CN101704965A - High-temperature-resistant liquid sealant - Google Patents
High-temperature-resistant liquid sealant Download PDFInfo
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- CN101704965A CN101704965A CN200910179334A CN200910179334A CN101704965A CN 101704965 A CN101704965 A CN 101704965A CN 200910179334 A CN200910179334 A CN 200910179334A CN 200910179334 A CN200910179334 A CN 200910179334A CN 101704965 A CN101704965 A CN 101704965A
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Abstract
The invention discloses a high-temperature-resistant liquid sealant, which comprises the following main components: hydrogenated nitrile rubber compound, methyl cyclohexane, butyl acetate, terpene phenolic resin, gas-phase silica, aluminum powder, plasticizers and coupling agents. The sealant has the following advantages of: 1, adopting hydrogenated nitrile rubber as base material and having capability of long-term use at a high temperature and good aging resistance; 2, adding high-temperature-resistant fillers to improve the heat resistance of the sealant; 3, adding the aluminum powder to improve the thermal conductivity of the sealant; 4, adopting an environment-friendly solvent system, taking the methyl cyclohexane and the butyl acetate as mixed solvent, having little smell and low toxicity and meeting requirements of environmental protection; and 5, adopting a preparation process high in solid content and low in viscosity and having construction convenience and suitability for injection and extrusion processes.
Description
Technical field:
The present invention relates to solvent-borne type liquid sealant field, is a kind of solvent type high-temperature-resistant liquid sealant specifically.
Background technology:
Liquid sealant is to be base-material by macromolecular materials such as natural or synthetic rubber, resin, fibers, allocating auxiliary agents such as weighting agent, toughner into mixes, it can contain also can not contain solvent, replacing solid gasket, solving and obtained good effect aspect leakage sealed, simultaneously easy to use, not high to the bonding surface precision prescribed, cost and labour intensity are low.Therefore, it is replenishing and improving the conventional solid sealing material.Solvent-borne type liquid sealant wherein has been widely used in fields such as motor car engine, oil pan sealing, mechanical seal because rate of drying is fast, easy to use.
The optimization of base mateiral is to improve one of main means of seal gum performance.The rubber that the solvent-borne type liquid sealant is commonly used has chloroprene rubber, chlorosulfonated polyethylene, paracril etc.But they in use can be subjected to the restriction of some self shortcomings and can't reach the result that people want, though have good oil-proofness, solvent resistance, weather-resistant and anti-ozone ageing as chloroprene rubber, winter hardiness is very poor; Chlorosulfonated polyethylene has good anti-ozone, ageing-resistant, resistant to chemical media, lower temperature resistance and electric insulating quality, but heating a few hours continuously under 121 ℃ or higher temperature, cracking promptly takes place in the sulfinyl chloro, the physical and mechanical properties of cross-linked rubber is reduced, and its low-temperature performance is also relatively poor; Paracril is celebrated so that oil-proofness is superior, and water tolerance and adhesivity are good, but paracril itself contains two keys, ozone resistance is poor, and use temperature can not surpass 120 ℃, if surpass this temperature, its physicals can reduce greatly, and poor performance at low temperatures, and temperature limit of brittleness is-20 ℃~-10 ℃.
Hydrogenated nitrile-butadiene rubber is exactly to improve its heat aging property for the oil-proofness that keeps paracril, and directly the cyano group to the paracril side chain only partly carries out a kind of glue kind that hydrogenation forms to carbon-to-carbon double bond selectively.After German Bayer AG in 1977 announces the patent of hydrogenated nitrile-butadiene rubber manufacture method, Nippon Zeon Co., Ltd. utilized the technology of oneself also to begin regular commercialization production in 1984, domestic also have many producers to set foot in the hydrogenated nitrile-butadiene rubber field, the trade mark is succeeded in developing at chemical research center, CNPC Lanzhou in 1999 to hydrogenated nitrile-butadiene rubber: LH-9901 and LH-9902.Hydrogenated nitrile-butadiene rubber has good low-temperature performance (60 ℃ of bendings are not split), excellent thermotolerance (can at 165 ℃ of following life-time service), excellent abrasive, high mechanical property (the big 35MPa of tensile strength), excellent resistance to medium and processing characteristics, can be used as the base-material of high-performance liquid seal gum.
Be usually used in the sealing of metal flange mating partss such as motor car engine, oil pan in view of liquid sealant, improve the thermal conductivity of seal gum, can effectively prevent and treat under the high-temperature work environment and accumulate in colloid by seal gum the time, influence the seal gum phenomenon in work-ing life because of heat spreads slowly.In addition, use high temperature resistant filler can improve the colloidal temperature tolerance.
At present, common solvent-borne type liquid sealant causes the applying glue post shrinkage big because solid content is low, general improves with the method that improves the glue solid content, but causes product viscosity too high and influence application property simultaneously again, can adopt and refine the viscosity that glue reduces glue.In addition, people are more and more higher to the attention degree of environmental problem, and some are usually used in the solvent of solvent-based adhesive, and the application at adhesive area is restricted as toluene, methylene dichloride etc.Therefore, it also is inevitable selecting the solvent system of low toxicity, environmental protection for use in the solvent-borne type liquid sealant.
Summary of the invention:
A kind of high-temperature-resistant liquid sealant that the object of the present invention is to provide, the employing hydrogenated nitrile-butadiene rubber is a base-material; Add high temperature resistant filler such as terpene phenolic resin and nano-cerium oxide and improve thermotolerance; Add aluminium powder and improve thermal conductivity; Through formulation optimization,, the methylcyclohexane of low toxicity little to distinguish the flavor of, butylacetate are mixed into the environmentally friendly solvent system, adopt rubber mixing technique, make the solid content height, and viscosity is low, and the applying glue post shrinkage is little, the solvent-borne type liquid sealant that application property is good.
A kind of high-temperature-resistant liquid sealant of the present invention is achieved in that its weight part proportioning is:
35~60 parts of hydrogenated nitrile-butadiene rubber rubber unvulcanizates
20~35 parts of methylcyclohexanes
10~18 parts of butylacetates
4~8 parts of terpene phenolic resins
2~4 parts of aerosils
5~15 parts of aluminium powders
1~3 part in softening agent
0.1~0.5 part of coupling agent
Described hydrogenated nitrile-butadiene rubber rubber unvulcanizate is for by weight ratio: hydrogenated nitrile-butadiene rubber: nano-cerium oxide: silica powder: pure aluminium silicate: carbon black N550: stearic acid=15~25: 1~10: 0~20: 0~20: 2~4: 0.1~0.5, and broken the getting final product in mixing even back;
Described terpene phenolic resin comes at least a among the SP-12 of specialization worker company limited of section, SP-46OB that the Shanghai sage comes specialization worker company limited of section, the SP-154 that the Shanghai sage comes specialization worker company limited of section for the Shanghai sage;
Described softening agent is at least a in dibutyl phthalate, dioctyl phthalate (DOP), the phthalic acid two certain herbaceous plants with big flowers esters;
Described coupling agent is at least a in γ-An Bingjisanyiyangjiguiwan, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, the γ-methacryloxypropyl trimethoxy silane.
The preparation method of a kind of high-temperature-resistant liquid sealant of the present invention is as follows:
By weight ratio, methylcyclohexane, butylacetate are added reactor, under 200~300 rev/mins stirring velocity, drop into hydrogenated nitrile-butadiene rubber rubber unvulcanizate, terpene phenolic resin, aerosil, aluminium powder, softening agent, coupling agent, stir 4~5 hours even to glue, be cooled to normal temperature, the finished product discharging.
The advantage of a kind of high-temperature-resistant liquid sealant of the present invention is:
1. use advanced framework material, the employing hydrogenated nitrile-butadiene rubber is a base-material, can be at life-time service under the hot conditions, and ageing-resistant performance is good;
2. good heat resistance adds the thermotolerance that high temperature resistant filler has improved seal gum;
3. thermal conductivity is good, adds the thermal conductivity that aluminium powder has improved seal gum, has effectively avoided heat to spread slowly and the accumulative phenomenon at colloid;
4. adopt the environmentally friendly solvent system, as mixed solvent, smell is little with methylcyclohexane, butylacetate, and toxicity is low, compliance with environmental protection requirements;
5. the applying glue post shrinkage is little, application property good, employing solid content height, the formulation technology that viscosity is low, easy construction, very suitable injection and expressing technique.
Embodiment:
Embodiment 1
By weight ratio, with 25 parts of methylcyclohexanes, 13 parts of adding reactors of butylacetate, under 300 rev/mins stirring velocity, drop into the hydrogenated nitrile-butadiene rubber rubber unvulcanizate (by weight ratio: hydrogenated nitrile-butadiene rubber: nano-cerium oxide: silica powder: pure aluminium silicate: carbon black N550: stearic acid=15: 3: 12: 5: 2: 0.1, broken the getting final product in mixing even back) 45 parts, 6.8 parts of terpene phenolic resin SP-46OB, 3.5 parts of aerosils, 5 parts of aluminium powders, 1.5 parts of dibutyl phthalates, 0.2 part of γ-An Bingjisanyiyangjiguiwan, stir 5 hours even to glue, be cooled to normal temperature, the finished product discharging.
Embodiment 2
By weight ratio, with 22 parts of methylcyclohexanes, 14 parts of adding reactors of butylacetate, under 300 rev/mins stirring velocity, drop into the hydrogenated nitrile-butadiene rubber rubber unvulcanizate (by weight ratio: hydrogenated nitrile-butadiene rubber: nano-cerium oxide: silica powder: pure aluminium silicate: carbon black N550: stearic acid=20: 5: 8: 7: 3: 0.3, broken the getting final product in mixing even back) 45 parts, terpene phenolic resin SP-125.5 part, 3.2 parts of aerosils, 8 parts of aluminium powders, 2 parts of dioctyl phthalate (DOP)s, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is 0.3 part, stir 5 hours even to glue, be cooled to normal temperature, the finished product discharging.
Embodiment 3
By weight ratio, with 22 parts of methylcyclohexanes, 14 parts of adding reactors of butylacetate, under 250 rev/mins stirring velocity, drop into the hydrogenated nitrile-butadiene rubber rubber unvulcanizate (by weight ratio: hydrogenated nitrile-butadiene rubber: nano-cerium oxide: silica powder: pure aluminium silicate: carbon black N550: stearic acid=25: 8: 2: 10: 4: 0.5, broken the getting final product in mixing even back) 43 parts, terpene phenolic resin SP-1545.5 part, 3.2 parts of aerosils, 10 parts of aluminium powders, 1.8 parts of phthalic acid two certain herbaceous plants with big flowers esters, 0.5 part of γ-methacryloxypropyl trimethoxy silane, stir 4.5 hours even to glue, be cooled to normal temperature, the finished product discharging.
Comparative example 4
By weight ratio, with 28 parts of toluene, 16 parts of adding reactors of butylacetate, under the stirring velocity that low whipping speed is 300 rev/mins, drop into the paracril rubber unvulcanizate (by weight ratio: paracril: silica powder: carbon black N550: stearic acid=25: 12: 3.6: 0.4, mixing even back is broken to get final product) 45 parts, terpene phenolic resin SP-1545.7 part, 3 parts of aerosils, 2 parts of dibutyl phthalates, 0.3 part of γ-An Bingjisanyiyangjiguiwan, stir 4 hours even to glue, be cooled to normal temperature, the finished product discharging.
The correlated performance of the liquid sealant of embodiment 1~3, comparative example 4 adopts following method test:
1. thermal conductivity: reference standard GB/T 3392-82 (plastics thermal conductivity test method is protected the flat plate heat method) carries out.
2. viscosity, solid content, resistance to pressure, resistance to medium: reference standard JB/T 4254-1999 (liquid sealant) carries out.
The correlated performance test result of the liquid sealant of embodiment 1~3, comparative example 4 is as shown in table 1 below.
Table 1
By last table result as can be seen, a kind of high-temperature-resistant liquid sealant of the present invention is compared with existing prior art (comparative example 4), and high-temperature pressure-proof is better; Thermal conductivity is good; Solid content height, viscosity are low, easy construction; Smell is little, and toxicity is low, and compliance with environmental protection requirements has good social benefit.
Main raw material(s) title, technical indicator:
1. hydrogenated nitrile-butadiene rubber
Model: bright Sheng Therban A3406
Acrylonitrile content (%): 34
2. methylcyclohexane
Rank: technical grade
Outward appearance: colourless liquid
Content (%): 〉=97
Supplier: the safe Xiang petrochemical industry in Guangzhou Science and Technology Ltd.
3. butylacetate
Rank: technical grade
Outward appearance: colourless transparent liquid
Content (%): 〉=97
Supplier: trade Co., Ltd is entered in the Dongguan City victory
4. stearic acid
Outward appearance: white is glossy wax shape small pieces xln slightly
Fusing point (℃): 71~72
Supplier: Henan Kang Di chemical industry company limited
5. aerosil
Outward appearance: white amorphous fine powder
Dioxide-containing silica (%): 〉=90
Supplier: Guangzhou Hua Lisen trade Co., Ltd
6. carbon black N550
Outward appearance: black powder
Iodine absorption value (g/kg): 43 ± 5
7. nano-cerium oxide
Content (%): 〉=99
Specific surface area (m
2/ g): 110~150
Supplier: Hangzhou red-spotted stonecrop nanosecond science and technology company limited
8. silica powder
Outward appearance: white or pale powder
Dioxide-containing silica (%): 〉=98
Oil number (%): 15~25
Order number: 260~325
Supplier: mountains and rivers, Lingshou County mineral products source mill
9. aluminium powder
Rank: A
Order number: 265~320
Active aluminum (%): 〉=82
Supplier: Xinji City, Hebei province aluminium powder hot difficult to understand factory
10. terpene phenolic resin SP-12
Fusing point (capillary tube technique, ℃): 57~66
Supplier: the Shanghai sage comes specialization worker company limited of section
11. terpene phenolic resin SP-46OB
Softening temperature (ring and ball method, ℃): 90~100
Supplier: the Shanghai sage comes specialization worker company limited of section
12. terpene phenolic resin SP-154
Fusing point (capillary tube technique, ℃): 74~88
Supplier: the Shanghai sage comes specialization worker company limited of section
13. dibutyl phthalate
Outward appearance: colourless oil liquid
Density (g/cm
3, 20 ℃): 1.042~1.048
14. dioctyl phthalate (DOP)
Outward appearance: transparent oily liquid
Density (g/cm
3, 20 ℃): 0.982~0.988
15. phthalic acid two certain herbaceous plants with big flowers esters
Outward appearance: transparent oily liquid
Density (g/cm
3, 20 ℃): 0.964~0.967
16. γ-An Bingjisanyiyangjiguiwan
Outward appearance: colourless transparent liquid
Boiling point (℃): 217
Content (%): 〉=97
Supplier: Jiangsu Chenguang Coincident Dose Co., Ltd.
17. γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane
Outward appearance: colourless transparent liquid
Boiling point (℃): 290
Content (%): 〉=97
Supplier: Jiangsu Chenguang Coincident Dose Co., Ltd.
18. γ-methacryloxypropyl trimethoxy silane
Outward appearance: colourless transparent liquid
Boiling point (℃): 255
Content (%): 〉=97
Supplier: Jiangsu Chenguang Coincident Dose Co., Ltd..
Claims (6)
1. a high-temperature-resistant liquid sealant is characterised in that, prescription is by weight ratio:
35~60 parts of hydrogenated nitrile-butadiene rubber rubber unvulcanizates
20~35 parts of methylcyclohexanes
10~18 parts of butylacetates
4~8 parts of terpene phenolic resins
2~4 parts of fumed silicas
5~15 parts of aluminium powders
1~3 part in softening agent
0.1~0.5 part of coupling agent.
2. a kind of high-temperature-resistant liquid sealant as claimed in claim 1 is characterised in that, the hydrogenated nitrile-butadiene rubber rubber unvulcanizate is for by weight ratio: hydrogenated nitrile-butadiene rubber: nano-cerium oxide: silica powder: pure aluminium silicate: carbon black N550: stearic acid=15~25: 1~10: 0~20: 0~20: 2~4: 0.1~0.5, and broken the getting final product in mixing even back.
3. a kind of high-temperature-resistant liquid sealant as claimed in claim 1 is characterised in that, terpene phenolic resin comes at least a among the SP-12 of specialization worker company limited of section, SP-460B that the Shanghai sage comes specialization worker company limited of section, the SP-154 that the Shanghai sage comes specialization worker company limited of section for the Shanghai sage.
4. a kind of high-temperature-resistant liquid sealant as claimed in claim 1 is characterised in that, softening agent is at least a in dibutyl phthalate, dioctyl phthalate (DOP), the phthalic acid two certain herbaceous plants with big flowers esters.
5. a kind of high-temperature-resistant liquid sealant as claimed in claim 1 is characterised in that, coupling agent is at least a in γ-An Bingjisanyiyangjiguiwan, γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane, the γ-methacryloxypropyl trimethoxy silane.
6. a kind of high-temperature-resistant liquid sealant as claimed in claim 1 is characterised in that, the preparation method is: by weight ratio, methylcyclohexane, butylacetate are added reactor, under 200~300 rev/mins stirring velocity, drop into hydrogenated nitrile-butadiene rubber rubber unvulcanizate, terpene phenolic resin, aerosil, aluminium powder, softening agent, coupling agent, stir 4~5 hours even to glue, be cooled to normal temperature, the finished product discharging.
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CN101704965B CN101704965B (en) | 2011-08-10 |
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CN101935505A (en) * | 2010-08-31 | 2011-01-05 | 广州市安泰化学有限公司 | High elasto-plasticity waterproof caulking sealant used in outdoor and preparation method thereof |
CN102433086A (en) * | 2010-09-29 | 2012-05-02 | 泰州五行消防水带有限公司 | Binder for hydrogenated butyronityile rubber hoses and preparation method |
CN102731870A (en) * | 2012-06-26 | 2012-10-17 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature resistant rubber |
CN102731871A (en) * | 2012-06-26 | 2012-10-17 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature 160 DEG C resistant rubber |
CN102731869A (en) * | 2012-06-26 | 2012-10-17 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature 150 DEG C resistant rubber |
CN104910580A (en) * | 2015-06-13 | 2015-09-16 | 陈新棠 | Plastic pipe |
CN105840047A (en) * | 2016-03-24 | 2016-08-10 | 浙江立恒建设有限公司 | Insulation mortar exterior wall external window leakage water control construction method |
CN106010433A (en) * | 2016-06-28 | 2016-10-12 | 华蓥市高科德电子科技有限公司 | Display screen sealant |
CN106380649A (en) * | 2016-10-12 | 2017-02-08 | 武汉鼎丰设备备件材料有限公司 | Easy-to-clean liquid sealing assembly |
CN110577772A (en) * | 2019-08-27 | 2019-12-17 | 中国航发北京航空材料研究院 | Surface protection sealing coating for integral fuel tank of airplane |
CN111576085A (en) * | 2020-05-28 | 2020-08-25 | 安庆盛华纸质包装有限公司 | Processing technology of high-strength and high-temperature-resistant laminating paper |
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2009
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CN101935505A (en) * | 2010-08-31 | 2011-01-05 | 广州市安泰化学有限公司 | High elasto-plasticity waterproof caulking sealant used in outdoor and preparation method thereof |
CN102433086B (en) * | 2010-09-29 | 2013-09-11 | 泰州五行消防水带有限公司 | Binder for hydrogenated butyronityile rubber hoses and preparation method |
CN102433086A (en) * | 2010-09-29 | 2012-05-02 | 泰州五行消防水带有限公司 | Binder for hydrogenated butyronityile rubber hoses and preparation method |
CN102731871B (en) * | 2012-06-26 | 2013-10-30 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature 160 DEG C resistant rubber |
CN102731869A (en) * | 2012-06-26 | 2012-10-17 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature 150 DEG C resistant rubber |
CN102731871A (en) * | 2012-06-26 | 2012-10-17 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature 160 DEG C resistant rubber |
CN102731870A (en) * | 2012-06-26 | 2012-10-17 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature resistant rubber |
CN102731869B (en) * | 2012-06-26 | 2013-11-06 | 芜湖宏达橡塑阀门制造有限公司 | High-temperature 150 DEG C resistant rubber |
CN104910580A (en) * | 2015-06-13 | 2015-09-16 | 陈新棠 | Plastic pipe |
CN105840047A (en) * | 2016-03-24 | 2016-08-10 | 浙江立恒建设有限公司 | Insulation mortar exterior wall external window leakage water control construction method |
CN106010433A (en) * | 2016-06-28 | 2016-10-12 | 华蓥市高科德电子科技有限公司 | Display screen sealant |
CN106380649A (en) * | 2016-10-12 | 2017-02-08 | 武汉鼎丰设备备件材料有限公司 | Easy-to-clean liquid sealing assembly |
CN110577772A (en) * | 2019-08-27 | 2019-12-17 | 中国航发北京航空材料研究院 | Surface protection sealing coating for integral fuel tank of airplane |
CN111576085A (en) * | 2020-05-28 | 2020-08-25 | 安庆盛华纸质包装有限公司 | Processing technology of high-strength and high-temperature-resistant laminating paper |
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