CN109666113A - A kind of high dioptrics polymerizable composition, polymerizable composition and application - Google Patents
A kind of high dioptrics polymerizable composition, polymerizable composition and application Download PDFInfo
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- CN109666113A CN109666113A CN201811544456.9A CN201811544456A CN109666113A CN 109666113 A CN109666113 A CN 109666113A CN 201811544456 A CN201811544456 A CN 201811544456A CN 109666113 A CN109666113 A CN 109666113A
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- Prior art keywords
- polymerizable composition
- compound
- resin
- composition
- dioptrics
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- 239000000203 mixture Substances 0.000 title claims abstract description 83
- -1 isocyanate compound Chemical class 0.000 claims abstract description 56
- 239000012948 isocyanate Substances 0.000 claims abstract description 51
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims description 64
- 229920005989 resin Polymers 0.000 claims description 64
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229920002578 polythiourethane polymer Polymers 0.000 abstract description 4
- 239000012260 resinous material Substances 0.000 abstract description 3
- 238000002347 injection Methods 0.000 description 20
- 239000007924 injection Substances 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000006096 absorbing agent Substances 0.000 description 9
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- BVOMRRWJQOJMPA-UHFFFAOYSA-N 1,2,3-trithiane Chemical compound C1CSSSC1 BVOMRRWJQOJMPA-UHFFFAOYSA-N 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 102000004377 Thiopurine S-methyltransferases Human genes 0.000 description 2
- 108090000958 Thiopurine S-methyltransferases Proteins 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BZYMNYMQGORRDS-UHFFFAOYSA-L (acetyloxy-methyl-trimethylstannyloxystannyl) acetate Chemical compound CC(=O)O[Sn](C)(OC(C)=O)O[Sn](C)(C)C BZYMNYMQGORRDS-UHFFFAOYSA-L 0.000 description 1
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical class O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 1
- CZUGFVDLYSJDJR-UHFFFAOYSA-N 2-(1,3,5-trithian-2-yl)ethanethiol Chemical compound SCCC1SCSCS1 CZUGFVDLYSJDJR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000002834 transmittance Methods 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a kind of high dioptrics polymerizable composition, polymerizable compositions, comprising: multi-thioalcohol compound shown in isocyanate compound and formula (I)；Wherein, a, b, c independently selected from 1~3 integer；The isocyanate compound includes one or more of alicyclic isocyanate compound and aliphatic isocyanates compound.The present invention selects multi-thioalcohol compound combination specific isocyanate compound shown in specific formula (I) that high dioptrics polymerizable composition, polymerizable composition is prepared, polythiourethane resinous materials are further prepared, dyeability is excellent, can meet the over-all properties in terms of high refractive index, Abbe number, heat resistance and the intensity of production optical lens.
Description
Technical field
The present invention relates to optical component technical fields, more particularly, to a kind of high dioptrics polymerizable composition, polymerizable composition and answer
With.
Background technique
The high refractive power resin of polyurethanes being polymerized by isocyanates and multi-thiol is primarily used to make city at present
The resin lens sold on field, index of refraction range are broadly divided into MR-7, MR-8, MR-10 and MR-174 tetra- 1.60~1.74
Major class.Since the light transmittance of polyurethane material, index of refraction are high, manufactured eyeglass is frivolous and imaging clearly, in addition to this, excellent
Mechanical property make this material impact resistance is strong not lose toughness again, machinability is good, suitable for popular diamond cut glasses
Production.
The polyurethane based resin of the sulfur-bearing of prior art patent disclosure, the alicyclic isocyanic acid indicated using formula (2), (3)
Ester compounds can obtain high Abbe number, and plastic lens heat-resist simultaneously.
Although but above-mentioned polyurethane material has high refractive index and heat resistance, cannot reach higher refractive index.In addition,
Mechanical strength of resin, which not enough will lead to, occurs the problem ruptured, yield rate is low in resin processing；And if heat resistance is low, it will appear
There is the problem of crack when using after coating processing.Heat resistance is high, then the tendency with mechanical strength of resin decline therefore need to be into one
Refractive index, heat resistance, the intensity of step improved resin reach the polymerizable composition, polymerizable composition of process requirements.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of high dioptrics polymerizable composition, polymerizable composition, originally
Inventing the high dioptrics provided has the characteristics that index of refraction is high, heat resistance is high, intensity is high with polymerizable composition, polymerizable composition.
The present invention provides a kind of high dioptrics polymerizable composition, polymerizable compositions, comprising:
Multi-thioalcohol compound shown in isocyanate compound and formula (I)；
Wherein, a, b, c independently selected from 1~3 integer；The isocyanate compound includes alicyclic isocyanate
Close one or more of object and aliphatic isocyanates compound.
Preferably, multi-thioalcohol compound shown in the formula (I) specifically:
Preferably, the alicyclic isocyanate compound includes 2,5- bis- (isocyanate group) two ring-[2.2.1]-heptan
Bis- (isocyanate group) two ring-[the 2.2.1]-heptane of alkane, 2,6-, bis- (isocyanatomethyl) hexamethylenes of 1,3-, the bis- (isocyanides of 1,4-
Sour carbomethoxy) one or more of hexamethylene and isophorone diisocyanate；
The aliphatic isocyanates compound includes penta diisocyanate of 1,5-, hexamethylene diisocyanate and 1,8- pungent
One or more of diisocyanate.
Preferably, the composition further includes one or more polyol compounds.
Preferably, the ratio of multi-thioalcohol compound shown in the isocyanate compound and formula (I) is with NCO/ (SH+OH)
Functional group's molar ratio computing be 0.5~3.0.
The present invention provides a kind of high dioptrics resins, as including that composition described in above-mentioned technical proposal any one is high
Dioptrics polymerizable composition, polymerizable composition solidifies to obtain.
The present invention provides a kind of preparation methods of high dioptrics resin characterized by comprising
Multi-thioalcohol compound cast polymerization shown in isocyanate compound and formula (I) is formed into high dioptrics resin.
Preferably, the cast polymerization forms lens specifically: by the polymerizable composition, polymerizable composition, ultraviolet absorber, demoulding
Agent, antioxidant, catalyst and toner mixing, obtain mixture, successively pass through deaeration, casting, one-step solidification, demoulding and two
Secondary solidification obtains.
The present invention provides a kind of high dioptrics elements, as including composition dioptrics resin described in above-mentioned technical proposal
It constitutes.
The present invention provides a kind of lens, which is characterized in that the high dioptrics element described in above-mentioned technical proposal is made.
The present invention provides the applications that composition described in claim any one is used to prepare optical articles.
Compared with prior art, the present invention provides a kind of high dioptrics polymerizable composition, polymerizable compositions, comprising: isocyanation esterification
Close multi-thioalcohol compound shown in object and formula (I)；Wherein, a, b, c independently selected from 1~3 integer；The isocyanates chemical combination
Object includes one or more of alicyclic isocyanate compound and aliphatic isocyanates compound.To reach index of refraction
Purpose high, heat resistance is high, intensity is high, the present invention are used while using isocyanates higher with glass transition temperature
Equally the sulfur heterocyclic ring multi-thiol containing alicyclic structure and isocyanates form high refractive power polymerizable composition, polymerizable composition.Present invention selection
High dioptrics polymerism group is prepared in multi-thioalcohol compound combination specific isocyanate compound shown in specific formula (I)
Object is closed, polythiourethane resinous materials are further prepared, dyeability is excellent, can meet the high refraction of production optical lens
Over-all properties in terms of rate, Abbe number, heat resistance and intensity.
Specific embodiment
The present invention provides a kind of high dioptrics polymerizable composition, polymerizable composition and application, those skilled in the art can use for reference this
Literary content, is suitably modified realization of process parameters.In particular, it should be pointed out that all similar substitutions and modifications are to art technology
It is it will be apparent that they shall fall within the protection scope of the present invention for personnel.Method of the invention and application by compared with
Good embodiment is described, related personnel obviously can not depart from the content of present invention, in spirit and scope to methods herein
It is modified or appropriate changes and combinations with application, carrys out implementation and application the technology of the present invention.
The present invention provides a kind of high dioptrics polymerizable composition, polymerizable compositions, comprising:
Multi-thioalcohol compound shown in isocyanate compound and formula (I)；
Wherein, a, b, c independently selected from 1~3 integer；Specifically, a can be 1,2,3；B can be 1,2,3；C can be with
It is 1,2,3.
The isocyanate compound includes in alicyclic isocyanate compound and aliphatic isocyanates compound
It is one or more of.
In this present invention, multi-thioalcohol compound shown in the formula (I) is preferred specifically:
Multi-thioalcohol compound shown in the formula (I) is most preferably:
According to the present invention, the isocyanate compound includes alicyclic isocyanate compound and aliphatic isocyanates
One or more of compound.
Specifically, the alicyclic isocyanate compound preferably includes bis- (isocyanate group) two rings-of 2,5-
Bis- (isocyanate group) two ring-[the 2.2.1]-heptane of [2.2.1]-heptane, 2,6-, bis- (isocyanatomethyl) hexamethylenes of 1,3-,
1,4- bis- (isocyanatomethyl) one or more of hexamethylenes and isophorone diisocyanate；It is bis- more preferably to include 2,5-
(isocyanate group) two ring-[2.2.1]-heptane and bis- (isocyanate group) two ring-[the 2.2.1]-heptane of 2,6-
The aliphatic isocyanates compound preferably includes penta diisocyanate of 1,5-, hexamethylene diisocyanate and 1,
One or more of pungent diisocyanate of 8-.
The present invention for said components source without limit, it is well known to those skilled in the art commercially available.
According to the present invention, the ratio of multi-thioalcohol compound shown in the isocyanate compound and formula (I) is with NCO/ (SH
+ OH) functional group's molar ratio computing be preferably 0.5~3.0；In the range of more preferably 0.8~1.5.
By the specific combination of above compound, obtained by being solidified with high refractive index, high Abbe number, high heat resistance
Property, high intensity and the excellent feature of dyeability, to be suitable for the processing of lens material.
In addition, in order to improve heat resistance of resin etc., can also be included in multi-thioalcohol compound shown in above-mentioned formula (I) with
Outer active dydrogen compounds can add other active hydrides again, and specially polyalcohol etc. has the work reacted with isocyanates
The compound, such as glycerol, ethylene glycol, mercaptoethanol etc. of property hydrogen.
The present invention provides a kind of preparation methods of high dioptrics polymerizable composition, polymerizable composition, comprising:
Multi-thioalcohol compound shown in isocyanate compound and formula (I) is mixed.
Concrete component and proportion of the present invention for multi-thioalcohol compound shown in the isocyanate compound and formula (I)
Above-mentioned to be clearly described, details are not described herein.
The present invention provides a kind of high dioptrics resins, as including that composition described in above-mentioned technical proposal any one is high
Dioptrics polymerizable composition, polymerizable composition solidifies to obtain.
The present invention is above-mentioned for the concrete component and proportion of above-mentioned high dioptrics polymerizable composition, polymerizable composition have been had clearly
Description, details are not described herein.
The present invention provides a kind of preparation methods of high dioptrics resin characterized by comprising
Multi-thioalcohol compound cast polymerization shown in isocyanate compound and formula (I) is formed into high dioptrics resin.
The present invention does not limit the order by merging of multi-thioalcohol compound shown in isocyanate compound and formula (I) especially
It is fixed, mixed proportion is determined with functional group's molar ratio of NCO/ (SH+OH), proportional region is 0.5~3.0, preferably 0.8~1.5
In the range of, further preferably in 0.85-1.15, within this range, the available resin for being suitable as lens material and using.
The refractive index of resin can according to need herein, by adjust isocyanate composition in isocyanate compound and
The type and composition ratio of active dydrogen compounds are controlled.Resin especially in the present embodiment is high refractive index, excellent
Select available 1.65 or more, the isocyanate compound of the resin of more preferable 1.69 or more refractive index and active dydrogen compounds
Combination and composition ratio.
The heat resistance of high dioptrics material of the invention is preferably 90 DEG C or more, is more preferably 95 DEG C or more, more preferably
100℃。
The refractive index of the polythiourethane resinoid obtained using preparation method of the invention is high, at the same have it is heat-resist,
Impact resistance and the excellent feature of dyeability.
In addition, when solidifying using polymerizable composition, polymerizable composition of the invention chain can be added using the well known method of forming according to purpose
The various substances such as extension agent, crosslinking agent, light stabilizer, ultraviolet absorber, antioxidant, anti-coloring agent.Polysulfide ammonia of the invention
Esters lens usually are polymerize to obtain by cast molding.
According to the present invention, it is preferred that the cast polymerization forms lens specifically:
The polymerizable composition, polymerizable composition, ultraviolet absorber, release agent, antioxidant, catalyst and toner are mixed, mixed
Object is closed, is successively obtained by deaeration, casting, one-step solidification, demoulding and secondary curing (annealing).
In order to adjust the reaction speed of polymerizable composition, polymerizable composition, well known catalysts can be added.Such as polyurethanes is urged
Agent dibutyl tin dilaurate, dibutyl tin dichloride, dimethyltin chloride, tetramethyl diacetoxy distannoxane etc.
Tin compound.The additive amount of catalyst is preferentially within the scope of 0.001wt%~1wt% of relative combination total monomer weight.
Ultraviolet absorber, release agent and toner of the present invention are preferably specially UV327, laureth and blue
Agent.
Its additive amount is preferably respectively 0.1%, 0.3% and 0.004%.
Specifically, mixed liquor is made in mixing above compound, mixed liquor method appropriate is defoamed as needed
Afterwards, the defoaming is preferably specially 1~1.5h of vacuum defoamation under -0.1~-0.09Mpa；
It injects in mold, usually slowly heating from low temperature to high temperature makes its polymerization.Polymerizing condition because use monomeric species,
Catalyst type, the difference of the shape of additive amount, injection mould and have very big difference, therefore can not limit, but the temperature of thermal polymerization
At -20~200 DEG C, polymerization time is 1~100 hour.Polymerization herein is specially by isocyanates, polythiol and several additives
After mixing, the process of heating is polymerization process.
Usually start under 5~40 DEG C of range temperatures, be to slowly warm up to 80~130 DEG C of range, heating time is 1~4
Hour.
After completing heating process, polymer is cooled to 70~80 DEG C of rear demoulding processing, anneals and is gathered at 120 DEG C
Resin lens after conjunction.
The present invention provides a kind of high dioptrics elements, as including composition dioptrics resin described in above-mentioned technical proposal
It constitutes.
The present invention provides a kind of lens, which is characterized in that the high dioptrics element described in above-mentioned technical proposal is made.
The lens being formed by curing by polymerizable composition, polymerizable composition of the invention can be used well known method and carry out subsequent add
Firmly, plated film etc. is handled, and then grinding back surface, antistatic process, light modulation processing can be carried out as needed etc..
Due to the plastic lens light weight and quality is thin, especially dioptric as the lens of glasses
Mirror is very suitable for, and can be used for diamond cut production method popular at present.
The present invention provides the applications that composition described in above-mentioned technical proposal any one is used to prepare optical articles.
The present invention provides a kind of high dioptrics polymerizable composition, polymerizable compositions, comprising: shown in isocyanate compound and formula (I)
Multi-thioalcohol compound；Wherein, a, b, c independently selected from 1~3 integer；The isocyanate compound includes alicyclic different
One or more of cyanate esters and aliphatic isocyanates compound.The present invention selects shown in specific formula (I)
High dioptrics polymerizable composition, polymerizable composition is prepared in multi-thioalcohol compound combination specific isocyanate compound, is further prepared into
To polythiourethane resinous materials, dyeability is excellent, can meet the production high refractive index of optical lens, Abbe number, heat resistance and
Over-all properties in terms of intensity.Material of the cured resin of polymerizable composition, polymerizable composition of the invention particularly suitable as high dioptrics product
Material, such as all have broad application prospects in fields such as eyeglass, camera guns.
In order to further illustrate the present invention, with reference to embodiments to a kind of high dioptrics polymerism provided by the invention
Composition and application are described in detail.The lens that polymerizable composition, polymerizable composition through the invention obtains make a service test and comment
Valence.Performance test refractive index, Abbe number, heat resistance, intensity are index.
Embodiment 1
At 20 DEG C, mixed being dissolved in the 2 of 69.3g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane
0.12g is as the dimethyltin chloride of catalyst, 0.06g laureth, 0.05g ultraviolet absorbing agent.Add 7.69g tri-
Glycol is stirred 0.5 hour, is made it completely dissolved.2,4, the 6- tri-thiol methyl-1s of 56.27g are added, 3,5- trithianes make it
Mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, after feed liquid bubble-free, 1 μm of PTFE filter mistake is utilized
It crosses, injects in the injection mould made of glass mold.Injection mould is put into baking oven, was to slowly warm up to through 22 hours from 25 DEG C
120 DEG C are polymerize.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.Further by gained resin at 120 DEG C
Annealing 3.5 hours.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.707, and Abbe number (ve) is 39,
Heat resistance is 112 DEG C, and it is 1000g or more that the 50% of impact resistance, which does not destroy weight, evaluation result is shown in table 1.
Embodiment 2
At 20 DEG C, mixed being dissolved in the 2 of 86.91g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane
0.12g is as the dimethyltin chloride of catalyst, 0.06g laureth, 0.05g ultraviolet absorbing agent.Add 5.83g second
Glycol is stirred 0.5 hour, is made it completely dissolved.2,4,6- tri- (the mercapto ethyls) -1 of addition 64.66g, 3,5- trithianes,
14.95g 2,5- bis- (thiopurine methyltransferase)-Isosorbide-5-Nitrae-dithiane, make its mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour,
After feed liquid bubble-free, using 1 μm of PTFE filter transition, inject in the injection mould made of glass mold.By injection mould
It is put into baking oven, was to slowly warm up to 120 DEG C from 25 DEG C through 22 hours and is polymerize.After polymerization, it is cooled to 70~80 DEG C and takes off
Mould obtains resin.Further gained resin is annealed 3.5 hours at 120 DEG C.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.699, and Abbe number (ve) is 30,
Heat resistance is 99 DEG C, and it is 1000g or more that the 50% of impact resistance, which does not destroy weight, evaluation result is shown in table 1.
Embodiment 3
It is at 20 DEG C, the 2 of 50.0g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane and 15.75g six are sub-
Methyl diisocyanate dissolution mixing, be added 0.11g as the dimethyltin chloride of catalyst, 0.06g laureth,
0.05g ultraviolet absorbing agent sufficiently dissolves.6.21g glycerol is added, stirs 0.5 hour, makes it completely dissolved.It is added 30.16g's
2,4,6- tri-thiol methyl-1s, the 2 of 3,5- trithianes and 22.96g, 4,6- tri-thiol ethyls -1,3,5- trithiane make its mixing
Dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, after feed liquid bubble-free, 1 μm of PTFE filter transition, note are utilized
Enter in the injection mould made of glass mold.Injection mould is put into baking oven, be to slowly warm up to from 25 DEG C within 22 hours 120 DEG C into
Row polymerization.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.Gained resin is further annealed 3.5 at 120 DEG C
Hour.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.689, and Abbe number (ve) is 38,
Heat resistance is 95 DEG C, and it is 1000g or more that the 50% of impact resistance, which does not destroy weight, evaluation result is shown in table 1.
Embodiment 4
At 20 DEG C, by the 2 of 66.0g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane and five methylene of 15.6g
After group diisocyanate mixing, dimethyltin chloride of the 0.14g as catalyst, 0.06g laureth, 0.05g is added
Ultraviolet absorbing agent.3.69g mercaptoethanol is added, stirs 0.5 hour, makes it completely dissolved.The 2,4,6- tri- of 77.59g is added
Mercaptoethyl -1,3,5- trithiane make its mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, feed liquid bubble-free
Afterwards, it using 1 μm of PTFE filter transition, injects in the injection mould made of glass mold.Injection mould is put into baking oven,
120 DEG C were to slowly warm up to from 25 DEG C through 22 hours to be polymerize.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.
Further gained resin is annealed 3.5 hours at 120 DEG C.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.695, and Abbe number (ve) is 35,
Heat resistance is 107 DEG C, and it is 1000g or more that the 50% of impact resistance, which does not destroy weight, evaluation result is shown in table 1.
Embodiment 5
At 20 DEG C, by the 2 of 63.1g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane and five methylene of 15.6g
After group diisocyanate mixing, dimethyltin chloride of the 0.14g as catalyst, 0.06g laureth, 0.05g is added
Ultraviolet absorbing agent.3.69g glycerol is added, stirs 0.5 hour, makes it completely dissolved.Formula III, formula IV and the formula of 71.69g is added
The mixture trithiane of V composition, makes its mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, feed liquid bubble-free
Afterwards, it using 1 μm of PTFE filter transition, injects in the injection mould made of glass mold.Injection mould is put into baking oven,
120 DEG C were to slowly warm up to from 25 DEG C through 22 hours to be polymerize.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.
Further gained resin is annealed 3.5 hours at 120 DEG C.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.688, and Abbe number (ve) is 36,
Heat resistance is 105 DEG C, and it is 1000g or more that the 50% of impact resistance, which does not destroy weight, evaluation result is shown in table 1.
Comparative example 1
At 20 DEG C, 0.10g is added into the 2 of 62.2g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane and makees
For the dimethyltin chloride of catalyst, 0.06g laureth, 0.05g ultraviolet absorbing agent mixed dissolution.Add 7.69g
Triethylene glycol is stirred 0.5 hour, is made it completely dissolved.4- mercapto methyl -1,8- dimercapto -3,6- the dithia that 25.9g is added is pungent
Alkane and 11.9g 2 mercapto ethanol, make its mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, feed liquid bubble-free
Afterwards, it using 1 μm of PTFE filter transition, injects in the injection mould made of glass mold.Injection mould is put into baking oven,
120 DEG C were to slowly warm up to from 25 DEG C through 20 hours to be polymerize.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.
Further gained resin is annealed 3.5 hours at 120 DEG C.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.600, and Abbe number (ve) is 41,
Heat resistance is 118 DEG C, evaluation result is shown in table 1.
Comparative example 2
At 20 DEG C, 0.03g is added into the 2 of 50.6g, 5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane and makees
For the dimethyltin chloride of catalyst, 0.09g laureth, 0.05g ultraviolet absorbing agent mixed dissolution.Add 7.69g
Triethylene glycol is stirred 0.5 hour, is made it completely dissolved.4- mercapto methyl -1,8- dimercapto -3,6- the dithia that 25.5g is added is pungent
Alkane and 23.9g pentaerythrite (3-thiopropionate), make its mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour,
After feed liquid bubble-free, using 1 μm of PTFE filter transition, inject in the injection mould made of glass mold.By injection mould
It is put into baking oven, was to slowly warm up to 120 DEG C from 25 DEG C through 20 hours and is polymerize.After polymerization, it is cooled to 70~80 DEG C and takes off
Mould obtains resin.Further gained resin is annealed 3.5 hours at 120 DEG C.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.594, and Abbe number (ve) is 41,
Heat resistance is 125 DEG C, evaluation result is shown in table 1.
Comparative example 3
At 20 DEG C, it is added into the m-xylylene diisocyanate and 10.8g hexa-methylene isocyanates of 43.6g
0.03g is as the dimethyltin chloride of catalyst, 0.09g laureth, 0.05g ultraviolet absorbing agent mixed dissolution.Add
Add 4.96g glycerol, stirs 0.5 hour, make it completely dissolved.4- mercapto methyl -1,8- dimercapto-the 3,6- two of 51.34g is added
Thia octane makes its mixed dissolution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, after feed liquid bubble-free, 1 μm is utilized
PTFE filter transition is injected in the injection mould made of glass mold.Injection mould is put into baking oven, through 18 hours from 25
DEG C being to slowly warm up to 120 DEG C is polymerize.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.Further by gained
Resin is annealed 3.5 hours at 120 DEG C.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.666, and Abbe number (ve) is 27,
Heat resistance is 116 DEG C, evaluation result is shown in table 1.
Comparative example 4
At 20 DEG C, dimethyl two of the 0.03g as catalyst is added to the m-xylylene diisocyanate of 42.5g
Stannic chloride, 0.05g laureth, 0.05g ultraviolet absorbing agent mixed dissolution.5.66g mercaptoethanol is added, stirring 0.5 is small
When, it makes it completely dissolved.4- mercapto methyl -1,8- dimercapto -3,6- dithia octane of 48.31g is added, keeps its mixing molten
Solution.In the case where vacuum degree is -0.095MPa deaeration 1 hour, after feed liquid bubble-free, 1 μm of PTFE filter transition, injection are utilized
In the injection mould made of glass mold.Injection mould is put into baking oven, was to slowly warm up to 120 DEG C of progress from 25 DEG C through 18 hours
Polymerization.After polymerization, it is cooled to 70~80 DEG C of demouldings and obtains resin.Further gained resin is annealed at 120 DEG C 3.5 small
When.
Gained resin is the high good resin of colorless and transparent property, and refractive index (ne) is 1.665, and Abbe number (ve) is 31,
Heat resistance is 90 DEG C, evaluation result is shown in table 1.
Table 1
A-1:2,5 (6)-bis- (isocyanate group) two ring-[2.2.1]-heptane
A-2: hexamethylene diisocyanate
A-3: pentamethylene isocyanates
A-4: m-xylylene diisocyanate
B-1:2,4,6- tri-thiol methyl-1,3,5- trithiane
B-2:2,5- bis- (thiopurine methyltransferase) -1,4- dithiane
B-3:4- mercapto methyl -1,8- dimercapto -3,6- dithia octane
B-4: pentaerythrite (3-thiopropionate)
B-5:2,4,6- tri-thiol ethyl -1,3,5- trithiane
B-6: the mixture trithiane that formula III, formula IV and formula V form
C-1: triethylene glycol
C-2: ethylene glycol
C-3: glycerol
C-4: mercaptoethanol
As can be seen from the above results, in Examples 1 to 4, using alicyclic isocyanate and combination, there are three mercapto alkane
The polymerizable composition, polymerizable composition of the mercaptan combination of the trithiane ring structure of base, the resin being formed by curing have high refractive power number and Gao Abei
Value, and have fabulous heat resistance and intensity.And in comparative example 1~4, although Abbe number, heat resistance and intensity difference can be obtained
Few material, but index of refraction is much smaller than the resin in embodiment.Therefore, the cured resin of polymerizable composition, polymerizable composition of the invention is special
It is not suitable as the material of high dioptrics product, such as before having wide application in fields such as eyeglass, camera guns
Scape.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of high dioptrics polymerizable composition, polymerizable composition characterized by comprising
Multi-thioalcohol compound shown in isocyanate compound and formula (I)；
Wherein, a, b, c independently selected from 1~3 integer；The isocyanate compound includes alicyclic isocyanate compound
One or more of with aliphatic isocyanates compound.
2. composition according to claim 1, which is characterized in that multi-thioalcohol compound shown in the formula (I) specifically:
3. composition according to claim 1, which is characterized in that the alicyclic isocyanate compound includes 2,5- bis-
Bis- (isocyanate group) two ring-[the 2.2.1]-heptane of (isocyanate group) two ring-[2.2.1]-heptane, 2,6-, the bis- (isocyanides of 1,3-
Sour carbomethoxy) hexamethylene, 1,4- bis- (isocyanatomethyl) one or more of hexamethylenes and isophorone diisocyanate；
The aliphatic isocyanates compound includes penta diisocyanate of 1,5-, hexamethylene diisocyanate and 1,8- Xin Eryi
One or more of cyanate.
4. composition according to claim 1, which is characterized in that the composition further includes polyol compound.
5. composition according to claim 4, which is characterized in that more shown in the isocyanate compound and formula (I)
The ratio of mercaptan compound is with functional group's molar ratio computing of NCO/ (SH+OH) for 0.5~3.0.
6. a kind of high dioptrics resin, which is characterized in that as including the folding of composition height described in Claims 1 to 5 any one
Optics polymerizable composition, polymerizable composition solidifies to obtain.
7. a kind of preparation method of high dioptrics resin characterized by comprising
Multi-thioalcohol compound cast polymerization shown in isocyanate compound and formula (I) is formed into high dioptrics resin.
8. a kind of high dioptrics element, which is characterized in that as including the high dioptrics resin structure of composition described in claim 5
At.
9. a kind of lens, which is characterized in that by including that high dioptrics element according to any one of claims 8 is made.
10. the application that composition described in Claims 1 to 5 any one is used to prepare optical articles.
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| US3297635A (en) * | 1963-05-31 | 1967-01-10 | Shell Oil Co | Process for curing polyepoxides and resulting products |
| JP2003160631A (en) * | 2001-11-28 | 2003-06-03 | Hoya Corp | Optical product prepared from thiol compound |
| CN1421444A (en) * | 2001-11-28 | 2003-06-04 | 保谷株式会社 | Thiol compound, process for producing the same compound and optical products containing the same compound |
| CN1459031A (en) * | 2000-09-14 | 2003-11-26 | 三菱瓦斯化学株式会社 | Composition for optical material |
| CN109503549A (en) * | 2018-11-27 | 2019-03-22 | 山东益丰生化环保股份有限公司 | A kind of preparation method and applications of the multi-thioalcohol compound of the structure of trithiane containing 1,3,5- |
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2018
- 2018-12-17 CN CN201811544456.9A patent/CN109666113A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3297635A (en) * | 1963-05-31 | 1967-01-10 | Shell Oil Co | Process for curing polyepoxides and resulting products |
| CN1459031A (en) * | 2000-09-14 | 2003-11-26 | 三菱瓦斯化学株式会社 | Composition for optical material |
| JP2003160631A (en) * | 2001-11-28 | 2003-06-03 | Hoya Corp | Optical product prepared from thiol compound |
| CN1421444A (en) * | 2001-11-28 | 2003-06-04 | 保谷株式会社 | Thiol compound, process for producing the same compound and optical products containing the same compound |
| CN109503549A (en) * | 2018-11-27 | 2019-03-22 | 山东益丰生化环保股份有限公司 | A kind of preparation method and applications of the multi-thioalcohol compound of the structure of trithiane containing 1,3,5- |
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Application publication date: 20190423 |