CN104845376A - Tin-free one-component deketoxime room-temperature vulcanized silicone rubber - Google Patents
Tin-free one-component deketoxime room-temperature vulcanized silicone rubber Download PDFInfo
- Publication number
- CN104845376A CN104845376A CN201510295386.8A CN201510295386A CN104845376A CN 104845376 A CN104845376 A CN 104845376A CN 201510295386 A CN201510295386 A CN 201510295386A CN 104845376 A CN104845376 A CN 104845376A
- Authority
- CN
- China
- Prior art keywords
- parts
- polydimethylsiloxane
- minutes
- deketoxime
- component
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses tin-free one-component deketoxime room-temperature vulcanized silicone rubber and a preparation method thereof. The silicon rubber is prepared from the following components in parts by weight: 100 parts of alpha, omega-dihydroxyl polydimethylsiloxane, 0-30 parts of polydimethylsiloxane, 10-100 parts of a reinforcement filler, 3-8 parts of a deketoxime siloxane crosslinking agent, 0.5-5 parts of a tackifier and 0.1-1 part of a catalyst; and the preparation method comprises the following steps: 1) adding the alpha, omega-dihydroxyl polydimethylsiloxane, the polydimethylsiloxane and the reinforcement filler to a kneading machine, mixing and dewatering at 110-160 DEG C for 30-360 minutes to obtain a base stock; and (2) adding the base stock and the deketoxime siloxane crosslinking agent to a planetary mixer at room temperature, stirring in vacuum for 10-60 minutes, adding the tackifier and the catalyst, and stirring in vacuum for 10-60 minutes. The tin-free one-component deketoxime room-temperature vulcanized silicone rubber does not contain a toxic organic tin compound, is relatively small in smell in a curing process, has relatively good adhesive property on various materials, and is free of three wastes generated in the production process and friendly to environment.
Description
Technical field
Single-component ketoxime removing type room temperature vulcanized (being called for short RTV) silicone rubber sealant that the present invention relates to a kind of Wuxi and preparation method thereof, can there is polycondensation and be cross-linked into not stanniferous silicone elastomer in sealing agent under envrionment temperature and water existent condition.This elastomerics is well bonding on various base material, can play effect that is bonding, sealing, be specially adapted to the occasion limiting tin use.α is comprised, alpha, omega-dihydroxy polysiloxane, polydimethylsiloxane, reinforced filling, ketoxime removing type siloxane crosslinker, tackifier and not stanniferous catalyzer in sealing agent.
Background technology
The performances such as silicon rubber has excellent weather-proof, resistance to irradiation, electrical isolation, hydrophobic, biochemistry is compatible, especially high and low temperature resistance be other any elastomericss institutes can not and, be obtained in aviation, machinery, automobile, electronics, health care and daily life and apply widely.
Condensed type single-component RTV silicon rubber does not need to heat at room temperature to get final product a cross-linking vulcanized class silicon rubber by the moisture in ingress of air.Ketoxime removing type, desacetoxy type, dealcoholizing-type, deacetone and de amide type etc. are divided into according to discharging micromolecular type time crosslinked.Wherein, ketoxime removing type RTV silicon rubber vulcanization appropriateness, the ketoxime smell discharged in solidification process is less, corrosion-free to other metals except having slight erosion to copper, being the kind that cost performance is the highest, is also the single-component RTV silicon rubber kind that sales volume is larger in the market.Organo-tin compound is as the catalyzer of single-component ketoxime removing type RTV silicon rubber, and its bio-toxicity had and environmental contamination are that people use the problem paid close attention to during silicon rubber always.
Just clearly organo-tin compound is listed in restricted Black List as far back as United Nations's prevention and control of marine pollution pact in 1974.89/677/EEC, 1999/51/EC and 2002/62/EC are crossed in European Union's successively issue, when regulation organotin mixture is used as the biocide in the free coating associated, can not commercially sell.Supplementary provision again afterwards, specifies from 1 day July in 2010, Theil indices must not be used in the consumer's goods to replace organo-tin compounds more than three of 0.1wt%; From 1 day January in 2012, Theil indices must not be used more than the dibutyl tin of 0.1wt% in the mixture of public's supply or article, wherein single component and two-pack RTV sealing agent and tackiness agent were also so limited from 1 day January in 2015.In addition, in Food Contact silicon rubber, then clearly organo-tin compound is prohibitted the use.
Single-component condensed type RTV silicon rubber mainly dealcoholizing-type and the deacetone of current Wuxi on the market, the domestic research that there is not yet about the single-component ketoxime removing type RTV silicon rubber of Wuxi is reported.
Summary of the invention
The object of the invention is the catalyzer proposing a kind of alternative organo-tin compound, still can solidify by Quick cross-linking when making not use organotin in single-component ketoxime removing type silicone rubber sealant, a kind of single-component ketoxime removing type silicon rubber of Wuxi is provided.
Another object of the present invention is also the preparation method of the single-component ketoxime removing type silicon rubber providing a kind of Wuxi, and the method technique is simple, be easy to control.
In order to realize object of the present invention, following technical scheme is proposed:
A single-component ketoxime removing type room temperature vulcanized silicone rubber for Wuxi, described silicon rubber is composed as follows by weight:
α, alpha, omega-dihydroxy polysiloxane 100 parts
Polydimethylsiloxane 0 ~ 30 part
Reinforced filling 10 ~ 100 parts
Ketoxime removing type siloxane crosslinker 3 ~ 8 parts
Tackifier 0.5 ~ 5 part
Catalyzer 0.1 ~ 1 part
Wherein, described α, alpha, omega-dihydroxy polysiloxane is the mixture of one or more in the siloxanes of 3000 ~ 80000 mPas of range of viscosities, and its molecular structural formula is HO [(R)
2siO]
nh, R are-CH
3,-C
2h
5or phenyl;
Described polydimethylsiloxane is the mixture of one or more in the silicone oil of 50 ~ 5000 mPas of range of viscosities, and its molecular structural formula is (CH
3)
3siO [(CH3)
2siO]
nsi (CH
3)
3;
Described reinforced filling is the mixture of one or more in gas-phase silica, light calcium carbonate, talcum powder, silicon powder, carbon black, titanium dioxide, aluminum oxide and aluminium hydroxide;
Described ketoxime removing type siloxane crosslinker is the mixture of one or more in the partial hydrolystate of methyl tributanoximo silane, vinyl tributyl ketoximyl silane, phenyl tributanoximo silane, four Diacetylmonoxime base silanes and above-mentioned linking agent;
Described tackifier are γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl triethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-(2, 3-glycidoxy) propyl trimethoxy silicane, γ-(2, 3-glycidoxy) propyl-triethoxysilicane, 3-[(2, 3)-epoxy third oxygen] hydroxypropyl methyl dimethoxysilane, isocyanatopropyl triethoxyl silane, the mixture of one or more in γ-urea propyl trimethoxy silicane,
Described catalyzer is organo-bismuth, and its molecular structural formula is Bi (OOCR)
3, R group is line style, branching C
1~ C
20, phenyl ring or biphenyl.
Described catalyzer is isocaprylic acid bismuth, tin dilaurate bismuth, bismuth neodecanoate or bismuth naphthenate.
The present invention also proposes the method for the single-component ketoxime removing type room temperature vulcanized silicone rubber described in preparation, and it is characterized in that, described preparation method comprises the following steps:
1) count by weight, by 100 parts of α, alpha, omega-dihydroxy polysiloxane, 0 ~ 30 part of polydimethylsiloxane, 10 ~ 100 parts of reinforced fillings join in kneader, and mixing dehydration 30 ~ 360 minutes in 110 ~ 160 DEG C, for subsequent use after obtaining base-material cooling;
2) at room temperature, base-material is joined in planetary mixer, count by weight, add 3 ~ 8 parts of ketoxime removing type siloxane crosslinkers, vacuum stirring adds 0.5 ~ 5 part of tackifier and 0.1 ~ 1 part of catalyzer after 10 ~ 60 minutes, vacuum stirring is discharging sealing preservation after 10 ~ 60 minutes.
The present invention selects de-ketoxime system, promotes cross-linking and curing reaction with organo-bismuth, obtains a kind of single-component ketoxime removing type RTV silicon rubber of Wuxi.Owing to have employed technique scheme, silicon rubber of the present invention has the following advantages:
One, not containing poisonous organo-tin compound, meet up-to-date EU criteria, can be used as Food Contact type silicon rubber and use;
Two, adopt de-ketoxime system, the smell in solidification process is less, and have good cementability to various material, cost performance is higher;
Three, use gas phase White Carbon black as reinforced filling, there is higher mechanical property;
Four, the organotin catalysts in traditional ketoxime removing type RTV silicon rubber is replaced with organo-bismuth by this invention, still maintain the properties of silicon rubber after curing speed faster and solidification, therefore the manufacturer of silicone rubber sealant only needs more catalyst changeout just can upgrading products rapidly;
Five, the production unit of sealing agent is conventional equipment, and preparation method is simple, and produces without the three wastes in production process, environmental friendliness.
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.
Embodiment
Count by weight, by α, alpha, omega-dihydroxy polysiloxane (when 25 DEG C, viscosity is 20000mPas) 100 parts, polydimethylsiloxane 10 parts, gas-phase silica 20 parts join in kneader, mixing dehydration 180 minutes in 120 DEG C, and after cooling, base-material is for subsequent use; At room temperature, base-material is joined in planetary mixer, count by weight, add 6 parts of vinyl tributyl ketoximyl silanes, vacuum stirring 30 minutes (vacuum tightness is-0.095 ~-0.1MPa), add 1.5 parts of γ-aminopropyl triethoxysilanes and 0.15 part of new certain herbaceous plants with big flowers acid bismuth, vacuum stirring is discharging sealing preservation after 30 minutes.
Comparative example
Count by weight, by α, alpha, omega-dihydroxy polysiloxane (when 25 DEG C, viscosity is 20000mPas) 100 parts, polydimethylsiloxane 10 parts, gas-phase silica 20 parts join in kneader, mixing dehydration 180 minutes in 120 DEG C, and after cooling, base-material is for subsequent use; At room temperature, base-material is joined in planetary mixer, count by weight, add 6 parts of vinyl tributyl ketoximyl silanes, vacuum stirring 30 minutes (vacuum tightness is-0.095 ~-0.1MPa), add 1.5 parts of γ-aminopropyl triethoxysilanes and 0.1 part of dibutyl tin laurate, vacuum stirring is discharging sealing preservation after 30 minutes.
Concrete verification experimental verification
By the performance of the single-component ketoxime removing type silicon rubber of following experimental test Wuxi of the present invention.
Testing method:
The glue sample of above-described embodiment and comparative example's single-component ketoxime removing type silicon rubber is evenly coated on the mould that thickness is 2mm, the initial and surface drying time of room temperature storage after 6 months by GB/T13477.5-2002 test; Solidify after 7 days, test Shao A hardness, tensile strength and elongation at break by GB/T 528-2009; The shearing resistance of aluminium-aluminium is tested by GB7124-2008; High temperature ageing condition is 250 DEG C of heating, 4 hours, 150 DEG C heating 200 hours; Hydrothermal aging condition is poach 48 hours, 70 DEG C of poach 7 days; Result is as shown in table 1.
The performance comparison test result of embodiment and comparative example's single-component ketoxime removing type silicon rubber
Table 1
As can be seen from the result of upper table, the single-component ketoxime removing type silicon rubber of the present invention by making organic bismuth catalyst obtain Wuxi, the silicon rubber stanniferous with same kind is compared, no matter the equal no significant difference of curing speed, mechanical property or ageing-resistant performance.
Although the present invention is own with preferred embodiment openly as above, they are not that the content that protection scope of the present invention should define with the claims of the application is as the criterion for limiting the present invention.Anyly have the knack of the art person, without departing from the spirit and scope of the present invention, the various change done or equivalently to replace, all should belong to protection scope of the present invention.
Claims (3)
1. a single-component ketoxime removing type room temperature vulcanized silicone rubber for Wuxi, is characterized in that, described silicon rubber is composed as follows by weight:
α, alpha, omega-dihydroxy polysiloxane 100 parts
Polydimethylsiloxane 0 ~ 30 part
Reinforced filling 10 ~ 100 parts
Ketoxime removing type siloxane crosslinker 3 ~ 8 parts
Tackifier 0.5 ~ 5 part
Catalyzer 0.1 ~ 1 part
Wherein, described α, alpha, omega-dihydroxy polysiloxane is the mixture of one or more in the siloxanes of 3000 ~ 80000 mPas of range of viscosities, and its molecular structural formula is HO [(R)
2siO]
nh, R are-CH
3,-C
2h
5or phenyl;
Described polydimethylsiloxane is the mixture of one or more in the silicone oil of 50 ~ 5000 mPas of range of viscosities, and its molecular structural formula is (CH
3)
3siO [(CH3)
2siO]
nsi (CH
3)
3;
Described reinforced filling is the mixture of one or more in gas-phase silica, light calcium carbonate, talcum powder, silicon powder, carbon black, titanium dioxide, aluminum oxide and aluminium hydroxide;
Described ketoxime removing type siloxane crosslinker is the mixture of one or more in the partial hydrolystate of methyl tributanoximo silane, vinyl tributyl ketoximyl silane, phenyl tributanoximo silane, four Diacetylmonoxime base silanes and above-mentioned linking agent;
Described tackifier are γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl triethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl triethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, γ-(2, 3-glycidoxy) propyl trimethoxy silicane, γ-(2, 3-glycidoxy) propyl-triethoxysilicane, 3-[(2, 3)-epoxy third oxygen] hydroxypropyl methyl dimethoxysilane, isocyanatopropyl triethoxyl silane, the mixture of one or more in γ-urea propyl trimethoxy silicane,
Described catalyzer is organo-bismuth, and its molecular structural formula is Bi (OOCR)
3, R group is line style, branching C
1~ C
20, phenyl ring or biphenyl.
2. silicon rubber according to claim 1, is characterized in that, described catalyzer is isocaprylic acid bismuth, tin dilaurate bismuth, bismuth neodecanoate or bismuth naphthenate.
3. prepare the method for single-component ketoxime removing type room temperature vulcanized silicone rubber as claimed in claim 1 or 2, it is characterized in that, described preparation method comprises the following steps:
1) count by weight, by 100 parts of α, alpha, omega-dihydroxy polysiloxane, 0 ~ 30 part of polydimethylsiloxane, 10 ~ 100 parts of reinforced fillings join in kneader, and mixing dehydration 30 ~ 360 minutes in 110 ~ 160 DEG C, for subsequent use after obtaining base-material cooling;
2) at room temperature, base-material is joined in planetary mixer, count by weight, add 3 ~ 8 parts of ketoxime removing type siloxane crosslinkers, vacuum stirring adds 0.5 ~ 5 part of tackifier and 0.1 ~ 1 part of catalyzer after 10 ~ 60 minutes, vacuum stirring is discharging sealing preservation after 10 ~ 60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510295386.8A CN104845376A (en) | 2015-06-02 | 2015-06-02 | Tin-free one-component deketoxime room-temperature vulcanized silicone rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510295386.8A CN104845376A (en) | 2015-06-02 | 2015-06-02 | Tin-free one-component deketoxime room-temperature vulcanized silicone rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104845376A true CN104845376A (en) | 2015-08-19 |
Family
ID=53845384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510295386.8A Pending CN104845376A (en) | 2015-06-02 | 2015-06-02 | Tin-free one-component deketoxime room-temperature vulcanized silicone rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104845376A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987788A (en) * | 2017-12-13 | 2018-05-04 | 广州汇纳新材料科技有限公司 | A kind of primary coat type of exempting from is used for ketoxime removing type single-component silicon rubber of the water-fast bonding of hydrophilic aluminium foil and preparation method thereof |
| CN109233620A (en) * | 2018-08-09 | 2019-01-18 | 成都拓利科技股份有限公司 | A kind of RTV anti-pollution flashover coating of organic solvent-free and preparation method thereof |
| CN111073591A (en) * | 2019-12-13 | 2020-04-28 | 深圳市丰盛源科技有限公司 | Single-component room temperature curing liquid silicone rubber and preparation method thereof |
| CN111286300A (en) * | 2020-04-01 | 2020-06-16 | 运研材料科技（上海）有限公司 | Room temperature vulcanized silicone rubber and preparation method and application thereof |
| CN114702676A (en) * | 2022-04-02 | 2022-07-05 | 深圳市康利邦科技有限公司 | Single-component low-viscosity fast-curing dealcoholization RTV silicone rubber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013430A (en) * | 2012-12-24 | 2013-04-03 | 成都硅宝科技股份有限公司 | Environment-friendly organosilicone sealant and manufacturing method thereof |
| CN104031389A (en) * | 2014-06-05 | 2014-09-10 | 浙江新安化工集团股份有限公司 | Humid-heat resisting room-temperature vulcanized silicone rubber composition |
-
2015
- 2015-06-02 CN CN201510295386.8A patent/CN104845376A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013430A (en) * | 2012-12-24 | 2013-04-03 | 成都硅宝科技股份有限公司 | Environment-friendly organosilicone sealant and manufacturing method thereof |
| CN104031389A (en) * | 2014-06-05 | 2014-09-10 | 浙江新安化工集团股份有限公司 | Humid-heat resisting room-temperature vulcanized silicone rubber composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987788A (en) * | 2017-12-13 | 2018-05-04 | 广州汇纳新材料科技有限公司 | A kind of primary coat type of exempting from is used for ketoxime removing type single-component silicon rubber of the water-fast bonding of hydrophilic aluminium foil and preparation method thereof |
| CN107987788B (en) * | 2017-12-13 | 2020-08-04 | 广州汇纳新材料科技有限公司 | Primer-free ketoxime removing type single-component silicone rubber for hydrophilic aluminum foil waterproof bonding and preparation method thereof |
| CN109233620A (en) * | 2018-08-09 | 2019-01-18 | 成都拓利科技股份有限公司 | A kind of RTV anti-pollution flashover coating of organic solvent-free and preparation method thereof |
| CN111073591A (en) * | 2019-12-13 | 2020-04-28 | 深圳市丰盛源科技有限公司 | Single-component room temperature curing liquid silicone rubber and preparation method thereof |
| CN111286300A (en) * | 2020-04-01 | 2020-06-16 | 运研材料科技（上海）有限公司 | Room temperature vulcanized silicone rubber and preparation method and application thereof |
| CN111286300B (en) * | 2020-04-01 | 2022-03-25 | 运研材料科技（上海）有限公司 | Room temperature vulcanized silicone rubber and preparation method and application thereof |
| CN114702676A (en) * | 2022-04-02 | 2022-07-05 | 深圳市康利邦科技有限公司 | Single-component low-viscosity fast-curing dealcoholization RTV silicone rubber and preparation method thereof |
| CN114702676B (en) * | 2022-04-02 | 2023-10-20 | 深圳市康利邦科技有限公司 | Single-component low-viscosity quick-solid dealcoholization RTV silicone rubber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104845376A (en) | Tin-free one-component deketoxime room-temperature vulcanized silicone rubber | |
| KR102244164B1 (en) | Moisture-curable hot melt silicone adhesive compositions including an alkoxy-functional siloxane reactive resin | |
| KR102207422B1 (en) | Multicomponent room temperature-curable organopolysiloxane composition, cured product of said composition, and molded product comprising said cured product | |
| CN103228733B (en) | Crosslinkable forms elastomeric self-adhesive polysiloxane composition | |
| CN106459582B (en) | Curable organosilicon composition | |
| CN109628058A (en) | A kind of organic silicon adhesive | |
| CN104710962B (en) | Room temperature vulcanized silicone rubber adhesive and preparation method thereof | |
| CN106190012B (en) | A kind of transparent high-intensitive Self-leveling piptonychia alcohol type single-component organic silicon glue and preparation method thereof | |
| EP2756040B1 (en) | Filled silicone composition, in situ preparation and use thereof | |
| CN104031389A (en) | Humid-heat resisting room-temperature vulcanized silicone rubber composition | |
| CN110003842A (en) | A kind of single-component dealcoholization-type room-temperature vulcanized organic polyorganosiloxane composition | |
| CN104497959A (en) | Single-composition room-temperature vulcanized silicone rubber sealant and preparation method thereof | |
| CN1389516A (en) | Self-adhesive heat-crosslinking single-component polysiloxane composition | |
| CN105419336B (en) | A kind of high-elongation dealcoholized type room temperature vulcanized silicone rubber and preparation method thereof | |
| JPWO2017164265A1 (en) | Curable resin composition, cured product thereof, and semiconductor device | |
| WO2017122712A1 (en) | Curable resin composition, cured object, encapsulation material, and semiconductor device | |
| JP6944119B2 (en) | Curable resin composition, cured product thereof, and semiconductor device | |
| CA2873669C (en) | Curable resin composition and primer composition | |
| CN104231290A (en) | Fluorosilicone rubber and silicone rubber bonding method | |
| CN111205816A (en) | Gray organic silicon rubber and preparation process thereof | |
| EP3448920B1 (en) | Improved method for producing moisture-sensitive products | |
| CN104231638A (en) | Tackifier for fluorosilicone rubber and silicone rubber and application and preparation method thereof | |
| JP2005213487A (en) | Room temperature-curing polyorganosiloxane composition | |
| CN109735302A (en) | A kind of silane-modified glue for tile and preparation method thereof | |
| CN113825805B (en) | Moldable silicone elastomers with selective non-primer adhesion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150819 |
|
| RJ01 | Rejection of invention patent application after publication |