CN100558757C - Contain polymerization initiator system and the prepared therefrom polymerisable compound of aluminum compound as curing inhibitors - Google Patents
Contain polymerization initiator system and the prepared therefrom polymerisable compound of aluminum compound as curing inhibitors Download PDFInfo
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- CN100558757C CN100558757C CNB2005800062346A CN200580006234A CN100558757C CN 100558757 C CN100558757 C CN 100558757C CN B2005800062346 A CNB2005800062346 A CN B2005800062346A CN 200580006234 A CN200580006234 A CN 200580006234A CN 100558757 C CN100558757 C CN 100558757C
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- organo
- compound
- aluminium
- aluminum
- borane
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Abstract
The present invention relates to a kind of composition that comprises organo-borane/amine complex and significant quantity aluminum compound, when it is used to suppress the curing of organo-borane/amine complex during as polymerization initiator system a part of with this aluminum compound in the polymerisable compound that is containing one or more monomers with olefinic degree of unsaturation, oligopolymer or polymkeric substance.The present composition can be used for containing polymerisable compound, binding compositions and the coating composition with compound of polymeric structure division under the radical polymerization condition.
Description
The application requires respectively on February 27th, 2004 and the U.S. Patent Application Serial Number 60/548,828 of submission on March 1st, 2004 and 60/548,987 right of priority.
Background of invention
The present invention relates to the novel curing inhibitors of a kind of amine-organo-borane complex polymerisation initiator; such polymerization starter is in U.S. Patent Application Publication No. 2002/0058764; the reference of people such as people, Skoultchi, Zharov such as Mottus of Miao Shuing and Pocius wherein; following relevant U.S. Patent Application Publication No. 2002/0025381,2002/0028894,2002/0031607,2002/0033227 and 2003/0120005 and initial U.S. Patent application 09/466,321 in be described and ask for protection.All these patent applications and patent all are incorporated herein by reference the amine-organo-borane complex polymerisation initiator that implements usefulness of the present invention owing to having comprised.
As described in U.S. Patent Application Publication No. 2002/0058764, need to solidify as required the polymerisable compound and the binding compositions of (initiated polymerization when needed).Curing composition major issue is the stability of composition as required, and this may cause making the functionality of handling the difficult viscosity rising of change and polymerisable compound or binding compositions to reduce.Disclosed many title complexs are containing in the composition of olefinic degree of unsaturation unstable in room temperature or near prior art under the room temperature.This unstable may cause that polymerization took place and may cause being unsuitable for required purposes before needs composition.
Therefore the initiator system that needs radical polymerization, this system is safety when handling, can spontaneous combustion, and can be used for forming as required the cure polymer system or can be used for solidified binding system as required.Also need in the presence of compound, have the more initiator system of high stability in addition, thereby improve solidified ability as required with olefinic degree of unsaturation.In addition also need be in room temperature or near thermally-stabilised under the room temperature and when the user needs, carry out polymeric polymerisable compound and binding system.
Summary of the invention
One embodiment of the invention are the compositions that contain organo-borane/amine complex and significant quantity aluminum compound, when it is used to suppress the curing of organo-borane/amine complex during as polymerization initiator system a part of with this aluminum compound in the polymerisable compound that is containing one or more monomers with olefinic degree of unsaturation, oligopolymer or polymkeric substance.Provide the non-limiting and representative description of available organo-borane and amine component in U.S. Patent Application Publication No. 2002/0058764 paragraph 0010, and aluminum compound is selected from formula Al
2R
6Organo-aluminium compound, wherein R is C
1-C
12Alkyl or C
1-C
12Alkoxyl group, and 6 R separately can be identical or different.
Another embodiment of the invention comprises a kind of organo-borane/amine complex that contains, and polymerisable compound of the monomer with olefinic degree of unsaturation, oligopolymer or the polymkeric substance of radical polymerization can take place for the aluminum compound of significant quantity and one or more.Other background about polymerisable compound, its use-pattern and application thereof is disclosed in the paragraph 0011 and 0012 of same Patent open source literature, and relevant with the present composition.
Title complex of the present invention is safety when handling, can spontaneous combustion and in room temperature or near stable under the room temperature, and therefore in room temperature or can initiated polymerization in the presence of the title complex dissociative initiator near not making under the room temperature.Polymeric composition of the present invention also can solidify by making the title complex disassociation as required in room temperature or near stable under the room temperature.
Detailed description of preferred embodiments
As described in the first seven row of the paragraph 0014 of U.S. Patent Application Publication No. 2002/0058764 and paragraph 0015, the organo-borane that uses in the composition is trialkylborane or alkyl-cycloalkyl borine.Preferred this borine is corresponding to formula 1:
B (R
2)
3Formula 1
Wherein B represents boron, R
2Be respectively C in each case
1-C
10Alkyl or C
3-C
10Cycloalkyl, perhaps two or more R
2Can be in conjunction with forming the cyclic aliphatic ring.Preferred organo-borane is boron triethyl, triisopropyl borine and three normal-butyl borines.
Various kinds of amine can be as complexing agent to form organo-borane/amine initiator title complex.U.S. Patent Application Publication No. 2002/0058764 discloses many available useful amine components (paragraph 0017-0044 is incorporated herein by reference).United States Patent (USP) 5,935,711 also disclose useful amine component (the 5th hurdle the 61st walks to the 7th hurdle the 61st row, is incorporated herein by reference).These patents provide the non-limiting and representative description of available amine component.
Multiple formula Al
2R
6Organo-aluminium compound can be selected among the present invention.R is C in preceding formula
1-C
12Alkyl or C
1-C
12Alkoxyl group, and 6 R separately can be identical or different.By expansion, for the following formula compound with even number alkyl and/or alkoxyl group, preceding formula can also conclusively show and be AlR
3And Al (R) (R '
2) compound.Radicals R can be the mixture of about 3 alkyl and about 3 alkoxyl groups.Term used herein " alkyl " and " alkoxyl group " comprise straight chain and branched group.
Within the scope of the present invention, the limiting examples of organo-aluminium compound comprises trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminum ethylate, aluminum isopropoxide, tri sec-butoxy aluminum, three tert.-butoxy aluminium, oxyethyl group diethyl aluminum, oxyethyl group diisobutyl aluminum, triethyl (three sec-butoxies) two aluminium, three normal-butyls (three isopropoxies), two aluminium and composition thereof.
Organo-aluminium compound can add as component in any stage of polymerisable compound preparation.Preferably directly organo-aluminium compound is joined in preformed organo-borane/amine complex, most preferably before adding amine, organo-aluminium compound is directly joined in the organo-borane.
The mol ratio of boron and aluminium is important in the composition.If the mol ratio of boron and aluminium is too high, undesirable viscosity may take place the polymerisable compound that then makes thus increases.If the mol ratio of boron and aluminium is too low, then the spontaneous combustion (the absolute ratio of composition spontaneous combustion depends on the organo-aluminium compound of use) of composition possibility perhaps adhesion problem may occur in adhesive application.The mol ratio of boron and aluminium is about 1.0: 1.0 to about 50.0: 1.0.The mol ratio of boron and aluminium is preferably about 10.0: 1.0 to about 30.0: 1.0.
Equally, the mol ratio of amine compound in the title complex and borane compound is also important.As (paragraph 45 disclosed in the U.S. Patent Application Publication No. 2002/0058764, be incorporated herein by reference), the mol ratio of amine compound and organoborane compounds is preferably about 3.0: 1.0 to about 1.0: 1.0, more preferably about 2.0: 1.0 to about 1.0: 1.0.
The present composition that contains organo-borane/amine complex and significant quantity aluminum compound can use known technology easily to prepare.Can add aluminum compound in any time in organo-borane/amine complex or the polymerisable compound preparation process.For most of amine/organo-borane combination, adding amine and organo-borane (or organo-borane/aluminum compound mixture) are unimportant with the order that forms organo-borane/amine complex.Usually under slowly stirring in inert atmosphere in conjunction with various components.Usually observe heat release, therefore advise cooling mixture.Have high vapour pressure as fruit component, temperature of reaction need be remained below about 70-80 ℃.In case with the material thorough mixing, just can be with the title complex cool to room temperature.Do not require the special storage condition, yet preferably title complex is remained in the closed container under the inert atmosphere and place shady and cool place.
Title complex of the present invention and composition are stable in the air.Here " stable in the air " is meant when when being stored in title complex in the closed container under room temperature (about 20-22 ℃) and other envrionment conditions (promptly not under the vacuum also not under inert atmosphere), can maintain as this title complex of polymerization starter and to use, yet this title complex also can easily store the several months under these conditions at least about fortnight." stable in the air " represents that also spontaneous combustion does not take place this title complex.
The polymerizable compound that can be used in the polymeric composition of the present invention comprises any monomer, oligopolymer, polymkeric substance or its mixture that contains the olefinic degree of unsaturation that radical polymerization can take place.U.S. Patent Application Publication No. 2002/0058764 (paragraph 46-48 with and reference, be incorporated herein by reference) the non-limiting and representative description of polymerizable compound and composition related to the present invention is provided.In addition, same patent application (paragraph 0052-0071 and paragraph 0073-0075 are incorporated herein by reference) also discloses about the purposes of described polymerisable compound and the detailed description of application.
Contain the binding compositions that part of of the present invention of amine-organo-borane title complex of significant quantity aluminum compound or polymerisable compound preferably at room temperature or more than room temperature, demonstrate thermostability.Thermostability used herein be meant that amine-organo-borane title complex does not dissociate and triggering composition in the polymerization of the alefinically unsaturated compounds that exists.Thermostability can be measured by the temperature that the mensuration composition viscosity begins to increase.Temperature when composition viscosity increases is preferably greater than about 40 ℃, more preferably greater than about 60 ℃, and most preferably greater than about 80 ℃.The viscosity increase shows that disassociation and initiated polymerization take place amine-organo-borane title complex.
Embodiment
Only provide the following example, and be not intended to limit the scope of claim for illustrative purpose.Except as otherwise noted, all umber and percentage number average are by weight.
The preparation of organo-borane/amine complex
394 cubic centimetres three normal-butyl borines (TNBB) adding is furnished with in the nitrogen purging flask of agitator.In the embodiment that uses aluminum compound, add aluminum compound so that the mol ratio of boron and aluminium is 10: 1-30: 1.So, with in 21 cubic centimetres three n-butylaluminum (TNBAL, boron and al mole ratio are 18.5: 1) the organo-borane solution that slowly adding is stirred, temperature is remained on below 55 ℃ in one embodiment.Perhaps, can add aluminum compound later on again at adding amine.The amine that weighs is placed closed feed containers and uses nitrogen purging.Then amine is added in the organo-borane solution and (have or do not exist aluminum compound of the present invention): 1-1: 3 so that the mol ratio of organo-borane and amine is 1.So, with in 242 cubic centimetres the TNBB/TNBAl solution of 3-METHOXY PROPYL AMINE (MOPA, the mol ratio of boron and nitrogen is 1: 1.47), temperature is remained on below 55 ℃ in this embodiment with a small amount of adding stirring.Stirred solution is about 30 minutes then.Test in the composition for preparing several parts of title complexs and here describe.Table 1 has comprised the composition data and the test result of title complex.
The preparation of polymerisable compound
The composition of test contains 15 weight part organo-borane/amine complexes (having or do not exist aluminiferous doping agent), and polyoxygenated enamine (Jeffamine T403), 7 weight part core-shell impact modifiers (Paraloid EXL 2691A) and 0.03 weight % antioxidant (2 with 70 parts by weight of acrylic acid resins (is that 270000 polymethylmethacrylate (PMMA) is formed by 79% methyl methacrylate (MMA) and 21%Mw), 8 weight parts, the 6-di-tert-butyl-4-methy phenol BHT) mixes.The composition that contains boron triethyl (TEB) does not contain BHT.After suitably mixing each batch of material, be placed in 8 ounces the jar.Use Brookfield Digital Viscometer HATDV II to measure initial viscosity at rotating speed as under the 20rpm with No. 7 spindles.
Heat stability testing
U.S. Patent Application Publication No. 2002/0058764 (paragraph 84 and 85 is incorporated herein by reference) discloses the several method of the thermostability of measuring binding compositions of the present invention or polymerisable compound.Here in the method for Shi Yonging, the viscosity by the periodic measurement polymerisable compound reaches the required time of 100,000 centipoises to be determined at 40 ℃ of following viscosity.
Prepare several jars of polymerisable compounds as mentioned above, place it in then and keep the fate (because higher sample stability, the composition that will contain TEB remains under 55 ℃) that provides in the data in the baking oven that temperature is set at 40 ℃.Sample is taken out from baking oven and make it be cooled to room temperature in that day of measuring viscosity, be generally 4-6 hour.After measuring viscosity sample is put back in the baking oven.Repeat this program up to sample generation gelling, the fate when check data has found that viscosity is 100,000 centipoises.Test result is summarised in the table 1.
Claims (7)
- One kind to contain organo-borane/amine complex and the mol ratio of boron and aluminium is provided be the composition of at least a organo-aluminium compound of 1.0: 1.0 to 50.0: 1.0 amount, it is used to suppress the curing of organo-borane/amine complex when this aluminum compound being used as the polymerization initiator system that contains the olefinic degree of unsaturation a part of.
- 2. composition as claimed in claim 1, wherein organo-aluminium compound has formula Al 2R 6, wherein R is selected from C 1-C 12Alkyl or C 1-C 12Alkoxyl group, and 6 R are identical or different separately.
- 3. composition as claimed in claim 1 or 2, wherein the mol ratio of boron and aluminium is 10.0: 1.0 to 30.0: 1.0.
- 4. any one described composition among the claim 1-3, wherein organo-aluminium compound is one or more in trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminum ethylate, aluminum isopropoxide, tri sec-butoxy aluminum, three tert.-butoxy aluminium, oxyethyl group diethyl aluminum, oxyethyl group diisobutyl aluminum, triethyl (three sec-butoxies) two aluminium, three normal-butyls (three isopropoxies), two aluminium.
- 5. any one described composition among the claim 1-4 wherein added organo-aluminium compound in the organo-borane before organo-borane and amine prepared in reaction organo-borane/amine complex.
- 6. any one described composition among the claim 1-4 wherein adds organo-aluminium compound in the organo-borane/amine complex of preparation.
- 7. one kind contains one or more monomers with olefinic degree of unsaturation, oligopolymer or polymkeric substance and as the polymerisable compound of the composition of any one among the claim 1-6 of initiator system.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US54882804P | 2004-02-27 | 2004-02-27 | |
| US60/548,828 | 2004-02-27 | ||
| US60/548,987 | 2004-03-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1926212A CN1926212A (en) | 2007-03-07 |
| CN100558757C true CN100558757C (en) | 2009-11-11 |
Family
ID=37818183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800062346A Expired - Fee Related CN100558757C (en) | 2004-02-27 | 2005-02-23 | Contain polymerization initiator system and the prepared therefrom polymerisable compound of aluminum compound as curing inhibitors |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100558757C (en) |
| ZA (1) | ZA200607994B (en) |
-
2005
- 2005-02-23 CN CNB2005800062346A patent/CN100558757C/en not_active Expired - Fee Related
-
2006
- 2006-09-26 ZA ZA200607994A patent/ZA200607994B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1926212A (en) | 2007-03-07 |
| ZA200607994B (en) | 2008-08-27 |
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Granted publication date: 20091111 Termination date: 20120223 |