DE4017941A1 - Hardenable compsn. for use as adhesive, encapsulating or casting resin - comprises di:isocyanate, poly:thiol, and catalyst - Google Patents
Hardenable compsn. for use as adhesive, encapsulating or casting resin - comprises di:isocyanate, poly:thiol, and catalystInfo
- Publication number
- DE4017941A1 DE4017941A1 DE19904017941 DE4017941A DE4017941A1 DE 4017941 A1 DE4017941 A1 DE 4017941A1 DE 19904017941 DE19904017941 DE 19904017941 DE 4017941 A DE4017941 A DE 4017941A DE 4017941 A1 DE4017941 A1 DE 4017941A1
- Authority
- DE
- Germany
- Prior art keywords
- curable composition
- composition according
- isocyanate
- formula
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 239000012948 isocyanate Substances 0.000 title claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 title claims description 10
- 239000000853 adhesive Substances 0.000 title abstract description 9
- 230000001070 adhesive effect Effects 0.000 title abstract description 9
- 150000003573 thiols Chemical class 0.000 title abstract description 7
- 238000005266 casting Methods 0.000 title abstract description 3
- 239000011347 resin Substances 0.000 title abstract description 3
- 229920005989 resin Polymers 0.000 title abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 34
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 7
- -1 aliphatic thiols Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- QKTDEIQCZDTQFH-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1,1-bis(sulfanyl)ethanol Chemical compound OCCOCCOCC(O)(S)S QKTDEIQCZDTQFH-UHFFFAOYSA-N 0.000 claims description 2
- YDQJXVYGARVLRT-UHFFFAOYSA-N Lepidine Natural products C=1C=CC(CC=2NC=CN=2)=CC=1OC=1C(OC)=CC=CC=1CC1=NC=CN1 YDQJXVYGARVLRT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012038 nucleophile Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 9
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000011521 glass Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 3
- 239000002904 solvent Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 6
- ZCJFQRUOMXMBBL-UHFFFAOYSA-N 3h-dithiole;2-[2-(2-hydroxyethoxy)ethoxy]ethanol Chemical compound C1SSC=C1.OCCOCCOCCO ZCJFQRUOMXMBBL-UHFFFAOYSA-N 0.000 description 5
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 4
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- GFTGBNWAHPDDAX-UHFFFAOYSA-N 2-[[dimethyl(2-sulfanylethyl)silyl]oxy-dimethylsilyl]ethanethiol Chemical compound SCC[Si](C)(C)O[Si](C)(C)CCS GFTGBNWAHPDDAX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum 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
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Die Erfindung bezieht sich auf eine härtbare Zusammensetzung, die in hinreichend kurzer Zeit vom flüssigen in den festen Zustand übergeht. Die erfindungsgemäße härtbare Zusammensetzung gestattet die Anwendung als dünner Film oder als Polymerkörper. Die härtbare Zusammensetzung ergibt transparente glasklare Produkte und eignet sich deshalb besonders in der optischen Industrie als Adhesiv, Fassungsklebstoff oder als Umhüllungsmaterial in der Mikroelektronik. Die härtbare Zusammensetzung ist ferner geeignet als Klebstoff für die feste Verbindung der unterschiedlichsten Materialien miteinander wie Kunststoff/Kunststoff, Kunststoff/Glas, Kunststoff/ Metall, Metall/Metall, Glas/Metall, Keramik etc. Die härtbare Zusammensetzung eignet sich deshalb für die Anwendung in der plastverarbeitenden Industrie, Möbelindustrie, im Maschinen- und Fahrzeugbau.The invention relates to a curable composition, which in a short time from the liquid to the solid state passes. The curable composition of the invention allows the application as a thin film or as a polymer body. The curable Composition results transparent transparent products and is suitable Therefore, especially in the optical industry as an adhesive, Cement adhesive or as a wrapping material in microelectronics. The curable composition is also useful as an adhesive for the firm connection of the most different materials with each other like plastic / plastic, plastic / glass, plastic / Metal, metal / metal, glass / metal, ceramic etc. The curable composition is therefore suitable for use in the plastic processing Industry, furniture industry, in machine and vehicle construction.
Aus der niedermolekularen organischen Chemie ist bekannt, daß sich Isocyanate mit Mercaptanen umsetzen und zu Thiourethanen führen. Die Reaktion ist durch Basen katalysierbar. Weiter ist bekannt, daß Diisocyanate mit difunktionellen Mercaptanen in Lösung, bevorzugt in Chlorbenzen oder o-Dichlorbenzen, zu Polymeren führen. Die Polymere werden als weiße Pulver beschrieben, die im Licht zur Zersetzung neigen und thermisch weniger beständig sind (E. Dyer, D. W. Osborne: J. Polymer Sci. 47 [1960], 361-371). Die Umsetzung erfordert darüber hinaus erhöhte Temperatur und lange Reaktionszeiten.From the low molecular weight organic chemistry is known that Isocyanates react with mercaptans and to thiourethanes to lead. The reaction is catalyzable by bases. Next is known that diisocyanates with difunctional mercaptans in solution, preferably in chlorobenzene or o-dichlorobenzene, to polymers to lead. The polymers are described as white powders in the Light tend to decompose and thermally less resistant (E. Dyer, D.W. Osborne: J. Polymer Sci. 47 [1960], 361-371). The implementation also requires elevated temperature and long reaction times.
Für eine Anwendung in den einleitend genannten Gebieten sind filmbildende Eigenschaften erforderlich, und es macht sich eine lösungsmittelfreie Substanzpolymerisation notwendig. Beides ist bisher nicht bekannt. Es ist auch nicht bekannt, wie der Polymerbildungsprozeß so gesteuert werden kann, daß er bei Raumtemperatur innerhalb technisch interessanter kurzer Reaktionszeiten abläuft und dabei der Übergang flüssige Mischung Polymerfilm erfolgt. For an application in the aforementioned areas are film-forming properties required, and it gets one solvent-free bulk polymerization necessary. Both are not known yet. It is also not known how the polymer formation process can be controlled so that it is at room temperature within technically interesting short reaction times Expires while doing the transition liquid mixture polymer film he follows.
Ziel der Erfindung ist die Schaffung einer härtbaren Zusammensetzung, die in anwendungstechnisch interessant kurzen Härtungszeiten lösungsmittelfrei vom flüssigen in den festen Zustand übergehen. Dabei sollen die flüssigen härtbaren Mischungen bei Raumtemperatur ausreichende Lagerstabilität aufweisen und die ausgehärteten Proben filmbildend sein.The aim of the invention is to provide a curable composition, in terms of application, interesting short curing times solvent-free from the liquid to the solid state pass. The purpose of the liquid curable mixtures Room temperature have sufficient storage stability and the cured samples be film-forming.
Die Aufgabe der Erfindung besteht darin, härtbare Zusammensetzungen zu schaffen, die bei langen Verarbeitungszeiten kurze Aushärtungszeiten benötigen. Überraschend und nicht vorhersehbar wurde gefunden, daß auf der Basis der Polyadditionsreaktion von höherfunktionellen Isocyanaten mit höherfunktionellen Thiolen härtbare Zusammensetzungen erhalten werden, die sich auszeichnen durch sehr gute Haftung an verschiedensten Materialien wie Glas, Quarz, CaF₂, Kunststoffen wie Polyurethan, Polyethern, Polyestern, Epoxidpolymeren etc. und die kurze Fixierzeiten und sehr lange Verarbeitungszeiten besitzen.The object of the invention is curable compositions to provide short cure times for long processing times need. Surprising and unpredictable was found to be based on the polyaddition reaction of higher functional isocyanates with higher functional thiols be obtained curable compositions which are distinguished due to very good adhesion to various materials such as glass, Quartz, CaF₂, plastics such as polyurethane, polyethers, polyesters, Epoxy polymers etc. and the short fixing times and very long Have processing times.
Erfindungsgemäß wird die Aufgabe durch eine härtbare Zusammensetzung so gelöst, daß sie Diisocyanate und Thiole der Funktionalität f≧2 sowie Katalysatoren enthält und rasch, bereits bei Raumtemperatur von dem flüssigen in den festen Zustand übergeht. Die ausgehärteten Mischungen der aliphatischen Dithiole und aliphatischen Diisocyanate besitzen eine Transparenz bis 250 nm. Vorzugsweise wird die härtbare Zusammensetzung so eingewogen, daß das Äquivalenzverhältnis der Gruppen -N=C=O : -SH = 1 : 1 beträgt. Es ist aber auch möglich, dieses Verhältnis der funktionellen Gruppen so zu variieren, daß sowohl die Isocyanat-Komponente als auch das Thiol überwiegt. Vorzugsweise beträgt das Verhältnis der funktionellen Gruppen dann 1 : 1,25.According to the invention, the object is achieved by a curable composition solved so that they diisocyanates and thiols of functionality f ≧ 2 and contains catalysts and rapidly, already at Room temperature passes from the liquid to the solid state. The cured mixtures of aliphatic dithiols and aliphatic diisocyanates have a transparency of up to 250 nm. Preferably, the curable composition is weighed in, the equivalence ratio of the groups -N = C = O: -SH = 1: 1. But it is also possible, this ratio of functional Groups to vary so that both the isocyanate component as well as the thiol outweighs. This is preferably Ratio of functional groups then 1: 1.25.
Systematische Untersuchungen ergaben, daß folgende Thiole besonders geeignet sind:Systematic investigations showed that the following thiols are especially are suitable:
Triglykoldithiol, HSCH₂CH₂OCH₂CH₂OCH₂CH₂SH
Octanthiol-1.8, HS(CH₂)₈SHTriglycol dithiol, HSCH₂CH₂OCH₂CH₂OCH₂CH₂SH
Octanethiol-1.8, HS (CH₂) ₈SH
oder als Thioglykolate:or as thioglycolates:
Anstelle der genannten monomeren Thiol-Verbindungen sind beispielsweise Präpolymere mit SH-Endgruppen der Formel 1, wie sie im WP 232 504 beschrieben sindInstead of the monomeric thiol compounds mentioned are, for example, prepolymers with SH end groups of the formula 1 , as described in WP 232,504
oder Prepolymere der Formel 2 vorteilhaft einzusetzenor to use prepolymers of the formula 2 advantageous
Die Reste R und R′ stehen für substituierte oder unsubstituierte aliphatische, aromatische, araliphatische, cycloaliphatische oder andere difunktionelle Reste. In Formel 1 verbinden sie Glycidylgruppen oder Thiolgruppen miteinander; in Formel 2 verbinden sie zwei Amid- oder Thiolgruppen miteinander.The radicals R and R 'are substituted or unsubstituted aliphatic, aromatic, araliphatic, cycloaliphatic or other difunctional radicals. In Formula 1 , they link together glycidyl groups or thiol groups; in formula 2 they combine two amide or thiol groups.
Als Isocyanate sind besonders geeignet:As isocyanates are particularly suitable:
Hexamethylendiisocyanat, O=C=N(CH₂)₆N=C=O
2,2,4-(2,4,4)-TrimethylhexamethylendiisocyanatHexamethylene diisocyanate, O = C = N (CH₂) ₆N = C = O
2,2,4- (2,4,4) -trimethylhexamethylene
Vorteilhaft sind anstelle der aufgeführten monomeren Diisocyanate Präpolymere der Formel 3 mit Isocyanatendgruppen einsetzbarAdvantageously, instead of the monomeric diisocyanates listed prepolymers of the formula 3 can be used with isocyanate groups
Anstelle reiner Einzelkomponenten können auch Mischungen verschiedener Isocyanate bzw. Thiole eingesetzt werden. Naturgemäß kann die härtbare Zusammensetzung aus der Isocyanat- Chemie bekannte Katalysatoren, vorzugsweise Nucleophile, Amin und/oder Alkohole enthalten. Vorteilhaft einsetzbar sind N- Methylmorpholin, Pyridin, Chinolin, Picoline, Lepidine, Collidine oder Aminosilane. Die optimale Katalysatorkonzentration beträgt vorzugsweise 0,01-10 Ma-%. Es ist möglich, den Katalysator direkt der härtbaren Zusammensetzung beizumischen. Es ist aber auch möglich, den Katalysator in geeigneter Weise auf die zu beschichtenden oder zu verklebenden Bauteile aufzutragen. Ferner kann es von Vorteil sein, die Bauteile mit geeigneten Haftvermittlern nach bekannten Verfahren zu beschichten. Auf diese Weise können sowohl die Festigkeit der Verklebung als auch die Klimastabilität positiv beeinflußt werden. Mit dieser Art Vorbehandlung verbunden ist ein nicht vorhersehbarer positiver Effekt: man kann nämlich auf diese Weise die Fixierzeiten für die Härtung steuern. Sie kann im Sekunden- oder Minutenbereich liegen, je nach Basizität des eingesetzten Katalysators.Instead of pure individual components and mixtures of various Isocyanates or thiols are used. Naturally, the curable composition of the Isocyanat- Chemistry known catalysts, preferably nucleophiles, amine and / or alcohols. Advantageously, N- Methylmorpholine, Pyridine, Quinoline, Picoline, Lepidine, Collidine or aminosilanes. The optimum catalyst concentration is preferably 0.01-10% by mass. It is possible to use the catalyst directly to mix the curable composition. It is also possible to coat the catalyst in a suitable manner or to apply components to be bonded. Furthermore, can It may be advantageous to use components with suitable adhesion promoters to coat according to known methods. That way you can both the strength of the bond and the climate stability positively influenced. Linked to this kind of pretreatment is an unpredictable positive effect: you can namely in this way control the fixing times for curing. you can be in the second or minute range, depending on the basicity of the catalyst used.
Ein weiterer Vorteil der erfindungsgemäßen härtbaren Zusammensetzung besteht in seiner erweiterten Transparenz bis 250 nm, wenn aliphatische Diisocyanate und aliphatische Dithiole eingesetzt werden. Die ausgehärteten Schichten besitzen eine ausgezeichnete Strahlenresistenz. So verändert selbst 100 Stunden Bestrahlung mit dem ungefilterten Licht einer Quecksilberhochdrucklampe nicht das UV/VIS-Spektrum. Solche Mischungen eignen sich daher besonders als UV-durchlässige Klebstoffe oder Schichten in der optischen Industrie.Another advantage of the curable composition of the invention consists in its extended transparency up to 250 nm, when aliphatic diisocyanates and aliphatic dithiols used become. The hardened layers have an excellent Radiation resistance. So changed even 100 hours Irradiation with the unfiltered light of a high-pressure mercury lamp not the UV / VIS spectrum. Such mixtures are suitable therefore especially as UV-transparent adhesives or layers in the optical industry.
Eine härtbare Mischung erhält man durch Vermischen von 2,103 g Trimethylhexamethylendiisocyanat und 1,823 g Triethylenglykoldithiol. Diese Mischung kann z. B. als Gießharz oder für Klebzwecke verwendet werden. In Tabelle 1 sind die Bedingungen enthalten, unter denen man feste, glasklare, transparente Festkörper erhält.A curable mixture is obtained by mixing 2.103 g Trimethylhexamethylene diisocyanate and 1.823 g triethylene glycol dithiol. This mixture can, for. B. as a casting resin or for Klebzwecke be used. Table 1 contains the conditions under which you get solid, crystal clear, transparent solids.
Die Durchlässigkeit einer 45-µm-Schicht beträgt bei 250 nm 55%.The transmissivity of a 45 μm layer is 55% at 250 nm.
1,682 g Hexamethylendiisocyanat werden mit 1,823 g Triethylenglykoldithiol vermischt. Die so erhaltene Mischung hat eine Topfzeit von 8 Tagen (ohne Katalysator), Fixierzeit: 5 h (0,5 Ma-% Picolin), Trennbarkeit: 100°C (nach 7 Tagen).1,682 g of hexamethylene diisocyanate are mixed with 1.823 g of triethylene glycol dithiol mixed. The mixture thus obtained has a pot life of 8 days (without catalyst), fixing time: 5 h (0.5% by mass of picoline), Separability: 100 ° C (after 7 days).
2,223 g Isophorondiisocyanat werden mit 2,546 g 1,3-Bismercaptoethyl- 1,1,3,3-tetramethyldisiloxan vermischt. Diese Mischung hat eine Topfzeit von 50 Tagen (ohne Katalysator); Fixierzeit: 2 min (1% N,N-Dimethylbenzylamin in Aceton); Trennbarkeit: 100°C (90 Tage).2.233 g of isophorone diisocyanate are mixed with 2.546 g of 1,3-bismercaptoethyl 1,1,3,3-tetramethyldisiloxane mixed. This mixture has a pot life of 50 days (without catalyst); Fixing time: 2 min (1% N, N-dimethylbenzylamine in acetone); Separability: 100 ° C (90 ° C) Days).
2,223 g Isophorondiisocyanat werden mit 1,823 g Triethylenglykodithiol und 0,1 Ma-% N-Methylmorpholin vermischt. Nach 15 min Reaktionszeit erhält man einen harten glasklaren Festkörper.2.233 g of isophorone diisocyanate are mixed with 1.823 g of triethylene glycol dithiol and 0.1% by mass of N-methylmorpholine. After 15 min reaction time you get a hard crystal-clear solid.
2,313 g Trimethylhexamethylendiisocyanat, 1,640 g Triethylenglykoldithiol, 0,433 g Pentaerythrit-tetrathioglykolat und 1 Ma-% 2,4,6- Kollidin werden vermischt. Topfzeit: 10 Tage (ohne Katalysator); mit Katalysator nach 15 min fest.2.313 g trimethylhexamethylene diisocyanate, 1.640 g triethylene glycol dithiol, 0.433 g of pentaerythritol tetrathioglycolate and 1% by mass of 2,4,6 Collidin are mixed. Pot life: 10 days (without catalyst); with catalyst after 15 min.
1,367 g Trimethylhexamethylendiisocyanat, 0,638 g Triethylenglykoldithiol, 0,648 g Pentaerythrit-tetrathioglykolat ergeben eine härtbare Mischung. Mit 0,5 Ma-% Pyridin erhält man nach 5 min einen harten, glasklaren Festkörper.1.367 g trimethylhexamethylene diisocyanate, 0.638 g triethylene glycol dithiol, 0.648 g of pentaerythritol tetrathioglycolate give a curable Mixture. With 0.5 M% pyridine is obtained after 5 min one hard, crystal clear solid.
1,000 g Prepolymer mit Isocyanatendgruppen, das aus 2 mol Trimethylhexamethylendiisocyanat und 1 mol Triethylenglykoldithiol synthetisiert wurde (Mn/VPO: 758), wird mit 0,290 g Triethylenglykoldithiol umgesetzt (0,1 Ma-% Dimethylbenzylamin). Nach 10 min erhält man einen hart-elastischen, glasklaren Festkörper.1.000 g of isocyanate-terminated prepolymer, which was synthesized from 2 moles of trimethylhexamethylene diisocyanate and 1 mol Triethylenglykoldithiol (M n / VPO: 758) is mixed with 0.290 g Triethylenglykoldithiol reacted (0.1% by mass dimethylbenzylamine). After 10 minutes, a hard-elastic, crystal-clear solid is obtained.
Claims (10)
Triglykoldithiol, HSCH₂CH₂OCH₂CH₂OCH₂CH₂SH
Octanthiol-1.8, HS(CH₂)₈SH oder die Thioglykolate: eingesetzt sind.4. curable composition according to claim 1 and 2, characterized in that as thiols, for example
Triglycol dithiol, HSCH₂CH₂OCH₂CH₂OCH₂CH₂SH
Octanethiol-1.8, HS (CH₂) ₈SH or the thioglycolates: are used.
2,2,4-(2,4,4)-Trimethylhexamethylendiisocyanat eingesetzt sind.6. A curable composition according to claim 1 to 5, characterized in that as isocyanates, for example, hexamethylene diisocyanate, O = C = N (CH₂) ₆N = C = O.
2,2,4- (2,4,4) -trimethylhexamethylene are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904017941 DE4017941A1 (en) | 1990-06-05 | 1990-06-05 | Hardenable compsn. for use as adhesive, encapsulating or casting resin - comprises di:isocyanate, poly:thiol, and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19904017941 DE4017941A1 (en) | 1990-06-05 | 1990-06-05 | Hardenable compsn. for use as adhesive, encapsulating or casting resin - comprises di:isocyanate, poly:thiol, and catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4017941A1 true DE4017941A1 (en) | 1991-12-12 |
Family
ID=6407789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19904017941 Withdrawn DE4017941A1 (en) | 1990-06-05 | 1990-06-05 | Hardenable compsn. for use as adhesive, encapsulating or casting resin - comprises di:isocyanate, poly:thiol, and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4017941A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006030029A1 (en) * | 2004-09-17 | 2006-03-23 | Akzo Nobel Coatings International B.V. | Coating composition based on thiol-nco curing |
| US7479653B2 (en) | 2003-12-04 | 2009-01-20 | Henkel Ag & Co Kgaa | UV curable protective encapsulant |
| JPWO2018079829A1 (en) * | 2016-10-31 | 2019-03-22 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and method for producing the same |
| CN114507168A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Isocyanate derivative, preparation method and application thereof, and lubricating grease composition |
| CN114763332A (en) * | 2021-01-15 | 2022-07-19 | 中国石油化工股份有限公司 | Isocyanate derivative, preparation method and application thereof, and lubricating grease composition |
-
1990
- 1990-06-05 DE DE19904017941 patent/DE4017941A1/en not_active Withdrawn
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7479653B2 (en) | 2003-12-04 | 2009-01-20 | Henkel Ag & Co Kgaa | UV curable protective encapsulant |
| WO2006030029A1 (en) * | 2004-09-17 | 2006-03-23 | Akzo Nobel Coatings International B.V. | Coating composition based on thiol-nco curing |
| JP2008513560A (en) * | 2004-09-17 | 2008-05-01 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Coating composition based on curing of thiol-NCO |
| EA012572B1 (en) * | 2004-09-17 | 2009-10-30 | Акцо Нобель Коатингс Интернэшнл Б.В. | Coating composition comprising one or more polythiols and use thereof (embodiments) |
| US7709555B2 (en) | 2004-09-17 | 2010-05-04 | Akzo Nobel Coatings International | Coating composition based on thiol-NCO curing |
| CN101044179B (en) * | 2004-09-17 | 2011-07-06 | 阿克佐诺贝尔国际涂料股份有限公司 | Coating composition based on thiol-NCO curing |
| JPWO2018079829A1 (en) * | 2016-10-31 | 2019-03-22 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and method for producing the same |
| KR20190055170A (en) * | 2016-10-31 | 2019-05-22 | 미쯔이가가꾸가부시끼가이샤 | Polymerizable composition for optical material, optical material and manufacturing method thereof |
| CN109906240A (en) * | 2016-10-31 | 2019-06-18 | 三井化学株式会社 | Polymerizable composition for optical material, optical material and its manufacturing method |
| EP3533814A4 (en) * | 2016-10-31 | 2020-07-01 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, optical material, and production method for optical material |
| KR102236777B1 (en) * | 2016-10-31 | 2021-04-05 | 미쯔이가가꾸가부시끼가이샤 | Polymerizable composition for optical material, optical material, and manufacturing method thereof |
| CN109906240B (en) * | 2016-10-31 | 2021-08-24 | 三井化学株式会社 | Polymerizable composition for optical material, and method for producing same |
| US11845828B2 (en) | 2016-10-31 | 2023-12-19 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, optical material, and producing method thereof |
| CN114507168A (en) * | 2020-10-28 | 2022-05-17 | 中国石油化工股份有限公司 | Isocyanate derivative, preparation method and application thereof, and lubricating grease composition |
| CN114763332A (en) * | 2021-01-15 | 2022-07-19 | 中国石油化工股份有限公司 | Isocyanate derivative, preparation method and application thereof, and lubricating grease composition |
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