GB2073227A - Non-curable Sealing Materials - Google Patents
Non-curable Sealing Materials Download PDFInfo
- Publication number
- GB2073227A GB2073227A GB8009797A GB8009797A GB2073227A GB 2073227 A GB2073227 A GB 2073227A GB 8009797 A GB8009797 A GB 8009797A GB 8009797 A GB8009797 A GB 8009797A GB 2073227 A GB2073227 A GB 2073227A
- Authority
- GB
- United Kingdom
- Prior art keywords
- groups
- group
- viscosity
- silicon
- polydiorganosiloxane
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
Abstract
A non-curable sealing material which increases in viscosity on contact with moisture, does not cure and substantially maintains its initial viscosity when stored away from moisture is obtained by mixing under substantially anhydrous conditions: (a) 100 parts by weight of a polydiorganosiloxane having terminal Si-OH groups and organic groups which are substituted or unsubstituted monovalent hydrocarbon radicals and having a viscosity of 0.5 m<2>/s or less at 25 DEG C, (b) from 1 to 500 parts by weight of a filler, and (c) an amount of an organosilicon compound sufficient to supply at least as many Si-N or Si-O-N groups as there are Si-OH groups in (a), said compound having two hydrolysable Si-N or Si-O-N groups per molecule. Component (c) may be e.g. a diorganosilane R<1>R<2>SiX2 or a siloxane <IMAGE> where R, R<1> and R<2> are each an unsubstituted or substituted monovalent hydrocarbon radical, n has a value in the range of from 0 to 30 inclusive, and X represents the hydrolysable group.
Description
SPECIFICATION
Noncurable Sealing Materials
The present invention relates to noncurable sealing materials.
Sealing materials can be roughly divided into noncurable sealing materials and curable sealing materials. Both types of materials are used for filling joints for the purpose of water-tightness and airtightness, and are widely utilized in construction and engineering work, vehicles, automobiles and airplanes. Especially in the case of construction work, these sealing materials are widely used at joints between various parts, to seal windows to window frames and to fill joints and gaps produced by the occurrence of cracks.
Noncurable glazier's putty and oily caulking materials are known as noncurable sealing materials.
The former consists primarily of oils and fats and the iatter also consists primarily of oils and fats, polybutene and alkyd resins. Thus, they have poor weather resistance. There is the drawback that the life of these noncurable sealing materials is short when they are used outdoors. There is also the drawback that they cannot be used at locations having high temperatures because of their poor heat resistance. In addition, such materials which comprise silicone oil sealing materials and sealing materials consisting primarily of nonreactive silicone oil and a filler have the drawback that separation of oil phase occurs easily. If a highly viscous silicone oil is used for decreasing the oil phase separation, the viscosity of the sealing material is increased and there is the drawback that workability during the sealing process decreases.
The present invention provides a new material without the drawbacks of the above-mentioned known common noncurable sealing materials.
This invention relates' to a non-curable sealing material comprising a composition which increases in viscosity on contact with moisture, does not cure and substantially maintains its initial viscosity when stored in a container which does not substantially allow moisture to penetrate, consisting essentially of a product obtained by mixing the following ingredients under substantially an hydros conditions::
(a) 100 parts by weight of a polydiorganosiloxane having silicon-atom-bonded hydroxyl groups
at the terminus of the molecule chains, the organic groups of the polydiorganosiloxane being
substituted or unsubstituted monovalent hydrocarbon radicals and said polydiorganosiloxane
having a viscosity of 0.5 m2/s or less at 250C, (b) from 1 to 500 parts by weight of a filler, and
(c) an amount of an organosilicon compound sufficient to supply silicon-bonded nitrogen groups
or groups having silicon-oxygen-nitrogen bonds in at least the same molar amount as the
total molar amount of silicon-atom-bonded hydroxyl groups in (a), said organosilicon
compound having two moisture hydrolysable groups per molecule and said groups being
selected from the group consisting of silicon-bonded nitrogen groups and groups having
silicon-oxygen-nitrogen bonds.
The components of this invention will be explained individually below. Component (a) is a polydiorganosiloxane of the following general formula having silicon atom-bound hydroxyl groups at the terminus of the molecular chain:
where R represents substituted or unsubstituted monovalent hydrocarbon radicals selected from among methyl, ethyl, propyl, octyl, phenyl, vinyl and 3,3,3-trifluoropropyl groups, and m is a number such that the viscosity at 250C is 0.5 m2/s or less. If the viscosity at 250C exceeds 0.5 m2/s, the workability when the composition is prepared by adding a filler, component (b) and a chain extension agent, component (c), and the workability and process when the composition is discharged from containers such as cartridges, tubes and plastic film containers, become very poor.In addition, if the viscosity is too low, the composition leaks out of the sealed container and the increase in viscosity is inadequate after filling a gap or cavity. The viscosity preferably ranges from 0.00005 to 0.05 m2/s.
The silicon-atom-bonded hydroxyl group at the terminus of the molecular chain is a functional group which is required for the condensation of component (a) with component (c) in the presence of moisture for obtaining higher molecular weight and higher viscosity.
Component (a) can be a polymer of a single viscosity or a mixture of two or more viscosities.
Component (b) of this invention is a filler which is used to modify the viscosity of component (a).
For example, the following fillers can be used: dry-process silica (fumed silica), wet-process silica (precipitated silica), diatomaceous earth, fine quartz powder, talc, mica powder, calcium carbonate, magnesium carbonate, carbon black asbestos powder and glass powder.
The amount of component (b) ranges from 1 to 500 parts by weight per 100 parts by weight of component (a). However, it is arbitrarily selected within the above-mentioned range according to the types of fillers used and in particular, the specific gravity and thickening ability, and according to the viscosity of organopolysiloxane. In the case of the fillers having a high thickening ability, i.e., dryprocess silica, wet-process silica, carbon black, asbestos powder, nonsurface-treated light and fine calcium carbonate, the amount used is relatively small, while in the case of the fillers having a relatively low thickening ability, i.e., diatomaceous earth, fine quartz powder, mica powder, surface-treated precipitated calcium carbonate and heavy calcium carbonate, the amount used is preferably higher.
Component (b) can be a single filler or a mixture of two or more fillers.
Component (c) is a component which helps increase molecular weight and viscosity by lengthening the polydiorganosiloxane chain, component (a), when the sealing material of this invention is discharged into air from a sealed container. That is, component (c) is a bifunctional diorganosilane or bifunctional diorganosiloxane which is hydrolysable with water. These compounds are generally expressed by the general formula: R1 R2SiX2 where R' and R2 are each an unsubstituted or substituted monovalent hydrocarbon radical and X is a hydrolysable group selected from the group consisting of silicon-bonded nitrogen groups and groups having silicon-oxygen-nitrogen bonds, or the general formula:
where R, R', R2 and X are defined above, and n has a value in the range of from 0 to 30 inclusive. In addition, the above-mentioned diorganosiloxane can contain a cyclic group. In these formulae, R, R1 and R2 represent alkyl groups such as methyl, ethyl, and propyl, alkenyl groups such as vinyl, allyl and butadienyl, aryl groups such as phenyl, xylenyl and naphthyl, cycloalkyl groups such as cyclohexyl, cycloalkenyl groups such as cyclohexenyl, aralkyl groups such as benzyl, alkaryl groups such as tolyl and xylyl, and their substituted groups. R, R' and R2 can be selected from the same or different groups.
X is a group which is hydrolysable with water and which is bonded to a silicon atom. Examples of the hydrolysable groups are amino groups
amido groups
imido groups
lactam groups
aminoxy groups
and oxime group
In these formulae, R3 to R12 each represent a hydrogen atom or unsubstituted or substituted monovalent hydrocarbon radical. Examples are the same as those described as examples of R, R1 and
R2. In terms of ease of preparation of silanes and siloxanes having these functional groups, R3 to R12 are preferably selected from among unsubstituted or substituted monovalent hydrocarbon radicals. R'3 and
R'4 represent alkylene groups.
Examples of component (c) are as follows:
aminosilanes and aminosiloxanes such as:
(CH3)2Si [NH(C4H9)]2 (CH3)2 Si [NH(C6H5)]2 (CH3)2Si [N(CH3)2]2 (CH3)(C6H5)Si [N(CH3)2]2
(CH3)2Si [N(C2H5)2]2 (CH3)(C6H5)Si[N(CH3)(C2H5)]2
aminoxysilanes and aminoxysiloxanes such as: (cH3 )2S1 [oN(cH3)2J2 (CH3)(C6H5)Si[ON(CH3)2]2
(CH3)2 Si [ON(CH3)(C2H5)]2
or oximesilanes and oximesiloxanes such as:
or amidosilanes and amidosiloxanes such as:
or imidosilanes and imidosiloxanes such as:
or lactamsilanes and lactamsiloxanes such as
Component (c) can be a single compound of two or more compounds.However, when two or more types are used in a mixture, an X group which is hydrolysable is preferably selected from the same type of group. The amount of organosilicon compound used is an amount sufficient to supply silicon-bonded nitrogen groups or groups having silicon-oxygen-nitrogen bonds in at least the same molar amount as the total molar amount (mol%) of silicon atom-bonded hydroxyl groups at the terminus of the molecular chain in component (a).
By so doing, the composition of this invention can be preserved for a iong period when prepared under substantially anhydrous conditions and when stored under substantially anhydrous conditions.
When it is discharged into air, a highly viscous product is obtained and an extremely viscous form of putty can be produced.
In addition to components (a), (b) and (c), a catalyst which accelerates the reaction between component (a) and component (c), e.g., diorganotin dicarboxylate, can be added. In addition, various additives which are generaily compounded in the conventional silicone oil sealing materials, e.g., inorganic pigments, organic pigments, heat resistance agents, tackiness-improving agents, antisagging agents, and flame retardants, can be added.
The composition of this invention can be produced as follows. For example, component (b) is added to component (a) and the mixture is blended in any of various types of blenders until a homogeneous mixture is obtained. After degassing, component (c) is added and the mixture is again blended until a homogeneous mixture is obtained. In this case, the moisture must be eliminated as much as possible from the mixture of component (a) and component (b), and component (c) must be added and blended under substantially anhydrous conditions. The obtained sealing material can be sucked up by a caulking gun and subsequently used in sealing work. Alternatively, the sealing material can be packed in a container which does not allow substantial amounts of moisture to permeate, e.g.
cartridges, aluminum foil tubes and plastic film containers, and sealed for preservation. Thereafter, the stored sealing material can be used when needed.
The sealing material of this invention has the following characteristics and effects: (1) If it is stored in a container which does not allow substantial amounts of moisture to permeate, the viscosity is unchanged after long-term storage; (2) because a polydiorganosiloxane having a low viscosity is used, it can be easily discharged from the container; (3) a gap or cavity can be easily filled; (4) the finishing work for the position filled is very easy; (5) the viscosity increases greatly in a time period of from one day to a few days after filling and an extremely viscous putty-like substance can be obtained; and (6) the obtained putty-like substance has excellent air-tightness and water-tightness, and no oil phase separation occurs after it is stored for a long period.This noncurable sealing material is especially useful as a sealing material for construction and civil engineering work.
The following examples are presented for illustrative purposes and should not be construed as limiting the scope of the invention which is delineated in the claims.
"Parts" indicated in the following examples means "parts by weight". The viscosity was the value at 250C. The atmosphere for the sealing work was as follows: 23-250C at 6065% relative humidity.
Example 1
Polydimethylsiloxane having hydroxyl terminal groups with a viscosity of 0.015 m2/s (100 parts) was well mixed with light, fine calcium carbonate without surface treatment (average particle size: 0.1 y and BET relative surface area: 7.5 m2/g) (45 parts). After degassing, dimethyldi(Nmethylacetamido)silane (8 parts) was added and the mixture was blended in a closed system without contact with moisture. The mixture obtained was packed in an aluminium tube. The material was squeezed out from the aluminium tube by hand and a vertical joint with a depth of 5 mm and a width of 8 mm, along a precast concrete plate, was filled with the contents of the aluminium tube. After 3 days, an extremely viscous putty had formed to a depth of 5 mm. After 6 months, no dripping had occurred nor was any separation of an oil phase observed.When this sealing material was stored in the aluminium tube at room temperature for 6 months, no changes occurred in its viscosity and it could still be squeezed out very easily by hand.
Example 2
Polydimethylsiloxane having hydroxyl terminal groups with a viscosity of 0.002 m2/s (100 parts) was well mixed with dry-process silica whose surface had been treated with trimethylchlorosilane as a hydrophobic treatment and whose BET relative surface area was 1 30 m2/g (20 parts). After degassing, methylvinyldi(N,N-diethylaminoxy)silane (10 parts) was added. The mixture was blended in a closed system without contact with moisture and the obtained mixture was packed in a paper cartridge whose interior surface was lined with aluminium foil. This paper cartridge was loaded in a hand gun. The content was squeezed out by hand and used to fill a horizontal groove between a plate of glass and an aluminium window sash (depth: 7 mm, width 4 mm). After 5 days, an extremely viscous putty had formed to a depth of 7 mm. After 6 months, no separation of an oil phase was found. When this sealing material was stored in the paper cartridge for 6 months, no changes occurred in viscosity and the sealing material could still be easily squeezed out using a hand gun.
Example 3
Dimethylsiloxane-methylphenylsiloxane copolymer having hydroxyl groups at the molecular chain
terminus with a viscosity of 0.008 m2/s (phenyl group content: 5 mol%). (100 parts) was well mixed
with dry-process silica having a BET relative surface area of 200 m2/g (10 parts). After degassing,
methylphenyldi(N-cyclohexylamino)silane (11 parts) was added and the mixture was blended in a
closed system without contact with moisture. The mixture was packed in a -cylindrical container made
of polyvinylidene chloride film and the container was wrapped with an evaporation-aluminized
polyvinylidene chloride film. After 6 months, the external evaporation-aluminized polyvinylidene
chloride film wrapper was taken off and the cylindrical container made of polyvinylidene chloride film
was loaded in a hand gun.The material was squeezed out by hand and a horizontal groove between
ALC panels (depth: 10 mm, width: 12 mm) was filled with the content. After 7 days, an extremely
viscous putty was formed to a depth of 10 mm. After 6 months, no separation of an oil phase was
found.
Example 4
Sealing materials were prepared using the following compounds as component (c) as shown in
Table I under the same conditions as in Example 1. The characteristics were evaluated and are shown
in Table I (below).
Example 5
In the sealing material as in Example 1, colloidal calcium carbonate (120 parts) (average particle
size: 0.04 , BET relative surface area: 31 m2/g) with a treated surface was used instead of the light,
fine calcium carbonate under the same conditions as in Example 1. The prepared sealing material was
packed in an aluminium tube. The material was squeezed out from the aluminium tube and a horizontal
groove between a plate of glass and an aluminium window sash (depth: 7 mm, width: 4 mm) was filled
with this sealing material. After 5 days, an extremely viscous putty had formed to a depth of 7 mm.
After 6 months, no separation of an oil phase had occurred. No changes occurred in its viscosity after
leaving this sealing material in the aluminium tube at room temperature and the contents could still be
squeezed out easily by hand.
Table 1
Days required
for forming
an extremely
Amount viscous putty Separation of
added Squeez- to a depth oil phrase Component (c) (parts) ability of 5 mum after 6 months a,co-Bis[dimethyl-
(N,N-diethylaminoxy)j dimethylsiloxane
(degree of poly
merization: 10) 20 good 3 days none
Methylvinyldi
(methylethyl
ketoxime)silane 10 good 5 days none
Claims (6)
1. A noncurable sealing material comprising a composition which increases in viscosity on contact with moisture, does not cure and substantially maintains its initial viscosity when stored in a container which does not substantially allow moisture to penetrate, consisting essentially of a product obtained by mixing the following ingredients under substantially anhydrous conditions::
(a) 100 parts by weight of a polydiorganosiloxane having silicon-atom-bonded hydroxyl groups
at the terminus of the molecule chains, the organic groups of the polydiorganosiloxane being
substituted or unsubstituted monovalent hydrocarbon radicals and said polydiorganosiloxane
having a viscosity of 0.5 m2/s or less at 250C,
(b) from 1 to 500 parts by weight of a filler, and
(c) an amount of an organosilicon compound sufficient to supply silicon-bonded nitrogen groups
or groups having silicon-oxygen-nitrogen bonds in at least the same molar amount as the
total molar amount of silicon-atom-bonded hydroxyl groups in (a), said organosilicon
compound having two moisture hydrolysable groups per molecule and said groups being
selected from the group consisting of silicon-bonded nitrogen groups and groups having
silicon-oxygen-nitrogen bonds.
2. The material according to claim 1 in which the viscosity at 25 OC of the polydiorganosiloxane of (a) is in the range of 0.00005 to 0.05 m2/s.
3. The material according to claim 1 or claim 2 in which the organosilicon compound of (c) is a diorganosilane of the general formula P1R2SiX2 where R1 and R2 are each an unsubstituted or substituted monovalent hydrocarbon radical and X represents the hydrolysable group.
4. The material-according to claim 1 or claim 2 in which the organosilicon compound of (c) is a siloxane of the average general formula
where R, R1 and R2 are each an unsubstituted or substituted monovalent hydrocarbon radical, n has a value in the range of from 0 to 30 inclusive, and X represents the hydrolysable group.
5. The material according to any of claims 1 to 4 in which the hydrolysable group is selected from the group consisting of an amino group, an amido group, an imido group, a lactam group, an aminoxy group and an oxime group.
6. A non-curable sealing material according to claim 1 substantially as herein described with reference to any of the specific examples.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8009797A GB2073227B (en) | 1980-03-24 | 1980-03-24 | Noncurable sealing materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8009797A GB2073227B (en) | 1980-03-24 | 1980-03-24 | Noncurable sealing materials |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2073227A true GB2073227A (en) | 1981-10-14 |
GB2073227B GB2073227B (en) | 1983-12-07 |
Family
ID=10512321
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8009797A Expired GB2073227B (en) | 1980-03-24 | 1980-03-24 | Noncurable sealing materials |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2073227B (en) |
-
1980
- 1980-03-24 GB GB8009797A patent/GB2073227B/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
GB2073227B (en) | 1983-12-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3294739A (en) | Method of making one component room temperature curing siloxane rubbers | |
US4087585A (en) | Self-adhering silicone compositions and preparations thereof | |
US3032528A (en) | Silicone elastomers | |
CA1063288A (en) | Curable compositions and process | |
JP2577150B2 (en) | Improved room temperature curable silicone composition | |
CA1142680A (en) | Room temperature vulcanizable silicone rubber compositions with sag-control | |
CA1144686A (en) | Room temperature curable organopolysiloxane compositions and methods for their preparation | |
US4673750A (en) | Auto-adhering one-component RTV silicone sealant composition utilizing glycidoxyalkyl substituted alkoxy-oxime silane as an adhesion promoter | |
US8030371B2 (en) | Organopolysiloxane compositions that harden into elastomers at ambient temperature in the presence of moisture | |
US3996184A (en) | Low modulus room temperature vulcanizable silicone elastomer with improved slump characteristics | |
JPS6340449B2 (en) | ||
EP0104179A1 (en) | Scavengers for one-component alkoxy-functional rtv compositions and processes. | |
JPH0649825B2 (en) | Room temperature curable organopolysiloxane composition | |
US20070249782A1 (en) | Organopolysiloxanes Comprising Nitrogen and Their Use in Cross-Linkable Materials | |
US5086107A (en) | Room temperature-curable organopolysiloxane composition | |
KR20100053619A (en) | Cross-linkable masses based on organosilicon compounds | |
JPS6115099B2 (en) | ||
US5246980A (en) | Two-part, ultralow modulus silicone sealant | |
US3280072A (en) | Organopolysiloxane elastomers | |
JPS58180554A (en) | Compound storable under water-free condition and bridgeable to elastomer at room temperature upon water content coming in | |
US4268452A (en) | Noncurable sealing materials | |
EP0457264A2 (en) | Two-part, ultra low modulus silicone sealant | |
CZ231294A3 (en) | Novel acceleration system for crosslinking of polymers which are solidified by the action of air humidity | |
US4360631A (en) | Flowable, room temperature vulcanizable silicone composition | |
US3607801A (en) | Organopolysiloxane compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |