CN103342979B - One-component room-temperature curing silicone composition with storage stability - Google Patents
One-component room-temperature curing silicone composition with storage stability Download PDFInfo
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- CN103342979B CN103342979B CN201310320614.3A CN201310320614A CN103342979B CN 103342979 B CN103342979 B CN 103342979B CN 201310320614 A CN201310320614 A CN 201310320614A CN 103342979 B CN103342979 B CN 103342979B
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- oximido
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Abstract
The invention provides a one-component room-temperature curing silicone composition with storage stability. The organosilicone sealant has better long-term storage stability and physical stability such as viscosity and extrudability and also has better curing properties during ageing. The room-temperature curing organosilicone sealant comprises the following components: (1) one or more silicon-hydroxyl terminated polydiorganosiloxanes, (2) at least one oximido containing organosilicone or organosiloxane, (3) at least one catalyst capable of catalyzing the crosslinking reaction (curing) of the room-temperature curing organosilicone sealant, and (4) an aminopropyl oximido organosilicone, wherein the oximido containing organosilicone or organosiloxane serves as a crosslinking agent, and the aminopropyl oximido organosilicone serves as an additive. The invention also provides a process for preparing the room-temperature curing silicone composition. The obtained one-component room-temperature curing system has high curing speed and good bonding properties and also has more excellent storage stability and aging properties.
Description
Technical field
The present invention relates to a kind of seal gum, more specifically relate to a kind of self-vulcanizing organosilicon sealant with single-component of storage-stable.
Background technology
The silicone sealant of self-vulcanizing is widely used in numerous areas because of the weather resistance of its excellence, and such as building is sealing adhesive, the encapsulation etc. of electronic material embedding and automobile mechanical packing ring and solar cell panel assembly; The solidification of single-component silicone fluid sealant is from outward appearance to inner essence, and the speed of solidification not only depends on the speed of response of linking agent, more depends on the speed of water in air part infiltration.According to use linking agent to remove through hydrolytic condensation the kind removing thing and different in kind, its organosilicon sealant system can be divided into neutral gum again, Aci-Jel etc., de-oxime type one component room temperature curing system wherein in neutral gum is because it is in workability, curing performance, adhesiveproperties, the performance of the aspect excellences such as mechanical property, and be applied in various industry; And oxime type self-vulcanizing silica gel is taken off for single-component, product comprises in production before using, and transport, and in storage process, resistance to overturning is vital;
In de-oxime type one component room temperature curing silicone glue, containing various ingredients, inevitably moisture is brought in system, and also has the infiltration of moisture in storage process.The existence of moisture is had a greatly reduced quality making the stability of whole system, the hydrolysis of its meeting initiating activity group, and then causes molecular chain condensation cross-linking, and system viscosity rises.Thus often need to add a large amount of water-retaining agents in system;
In addition, under normal circumstances, organo-tin compound is used in self-vulcanizing silicone adhesive as condensation catalyst; But these tin compounds catalysis can not wish the side reaction that occurs yet simultaneously, cause the fracture of polymerizable organosilicon molecular chain under the effect of alcohol, finally can form the low activity organopolysiloxane segment replaced with alkoxyl group, reduce and even lose reactive behavior, lose crosslinking ability, impact solidification;
The currently known methods increasing single-component silicone fluid sealant system storage stability is comprised:
Excessive linking agent or water-retaining agent is added in one component room temperature curing system; But what too much the use of water-retaining agent can cause system to be solidified is slow, and the change of cross-linked form is also disadvantageous from cost;
US Patent No. 4417042 describes a kind of scavenging agent for single-component dealcoholization-type self-vulcanizing organosilicon systems, and this scavenging agent is the compound with silazine link, such as hexamethyldisilazane; Due to the reactive behavior that it is relatively high, this silicon-nitrogen compound can react with water or alcohol, thus reaches the effect making stable system; But not only cost is high for this kind of silicon-nitrogen compound, and system solidification and adhesiveproperties can be damaged;
In another kind is attempted, US Patent No. 5286892 describes and is a kind ofly used in dealcoholized cold curing silicone system using the compound with 2-alkoxyl group silication propionic ester structure as hydroxyl scavenging agent, this compound can react with alcoholic extract hydroxyl group and reach the object eliminating alcohol, thus improves storage property and the aging resistance of integral system; But fundamentally do not reduce or eliminate the existence of alkoxyl group, also can introduce other organic molecules in addition and produce as by product;
In addition, in system, the use of minimizing or alternative organotin catalysts is also attempted, and such as, in US Patent No. 3334067, the inner complex of titanium or aluminium is used by the catalyzer as curing reaction, but its catalytic effect also can cause the problem of xanthochromia while declining.And other organic titanate class catalyzer, such as, describe in patent EP747443, the instability containing the organosilicon systems viscosity based on hydroxy-terminated polysiloxane can be caused, and because it is to the susceptibility of organic amine, general is limited therewith to use based on the sticking power additive of amido organosilane; And the consumption reducing organotin catalysts can affect the effect of system solidification;
This just requires a kind of de-oxime type one component room temperature cured silicone system, while identical curing performance can be had, there is higher storage and stability to aging, comprise composition system physicals in production and transport storage, comprise viscosity, the stability of the performances such as outward appearance, also comprise it in the stability of storing the curing performance in weathering process simultaneously, comprise its surface drying, skinning, crosslinked, the stability of the performances such as solidification.
Summary of the invention
The object of the invention is the one component room temperature cured silicone combination proposing a kind of storage-stable, utilize this kind of composition while not changing its curing performance, storage and the stability to aging of system can be improved.
In order to thought object of the present invention, following technical scheme is proposed:
A kind of storage-stable single-component moisture-curable silicon composition, described composition is made up of following component by weight:
Hydroxy-end capped organopolysiloxane A 15% ~ 90%;
Crosslinking agent B 0.5% ~ 10%;
Catalyzer C 0.01% ~ 5%;
Amine propyl group oximino silane D 0.1 ~ 5%;
Additive E; Wherein,
Described hydroxy-end capped poly-organopolysiloxane A is expressed as HO-(SiR
8r
9-O)
nh, wherein n makes the integer of its viscosity between 1000 to 500000 centipoises, R
8with R
9unit price hydrocarbon group and monovalent halogenated alkyl can be selected from respectively;
Described crosslinking agent B is the organic ketone oximino silane containing multiple oximido, is expressed as R
nsi (ON=CR
2r
3)
4-n, wherein, independently selected from the aryl of the thiazolinyl of the alkyl of C1-C10, C2-C10, the cycloalkyl of C3-C8 or C6-C14 at every turn when R occurs, R
2and R
3independently selected from the alkyl of C1-C10 at every turn when occurring; N is 0, m is 1,2 or 3; Or n is 1, m is 1 or 2;
Described amine propyl group oximino silane D can be expressed as R
4 bh
2-bnC
3h
6si (X)
a(Y)
3-a, wherein, R
4saturated or the unsaturated alkyl of the straight chain be made up of 1 to 20 carbon, side chain or ring-type, aryl, or this kind of alkyl, the aryl that contain other substituted radicals; Substituent X is alkoxy grp: be expressed as-OR
5, wherein R
5the alkane be made up of 1 to 6 carbon; Substituting group Y is oximido group: be expressed as-ONC(R
6) (R
7) wherein R
6, R
7the identical or different alkane be made up of 1 to 10 carbon; Wherein a and b is the integer of 0 to 2;
Described additive E is one or more of Paris white, white carbon black, silicon powder, carbon black or aluminum oxide.
This kind of alkyl of other substituted radicals described, aryl is amino for containing, and epoxy group(ing) is acrylate-based, sulfydryl, ester group, this kind of alkyl that ethers group replaces, aryl; Described R
5for methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl.
Described oximido group comprises acetone oximido, methyl ethyl ketone oximido, methyl propyl ketone oximido, methyl butyl ketone oximido or mibk oximido.
In the expression formula of described hydroxy-end capped poly-organopolysiloxane A, R
8with R
9methyl, ethyl, vinyl or phenyl can be selected from respectively.
The organo-tin compound of described catalyzer C is selected from dibutyl tin dilaurate, dibutyl tin acetate or dioctyl tin cinnamic acid tin.
The consumption of described crosslinking agent B is 2% to 5%, and the consumption of described catalyzer C is 0.03% to 1%, and the consumption of described amine propyl group oximino silane D is 0.5% ~ 3%.
The consumption of described catalyzer C is 0% to 1%, and the consumption of described amine propyl group oximino silane D is 1% ~ 2%.
Described crosslinking agent B is alkoxyl group-one oximino silane, is expressed as R
n-Si (OR
1)
m(ON=CR
2r
3)
4-n-m, wherein, independently selected from the aryl of the thiazolinyl of the alkyl of C1-C10, C2-C10, the cycloalkyl of C3-C8 or C6-C14 at every turn when R occurs; R
1, R
2and R
3independently selected from the alkyl of C1-C10 at every turn when occurring; N is 0, m is 1,2 or 3; Or n is 1, m is 1 or 2.
The de-oxime type one component room temperature cured silicone system that this patent proposes, can while there is the curing performance identical with traditional system, higher storage and stability to aging can be had, comprising composition producing and system physicals stable in transport storage, comprising viscosity, the stability of the performances such as outward appearance, also comprise it in the stability of storing the curing performance in weathering process simultaneously, comprise its surface drying, skinning, crosslinked, the performances such as solidification.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.Per-cent in following examples is all weight percentage;
comparison example,
Hydroxy-end capped polydimethylsiloxane (107 glue, 20,000 centipoise) 11.88%, hydroxy-end capped polydimethylsiloxane (107 glue, 40,000 centipoise) 34.64%, the polydimethyl siloxane fluid (201 silicone oil, viscosity is 1000 centipoises) 4.95% of methyl blocking; Filler: Paris white 39.58%, white carbon black 4.95%, under water proof condition, mixes in mixing machine.Add vinyl tributyl ketoximyl silane 2.96%, then order adds organotin catalysts 0.05%, amine propyl trimethoxy silicane 0.99%, continue to mix in mixing machine, experimental result is see subordinate list;
embodiment one,
Hydroxy-end capped polydimethylsiloxane (107 glue, 20,000 centipoise) 11.88%, hydroxy-end capped polydimethylsiloxane (107 glue, 40,000 centipoise) 34.64%, the polydimethyl siloxane fluid (201 silicone oil, viscosity is 1000 centipoises) 4.95% of methyl blocking; Filler: Paris white 39.58%, white carbon black 4.95%, under water proof condition, mixes in mixing machine.Add vinyl tributyl ketoximyl silane 2.96% weight part, then order adds organotin catalysts 0.05%, the amine propyl group oximino silane 0.99% of this patent description, continue to mix in mixing machine, experimental result is see subordinate list;
embodiment two,
Hydroxy-end capped polydimethylsiloxane (107 glue, 20,000 centipoise) 11.88%, hydroxy-end capped polydimethylsiloxane (107 glue, 40,000 centipoise) 34.64%, the polydimethyl siloxane fluid (201 silicone oil, viscosity is 1000 centipoises) 4.95% of methyl blocking; Filler: Paris white 39.58%, white carbon black 4.95%, under water proof condition, mixes in mixing machine; Add the amine propyl group oximino silane 0.99% of this patent description, then order adds vinyl tributyl ketoximyl silane 2.96%, organotin catalysts 0.05%, continue to mix in mixing machine, experimental result is see subordinate list;
performance test
surface drying time:
Adopt the testing method of GB13477, the surface drying time of test seal gum;
deep cure:
Seal gum is injected the PE circular die that thickness is 15 millimeters, be positioned over 23C, under the condition of 50% relative humidity, after 24 hours, sample is taken out, measure the curing depth (test glue has formed the elastomeric degree of depth) of glue respectively; Repeat above-mentioned test process, and solidification 48 hours and 3 days, after 4 days and 8 days, tested its curing depth;
extrudability:
Adopt ASTM C603 standard method of test, test composition extrudability.
Table one, single-component takes off the aging extrusion performance contrast of oxime silicon composition:
| Extrudability (second) | Comparison example | Embodiment one | Embodiment two |
| Initially | 28 | 33 | 34 |
| 80 DEG C 6 days aging | 50 | 36 | 35 |
| 80 DEG C 10 days aging | 60 | 40 | 40 |
| 80 DEG C 14 days aging | Be greater than 100 | 40 | 42 |
Table two, single-component takes off the aging surface drying performance comparison of oxime silicon composition:
| SCT(minute) | Comparison example | Example one | Example two |
| Initially | 53 | 54 | 53 |
| 80 DEG C 6 days aging | 115 | 46 | 47 |
| 80 DEG C 10 days aging | 178 | 47 | 48 |
| 80 DEG C 14 days aging | Be greater than 200 | 47 | 49 |
Table three, single-component takes off oxime silicone composition performance comparison:
| Curing depth (mm) | Comparison example | Example one | Example two |
| 1 day curing depth | 2.6 | 1.9 | 2.8 |
| 2 days curing depths | 4.5 | 3.7 | 5.7 |
| 3 days curing depths | 6.4 | 5.2 | 7.4 |
| 4 days curing depths | 7.3 | 6.5 | 8.5 |
| 8 days curing depths | 9.7 | 9.2 | 11.0 |
Self-vulcanizing silicon composition mixes in proportion in Speedmixer equipment, the solidification of all samples and test be 23 DEG C, carry out in the environment of 50% relative humidity;
Above-described specific embodiment; further detailed description has been carried out to object of the present invention, technical scheme and beneficial effect; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. a storage-stable single-component moisture-curable silicon composition, described composition is made up of following component by weight:
Hydroxy-end capped organopolysiloxane A 15% ~ 90%;
Crosslinking agent B 0.5% ~ 10%
Catalyzer C 0.01% ~ 5%;
Amine propyl group oximino silane D 0.1 ~ 5%;
Additive E; Wherein,
Described hydroxy-end capped poly-organopolysiloxane A is expressed as HO-(SiR
8r
9-O)
nh, wherein n makes the integer of its viscosity between 1000 to 500000 centipoises, R
8with R
9be selected from unit price hydrocarbon group and monovalent halogenated alkyl respectively;
Described crosslinking agent B is the organic ketone oximino silane containing multiple oximido, is expressed as R
nsi (ON=CR
2r
3)
4-n, wherein, independently selected from the aryl of the thiazolinyl of the alkyl of C1-C10, C2-C10, the cycloalkyl of C3-C8 or C6-C14 at every turn when R occurs, R
2and R
3independently selected from the alkyl of C1-C10 at every turn when occurring;
Described amine propyl group oximino silane D is expressed as R
4 bh
2-bnC
3h
6si (X)
a(Y)
3-a, wherein, R
4saturated or the unsaturated alkyl of the straight chain be made up of 1 to 20 carbon, side chain or ring-type, aryl, or this kind of alkyl, the aryl that contain other substituted radicals; Substituent X is alkoxy grp: be expressed as-OR
5, wherein R
5the alkyl be made up of 1 to 6 carbon; Substituting group Y is oximido group: be expressed as-ONC(R
6) (R
7) wherein R
6, R
7it is the identical or different alkyl be made up of 1 to 10 carbon; A is the integer of 0 to 2, and b is 2;
Described additive E is one or more of Paris white, white carbon black, silicon powder, carbon black or aluminum oxide;
This kind of alkyl of other substituted radicals described, aryl is amino for containing, epoxy group(ing), sulfydryl, ester group, this kind of alkyl that ethers group replaces, aryl; Described R
5for methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl;
Described oximido group comprises acetone oximido, methyl ethyl ketone oximido, methyl propyl ketone oximido, methyl butyl ketone oximido or mibk oximido;
In the expression formula of described hydroxy-end capped poly-organopolysiloxane A, R
8with R
9be selected from methyl, ethyl, vinyl or phenyl respectively;
The organo-tin compound of described catalyzer C is selected from dibutyl tin dilaurate, dibutyl tin acetate or dioctyl tin cinnamic acid tin.
2. silicon composition according to claim 1, is characterized in that, the consumption of described crosslinking agent B is 2% to 5%, and the consumption of described catalyzer C is 0.03% to 1%, and the consumption of described amine propyl group oximino silane D is 0.5% ~ 3%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571199B (en) * | 2013-11-21 | 2015-08-05 | 山东大学 | The preparation method of the de-oxime type silicone seal of resistance to-100 DEG C of low temperature |
| CN103571198B (en) * | 2013-11-21 | 2015-10-21 | 山东大学 | The preparation method of the de-oxime type silicone seal of resistance to-120 DEG C of low temperature |
| CN107652942A (en) * | 2017-10-24 | 2018-02-02 | 山东永安胶业有限公司 | High extrudability silicone sealant of low-density and preparation method thereof |
| CN107936562B (en) * | 2017-11-06 | 2021-05-11 | 浙江衢州硅宝化工有限公司 | Non-corrosive ketoxime type room temperature curing silicone rubber and preparation method thereof |
| CN108239519B (en) * | 2018-01-02 | 2020-11-27 | 深圳市广业电子科技有限公司 | Fast-curing one-component room-temperature-curing organic silicon composition |
| TWI704179B (en) * | 2018-12-07 | 2020-09-11 | 財團法人工業技術研究院 | Thermoplastic vulcanizate and manufacturing method thereof |
| CN115197673B (en) * | 2022-08-03 | 2023-03-03 | 江西天永诚高分子材料有限公司 | Low-toxicity single-component photovoltaic frame silicone sealant and preparation method thereof |
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| US20080293865A1 (en) * | 2007-05-25 | 2008-11-27 | Norio Kameda | Room temperature-curable organopolysiloxane composition |
| CN102167965A (en) * | 2011-01-13 | 2011-08-31 | 霍尼韦尔综合科技(中国)有限公司 | Bi-component room-temperature cured silicone sealant |
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| CN102924494A (en) * | 2012-10-19 | 2013-02-13 | 北京天山新材料技术股份有限公司 | Novel organic oximido silicon compound and preparation method and application thereof |
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| US5569750A (en) * | 1994-05-24 | 1996-10-29 | Alliedsignal Inc. | RTV silicone compositions using aminohydrocarbyl-substituted ketoximinosilanes |
| CN101333427B (en) * | 2007-06-30 | 2012-10-10 | 湖北回天胶业股份有限公司 | Adhesive monocomponent organosilicon sealant |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080293865A1 (en) * | 2007-05-25 | 2008-11-27 | Norio Kameda | Room temperature-curable organopolysiloxane composition |
| CN102167965A (en) * | 2011-01-13 | 2011-08-31 | 霍尼韦尔综合科技(中国)有限公司 | Bi-component room-temperature cured silicone sealant |
| CN102532907A (en) * | 2011-12-07 | 2012-07-04 | 北京天山新材料技术股份有限公司 | Preparation method of oil-resistant room temperature vulcanization deoximation silicon rubber |
| CN102924494A (en) * | 2012-10-19 | 2013-02-13 | 北京天山新材料技术股份有限公司 | Novel organic oximido silicon compound and preparation method and application thereof |
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