CN101180334B - Crosslinkable silane-terminated polymer and sealant composition made with same - Google Patents

Crosslinkable silane-terminated polymer and sealant composition made with same Download PDF

Info

Publication number
CN101180334B
CN101180334B CN2006800124807A CN200680012480A CN101180334B CN 101180334 B CN101180334 B CN 101180334B CN 2006800124807 A CN2006800124807 A CN 2006800124807A CN 200680012480 A CN200680012480 A CN 200680012480A CN 101180334 B CN101180334 B CN 101180334B
Authority
CN
China
Prior art keywords
appearance
silane
group
polymkeric substance
crosslinkable
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.)
Expired - Fee Related
Application number
CN2006800124807A
Other languages
Chinese (zh)
Other versions
CN101180334A (en
Inventor
谢恩·J·兰登
布鲁斯·A·沃尔德曼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Momentive Performance Materials Inc
Original Assignee
Momentive Performance Materials Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US11/292,045 external-priority patent/US7417105B2/en
Application filed by Momentive Performance Materials Inc filed Critical Momentive Performance Materials Inc
Publication of CN101180334A publication Critical patent/CN101180334A/en
Application granted granted Critical
Publication of CN101180334B publication Critical patent/CN101180334B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

A crosslinkable silane-terminated polymer is provided which includes the reaction product of an isocyanate-terminated prepolymer and a silane possessing a plurality of hydrolysable sites and at least one active hydrogen-containing group which is reactive for isocyanate, the silane upon hydrolysis produces a reduced amount of volatile organic compound compared to that produced by the hydrolysis of a silane possessing an equivalent number of hydrolyzable sites all of which are hydrolyzable alkoxy groups.

Description

Crosslinkable Silante terminated polymkeric substance and with the encapsulant composition of its preparation
The cross reference of related application
The sequence number that the present invention's requirement was submitted on February 15th, 2005 is 60/655,976 U.S. Provisional Application No., and its content is introduced this paper for your guidance.
Background of invention
Carbamate prepolymer has been carried out modification in the past,, improved or increased their fundamental property through some or all NCO being carried out end-blocking with various organic functional property silane.In these methods, USP 3,632,557 have instructed with primary and secondary aliphatic amino silane the polyurethane prepolymer of routine have been carried out complete end-blocking.USP 3,979,344 have recorded and narrated the silicone terminated organic encapsulant compositions of room-temperature-curable in detail, and it comprises a spot of 3-(N-2-aminoethyl) aminopropyl trimethoxysilane end-capping reagent to improve the curing speed of sealing agent.USP 4,222,925 recorded and narrated in detail with at USP 3,979, the identical compsn that provides in 344, but also introduced the carbon black filler of enhanced.Having improved elongation is to adopt Silante terminated polyether polyols with reduced unsaturation preparation with flexible sealing agent; Said Silante terminated polyether polyols with reduced unsaturation is by USP 4; Have that at least one dialkoxy and silane monomer with the organic functional base of at least one active hydrogen atom obtain in 645,816.
But, with the end capped polyurethane prepolymer of primary amino functional silanes contain can with the further reactive activity Wasserstoffatoms of terminal isocyanate groups.The polymkeric substance that this reactivity can cause not expecting and the stability of encapsulant composition.Several Methods has been instructed use secondary amino group functional silanes end-capping reagent.For example, USP 4,374,237 have instructed curable isocyanate-terminated polyurethane prepolymer, and at least a portion of its isocyanate terminated base is reacted with the secondary amine that comprises the silane monomer with two trialkoxy silane bases.USP 4,474,933 have described with various uncles and the amino-silane terminated crosslinkable urethane resin mixture of secondary difunctionality.Recently, USP 5,364,955 have instructed the end capped polyurethane prepolymer of N-alkoxysilylalkyl aspartate to reach the purposes by the encapsulant composition of its manufacturing.
Therefore, need a kind of end-capping reagent, allow the silylated polyurethane resin of low VOC with generation based on silane.Also need a kind of adhesion promotor, allow sealing agent, tackiness agent and the coating of low VOC with generation based on silane.
Summary of the invention
According to one embodiment of the invention; Crosslinkable Silante terminated polymkeric substance is provided; It comprises the reaction product of isocyanate-terminated prepolymer and silane; Said silane have a plurality of hydrolyzable sites and to NCO have reactive at least one comprise the group of active hydrogen; The amount of the volatile organic compounds that said silane produces when hydrolysis, what have similar number all is that the amount of the volatile organic compounds that silane hydrolyzate produced in the hydrolyzable site of hydrolyzable alkoxyl group reduces than every mole, thereby forms Silante terminated polymkeric substance.
The present invention also comprises compsn, sealing agent, coating and the tackiness agent for example made by aforementioned crosslinkable Silante terminated polymkeric substance.
" volatile organic compounds " statement (VOC) among this paper is interpreted as being applicable to and referring to so pure basically organic cpds; Its EPA according to the U.S. (U.S. environmental protection general administration) method 24 is volatile; Or be not inconsistent the concrete standard that is combined into the formulation of European various countries about vp or boiling point, perhaps in european union directive 2004/42/EC, be enumerated as VOC.The object lesson of this VOCs comprises methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, acetoxysilane, 2-methyl cellosolve, or the like.
With reference to following specification sheets and appended claim, various further features of the present invention, aspect and advantage will be more obvious.
Detailed Description Of The Invention
The present invention provides crosslinkable Silante terminated polymkeric substance; It comprises the reaction product of isocyanate-terminated prepolymer and silane; Said silane have a plurality of hydrolyzables site and to NCO have reactive at least one comprise the group of active hydrogen; The amount of the volatile organic compounds that said silane produces when hydrolysis all is that the amount of the volatile organic compounds that silane hydrolyzate produced in the hydrolyzable site of hydrolyzable alkoxyl group reduces than what have similar number.
Through roughly stoichiometric isocyanate-terminated polyurethane prepolymer and stoichiometric silane compound are hereinafter described roughly reacted, can prepare Silante terminated polymkeric substance of the present invention.Generally use the excessive a little silane compound of mole number, thereby guarantee that all are present in the complete reaction of the terminal isocyanate groups on the prepolymer.Usually be reflected under the existence that does not have moisture and carry out; TR is 0 ℃ to 150 ℃ in the first embodiment; If necessary can also be higher, TR is about 20 ℃ to 100 ℃ in second embodiment, guarantees the good contact between the reactant with mixing.In addition, can use inert diluent to promote reaction if necessary.Though reaction is normally carried out under barometric point, if necessary, also can adopt and be higher or lower than barometric point.Choose wantonly and can under anhydrous condition, in such as the inert atmosphere of nitrogen coating, carry out the reaction between isocyanate prepolymer and the silane.
Usually under the condition that catalyzer exists, make excessive organic two-or many-isocyanic ester react with polyvalent alcohol or polyvalent alcohol combination, thereby prepare suitable in the present invention isocyanate-terminated polyurethane prepolymer.According to the situation of the polyvalent alcohol of selecting, the mol ratio of NCO and OH is generally about 1.2 to 4.0.And technology relevant summary chemical with the urethane polymer of producing this prepolymer is found in the Polyurethanes:Chemistryand Technology of Saunders and Frisch; (New York is among 1963 (Part I) and 1964 (the Part II) for Interscience Publishers.
Can use any suitable organic diisocyanate of aliphatic series, alicyclic, araliphatic (araliphatic) or aromatics.Suitable organic diisocyanate comprises that inferior phenyl ester between two isocyanic acids, two isocyanic acids are to inferior phenyl ester, diphenylmethanediisocyanate, p-diaminodiphenyl vulcabond, naphthalene-1; 5-vulcabond, hexamethylene diisocyanate, decamethylene vulcabond, dianisidine vulcabond, eylylene diisocyanate, two (2-isocyanatoethyl) fumarate, two (2-isocyanatoethyl) hexamethylene-4-alkene-1, two (2-isocyanatoethyl) carbonic ether, 2; 4-tolylene diisocyanate, 2; 6-tolylene diisocyanate, 4; 4 ' diphenylmethanediisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride-4; 4 '-vulcabond, comprise 2; 4-and 4; The various liquid diphenylmethanediisocyanates of 4 ' isomer mixture, Desmodur N
Figure 2006800124807_0
, or the like, and composition thereof.Can also use other organic diisocyanate as known in the art among the present invention, for example at Siefken, Annalen, 565, disclosed among the 122-135 (1949).Again according to another embodiment of the invention; Isocyanate-functional property monomer is 2; 4-and 4; The mixture of 4 ' diphenylmethanediisocyanate (MDI) can be buied from Bayer by trade name Mondur
Figure 2006800124807_1
ML.
When the isocyanate-terminated polyurethane prepolymer of preparation, with the reaction of organic diisocyanate in can use one or more two pure and mild triols.Such polyvalent alcohol has about 250 to about 20,000 molecular weight in the first embodiment, in second embodiment, has about 1000 to about 15,000 molecular weight.
In addition, polyvalent alcohol can be polyethers or polyester polyol.Can be used for the polyether glycol with low-unsaturation-degree of the present invention is known substantially, for example is described in EP-A 283 148 and USP 3,278,457,3,278,458,3,278; 459,3,427,256,3,427,334,3,427; 335,3,829,505,3,941,849,4,355; 188, in 4,472,560 and 4,721,818, their content is introduced into this paper for your guidance.
Operable suitable polyvalent alcohol comprises polyether polyols, polyoxy alkylidene triol, polytetramethylene glycol, polycaprolactone glycol and triol in the above-mentioned polyurethane prepolymer of preparation, or the like.
Also according to another embodiment of the invention, polyvalent alcohol is a W 166, and the equivalent weight scope is about 500 to about 6000 and all scopes therebetween.
Prepare the operable suitable catalyst of above-mentioned polyurethane prepolymer and be selected from organic bases, carboxylic acid and organometallic compound usually, include the complex compound or the carboxylate salt of organic titanate and lead, cobalt, iron, nickel, zinc and tin.The object lesson of catalyzer comprises dibutyl tin laurate, dibutyltin diacetate, sad dibutyl tin, dioctyl tin maleate, Dibutyltin oxide, stannous octoate, stannous acetate and such as the titanium compound of 2-Ethylhexyl Alcohol titanium.The addition of catalyzer in the first embodiment can for the pre-polymer formulations gross weight about 0.01 to about 1 weight %; In second embodiment be the pre-polymer formulations gross weight about 0.05 to about 0.5 weight %, be about 0.1 to 0.2 weight % of pre-polymer formulations gross weight in the 3rd embodiment.
As definition in this article, the VOC that produces during hydrolysis amount reduces, and therefore be applicable to and the silane of Silante terminated polymkeric substance among preparation this paper comprise the silane with following general formula:
[Y [G (SiX uZ b vZ c w) s] r] n(formula 1)
Wherein the G of each appearance is independently selected from and comprises following group group: the one or more Wasserstoffatomss by alkyl, thiazolinyl, aryl or aralkyl are substituted resulting polyad; Perhaps serve as reasons and remove the available molecular moiety of one or more Wasserstoffatomss of assorted carbon, G contains and has an appointment 1 to about 30 carbon atoms; The X of each appearance is independently selected from-Cl ,-Br, R 1O-, R 1C (=O) O-, R 1R 2C=NO-, R 1R 2NO-or R 1R 2N-,-R 1,-(OSiR 1R 2) t(OSiR 1R 2R 3) and-O (R 10CR 11) fOH-,-HN (R 10CR 11) fNH 2,-OOC (R 10CR 11) fCOOH ,-O (R 10CR 11) fNH 2,-O (R 10CR 11) fCOOH ,-HN (R 10CR 11) fOH, the wherein R of each appearance 1, R 2, R 3, R 10And R 11Be R independently; The Z of each appearance bBe independently selected from (O-) 0.5, [O (R 10CR 11) fO-] 0.5, [HN (R 10CR 11) fN (H)-] 0.5, [OOC (R 10CR 11) fCOO-] 0.5, [O (R 10CR 11) fN (H)-] 0.5[O (R 10CR 11) fCOO-] 0.5, the R of each appearance wherein 10And R 11Be R independently; The Z of each appearance cBe independently selected from-O (R 10CR 11) fO-,-HN (R 10CR 11) fN (H)-,-OOC (R 10CR 11) fCOO-,-O (R 10CR 11) fN (H)-with-O (R 10CR 11) fCOO-, the wherein R of each appearance 10And R 11Be R independently; The R of each appearance is independently selected from and comprises following group group: hydrogen; Straight chain, ring-type or branched-chain alkyl, and can contain undersaturated thiazolinyl, aryl and aralkyl; The molecular moiety that perhaps obtains for the one or more Wasserstoffatomss that remove assorted carbon; The R of each appearance comprises 1 to about 20 carbon atoms; The subscript f of each appearance is 1 to about 15 integer, and the n of each appearance is 1 to about 100 integer, condition be when n greater than 1 the time, v is greater than 0, and Z bAll valencys Siliciumatom and its bonding are all arranged; The subscript u of each appearance is 0 to about 3 integer, and the subscript v of each appearance is 0 to about 3 integer, and the subscript w of each appearance is 0 to about 1 integer; Condition is u+v+2w=3; The subscript r of each appearance is 1 to about 6 integer, and the subscript t of each appearance is 0 to about 50 integer, and the subscript s of each appearance is 1 to about 6 integer; The Y of each appearance is that valence state is the organic functional base of r; At least a ring-type of the organic functional property silane of formation ring-type and bridging and the organic functional property silane of bridging contain the Z of at least one appearance bOr Z c
Group Y comprises unit price organic functional base (r=1), divalence organic functional base (r=2), trivalent organic functional base (r=3), tetravalence organic functional base (r=4) among this paper, and the organic functional base of higher valence state, is called multivalence organic functional base among this paper.Term multivalence organic functional base among this paper is understood to include unit price, divalence, trivalent and quaternary organic functional base.According to another embodiment of the present invention, the Y in the above-mentioned general formula 1 is CH 2=CH-, CHR=CH-or CR 2=CH-.
Another embodiment of the present invention comprises unit price organic functional base among this paper, like sulfydryl with such as the acyloxy of acryloxy, methacryloxy and acetoxyl group.Another embodiment of the present invention comprises the unit price epoxy group(ing) among this paper, like glycidoxy, and-O-CH 2-C 2H 3O; Epoxy group(ing) cyclohexyl ethyl ,-CH 2-CH 2-C 6H 9O; The epoxy group(ing) cyclohexyl ,-C 6H 9O; Epoxy group(ing) ,-CR 6The CR of (-O-) 4R 5Another embodiment of the present invention comprises unit price organic functional base such as hydroxyl, carbamate groups ,-NR among this paper 4C (=O) OR 5Urethane groups ,-OC (=O) NR 4R 5The thiocarbamate base ,-NR 4C (=O) SR 5The sulfo-urethane groups ,-SC (=O) NR 4R 5The thionocarbamate base ,-NR 4C (=S) OR 5The thion urethane groups ,-OC (=S) NR 4R 5Dithiocarbamate groups ,-NR 4C (=S) SR 5With the dithio urethane groups ,-SC (=S) NR 4R 5Another embodiment of the present invention comprises unit price organic functional base among this paper, like dimaleoyl imino; Toxilic acid ester group and substituted toxilic acid ester group; Fumaric acid ester group and substituted fumaric acid ester group; Itrile group, CN; Chaff lemon imide.Another embodiment of the present invention comprises unit price organic functional base such as cyanate ester based ,-OCN among this paper; NCO ,-N=C=O; Thiocyanate groups ,-SCN; Isothiocyanate group ,-N=C=S; And ether ,-OR 4Another embodiment of the present invention comprises unit price organic functional base such as fluorine-based ,-F among this paper; Chloro ,-Cl; Bromo ,-Br; Iodo ,-I; And thioether group-SR 4Another embodiment of the present invention comprises unit price organic functional base such as disulfide group ,-S-SR among this paper 4Three sulfenyls ,-S-S-SR 4Four sulfenyls ,-S-S-S-SR 4Five sulfenyls ,-S-S-S-S-SR 4Six sulfenyls ,-S-S-S-S-S-SR 4With many sulfenyl-S xR 4Another embodiment of the present invention comprises unit price organic functional base such as xanthogenic acid ester group among this paper ,-SC (=S) OR 4The trithiocarbonic acid ester group ,-SC (=S) SR 4The dithiocarbonic acid ester group ,-SC (=O) SR 4Urea groups, NR 4C (=O) NR 5R 6Thion urea groups (also being known as the sulfo-urea groups) ,-NR 4C (=S) NR 5R 6Carboxamido-group, R 4C (=O) NR 5-with-C (=O) NR 4R 5-; Thion carboxamido-group (also being known as the thioamides base), R 4C (=S) NR 4-; Unit price is melamine-based; Close base with unit price cyanuric acid root.Another embodiment of the present invention comprises unit price organic functional base such as primary amino ,-NH among this paper 2Secondary amino group ,-NHR 4Amino with uncle ,-NR 4R 5The unit price diamino-,-NR 4-L 1-NR 5R 6The unit price triamino ,-NR 4-L 1(NR 5R 6) 2With-NR 4-L 1-NR 5-L 2-NR 6R 7With unit price tetramino ,-NR 4-L 1(NR 5R 6) 3,-NR 4-L 1-NR 5-L 2-NR 6-L 3-NR 7R 8With-NR 4-L 1-N (L 2NR 5R 6) 2The L of each appearance wherein 1, L 2And L 3Be independently selected from the group that regards to the structure that G provides; The R of each appearance 4, R 5, R 6, R 7And R 8Independently by on regard to one of structure that R enumerates and provide; The subscript x of each appearance provides by 1 to 10 independently.
Another embodiment of the present invention comprises divalence organic functional base such as epoxy group(ing) among this paper, the C (O-) CR of-(-) 4R 5With-CR 5The CR of (-O-) 4-.Another embodiment of the present invention comprises divalence organic functional base such as carbamate groups among this paper, the NC of-(-) (=O) OR 5Urethane groups ,-OC (=O) NR 4-; The thiocarbamate base, the NC of-(-) (=O) SR 5The sulfo-urethane groups ,-SC (=O) NR 4-; The thionocarbamate base, the NC of-(-) (=S) OR 5The thion urethane groups ,-OC (=S) NR 4-; Dithiocarbamate groups, the NC of-(-) (=S) SR 5The dithio urethane groups ,-SC (=S) NR 4-; And ether ,-O-.Another embodiment of the present invention comprises divalence organic functional base such as toxilic acid ester group and substituted toxilic acid ester group among this paper; Fumaric acid ester group and substituted fumaric acid ester group.Another embodiment of the present invention comprises thioether group ,-S-among this paper; Disulfide group ,-S-S-; Three sulfenyls ,-S-S-S-; Four sulfenyls ,-S-S-S-S-; Five sulfenyls ,-S-S-S-S-S-; Six sulfenyls ,-S-S-S-S-S-S-; With many sulfenyl-S x-.Another embodiment of the present invention comprises divalence organic functional base such as xanthogenic acid ester group among this paper ,-SC (=S) O-; The trithiocarbonic acid ester group ,-SC (=S) S-; Dithiocarbonic acid ester group-SC (=O) S-; Urea groups, the NC of-(-) (=O) NR 4R 5With-NR 4C (=O) NR 5-; The thion urea groups is called the sulfo-urea groups more, the NC of-(-) (=S) NR 4R 5With-NR 4C (=S) NR 5-; Carboxamido-group, R 4C (=O) N (-)-with-C (=O) NR 4-; The thion carboxamido-group is called more and is thioamides base, R 4C (=S) N (-)-; Divalence is melamine-based; Divalence cyanuric acid root closes base.Another embodiment of the present invention comprises divalence organic functional base such as secondary amino group ,-NH-among this paper; Uncle is amino ,-NR 4-; The diamino-of divalence, the N-L of-(-) 1-NR 4R 5With-NR 4-L 1-NR 5-; The triamino of divalence, (-) NR 4) 2-L 1-NR 5R 6,-(-) N-L 1-NR 5-L 2-NR 6R 7,-NR 4-L 1-N (-)-L 2-NR 5R 6With-NR 4-L 1-NR 5-L 2-NR 6-; With the tetramino of divalence, the N-L of-(-) 1-(NR 5R 6) 3, (NR 4) 2-L 1-(NR 5R 6) 2,-(-) N-L 1-NR 4-L 2-NR 5-L 3-NR 6R 7,-NR 4-L 1-N (-)-L 2-NR 5-L 3-NR 6R 7,-NR 4-L 1-NR 5-L 2-N (-)-L 3-NR 6R 7,-NR 4-L 1-NR 5-L 2-NR 6-L 3-NR 7-, the N-L of-(-) 1-N (L 2NR 5R 6) 2(NR 4L 1-) 2N-L 2NR 5R 6The L of each appearance wherein 1, L 2And L 3Be independently selected from the group that regards to the structure that G provides; The R of each appearance 4, R 5, R 6And R 7Independently by on regard to one of structure that R enumerates and provide; The subscript x of each appearance is 1 to 10 to provide by x independently.
Another embodiment of the present invention comprises trivalent organic functional base such as epoxy group(ing) among this paper, the C (O-) CR of-(-) 4-.Another embodiment of the present invention comprises trivalent organic functional base such as carbamate groups among this paper, the NC of-(-) (=O) O-; The thiocarbamate base, the NC of-(-) (=O) S-; The thionocarbamate base, the NC of-(-) (=S) O-; And dithiocarbamate groups, the NC of-(-) (=S) S-.Urea groups, the NC of-(-) (=O) NR 4-; The thion urea groups is also referred to as the sulfo-urea groups, the NC of-(-) (=S) NR 4-; Carboxamido-group ,-C (=O) N (-)-; The thion carboxamido-group is also referred to as the thioamides base ,-C (=S) N (-)-; Trivalent is melamine-based; Close base with trivalent cyanuric acid root.Another embodiment of the present invention comprises trivalent organic functional base such as uncle's amino among this paper ,-N (-)-; Tervalent diamino-, the N-L of-(-) 1-NR 4-; Tervalent triamino, (NR 4) 3-L 1, (NR 4) 2-L 1-NR 5-, the N-L of-(-) 1-N (-)-L 2-NR 3R 4,-NR 4-L 1-N (-)-L 2-NR 5-with-(-) N-L 1-NR 4-L 2-NR 5-; With tervalent tetramino, the N-L of-(-) 1-N (-)-L 2-NR 5-L 3-NR 3R 4,-NR 4-L 1-N (-)-L 2-N (-)-L 3-NR 3R 4,-(-) N-L 1-NR 5-L 2-N (-)-L 3-NR 3R 4,-NR 4-L 1-N (-)-L 2-NR 3-L 3-NR 4-, the N-L of-(-) 1-N (L 2NR 3R 4) (L 2NR 5-) and (NR 4L 1-) 3N; The L of each appearance wherein 1, L 2And L 3Be independently selected from the group that regards to the structure that G provides; The R of each appearance 4, R 5And R 6Independently by on regard to one of structure that R enumerates and provide.
Another embodiment of the present invention comprises tetravalence organic functional base such as epoxy group(ing) among this paper, the C of-(-) (O-) C (-)-; Another embodiment of the present invention comprises tetravalence organic functional base such as urea groups among this paper, the NC of-(-) (=O) N (-)-; Thion urea groups (being also referred to as the sulfo-urea groups), the NC of-(-) (=S) N (-)-; Melamine-based with tetravalence.Another embodiment of the present invention comprises tetravalence organic functional base quaternary diamino-, the N-L of-(-) among this paper 1-N (-)-; The quaternary triamino, (NR 4) 4-L 1-, (NR 4) 2-L 1-N (-)-, the N-L of-(-) 1-N (-)-L 2-NR 3-with-(-) N-L 1-NR 4-L 2(-)-; With the quaternary tetramino, the N-L of-(-) 1-N (-)-L 2-N (-)-L 3-NR 4R 3,-NR4-L 1-N (-)-L 2-N (-)-L 3-NR 3-, the N-L of-(-) 1-NR 4-L 2-NR 3-L 3-N (-)-with-(-) N-L 1-N (L 2NR 3-) 2The L of each appearance wherein 1, L 2And L 3Be independently selected from the group that regards to the structure that G provides; The R of each appearance 4And R 5Independently by on regard to one of structure that R enumerates and provide.
Another embodiment of the present invention comprises polyvalent organic functional base among this paper, such as but not limited to the multivalence alkyl; Pentavalent melamine-based, (NR 3) (N-) 2C 3N 3Sexivalent is melamine-based, (N-) 3C 3N 3The triamino of pentavalent, the N-L of-(-) 1-N (-)-L 2-N (-)-; The tetramino of pentavalent, the N-L of-(-) 1-N (-)-L 2-N (-)-L 3-NR 3-, the N-L of-(-) 1-NR 3-L 2-N (-)-L 3-N (-)-and [(-) N-L 1-] 2N-L 2NR 3-; With the sexivalent tetramino, the N-L of-(-) 1-N (-)-L 2-N (-)-L 3-N (-)-and [(-) N-L 1-] 3N; The L of each appearance wherein 1, L 2And L 3Be independently selected from the group that regards to the structure that G provides; The R of each appearance 4Independently by on regard to one of structure that R enumerates and provide.
Use in this article, glycol, hydrocarbon two pure and mild difunctional alcohols refer to any structure that is provided by formula 2:
HO (R 10CR 11) fOH (formula 2)
Wherein f, R 10And R 11Definition as above.According to the structure that formula 2 provides, the representative of these structures wherein two Wasserstoffatomss by OH metathetical hydrocarbon or assorted carbon.
Use in this article, dialkoxy and difunctionality alkoxyl group refer to like defined any hydrocarbon glycol among this paper, and wherein the Wasserstoffatomss of two OH bases remove, and have obtained the base of divalence, and structure is provided by formula 3:
-O (R 10CR 11) fO-(formula 3)
Wherein f, R 10And R 11Definition as above.
Use in this article, the ring-type dialkoxy refers to silane or group, and cyclisation wherein is to form around silicon through each two Sauerstoffatom that all are connected to common divalence hydrocarbon or assorted carbon back, as common in the glycol.Ring-type dialkoxy among this paper is by Z cRepresentative.
With in this article, the bridging dialkoxy refers to silane or group, wherein two different Siliciumatoms each all with a Sauerstoffatom bonding, said Sauerstoffatom again with this paper in the common divalence hydrocarbon or the assorted carbon back bonding that define, as common in the glycol.Bridging dialkoxy among this paper is by Z bRepresentative.
Use in this article, ring-type and bridging refer to such silane or group, only comprise that ring does not have bridge; Only comprise not ring of bridge; With comprise ring and the two arbitrary combination of bridge.Therefore; The silane of ring-type and bridging possibly mean; For example; The silane of Siliciumatom and ring-type dialkoxy bonding, Siliciumatom not with ring-type dialkoxy bonding only with the silane of the two ends bonding of end of silane, silicon and the bridging dialkoxy of the dialkoxy bonding of bridging and ring-type dialkoxy, Siliciumatom not with the silane of dialkoxy bonding (as long as in the identical molecule at least one other Siliciumatom and at least one ring-type or bridging dialkoxy bonding), or the like.
Use in this article, hydrocarbon based diol refers to the glycol that on hydrocarbon or assorted carbon structure, comprises two OH bases.Term " hydrocarbon based diol " is meant such situation, and promptly the skeleton between two Sauerstoffatoms is made up of two carbon-oxygen bonds around C-C between carbon atom, the carbon atom and the alkoxyl group end fully.Assorted carbon in the structure occurs with the side group of carbon skeleton.
The deemed appropriate in this article divalent alcohol of the structure that formula 2 provides, in some object lessons, more commonly used to term be glycol, by with two OH associating concrete hydrocarbon of base or assorted carbon-based group as prefix.Instance comprises NSC 6366,1,3 butylene glycol and 2-methyl-2,4-pentanediol.Provide the deemed appropriate in this article dialkoxy of group of structure by formula 3, by with two OH associating concrete hydrocarbon of base or assorted carbon-based group as prefix.Therefore, for instance, glycol, NSC 6366,1,3 butylene glycol and 2-methyl-2,4-pentanediol correspond respectively to dialkoxy, inferior new penta dioxy base, 1,3-fourth dialkoxy and 2-methyl-2,4-penta dialkoxy in this article.
The used ring-type and the dialkoxy organic functional property silane of bridging among this paper, wherein silane derived from divalent alcohol, be commonly referred to glycol, correspondingly be alkylene dioxo base silane (glycoxysilane).In addition, the organic functional property dialkoxy silicane of ring-type of using among this paper and bridging, wherein silane derived from glycol, to be commonly referred to be glycol, correspondingly is called dialkoxy silicane.
Use in this article, mark (O-) 0.5[O (R 10CR 11) f] O-] 0.5Be meant half of siloxanes Si-O-Si and half of bridging dialkoxy respectively.These marks and Siliciumatom together use, and they are included among this paper, are used for representing the half the of Sauerstoffatom respectively, i.e. half the with concrete silicon atom bonding, or the expression dialkoxy is half the, i.e. half the with concrete silicon atom bonding.It should be understood that Sauerstoffatom or dialkoxy second half and appear at other position, somewhere in the described bulk molecule structure with the bonding of silicon.Therefore, (O-) 0.5Siloxanes and [O (R 10CR 11) f] O-] 0.5Dialkoxy occupy the centre of the chemical bond that two Siliciumatoms that separate are kept together, and no matter these two Siliciumatoms appear at intermolecular still intramolecularly.At [O (R 10CR 11) f] O-] 0.5Situation under, if alkyl (R 10CR 11) fBe asymmetric, [O (R then 10CR 11) f] O-] 0.5Arbitrary end can with any bonding in two required Siliciumatoms of the structure that provides for perfect 1.
Use in this article, the ring-type inner complex refers to silane or group, and cyclisation wherein is to form around silicon through each two Sauerstoffatom that all are connected to common divalence hydrocarbon or assorted carbon back, as common in the glycol.Ring-type chelate group among this paper is by Z cRepresentative.With in this article, the bridging base refers to silane or group, wherein two different Siliciumatoms each all with a Sauerstoffatom bonding, said Sauerstoffatom again with this paper in the common divalence hydrocarbon or the assorted carbon back bonding that define, as common in the glycol.Bridging base among this paper is by Z bRepresentative.Use in this article, ring-type and bridging refer to such silane or base: only comprise that ring does not have bridge; Only comprise not ring of bridge; With comprise ring and the two arbitrary combination of bridge.Therefore; The silane of ring-type and bridging possibly represented; For example; The silane that the silane of one end of silane, silicon and bridging base that the silane of Siliciumatom and ring-type chelate group bonding, Siliciumatom only do not close with the bridging base key with ring-type chelate group bonding and the two ends bonding of ring-type chelate group, Siliciumatom do not close with inner complex or bridging base key (as long as at least one other Siliciumatom and at least one ring-type or bridging base key close in the identical molecule), or the like.
In a comparable manner, bifunctional amine's (formula 4 is described) and dicarboxyl naphthenic acid (formula 5 is described) can replace above-mentioned difunctional alcohol
H 2N (R 10CR 11) fNH 2(formula 4)
HOOC (R 10CR 11) fCOOH (formula 5)
Wherein under two kinds of situation, f, R 10And R 11Definition as above.Representational example includes but not limited to, the quadrol under the situation of diamines, 1,3-diaminopropanes and 1,4-diaminobutane and succsinic acid, hexanodioic acid and caproic acid.
In addition, mixing functional group's amine (formula 6) and acid (formula 7) also are applicable to the present invention.
HO (R 10CR 11) fNH 2(formula 6)
HO (R 10CR 11) fCOOH (formula 7)
Representational example includes but not limited to thanomin and oxyacetic acid respectively.
The same with the situation of above difunctional alcohol, bifunctional amine and carboxyl naphthenic acid are from two-NH 2With remove Wasserstoffatoms in each of-COOH base and generate divalent radical, its structure is provided by formula 8 and formula 9 respectively:
-HN (R 10CR 11) fN (H)-(formula 8)
-OOC (R 10CR 11) fCOO-(formula 9)
The alkanolamine and the alcohol acid that mix the functional group produce similarly mixing double-basis after taking hydrogen by force, respectively suc as formula shown in 10 and 11:
-O (R 10CR 11) fN (H)-(formula 10)
-O (R 10CR 11) fCOO-(formula 11)
Use in this article, alkyl comprises straight chain, side chain and cyclic alkyl; Thiazolinyl comprises any straight chain, side chain or the ring-type thiazolinyl that contains one or more carbon-to-carbon double bonds, and the position of substitution here can be other position of carbon-to-carbon double bond or group.In addition, alkynyl comprises and contains one or more carbon-to-carbon triple bonds and choose any straight chain, side chain or the ring-type alkynyl that also contains one or more carbon-to-carbon double bonds wantonly that the position of substitution here can be other position of carbon-to-carbon triple bond, carbon-to-carbon double bond or group.The object lesson of alkyl comprises methyl, ethyl, propyl group, isobutyl-.The object lesson of thiazolinyl comprises vinyl, propenyl, allyl group, methylallyl, ethylidene norbornane, ethylidene norcamphyl, ethylidene norbornene and ethylidene norbornenyl.The object lesson of alkynyl comprises ethynyl, propargyl and methylacetylenyl.
Use in this article, aryl comprises any aromatic hydrocarbon that one of them Wasserstoffatoms is removed; Aralkyl comprise wherein one or more Wasserstoffatomss by the same and/or different aryl of similar number (as defining among this paper) substituting group substituted any above-mentioned alkyl; Alkaryl (arenyl) comprise wherein one or more Wasserstoffatomss by the same and/or different alkyl of similar number (as defining among this paper) substituting group substituted any above-mentioned aryl.The object lesson of aryl comprises phenyl and naphthyl.The object lesson of aralkyl comprises benzyl and styroyl.The object lesson of alkaryl comprises tolyl and xylyl.
Use in this article, naphthenic base, cycloalkenyl group and cycloalkynyl radical also comprise two rings, three ring and higher ring structures, and with the further substituted above-mentioned ring structure of alkyl, thiazolinyl and/or alkynyl.Representational example comprises norcamphyl, norbornene, ethyl norcamphyl, ethyl norbornene, ethyl cyclohexyl, ethyl-cyclohexene base, cyclohexyl ring hexyl and cyclododecatrienyl.
Use in this article, the assorted carbon of term refers to any such hydrocarbon structure, and wherein the C-C skeleton is interrupted by the bonding with nitrogen and/or Sauerstoffatom; Or wherein the C-C skeleton is interrupted by the bonding with the atomic group of nitrogenous and/or oxygen, for example cyanurate (C 3N 3O 3).Therefore; Assorted carbon includes but not limited to side chain, straight chain, ring and/or many cycloaliphatic hydrocarbon, and optional containing by means of each ether functional group who all forms with the Sauerstoffatom of two independent carbon atom bondings, tertiary amine functional group that each all forms with the nitrogen-atoms of three independent carbon atom bondings, melamine-based and/or cyanuric acid root closed base; Aromatic hydrocarbon; With the aromatic hydrocarbons of deriving that obtains that replaces above-mentioned aromatic hydrocarbon with branched-chain or straight-chain alkyl, thiazolinyl, alkynyl, aryl and/or aralkyl.
The representative example of G comprises :-(CH 2) m-, wherein m is 1 to 12; The diethylidene hexanaphthene; 1,2,4-triethylene hexanaphthene; Diethylidene benzene; Phenylene;-(CH 2) p-, wherein p is 1 to 20, representative is further substituted terminal linear alkyl in the end of the other end, for example-CH 2-,-CH 2CH 2-,-CH 2CH 2CH 2-with-CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-, and their beta substitution analogue, for example-CH 2(CH 2) qCH (CH 3)-, q here is zero to 17;-CH 2CH 2C (CH 3) 2CH 2-; Can be from methylallyl chloride deutero-structure ,-CH 2CH (CH 3) CH 2-; Can be from Vinylstyrene deutero-any structure, for example-CH 2CH 2(C 6H 4) CH 2CH 2-with-CH 2CH 2(C 6H 4) CH (CH 3)-, the mark C here 6H 4Represent dibasic phenyl ring; Can be from any structure of diallyl benzenesulfonamide derivative, for example-CH 2CH (CH 3) (C 6H 4) CH (CH 3) CH 2-, the mark C here 6H 4Represent dibasic phenyl ring; Can be from divinyl deutero-any structure, for example-CH 2CH 2CH 2CH 2-,-CH 2CH 2CH (CH 3)-with-CH 2CH (CH 2CH 3)-; Can be from m-pentadiene deutero-any structure, for example-CH 2CH 2CH 2CH (CH 3)-,-CH 2CH 2CH (CH 2CH 3)-with-CH 2CH (CH 2CH 2CH 3)-; Can be from isoprene deutero-any structure, for example-CH 2CH (CH 3) CH 2CH 2-, CH 2CH (CH 3) CH (CH 3)-,-CH 2C (CH 3) (CH 2CH 3)-,-CH 2CH 2CH (CH 3) CH 2-,-CH 2CH 2C (CH 3) 2-with-CH 2CH [CH (CH 3) 2]-;-CH 2CH 2-norcamphyl-,-CH 2CH 2-cyclohexyl-any isomer; Can be by norbornane, hexanaphthene, pentamethylene, tetrahydro-dicyclopentadiene or ring dodecylene through losing any double-basis that two Wasserstoffatomss obtain; Can be from PC 560 ,-CH 2CH (4-methyl isophthalic acid-C 6H 9-) CH 3The deutero-structure, the mark C here 6H 9Representative lacks the isomer of substituted three substituted cyclohexane rings on 2 positions; Can be from any structure that contains mono-vinyl of trivinyl hexanaphthene deutero-, for example CH 2CH 2(vinyl C 6H 9) CH 2CH 2-and CH 2CH 2(vinyl C 6H 9) CH (CH 3)-, the mark C here 6H 9Represent any isomer of three substituted cyclohexane rings; Can be from containing the unsaturated structure of any list of myrcene deutero-of three replacement C=C, for example
-CH 2CH[CH 2CH 2CH＝C(CH 3) 2]CH 2CH 2-、
-CH 2CH[CH 2CH 2CH＝C(CH 3) 2]CH(CH 3)-、
-CH 2C[CH 2CH 2CH＝C(CH 3) 2](CH 2CH 3)-、
-CH 2CH 2CH[CH 2CH 2CH＝C(CH 3) 2]CH 2-、
-CH 2CH 2(C-) (CH 3) [CH 2CH 2CH=C (CH 3) 2] and
-CH 2CH [CH (CH 3) [CH 2CH 2CH=C (CH 3) 2]]-; With can from lack three replace C=C the unsaturated structure of any list of myrcene deutero-, for example
-CH 2CH(CH＝CH 2)CH 2CH 2CH 2C(CH 3) 2-、
-CH 2CH(CH＝CH 2)CH 2CH 2CH[CH(CH 3) 2]-、
-CH 2C(＝CH-CH 3)CH 2CH 2CH 2C(CH 3) 2-、
-CH 2C(＝CH-CH 3)CH 2CH 2CH[CH(CH 3) 2]-、
-CH 2CH 2C(＝CH 2)CH 2CH 2CH 2C(CH 3) 2-、
-CH 2CH 2C(＝CH 2)CH 2CH 2CH[CH(CH 3) 2]-、
-CH 2CH=C (CH 3) 2CH 2CH 2CH 2C (CH 3) 2-with
-CH 2CH＝C(CH 3) 2CH 2CH 2CH[CH(CH 3) 2]。
The representative example of R base is H; The side chain and the straight chained alkyl of 1 to 20 carbon atom; For example methyl, ethyl, propyl group, sec.-propyl, butyl, octenyl, cyclohexyl, phenyl, benzyl, tolyl, allyl group, methoxy ethyl, ethoxyethyl group dimethyl aminoethyl, cyanoethyl, or the like.In another embodiment, representational R 10And R 11Base is hydrogen, methyl and ethyl, and wherein hydrogen and methyl are most preferred.Again in another embodiment, representational R 1And R 2Base can be hydrogen, methyl, ethyl, propyl group.In going back an embodiment, R 3, R 4, R 5, R 6, R 7And R 8The representative example of base can be H, C 1To C 4The straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, heptyl, octyl group, and aryl, for example phenyl, benzyl, or the like.
The object lesson of X is methoxyl group, oxyethyl group, propoxy-, isopropoxy, isobutoxy, acetoxyl group, methoxy ethoxy and oximido; And derived from glycol, promptly be known as the unit price alkoxyl group of " unsettled glycol "; Specifically, contain the group of pure and mild alkoxyl group, for example-O-CH 2CH-OH), like terepthaloyl moietie, Ucar 35, NSC 6366,1, ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol, 2-methyl-2,4-pentanediol, 1,4-butyleneglycol, cyclohexanedimethanol and pinacol.In another embodiment, the object lesson of X is methoxyl group, acetoxyl group and oxyethyl group, and derived from glycol such as terepthaloyl moietie, Ucar 35, NSC 6366,1; Ammediol, 2-methyl isophthalic acid; Ammediol, 1,3 butylene glycol and 2-methyl-2, the unit price alkoxyl group of 4-pentanediol.
Z bAnd Z cObject lesson can be for derived from glycol such as terepthaloyl moietie, Ucar 35, NSC 6366,1; Ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol, 2-methyl-2; 4-pentanediol, 1, the divalence alkoxyl group of 4-butyleneglycol, cyclohexanedimethanol and pinacol.In another embodiment, Z bAnd Z cObject lesson be derived from glycol such as terepthaloyl moietie, Ucar 35, NSC 6366,1, ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol and 2-methyl-2, the divalence alkoxyl group of 4-pentanediol is preferred.The alkoxyl group of divalence is derived from glycol, as 1, and ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol and 2-methyl-2,4-pentanediol.Bridging (the Z of the organic functional property silane of ring-type among this paper and bridging b) content must keep enough low, thereby prevent that molecular-weight average is excessive and crosslinked, and this will cause gelling.
Other embodiment be in its Chinese style 1 v and w can so that the w/v ratio between 1 to 9; X is RO-, RC (=O) O-; Z bAnd Z cCan be derived from glycol: 1, ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol and 2-methyl-2,4-pentanediol; R is C 1To C 4Alkyl and H; G is the divalence straight chained alkyl of 2 to 18 carbon atoms.Other embodiment comprises between 2 to 8 those of w/v wherein; X is oxyethyl group or one or more unsettled glycol, and said unsettled glycol is derived from glycol: 1, and ammediol, 2-methyl isophthalic acid, ammediol, 1,3 butylene glycol and 2-methyl-2,4-pentanediol; G is C 2-C 12The straight chained alkyl verivate.Another embodiment is that the v of its Chinese style 1 is 0; X is RO-, RC (=O) O-; R is C 1To C 4Alkyl and H; G is the divalence straight chained alkyl of 2 to 18 carbon atoms.
The representative instance of the organic functional property silane of ring-type of describing among the present invention and bridging comprises: 2-(2-methyl-2,4 penta dialkoxy (ethoxymethyl) siloyl group)-1-propylamine; 2-(2-methyl-2,4-penta dialkoxy isopropoxy silyl)-1-propylmercaptan; 2-(2-methyl-2,4-penta dialkoxy methyl-silicane base)-1-propyl chloride; 2-(2-methyl-2,4-penta dialkoxy phenyl silyl)-1-propyl bromide; 3-(1,3-fourth dialkoxy (ethoxymethyl) siloyl group)-1-propyl iodide; 3-(1,3-fourth dialkoxy isopropoxy silyl)-1-propyl chloride; N-[3-(1, the 3-third dialkoxy (ethoxymethyl) siloyl group)-1-propyl group] aniline; N-[3-(1, the 3-third dialkoxy isopropoxy silyl)-1-propyl group] methylamine; 3-(1, the 2-third dialkoxy (ethoxymethyl) siloyl group)-1-propyl glycidyl ether and methylacrylic acid 3-(1, the 2-third dialkoxy isopropoxy silyl)-1-propyl ester, the two can be derived from Ucar 35; Vinylformic acid 3-(1,2-second dialkoxy (ethoxymethyl) siloyl group)-1-propyl ester and acetic acid 3-(1,2-second dialkoxy isopropoxy silyl)-1-propyl ester, the two can be derived from terepthaloyl moietie; 3-(inferior new penta dioxy base oxethyl silyl)-1-propylamine and 3-(inferior new penta dioxy base isopropoxy silyl)-1-propyl glycidyl ether, the two can be derived from NSC 6366; Vinylformic acid 3-(2,3-dimethyl--2,3-fourth dialkoxy (ethoxymethyl) siloyl group)-1-propyl ester and methylacrylic acid 3-(2,3-dimethyl--2,3-fourth dialkoxy isopropoxy silyl)-1-propyl ester, the two can be derived from pinacol; 3-(2,2-diethylammonium-1, the 3-third dialkoxy (ethoxymethyl) siloyl group)-1-propylmercaptan; S-[3-(2,2-diethylammonium-1, the third dialkoxy isopropoxy silyl)-1-propyl group] ethyl-sulfide; Two [3-(2-methyl isophthalic acid, the 3-third dialkoxy (ethoxymethyl) siloyl group)-1-propyl group] disulphide; Two [3-(2-methyl isophthalic acid, the 3-third dialkoxy isopropoxy silyl)-1-propyl group] trisulphide; Two [3-(1,3-fourth dialkoxy methyl-silicane base)-1-propyl group] tetrasulfide; Two [3-(1, the 3-third dialkoxy methyl-silicane base)-1-propyl group] thioether; 3-(1, the 3-third dialkoxy phenyl silyl)-1-propyl group glycidyl thioether; Three-N, N ', N " [3-(1, the 2-third dialkoxy methyl-silicane base)-1-propyl group] trimeric cyanamide and three-N, N ', N " [3-(1, the 2-third dialkoxy phenyl silyl)-1-propyl group] trimeric cyanamide, the two can be derived from Ucar 35; 3-(1,2-second dialkoxy methyl-silicane base)-1-propyl chloride and 3-(1,2-second dialkoxy phenyl silyl)-1-propyl bromide, the two can be derived from terepthaloyl moietie; Acetic acid 3-(inferior new penta dioxy ylmethyl silyl)-1-propyl ester and sad 3-(inferior new penta dioxy base phenyl silyl)-1-propyl ester, the two can be derived from NSC 6366; 3-(2,3-dimethyl--2,3-fourth dialkoxy methyl-silicane base)-1-propylamine and 3-(2,3-dimethyl--2,3-fourth dialkoxy phenyl silyl)-1-propylamine, the two can be derived from pinacol; Vinylformic acid 3-(2,2-diethylammonium-1, the 3-third dialkoxy methyl-silicane base)-1-propyl ester; Methylacrylic acid 3-(2,2-diethylammonium-1, the 3-third dialkoxy phenyl silyl)-1-propyl ester; 3-(2-methyl isophthalic acid, the 3-third dialkoxy ethyl silicane base)-1-propyl glycidyl ether; Acetic acid 3-(2-methyl isophthalic acid, the 3-third dialkoxy phenyl silyl)-1-propyl ester; Vinylformic acid 2-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-ethyl ester; 2-(2-methyl-2,4-penta dialkoxy methoxy methyl siloyl group)-1-monobromoethane; Phenylsulfonic acid 2-(2-methyl-2,4-penta dialkoxy methyl-silicane base)-1-ethyl ester; Methylacrylic acid 2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group methyl esters; 2-methyl-2,4-penta dialkoxy isopropoxy silyl monobromomethane; Inferior new penta dioxy base propoxy-silyl methylamine; The inferior third dioxy ylmethyl silyl thiomethyl alcohol; Inferior new penta dioxy base ethyl silicane ylmethyl glycidyl ether; Butyric acid 2-(inferior new penta dioxy base isopropoxy silyl)-1-ethyl ester; Propionic acid 2-(inferior new penta dioxy ylmethyl silyl)-1-ethyl ester; Vinylformic acid 2-(1,3-fourth dialkoxy methyl-silicane base)-1-ethyl ester; Methylacrylic acid 3-(1,3-fourth dialkoxy isopropoxy silyl)-4-butyl ester; 3-(1,3-fourth dialkoxy ethyl silicane base)-1-propylmercaptan; Methanesulfonic 3-(1,3-fourth dialkoxy methyl-silicane base)-1-propyl ester; 6-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-hexylamine; Vinylformic acid 1-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) the siloyl group)-own ester of 5-; Methylacrylic acid 8-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-monooctyl ester; 10-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-decyl glycidyl ether; Trifluoromethayl sulfonic acid 3-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-propyl ester; 3-(2-methyl-2,4-penta dialkoxy propoxy-silyl)-1-propylamine; N-[3-(2-methyl-2,4-penta dialkoxy isopropoxy silyl)-1-propyl group] quadrol; Three-N, N ', N " [3-(2-methyl-2,4-penta dialkoxy butoxy silyl)-1-propyl group] Diethylenetriaminee (DETA); Four-N; N '; N "; N
Figure 2006800124807_2
-[3-(2-methyl-2,4-penta dialkoxy isopropoxy silyl)-1-propyl group] triethylenetetramine; Two-(3-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-propyl group) sulfide; 6-(1,3-fourth dialkoxy (ethoxymethyl) siloyl group)-1-hexylamine; 1-(1,3-fourth dialkoxy (ethoxymethyl) siloyl group)-5-hexyl glycidyl ether; Vinylformic acid 8-(1,3-fourth dialkoxy (ethoxymethyl) siloyl group)-1-monooctyl ester; Methylacrylic acid 10-(1,3-fourth dialkoxy (ethoxymethyl) siloyl group)-1-ester in the last of the ten Heavenly stems; Two-(3-(2-methyl-2,4-penta dialkoxy (ethoxymethyl) siloyl group)-1-propyl group) thioether;
[HN(CH 2CH 3)CH 2CH(CH 3)CH 2Si(OCH 3)(HNCH 2-CH 2NH)]；
[[HN(CH 2CH 3)CH 2CH(CH 3)CH 2Si(OCH 3) 2] 2(HNCH 2CH 2NH)]；
[HN(CH 2CH 3)CH 2CH(CH 3)CH 2Si(OCH 3)(HNCH 2-CH 2CH 2NH)]；
[[HN(CH 2CH 3)CH 2CH(CH 3)CH 2Si(OCH 3) 2] 2(HNCH 2CH 2CH 2NH)]；
[H 2NCH 2CH 2CH 2Si(OCH 3)(HNCH 2CH 2NH)]；
[HSCH 2CH 2CH 2Si(OCH 3)(HNCH 2CH 2NH)]；
[H 2NCH 2CH 2NHCH 2CH 2CH 2Si(OCH 3)(HNCH 2CH 2NH)]；
[[H 2NCH 2CH 2NHCH 2CH 2CH 2Si(OCH 3) 2] 2(HNCH 2CH 2NH)]；
[HN(CH 2CH 3)CH 2CH(CH 2)CH 2Si(OCH 3)(O 2CCH 2CH 2CO 2)]；
[H 2NCH 2CH 2CH 2Si(OCH 3)(O 2CCH 2CH 2CO 2)]；
[[H 2NCH 2CH 2CH 2Si(OCH 3) 2] 2(O 2CCH 2CH 2CO 2)]；
[H 2NCH 2CH 2CH 2Si(OCH 2CH 3)(O 2CCH 2CH 2CO 2)]；
[HN(C 6H 5)CH 2CH 2CH 2Si(OCH 3)(O 2CCH 2CH 2CO 2)]；
[CH 2＝C(CH 3)CO 2CH 2CH 2CH 2Si(OCH 3)(O 2CCH 2CH 2CO 2)]；
[[CH 2＝C(CH 3)CO 2CH 2CH 2CH 2Si(OCH 3) 2] 2(O 2CCH 2CH 2CO 2)]；
[CH 2＝C(CH 3)CO 2CH 2CH 2CH 2Si(OCH 3)(HNCH 2CH 2NH)]；
[(CH 2CH 2O)CH 2CH 2OCH 2CH 2CH 2Si(OCH 3)(O 2CCH 2CH 2CO 2)]；
[H 2NC(O)HNCH 2CH 2CH 2Si(OCH 3)(HNCH 2CH 2CH 2NH)]；
[H 2NC(O)HNCH 2CH 2CH 2Si(OCH 3)(O 2CCH 2CH 2CO 2)]；
[[H 2NC(O)HNCH 2CH 2CH 2Si(OCH 3) 2] 2(O 2CCH 2CH 2CO 2)]；
[HN(CH 2CH 3)CH 2CH(CH 2)CH 2Si(OCH 3)(HNCH 2CH 2O)]；
[H 2NCH 2CH 2CH 2Si(OCH 3)(HNCH 2CH 2O)]；
[[HN(C 6H 5)CH 2CH 2CH 2Si(OCH 3) 2] 2(HNCH 2CH 2O)]；
[(CH 2CH 2O) CH 2CH 2OCH 2CH 2CH 2Si (OCH 3) (HNCH 2CH 2O)]; With
[[H 2NCH 2CH 2CH 2Si(OCH 3) 2] 2(HNCH 2CH 2O)。
In another embodiment; Ring-type organic functional property silane is the ring-type of 3-chloro-1-propyl-triethoxysilicane (3-triethoxysilyl-1-propyl chloride) and the analogue of bridging; As the starting point material of making silane coupling agent; Said silane coupling agent is polysulfide silanes for example, as being called the triethoxysilylpropyltetrasulfide tetrasulfide of TESPT among this paper, is called the triethoxysilylpropyltetrasulfide disulphide of TESPD among this paper.The haloalkyl silane of ring-type and bridging is the novel outstanding surrogate of 3-triethoxysilyl-1-propyl chloride, is used to expect to reduce the aspect of VOC discharging.
The organic functional property silane of ring-type that comprises among this paper and bridging can comprise the one-component or the various mixture of one ring-type and bridging organic functional property silane components; Said silane components only contains the simple function alkoxyl group, and optional other material that also comprises.Compound method produces the distribution of various silane, and wherein the mixture of starting ingredient is used to produce the purpose of mixture of the organic functional property silane product of ring-type and bridging.In addition; Be understood that; The partial hydrolysate and/or the condensation product of the organic functional property silane of these ring-types and bridging; Being also referred to as is the organic functional property siloxanes and/or the silanol of ring-type and bridging, and the by product that can be used as the most methods of the organic functional property silane for preparing ring-type and bridging comprises in the silane in this article.In addition; When storing the organic functional property silane of ring-type and bridging; Especially under the condition of humidity or when when preparation remaining residual water-content not preparation subsequently during under the condition removed fully, partial hydrolysate and/or condensation product possibly appear.In addition, through introducing appropriate chemical metering or excessive water among the silane preparation method who describes in this article, can formulate the extremely basic hydrolysis of part of the organic functional property silane of ring-type and bridging intentionally.In addition, through introducing appropriate chemical metering or excessive water among the silane preparation method who describes in this article, can formulate the content of siloxane of the organic functional property silane of ring-type and bridging intentionally.The structrual description that the silane structure that comprises hydrolysate and siloxanes among this paper is provided by formula 1, wherein Z b=(O-) 0.5Subscript v and/or the subscript u of X=OH can be sizable, promptly mean fully greater than zero.
In another embodiment of the present invention, the ring-type and the generation of bridging organic functional property silane that comprise secondary amine and/or sulfydryl have bigger elastic polymkeric substance.In other words, comprise the polymkeric substance that the organic functional property silane of secondary amine and/or sulfydryl generates and have the crosslinkable density that is lower than the conventional silane that comprises primary amino.
Through the substituted organic functional property silane of alkoxyl group and glycol exist or do not exist transesterification reaction under the catalyzer situation, through organic functional property silyl halides and glycol esterification, or, can prepare the silica-based silane compound of band heterocycle that comprises in this article through making substituted alkene carry out the silane of hydrosilation with generation ring-type and bridging with comprising the silica-based silicon hydride of heterocycle.
The transesterification reaction of substituted organic functional property silane of alkoxyl group and glycol can be carried out being with or without under the situation of catalyzer.Catalyzer can be acid, alkali or transition-metal catalyst.Suitable acid catalyst is hydrochloric acid, tosic acid or the like.Typical alkaline catalysts is sodium methylate, sodium ethylate.Suitable transition-metal catalyst is metatitanic acid tetra isopropyl ester and dibutyl tin laurate.
During the esterification of organic functional property silyl halides and glycol, glycol is added in the silyl halides, and remove the hydrogen halide that forms.Through spraying nitrogen or can removing hydrogen halide through step-down.Can remove any residual halogen through adding such as the alcohol of methyl alcohol, ethanol, Virahol etc.
In another embodiment of the present invention, react with distillation synchronously through the catalytic mixtures that makes organic functional property silane reaction thing and glycol, can prepare glycol deutero-organic functional property silane.Reaction causes the alcohol exchange of one or more optionally alkoxyl groups on the Siliciumatom of organic functional property silane reaction thing and glycol.Reaction is removed through distillation and is had more volatile by-product alcohol driving.Appropriate catalyst comprises: acid, and like tosic acid, sulfuric acid, hydrochloric acid, chlorosilane, Mono Chloro Acetic Acid, phosphoric acid, their mixture, or the like; Alkali is like sodium ethylate; With the catalyzer that contains transition metal, like titanium alkoxide, titanium-containing chelate thing, zirconium alkoxides, contain zirconium chelate and composition thereof.
In yet another embodiment of the invention; Mixture through catalysis organic functional property silane and glycol can prepare glycol deutero-organic functional property silane; In one embodiment of the invention, mol ratio is every mole of alkoxyl group-silyl of desiring transesterify at least about 0.5 mole glycol.According to another embodiment of the invention, the mol ratio for trialkoxy silane is about 0.5 to about 1.5.Based on yet another embodiment of the invention, be about 1.0 to about 1.5 for the mol ratio of trialkoxy silane.In each aforesaid embodiment; Range of reaction temperature can be from about 10 ℃ to about 150 ℃; In another embodiment from about 30 ℃ to 90 ℃, the scope that keep-ups pressure simultaneously from about 0.1 to about 2000mm Hg (definitely), in another embodiment from about 1 to about 80mmHg (definitely).Excessive glycol can be used for increasing speed of reaction.
In another embodiment, can under required temperature of reaction and vacuum condition, glycol be joined in the organic functional property silane lentamente through when catalyzer exists, thus preparation glycol deutero-organic functional property silane.If desired, can utilize neutralization procedure neutralize employed any acid or alkaline catalysts, thereby improve the storage characteristics of product.
Randomly, can in this process, use inert solvent, the effect of this solvent can be thinner, carrier, stablizer, backflow auxiliary agent or heat-generating agent.In general, can use any inert solvent, promptly can not get among the reaction or and produce dysgenic solvent reaction.In one embodiment, solvent is for being liquid and boiling point at about below 150 ℃ those under normal operation.Example comprises aromatic substance, hydrocarbon, ether, aprotic solvent and chlorinated hydrocarbon solvent, like toluene, YLENE, hexane, butane, Anaesthetie Ether, N, methyl-sulphoxide, tetracol phenixin, methylene dichloride, or the like.
Can be through formula 1 silane that obtains by the difunctional reactant thing of formula 4-11 with the preparation of the similar step of above-mentioned diol reactant to formula 2 and 3.
In another embodiment of the present invention; Through a fluid stream with the continuous pre-mixing organic functional property of suitable ratio silane reaction thing, two pure and mild catalyzer (during use); Then premixed reactant is incorporated in the reaction distillation system; Can prepare glycol deutero-organic functional property silane, in one embodiment, the reaction distillation system is the thin film distillation device of work under required temperature of reaction and vacuum condition.Under vacuum condition, in film, react the removal that to quicken pure by product, improve the speed of transesterification reaction.The chemical equilibrium that evaporation and the removal of by-product alcohol from film makes reaction is towards helping forming the product of expectation and the minimized direction of the side reaction of not expecting being moved.
The previous embodiments of method comprises following step among this paper:
A) the Thin Film medium is reacted, the Thin Film medium comprises organic functional silanes (for example carbothioic acid ester silane), two pure and mild catalyzer, so that glycol deutero-organic functional property silane and by-product alcohol to be provided;
B) the evaporation by-product alcohol reacts to drive from film;
C) reclaim glycol deutero-organic functional property silane reaction product;
D) optional through the condensing and recycling by-product alcohol; With
E) in optional with glycol deutero-organic functional property silane product to improve its stability in storage.
The glycol that in aforesaid continuous film method, adopts and the mol ratio of organic functional property silane will depend on that hope is by the number of the alkoxyl group of diol replaces.In an embodiment of film process, the stoichiometry equivalent mol ratio of employing is 1, two alkoxyl groups of one of them diol replaces.In general, for implementing this embodiment, the variation range of the mol ratio of glycol and organic functional property silane can be for desiring by about 95 to about 125% of the stoichiometry of each alkoxyl group-silyl of transesterify equivalence.In a specific embodiment, the molar ratio range of glycol and organic functional property silane can be about 100 to about 110% of stoichiometry equivalence.In another embodiment, for the mol ratio of glycol and organic functional property silane, molar ratio range can be about 100 to about 105% of stoichiometry equivalence.One skilled in the art will appreciate that excessive glycol can be used for increasing speed of reaction, but this there is not remarkable advantages usually when in film, reacting, and has just increased expense.
Film-forming apparatus and method are not crucial, can be any as known in the art.The device of known typical comprises falling liquid film or scraped film evaporator.Minimum film thickness and flow velocity depend on the minimum moistening speed of film formation surface.Maximum film thickness degree and flow velocity depend on the spotting out of film and equipment.Heating through film, through reduce on the film pressure or through both combination, can effectively carry out the evaporation of alcohol from film.The preferred gentle heating and the pressure of reduction of adopting, thus glycol deutero-organic functional property silane among the present invention formed.Implement the optimum temps of film process and alkoxyl group and the glycol that pressure (vacuum tightness) will depend on the concrete initial organic functional property silane that uses in the method.
Compare with the traditional coupling agent, adhesion promotor and the linking agent that in known art, have extensive use, the silane among this paper provides significant advantage.The organic functional property silane of these ring-types and bridging has reduced the amount of the volatile constituent that produces during use.Volatile constituent endangers safety and contaminate environment.The tradition coupling agent; For example comprise aminosilane, as derive from Silquest A-1110 of GE.Comprise three methoxyl groups on its each Siliciumatom in its molecular structure; This causes the setting up period at the sealing agent preparation; Each mole silane silicon equivalent weight will discharge nearly three moles methyl alcohol, and wherein the silicon of silane plays adherent effect between reinforcing sealant compsn and the matrix.Therefore the release of methyl alcohol is very disadvantageous, because it is inflammable, can cause the danger of catching fire, and because it goes far towards the discharging of VOC, thereby environment is had potential harm.Modification organic functional property silane described herein through the quantity discharged with methyl alcohol be limited to each silane equivalent be merely one mole, be lower than one mole or even be substantially zero the mole methyl alcohol, can make this problem be able to avoid or alleviate greatly.
According to exemplary embodiment of the present invention; The method for preparing silane is provided; It is included under the situation that has or do not exist catalyzer at least a organic functional property silane and glycol is reacted, thereby glycol deutero-organic functional property silane is provided.
The organic functional property silane of ring-type that comprises among this paper and bridging can comprise the one-component or the various mixture of the organic functional property silane components of single ring-type and bridging; Organic functional property silane components only contains monofunctional, and optional other material that also comprises.Compound method produces the distribution of various silane, and wherein the mixture of starting ingredient is used to produce the purpose of mixture of the dialkoxy organic functional property silane product of ring-type and bridging.In addition; Be understood that; The partial hydrolysate and/or the condensation product of the organic functional property silane of these ring-types and bridging; Being also referred to as is the organic functional property siloxanes and/or the silanol of ring-type and bridging, and the by product that can be used as the most methods of the organic functional property silane for preparing ring-type and bridging is included in the silane of this paper.In addition; When the organic functional property silane that stores ring-type and bridging; Especially under the condition of humidity, or when preparation the time remaining residual water-content not preparation subsequently during following time of condition of being removed fully, partial hydrolysate and/or condensation product possibly appear.In addition, through introducing suitable stoichiometry or excessive water among the silane preparation method who describes in this article, can formulate the part and even the significantly hydrolysis of the organic functional property silane of ring-type and bridging wittingly.In addition, through introducing appropriate chemical metering or excessive water among the silane preparation method who describes in this article, can formulate the content of siloxane of the organic functional property silane of ring-type and bridging wittingly.
According to another embodiment of the invention; Any organic functional property silane with amino and/or mercapto functional group; Can react with being applicable to the isocyanate-terminated polyurethane prepolymer that forms the silylanizing urethane polymer; Here the NCO of amino and/or mercapto functional group and prepolymer reacts, and forms to have the silylanizing urethane polymer that reduces the VOC characteristic.
Through above-mentioned Silante terminated polyether polyols with reduced unsaturation, curing catalysts and one or more conventional func auxiliary agents such as filler, softening agent, thixotrope, inhibitor, U.V. stablizer and adhesion promotor are thoroughly mixed, can obtain encapsulant composition from above-mentioned Silante terminated polyether polyols with reduced unsaturation.Use double planetary mixer (batch formula) can reach effective mixing of various components.Yet, also can adopt the successive method to make sealing agent.Usually, down Silante terminated polyether polyols with reduced unsaturation, filler, stablizer and softening agent were mixed about 60 to about 90 minutes at about 60 ℃.After being cooled to about 50 ℃, add required silane adhesion promoter, dewatering agent and curing catalysts, with mixture stir about 30 minutes.
Silane above-mentioned among suitable silane and this paper is identical.
Filler comprises: use abrasive particle, deposition and the colloidal lime carbonate crossed such as stearate or stearic compound treatment; Enhanced silicon-dioxide is like the silicon-dioxide and the silica gel of aerosil, precipitated silica, silica gel and hydrophobization; Pulverize and quartz, aluminum oxide, white lake, titanium hydroxide, zeyssatite, red stone, carbon black and the graphite of abrasive particle, perhaps for example such as the clay of kaolin, wilkinite or polynite.These fillers can be used alone or in combination.In the first embodiment, with respect to per 100 parts of Silante terminated polymkeric substance, filler content can reach 200 parts; In second embodiment; With respect to per 100 parts of Silante terminated polymkeric substance, filler content about 80 is to about 150 parts, in the 3rd embodiment; With respect to per 100 parts of Silante terminated polymkeric substance, about 100 parts of filler content.
Normally used softening agent is applicable to the present invention in this field, in order to the increase elongation, thereby helps to use higher levels of filler.The softening agent of example comprises dibenzoate of phthalic ester, dipropylene glycol and Diethylene Glycol and composition thereof, epoxidised VT 18, or the like.Dioctyl phthalate and di-isodecyl be a useful source may include trade names Jayflex
Figure 2006800124807_4
DOP and Jayflex
Figure 2006800124807_5
DIDP purchased from ExxonMobil? Chemical ones.Dibenzoate can be purchased from Velsicol? Chemical? Corporation's Benxoflex
Figure 2006800124807_6
9-88, Benxoflex 400.In the first embodiment; With respect to per 100 parts of Silante terminated polyether polyols with reduced unsaturation, the typical amount of softening agent is up to about 100 parts, in second embodiment; With respect to per 100 parts of Silante terminated polyether polyols with reduced unsaturation, this amount is about 40 to about 80 parts.
Usually U.V. and/or inhibitor have been introduced in the encapsulant composition of the present invention; In the first embodiment; Its weight range is to be about 0 to about 5 parts with respect to per 100 parts of Silante terminated polyether polyols with reduced unsaturation; In second embodiment, its weight range is to be about 0.5 to about 2.0 parts with respect to per 100 parts of Silante terminated polyether polyols with reduced unsaturation.Representative additives include, but are not limited to, Tinuvin
Figure 2006800124807_8
770, Tinuvin
Figure 2006800124807_9
327, Tinuvin
Figure 2006800124807_10
213, Tinuvin
Figure 2006800124807_11
622 and Irganox
Figure 2006800124807_12
1010.These stablizers can be used alone or in combination.
Suitable curing catalysts is identical with the catalyzer of above-mentioned polyurethane preformed polymer.According to another embodiment of the present invention, curing catalysts can be for being selected from the metal catalyst of tin or titanium.
Various thixotropic agent or anti-sagging agent comprise the clay and the polymeric amide of various castor, aerosil, processing.With respect to per hundred parts of silylated urethane component, about 1 to about 10 parts usually of these content of additive.According to another embodiment of the invention, with respect to per hundred parts of silylated urethane component, these content of additive about 1 are to about 6 parts.Thixotropes including those that can be purchased: purchased from Degussa's Aerosil
Figure 2006800124807_13
, from Cabot's Cab-O-Sil
Figure 2006800124807_14
TS? 720, purchased from CasChem of Castorwax
Figure 2006800124807_15
, purchased from Rheox of Thixatrol
Figure 2006800124807_16
and Thixcin and purchased from the King? Industries of Disparlon .
According to another embodiment of the invention, after mixing, can with sealing agent about 23 ℃ with about 50% relative humidity under solidified 3 days, and about 37 ℃ with about 95% relative humidity under solidified again 4 days.(American Society for Testingand Materials, method D 412 ASTM) stretches, tears with D 624 and extends test, confirms the physicals of solidified sealing agent to adopt American Society Testing and Materials then.
Polymkeric substance of the present invention hardens or is solidified into crosslinked three-dimensional network when being exposed to moisture (steam, liquid water, Aquo System etc.).Solidification rate depends on free air temperature, relative humidity or the like.According to another embodiment of the present invention, use this polymkeric substance with the form of encapsulant composition, said encapsulant composition comprises polymkeric substance and promotes crosslinked polymer or hardened catalyzer.These compsns also constitute integral part of the present invention.
Silane of the present invention also is suitable as in those high expectations has the adhesion promotor in the encapsulant composition of the adhesive power surperficial to another.In this application, add silane in the batching later stage of sealing agent or binder compsn usually.The usage level of these materials is normally such; Be in the first embodiment compsn about 0.25 to about 5 weight %; In second embodiment be compsn about 0.50 to about 2.5 weight %, be 0.8 to 1.5 weight % of compsn in the 3rd embodiment.Except silane of the present invention, suitable adhesion promotor can include but not limited to available from the Silquest of General Electric Company A-1120 silane, Silquest
Figure 2006800124807_20
A-2120 silane, Silquest
Figure 2006800124807_21
A-1170 silane and Silquest A-187 silane.
According to another typical embodiments of the present invention; A kind of encapsulant composition is provided; It comprises silane adhesion promoter and one or more are selected from the optional member of thixotropic agent, softening agent, stablizer, pigment and filler; The amount of the volatile organic compounds that described silane adhesion promoter produces when hydrolysis all is that the amount of the volatile organic compounds that silane hydrolyzate produced in the hydrolyzable site of hydrolyzable alkoxyl group reduces than what have similar number.
According to another exemplary of the present invention; A kind of encapsulant composition is provided; It comprises silylated polyurethane resin, catalyzer, silane adhesion promoter and one or more are selected from the optional member of thixotropic agent, softening agent, stablizer, pigment and filler; The amount of the volatile organic compounds that described silane adhesion promoter produces when hydrolysis all is that the amount of the volatile organic compounds that silane hydrolyzate produced in the hydrolyzable site of hydrolyzable alkoxyl group reduces than what have similar number.
Crosslinkable of the present invention or hardenable Silante terminated polymkeric substance are applicable to application of paints, and are applicable to that buildings, aircraft, bathroom fixtures, automobile equipment maybe need have the elongation of improvement and joint filling and the sealing applications under the flexible elastomer polymer occasion.The another kind of desirable characteristic of these crosslinkable polymers is, they can be applied on tide or the wet surface and be cured as crosslinked elastomerics, and do not have adverse influence, and cured product is just becoming not sticking in the relatively short time.In addition, cured polymer of the present invention self or strong to adhesivity under the assistance of priming paint such as various substrate of glass, pottery, timber, metal, macromolecular material etc., this makes it to be particularly suitable for the joint filling of any kind, glued or laminated application.
Cured polymer of the present invention provides the combination of the ideal performance of the Silante terminated polyether polyols with reduced unsaturation of-oxyl; Like tear strength, ductility, elastic restoring force; Or the like, provide the elongation that improves with flexible and simultaneously than the ideal performance of low elastic modulus.Elongation that improves and lower Young's modulus for example, can significantly reduce the stress to substrate interface place polyurethane sealant in the expansion of seam with between the systole.These character help to make the adhesion failure of sealing agent to minimize.
Though with reference to many embodiments invention has been described, those skilled in the art will appreciate that under the situation that does not depart from the scope of the invention can carry out various variations, its key element can substitute with equivalent elements.In addition, under the situation that does not depart from essential scope of the present invention, multiple modification be can make, thereby specific situation or material adapted to instruction of the present invention.Therefore, the present invention is not limited to any specific embodiment disclosed herein.
Following limiting examples is to further specify of the present invention.
Embodiment 1
This embodiment is the preparation of clear organic functional property silane (being called silane A) for example, and it will be used as the end-capping reagent of producing in the silylated polyurethane resin (SPUR) after a while.
Embodiment 1: the preparation of silane A
Silane A prepares by following method: in the 250mL round-bottomed flask, mix N-ethyl-(3-diethoxymethyl the silyl)-2-methyl propylamine of 128.6 grams (0.55 mole), the 2-methyl-2 of 74.1 grams (0.63 mole); 4-pentanediol (74.1g; 0.63 mole) with 4.6 restrain (0.014 mole) alcohol sodium solution (21wt.% ethanolic soln), five plate Oldershaw distillation towers, short-path distillation head, receiving bottle, temp probe and heating jacket are housed on the said round-bottomed flask.Then under the vacuum of about 30mmHg with flask be heated to about 45 ℃ to remove ethanol.During temperature rises to 95 ℃ about 5 hours gradually, vacuum tightness is slowly brought up to 0.5mmHg.Under 0.5mmHg, 110 to 116 ℃ of bottle temperature, 55 to 75 ℃ of head temperature with unreacted 2-methyl-2,4-pentanediol stripping.Under the gentle 82-84 ℃ of head temperature of 110-116 ℃ of bottle,, obtain about 115.3 gram silane A of theoretical yield 80.1% with the product distillation.
Embodiment 2 and comparative example 1
Embodiment 2 has described with silane A (embodiment 1) as end-capping reagent, preparation SPUR polymkeric substance.The comparative example 1 that provides as contrast has been described with N-ethyl-(diethoxymethyl silyl)-2-methyl propylamine as end-capping reagent, preparation SPUR polymkeric substance.Use isophorone vulcabond (IPDI) to be prepared in the NCO blocked prepolymer that to use in these examples.
Adopt following method to carry out the preparation of embodiment 2 and comparative example 1 independently.In reactor drum, sweep the polyol component drying that makes by amount shown in the table 1 through stirring with 80 ℃ nitrogen spray, reduce to 200ppm or lower up to the moisture content of polyvalent alcohol.Then reactor cooling is arrived about 45 ℃.Press the amount shown in the table 1 then, join in the exsiccant polyol component IPDI and mixing.After about five minutes, catalyzer is joined in the mixture of resulting dry polyvalent alcohol and IPDI by amount shown in the table 1.Under continuously stirring, resulting dry polyvalent alcohol, IPDI and mixture of catalysts are heated to about 75 ℃.Make temperature remain on 75 ℃, whenever adopted positive dibutylamine titration measuring NCO content, until reaching theoretical detent position at a distance from one and a half hours.Then, by the amount shown in the table 1 end-capping reagent shown in the table 1 is joined in the mixture.Be reflected under 75 ℃ the temperature and carry out, up to confirming that through titration reaction accomplishes.Duration of the reaction is about 24 to about 28 hours.
The prescription of table 1: embodiment 2 and comparative example 1
Composition Embodiment 2 Comparative example 1
Acclaim
Figure 2006800124807_23
Polyvalent alcohol 8200 (available from Bayer) 		400 grams 400 grams
Isophorone vulcabond (IPDI) 14.9 gram 14.9 gram
Dibutyl tin laurate (10%DMM PPG solution) 10ppm 12ppm
Silane A (embodiment 1) 9.0 gram -
N-ethyl-(diethoxymethyl silyl)-2-methyl propylamine - 7.1 gram
Viscosity to embodiment 2 and comparative example 1 is measured.Through adding the catalyzer of 1 weight %, pour into a mould the thick thin slice of 2.5mm of embodiment 2 and comparative example 1 respectively, thereby prepare independently sample then.In order to realize solidifying, thin slice was placed 3 days in the chamber of 90% humidity and 38 ℃.Then thin slice was placed 4 days in 50 ℃ of baking ovens again.After the curing, cut out " dog bone shape " sample from thin slice, the physicals of working sample is listed in the following table 2.
The physical properties of table 2: embodiment 2 and comparative example 1
SPUR resin viscosity (cP) Tensile strength (psi) Young's modulus (psi) Elongation Hardness (SHORE A)
Embodiment 2 345,000 95.3 47.9 557.1 ?13.3
Comparative example 1 185,000 76.9 47.9 450 ?9.5
Embodiment 3 and comparative example 2
According to the step identical with the above embodiments 2 and comparative example 1, with composition shown in the table 3 and amount, preparation embodiment 3 and comparative example 2.Use methylene radical diphenylene vulcabond (MDI) to be prepared in the NCO blocked prepolymer that to use in these examples.
The prescription of table 3: embodiment 3 and comparative example 2
Composition Embodiment 3 Comparative example 2
Acclaim Polyvalent alcohol 4200 (available from Bayer) 400 grams 400 grams
Methylene radical diphenylene vulcabond (MDI) 37.3 gram 37.3 gram
Catalyzer (dibutyl tin laurate, 10%DMM PPG solution) 4.5ppm 10ppm
Silane A (embodiment 1) 27.1 gram -
N-ethyl-(3-diethoxymethyl silyl)-2-methyl propylamine - 21.4 gram
Physics and mechanical property are listed in the following table 4.
The physical properties of table 4: embodiment 3 and comparative example 2
SPUR resin viscosity (cP) Tensile strength (psi) Young's modulus (psi) Elongation Hardness (SHORE A)
Embodiment 3 192,000 120.0 157.6 123.1 29.0
Comparative example 2 180,600 129.1 184.2 134.1 26.3
Embodiment 4 and 5
The preparation of the for example clear organic functional property silane (being called silane B and C respectively) of these embodiment, it is at the adhesion promotor that is used as afterwards in the encapsulant composition.
Embodiment 4: the preparation of silane B
Silane B prepares by following method: in 5 L round-bottomed flasks, mix the 3-aminopropyl triethoxysilane of 2306 grams (10.4 moles), the 2-methyl isophthalic acid of 936 grams (10.4 moles); The alcohol sodium solution (21wt.% ethanolic soln) of ammediol and 13.95 grams (0.036 mole), magnetic agitation, 12 is housed on the said round-bottomed flask " Webster separation column (vigreux column), short-path distillation head, receiving bottle, temp probe and heating jacket.Under the vacuum of 120mmHg, flask is heated to 60 ℃ to remove ethanol.Rise to 85 ℃ 5 hours gradually in temperature during vacuum tightness is brought up to 0.5mmHg gradually, simultaneously with the ethanol stripping.Reclaim out about 2221 gram silane B.
Embodiment 5: the preparation of silane C
Prepare silane C by following method: in the 500mL round-bottomed flask, mix the 3-aminopropyl methyldiethoxysilane of 199.9 grams (1.05 moles), the 2-methyl isophthalic acid of 94.2 grams (1.05 moles); The alcohol sodium solution (21wt.% ethanolic soln) of ammediol and 7.0 grams (0.02 mole), magnetic agitation, 12 is housed on the said round-bottomed flask " Webster separation column, short-path distillation head, receiving bottle, temp probe and heating jacket.Under the vacuum of 120mmHg, flask is heated to 60 ℃ to remove ethanol.Rise to 85 ℃ 5 hours gradually in temperature during vacuum tightness is brought up to 0.5mmHg gradually, simultaneously with the ethanol stripping.Reclaim out about 197.2 gram silane C.
Embodiment 6-8; Comparative example 3
Embodiment 6: the preparation of encapsulant composition
Embodiment 6 is the preparation of clear encapsulant composition for example.Through in Ross PDM powder blenders, each composition is mixed the preparation encapsulant composition by amount shown in the following table 5 and mixing time.
Table 5: the prescription of encapsulant composition
Mixing step Composition Weight percent Mixing time
1 Silylated polymer (Silquest
Figure 2006800124807_25
Y15735 is available from GE) 		23.08 30 minutes
Tinuvins 213, stablizer 0.23
Tinuvins 622L, stablizer 0.23
2 (joining in the mixture that step 1 obtains) SiO 2(thixotropic agent) 1.13 30 minutes
3 (joining in the mixture that step 2 obtains) Lime carbonate (Ultra Pflex
Figure 2006800124807_26
, available from Specialty Minerals) 		8.31 20 minutes
Lime carbonate (High Pflex
Figure 2006800124807_27
, available from Specialty Minerals) 		5.54
4 (joining in the mixture that step 3 obtains) Di Iso Decyl Phthalate (DIDP, softening agent) 9.23 20 minutes
5 (joining in the mixture that step 4 obtains) Lime carbonate (Ultra Pflex
Figure 2006800124807_28
, available from Specialty Minerals) 		16.62 20 minutes
Lime carbonate (High Pflex , available from Specialty Minerals) 11.08
6 (joining in the mixture that step 5 obtains) Di Iso Decyl Phthalate (DIDP, softening agent) 9.23 20 minutes
7 (joining in the mixture that step 6 obtains) Lime carbonate (Ultra Pflex
Figure 2006800124807_30
, available from Specialty Minerals) 		8.31 1 hour 40 minutes
Lime carbonate (High Pflex
Figure 2006800124807_31
, available from Specialty Minerals) 		5.54
TiO 2(pigment) 1.16
After encapsulant composition is thoroughly mixed, the encapsulant composition of embodiment 6 is divided into three equal parts, be respectively applied for embodiment 7 and 8 and the preparation of comparative example 3.
Embodiment 7 and 8; Comparative example 3
What embodiment 7 and 8 described is to comprise embodiment 4 and embodiment 5 respectively, with the preparation of the physical mixture of the encapsulant composition of catalyzer and embodiment 6.The comparative example 3 that provides as contrast is described is the preparation of physical mixture that comprises the encapsulant composition of 3-aminopropyl triethoxysilane, catalyzer and embodiment 6.
Method by following prepares physical mixture: by the amount shown in the table 6 encapsulant composition of embodiment 6 and silane are packed in Flack Tek
Figure 2006800124807_32
flash mixer, mixed about one to two minute with 2000rpm.Then, catalyzer is joined in the resulting mixture, mixed about one minute with 2000rpm by the amount shown in the table 6.
Table 6: the composition of physical mixture
Composition Embodiment 7 (weight percent) Embodiment 8 (weight percent) Comparative example 3 (weight percent)
Silane B (embodiment 4) 0.57 - -
Silane C (embodiment 5) - 0.57 -
The 3-aminopropyl triethoxysilane is available from the Sliquest of GE Advanced Materials
Figure 2006800124807_33
A-1110 		- - 0.57
Encapsulant composition (embodiment 6) 99.4 99.4 99.4
Dibutyl tin laurate, catalyzer 0.3 0.3 0.3
Embodiment 9-10: comparative example 4
These examples illustrate the curing of physical mixture of embodiment 7-8 and the comparative example 3 of preceding text.
A part of physical mixture of embodiment 7-8 and comparative example 3 is configured as the 2.5mm thin slice independently.In order to realize the curing of physical mixture, thin slice was placed three days in the high humidity chamber of 90% humidity and 38 ℃.Then thin slice was placed 4 days in 50 ℃ of baking ovens.After the curing, use punch press and mould from solidify thin slice, to cut out sample.According to ASTM D412 all samples is measured its breaking tension, elongation and modulus.The physics and the mechanical property of solidified sample are listed in the following table 7.
Table 7: the physical properties of solidified physical mixture
Embodiment Adhesion promotor Tensile strength (psi) Young's modulus (psi) 100% modulus (psi) Elongation (per-cent) Tear strength (Lb/in) Hardness (Shore A)
9 Embodiment 4 164.5 120.4 80.3 342.0 23.1 21.0
10 Embodiment 5 152.0 114.9 80.5 433?3 26.2 26.0
Comparative example
3 The 3-aminopropyl triethoxysilane 175.9 62.0 57.2 626.4 40.4 22.0
Place in glass, aluminium and the PVC substrate through rest part, prepare other sample physical mixture.Be to realize the curing of sample, initially the substrate that has physical mixture on it was placed 3 days in the high humidity chamber of 90% humidity and 38 ℃.Then substrate was placed 4 days in the low humidity chamber of 50% humidity and 23 ℃.Next substrate was placed 7 days in 23 ℃ of water-baths.After the curing, measure the stripping strength of all samples.The physics and the mechanical property of solidified sample are listed in the following table 8.
Table 8: the stripping strength of solidified sample
Substrate Embodiment 9 Embodiment 10 Comparative example 4
Average stripping strength (lbs/in) Failure type Average stripping strength (lbs/in) Failure type Average stripping strength (lbs/in) Failure type
Aluminium 18.0 100% adhesive aggregation 11.9 90% adhesive aggregation 17.6 100% adhesive aggregation
Glass 25.6 100% adhesive aggregation 6.4 40% adhesive aggregation 11.5 100% adhesive aggregation
PVC 17.1 100% adhesive aggregation 12.7 100% adhesive aggregation 15.7 100% adhesive aggregation
Embodiment 11 and 12
Adopt and same recipe and preparation method at the said sealing agent of embodiment 6-8; Preparation embodiment 11 and 12; Different is; Used silylated polyurethane prepolymer is the WSP 725-80 available from witton Chemicals; Used adhesion promotor is respectively Silquest
Figure 2006800124807_34
Y-15656 and Silquest
Figure 2006800124807_35
Y-15686, and the two is all available from GE Advanced Materials.
In addition, adopt the test procedure described in the embodiment 9-10 here.Test result is listed in the following table 9.
Table 9
Embodiment Adhesion promotor Tensile strength (psi) 100% modulus (psi) Elongation (per-cent) Stripping strength (lb/in)
Aluminium Glass PMMA
11 Silquest
Figure 2006800124807_36
Y-15656 		188.5 39.2 890 29.7 33.3 18.3
12 Silquest
Figure 2006800124807_37
Y-15686 		187.1 36.3 844 38.0 36.8 22.6
*All tests cause the 80-100% adhesive aggregation to lose efficacy
In a word, compare with present employed silane, silane of the present invention demonstrates performance equal or that improve, and aspect minimizing volatile organic compounds quantity discharged, significant benefit is provided.
Though with reference to many exemplary invention has been described, those skilled in the art will appreciate that under the situation that does not depart from the scope of the invention to carry out various variations that its key element can substitute with equivalent elements.In addition, under the situation that does not depart from essential scope of the present invention, multiple modification be can make, thereby specific situation or material adapted to according to instruction of the present invention.Therefore, the present invention is not limited to any specific typical embodiments disclosed herein.

Claims (32)

1. crosslinkable Silante terminated polymkeric substance; It comprises the reaction product of isocyanate-terminated prepolymer and silane; Said silane have a plurality of hydrolyzables site and to isocyanic ester have reactive at least one comprise the group of active hydrogen; The amount of the volatile organic compounds that said silane produces when hydrolysis all is that the amount of the volatile organic compounds that silane hydrolyzate produced in the hydrolyzable site of hydrolyzable alkoxyl group reduces than what have similar number
Wherein silane has following general formula:
[Y [G (SiX uZ b vZ c w) s] r] n(formula 1)
Wherein the G of each appearance is independently selected from following group group: the one or more Wasserstoffatomss by alkyl, thiazolinyl, aryl or aralkyl are substituted resulting polyad, and G contains 1 to 30 carbon atom;
The X of each appearance is independently selected from R 1O-, R 1C (=O) O-, R 1R 2C=NO-, R 1R 2NO-, R 1R 2N-,-R 1,-(OSiR 1R 2) t(OSiR 1R 2R 3) and-O (R 10CR 11) fOH, the wherein R of each appearance 1, R 2, R 3, R 10And R 11Be R independently;
The Z of each appearance bBe independently selected from [O (R 10CR 11) fO-] 0.5, [HN (R 10CR 11) fN (H)-] 0.5, [OOC (R 10CR 11) fCOO-] 0.5, [O (R 10CR 11) fN (H)-] 0.5[O (R 10CR 11) fCOO-] 0.5, the R of each appearance wherein 10And R 11Be R independently; The Z of each appearance cBe independently selected from-O (R 10CR 11) fO-,-HN (R 10CR 11) fN (H)-,-OOC (R 10CR 11) fCOO-,-O (R 10CR 11) fN (H)-with-O (R 10CR 11) fCOO-, the wherein R of each appearance 10And R 11Be R independently;
The R of each appearance is independently selected from following group group: hydrogen, straight chain, ring-type or branched-chain alkyl, thiazolinyl, aryl and aralkyl; The group that obtains with a Wasserstoffatoms that removes assorted carbon, wherein the R of each appearance comprises 1 to 20 carbon atom;
The subscript f of each appearance is 1 to 15 integer;
The n of each appearance is 1 to 100 integer, condition be when n greater than 1 the time, v is greater than 0, and Z bAll valencys Siliciumatom and its bonding are all arranged;
The subscript u of each appearance is 0 to 3 integer;
The subscript v of each appearance is 0 to 3 integer;
The subscript w of each appearance is 0 to 1 integer, and condition is u+v+2w=3;
The subscript r of each appearance is 1 to 6 integer;
The subscript t of each appearance is 0 to 50 integer;
The subscript s of each appearance is 1 to 6 integer;
Wherein said crosslinkable Silante terminated polymkeric substance contains the Z of at least one appearance bOr Z c
2. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein isocyanate-terminated prepolymer is the reaction product of POLYMETHYLENE POLYPHENYLISOCYANATE and polyvalent alcohol.
3. the crosslinkable Silante terminated polymkeric substance of claim 2, wherein POLYMETHYLENE POLYPHENYLISOCYANATE is selected from the organic diisocyanate of aliphatic series and aromatics.
4. the crosslinkable Silante terminated polymkeric substance of claim 2, wherein the molecular weight ranges of polyvalent alcohol is 1,000 to 20,000.
5. the crosslinkable Silante terminated polymkeric substance of claim 2, wherein polyvalent alcohol is selected from glycol, triol, polyester polyol, polyether glycol and arbitrary combination thereof.
6. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein Y is a unit price organic functional base.
7. the crosslinkable Silante terminated polymkeric substance of claim 6, wherein unit price organic functional base selected from mercapto ,-OH ,-NH 2With-NHR 4
8. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein G is selected from: the diethylidene hexanaphthene, 1,2,4-triethylene hexanaphthene, diethylidene benzene, phenylene, m be 1 to 12-(CH 2) m-and q be zero to 17-CH 2(CH 2) qCH (CH 3)-.
9. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein R 10And R 11Be selected from hydrogen, methyl and ethyl independently of one another.
10. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein R 1And R 2Be independently selected from hydrogen, methyl, ethyl and propyl group.
11. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein R 3, R 4, R 5, R 6, R 7And R 8Be independently selected from phenyl, methyl, butyl, H and ethyl.
12. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein X is selected from methoxyl group, oxyethyl group, isobutoxy, propoxy-, isopropoxy, acetoxyl group, methoxy ethoxy, oximido and derived from the unit price alkoxyl group of glycol.
13. the crosslinkable Silante terminated polymkeric substance of claim 1, wherein v is 0, and X is R 1O-or R 1C (=O)-, R wherein 1Be C 1To C 4Alkyl or hydrogen, G are the divalence straight-chain alkyl-sub-s of 2 to 18 carbon atoms.
14. the crosslinkable Silante terminated polymkeric substance of claim 1, itself and catalyst mix, the amount of said catalyzer is enough to when being exposed to moisture, solidify said polymkeric substance, thereby forms the Silante terminated polymkeric substance of moisture curable.
15. the curing compsn of claim 1.
16. the encapsulant composition of moisture curable, it comprises the Silante terminated polymkeric substance of moisture curable as claimed in claim 14 and the combination of at least a filler.
17. curing sealant according to claim 16.
18. tackiness agent or coating composition comprise the crosslinkable Silante terminated polymkeric substance of claim 14.
19. encapsulant composition; It comprises silylated urethane resin, catalyzer and promotion adherent silane; The amount of the volatile organic compounds that said silane produces when hydrolysis; Than what have similar number all is that the amount of the volatile organic compounds that silane hydrolyzate produced in the hydrolyzable site of hydrolyzable alkoxyl group reduces
Wherein said silane has following general formula:
[Y [G (SiX uZ b vZ c w) s] r] n(formula 1)
Wherein the G of each appearance is independently selected from following group group: the one or more Wasserstoffatomss by alkyl, thiazolinyl, aryl or aralkyl are substituted resulting polyad, and G contains 1 to 30 carbon atom;
The X of each appearance is independently selected from R 1O-, R 1C (=O) O-, R 1R 2C=NO-, R 1R 2NO-, R 1R 2N-,-R 1,-(OSiR 1R 2) t(OSiR 1R 2R 3) and-O (R 10CR 11) fOH, the wherein R of each appearance 1, R 2, R 3, R 10And R 11Be R independently;
The Z of each appearance bBe independently selected from [O (R 10CR 11) fO-] 0.5, [HN (R 10CR 11) fN (H)-] 0.5, [OOC (R 10CR 11) fCOO-] 0.5, [O (R 10CR 11) fN (H)-] 0.5[O (R 10CR 11) fCOO-] 0.5, the R of each appearance wherein 10And R 11Be R independently; The Z of each appearance cBe independently selected from-O (R 10CR 11) fO-,-HN (R 10CR 11) fN (H)-,-OOC (R 10CR 11) fCOO-,-O (R 10CR 11) fN (H)-with-O (R 10CR 11) fCOO-, the wherein R of each appearance 10And R 11Be R independently;
The R of each appearance is independently selected from following group group: hydrogen, straight chain, ring-type or branched-chain alkyl, thiazolinyl, aryl and aralkyl; The group that obtains with a Wasserstoffatoms that removes assorted carbon, wherein the R of each appearance comprises 1 to 20 carbon atom;
The subscript f of each appearance is 1 to 15 integer;
The n of each appearance is 1 to 100 integer, condition be when n greater than 1 the time, v is greater than 0, and
Z bAll valencys Siliciumatom and its bonding are all arranged;
The subscript u of each appearance is 0 to 3 integer;
The subscript v of each appearance is 0 to 3 integer;
The subscript w of each appearance is 0 to 1 integer, and condition is u+v+2w=3;
The subscript r of each appearance is 1 to 6 integer;
The subscript t of each appearance is 0 to 50 integer;
The subscript s of each appearance is 1 to 6 integer;
The organic functional property silane of at least a ring-type and bridging that wherein constitutes the organic functional property silane of ring-type and bridging contains the Z of at least one appearance bOr Z c
20. the encapsulant composition of claim 19, wherein Y is a unit price organic functional base.
21. the encapsulant composition of claim 20, wherein unit price organic functional base be selected from-OH ,-NR 4C (=O) OR 5,-OC (=O) NR 4R 5,-NR 4C (=O) SR 5,-SC (=O) NR 4R 5,-NR 4C (=S) OR 5,-OC (=S) NR 4R 5,-NR 4C (=S) SR 5,-SC (=S) NR 4R 5,-NR 4C (=O) NR 5R 6,-NR 4C (=S) NR 5R 6, R 4C (=O) NR 5-,-C (=O) NR 4R 5-, R 4C (=S) NR 4-,-NH 2With-NHR 4, the R of each appearance wherein 4, R 5And R 6Independently by on regard to one of structure that R enumerates and provide.
22. the encapsulant composition of claim 19, wherein G is selected from: the diethylidene hexanaphthene, 1,2,4-triethylene hexanaphthene, diethylidene benzene, phenylene, m be 1 to 12-(CH 2) m-and q be zero to 17-CH 2(CH 2) qCH (CH 3)-.
23. the encapsulant composition of claim 19, wherein R 10And R 11Be selected from hydrogen, methyl and ethyl independently of one another.
24. the encapsulant composition of claim 19, wherein R 1And R 2Be independently selected from hydrogen, methyl, ethyl and propyl group.
25. the encapsulant composition of claim 19, wherein R 3, R 4, R 5, R 6, R 7And R 8Be independently selected from phenyl, methyl, butyl, hydrogen and ethyl.
26. the encapsulant composition of claim 19, wherein X is selected from methoxyl group, oxyethyl group, isobutoxy, propoxy-, isopropoxy, acetoxyl group, methoxy ethoxy, oximido and derived from the unit price alkoxyl group of glycol.
27. the encapsulant composition of claim 19, wherein v is 0, and X is R 1O-or R 1C (=O)-, R wherein 1Be C 1To C 4Alkyl or hydrogen, G are the divalence straight-chain alkyl-sub-s of 2 to 18 carbon atoms.
28. the encapsulant composition of claim 19, wherein the amount scope of silane adhesion promoter is 0.25 to 5 weight % of encapsulant composition.
29. the encapsulant composition of claim 19, the amount of wherein said catalyzer are enough to when being exposed to moisture, solidify said compsn.
30. the encapsulant composition of claim 29, wherein catalyzer is the metal catalyst that is selected from tin or titanium compound.
31. through solidifying the sealing agent that obtains according to the encapsulant composition of claim 29.
32. the encapsulant composition of claim 19 also comprises the composition that one or more are selected from thixotropic agent, softening agent, stablizer, pigment and filler.
CN2006800124807A 2005-02-15 2006-02-14 Crosslinkable silane-terminated polymer and sealant composition made with same Expired - Fee Related CN101180334B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US65597605P 2005-02-15 2005-02-15
US60/655,976 2005-02-15
US11/292,045 2005-12-01
US11/292,045 US7417105B2 (en) 2005-02-15 2005-12-01 Crosslinkable silane-terminated polymer and sealant composition made with same
PCT/US2006/005126 WO2006088839A2 (en) 2005-02-15 2006-02-14 Crosslinkable silane-terminated polymer and sealant composition made with same

Publications (2)

Publication Number Publication Date
CN101180334A CN101180334A (en) 2008-05-14
CN101180334B true CN101180334B (en) 2012-04-04

Family

ID=39406006

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006800124807A Expired - Fee Related CN101180334B (en) 2005-02-15 2006-02-14 Crosslinkable silane-terminated polymer and sealant composition made with same

Country Status (2)

Country Link
CN (1) CN101180334B (en)
ZA (1) ZA200706688B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8809479B2 (en) * 2009-05-01 2014-08-19 Momentive Performance Materials Inc. Moisture curable silylated polymer compositions containing reactive modifiers
DE102009046269A1 (en) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Urea-bound alkoxysilanes for use in sealants and adhesives
CN112243454B (en) * 2018-06-14 2022-03-22 3M创新有限公司 Method of treating a surface, surface modified abrasive particles and resin bonded abrasive articles

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1200742A (en) * 1995-09-26 1998-12-02 阿迈隆国际公司 Polysiloxane polyurethane compositions
CN1365379A (en) * 1999-06-08 2002-08-21 罗狄亚化学公司 Compositions based on organopolysiloxanes and silylated polymer cured into elastomers at room temperature in the presence of moisture
US20030199619A1 (en) * 2002-04-23 2003-10-23 Crompton Corporation Blocked mercaptosilane hydrolyzates as coupling agents for mineral-filled elastomer compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1200742A (en) * 1995-09-26 1998-12-02 阿迈隆国际公司 Polysiloxane polyurethane compositions
CN1365379A (en) * 1999-06-08 2002-08-21 罗狄亚化学公司 Compositions based on organopolysiloxanes and silylated polymer cured into elastomers at room temperature in the presence of moisture
US20030199619A1 (en) * 2002-04-23 2003-10-23 Crompton Corporation Blocked mercaptosilane hydrolyzates as coupling agents for mineral-filled elastomer compositions

Also Published As

Publication number Publication date
CN101180334A (en) 2008-05-14
ZA200706688B (en) 2008-11-26

Similar Documents

Publication Publication Date Title
CA2205106C (en) Polyurethane prepolymers having alkoxysilane and hydantoin groups and their use for the manufacture of sealants
JP6329481B2 (en) Moisture curable silylated polymer composition with improved adhesion to concrete
JP5706062B2 (en) Cross-linked silane-terminated polymer and sealing material composition produced using said polymer
JP4616992B2 (en) Polyurethane prepolymer having alkoxysilane end groups, process for its production and its use for the production of sealing substances
JP4559522B2 (en) Process for the preparation of prepolymers which harden into improved sealants and products comprising the same
JP4588950B2 (en) Aminosilane-containing condensation-crosslinking polyurethane composition, process for its production and use thereof
JP5815603B2 (en) Moisture curable silylated polymer resin composition
US20090075096A1 (en) Organoalkoxysilanes
JP2007510765A (en) Moisture curable polyetherurethane having reactive silane groups and use thereof
MX2007013366A (en) Moisture-curable composition featuring increased elasticity.
US6440573B1 (en) Secondary amine-functional silanes, silane-functional polymers therefrom, and resulting cured polymers
US6803445B2 (en) Moisture curable polyurethane and/or epoxy resin composition and storage stabilizer contained therein
JP2010202886A (en) Polymer containing 3-(n-silylalkyl)aminopropeonic acid ester group and using thereof
CN101180334B (en) Crosslinkable silane-terminated polymer and sealant composition made with same
JP3727558B2 (en) One-part moisture-curing urethane resin composition
JPH0219866B2 (en)
JP2004123900A (en) Curable composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120404

Termination date: 20200214

CF01 Termination of patent right due to non-payment of annual fee