several.
10. any polyurethane binary mercaptan prepolymer of Claims 1 to 4 is preparing the application in photosensitive resin.
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| CN111450307A (en) * | 2020-04-08 | 2020-07-28 | 江南大学 | Preparation method of double-component medical adhesive |
| CN111558171A (en) * | 2020-05-18 | 2020-08-21 | 京东方科技集团股份有限公司 | Phototherapy device and method for manufacturing carbon quantum dots |
| CN111558171B (en) * | 2020-05-18 | 2022-08-12 | 京东方科技集团股份有限公司 | Phototherapy device and method for manufacturing carbon quantum dots |
| CN112759734A (en) * | 2020-12-28 | 2021-05-07 | 山东益丰生化环保股份有限公司 | Polythiourethane resin for 3D printing display material and synthetic method and application thereof |
| CN113307929A (en) * | 2021-06-15 | 2021-08-27 | 南京林业大学 | Reprocessable terpene-based polysiloxane waterborne polyurethane with self-repairing performance, preparation method and reprocessing application thereof |
| CN113307929B (en) * | 2021-06-15 | 2022-05-27 | 南京林业大学 | Reprocessable terpene-based polysiloxane waterborne polyurethane with self-repairing performance, preparation method and reprocessing application thereof |
| CN114989384A (en) * | 2022-03-28 | 2022-09-02 | 天津科技大学 | Lignin-based polyurethane polythiol prepolymer, photosensitive resin composition, and preparation methods and applications thereof |
| CN114989384B (en) * | 2022-03-28 | 2024-02-20 | 天津科技大学 | Lignin-based polyurethane polythiol prepolymer, photosensitive resin composition, and preparation methods and applications thereof |
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|---|---|
| CN110358040A (en) | 2019-10-22 |
| CN108892763B (en) | 2019-08-30 |
| CN110358040B (en) | 2021-06-18 |
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