CN104017369A - Preparation method of silicon rubber foam material with high tensile strength - Google Patents

Preparation method of silicon rubber foam material with high tensile strength Download PDF

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Publication number
CN104017369A
CN104017369A CN201410273779.4A CN201410273779A CN104017369A CN 104017369 A CN104017369 A CN 104017369A CN 201410273779 A CN201410273779 A CN 201410273779A CN 104017369 A CN104017369 A CN 104017369A
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China
Prior art keywords
silicon rubber
rubber foam
preparation
high tensile
foam material
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CN201410273779.4A
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Chinese (zh)
Inventor
翟文涛
郑文革
陈忠
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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Priority to CN201410273779.4A priority Critical patent/CN104017369A/en
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Abstract

The invention discloses a preparation method of a silicon rubber foam material with high tensile strength. According to the method which uses graphene as a reinforcing agent, based on 100 parts of silicon rubber, the mechanical tensile strength of the silicon rubber foam material can be effectively improved just by adding 1-20 parts of graphene, so that the problem that in the prior art for preparing the silicon rubber foam material, the content of the reinforcing agent is high and the silicon rubber foam strength is less is solved.

Description

A kind of preparation method with the silicon rubber foam material of high tensile
Technical field
The present invention relates to preparation method's technical field of silicon rubber foam material, particularly relate to a kind of preparation method with the silicon rubber foam material of high tensile.
Background technology
Silicon rubber alternately forms main chain by siloxane bond, half organic half inorganic polymer that contains organic group on its side chain, have benefited from the singularity of its structure, the silicon rubber foam that the silicon rubber of take is prepared as matrix have many other rubbery foams the excellent properties that can not simultaneously possess, as good high and low temperature resistance, excellent insulativity, chemical stability and physiology inertia etc., be widely used in chemical industry, electronics, military project, aerospace etc.
In process for processing and use procedure, the mechanical property of silicon rubber foam, is one of its main performance such as tensile strength, elongation at break etc.For example, in the processes such as carrying, curling, cutting, if there is no higher mechanical strength, often can occur to rupture or damaged situation; In use procedure, also can have to adopt extra equipment or technique to prevent fracture or the breakage of silicon rubber foam because silicon rubber foam mechanical strength is too low.
But, in the situation that not adding strengthening agent, the mechanical properties such as the tensile strength of silicon rubber foam, elongation at break are poor, product application scope is minimum, therefore often need to add various fillers in the preparation process of silicon rubber foam, to improve silicon rubber foam mechanical property, widen product application scope.
At present, the strengthening agent using while preparing silicon rubber foam comprises silicon-dioxide, calcium carbonate, carbon black, zinc oxide, aluminum oxide etc., and wherein silicon-dioxide is the most frequently used strengthening agent of silicon rubber foam.But the problems such as these strengthening agent ubiquity add-ons are many, difficulty of processing large, reinforcement efficiency is low.
Silicon-dioxide during as the strengthening agent of silicon rubber foam, comprises vapor phase process or precipitated silica, hydrophilic or hydrophobic.For example, Chinese patent CN1884378A disclose a kind of using silicon rubber, precipitated silica or thermal silica as strengthening agent, constitution controller, pore former and additional crosslinker be crosslinked with electron beam or gamma Rays after mixing, thereby then wash pore former, obtains open-cells silicon rubber foam material; Chinese patent CN101781464A discloses a kind of by crosslinked with electron beam or gamma Rays after silicon rubber, white carbon black, constitution controller, whipping agent, frothing aid and additional crosslinker mixing moulding, and then foamable also further carries out the method that secondary crosslinking obtains silicon rubber foam.
But, precipitated silica (white carbon black) particle is larger, and normally micron dimension, often needs very high loading level could improve a little the mechanical property of silicon rubber foam.Fumed silica is better than precipitated silica to the mechanics reinforced effects of silicon rubber foam, but thereby fumed silica is easily reunited and is made its dispersiveness in silicon rubber poor, therefore usually need to add the constitution controllers such as small molecules silicone oil to improve its dispersiveness, caused reducing the flame retardant resistance of silicon rubber foam.Meanwhile, generally speaking, no matter add precipitated silica or fumed silica at present, all have such problem: add-on has impact to the density of silicon rubber foam at most, add-on does not reach enough mechanical strengths at least.For example, in aforementioned Chinese patent CN1884378A, add 25 grams of thermal silicas in 100 grams of silicon rubber, not only strengthening agent add-on is many, has increased difficulty of processing, and the tensile strength of prepared silicon rubber foam is only 0.71MPa.
The strengthening agent of silicon-dioxide and other kinds is carried out composite, the intensity of silicon rubber foam is not improved substantially yet.
For example, in Chinese patent CN102093718A, add 50Kg nano silicon and 30Kg polynite as strengthening agent in 100Kg silicon rubber, the tensile strength of prepared silicon rubber foam is only also 0.41MPa.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of preparation method of silicon rubber foam material, utilizes the method can make the silicon rubber foam material with high tensile.
In order to realize above-mentioned technical purpose, the inventor finds in research practice is explored, when preparing silicon rubber foam material, using Graphene as strengthening agent, the silicon rubber foam making has except having advantages of general silicon rubber foam, light weight for example, heat insulation, impact resistance is good, outside the advantage such as the good and chemical stability of high and low temperature resistance is good, also there is excellent mechanical stretch intensity, more than its mechanical stretch intensity can reach 1.0MPa, each component concentration is adjusted, more than its mechanical stretch intensity can reach 1.2MPa, further preferably can reach 1.3~2.8MPa.
Particularly, the technical solution adopted in the present invention is: a kind of preparation method with the silicon rubber foam material of high tensile, and take silicon rubber, whipping agent, frothing aid, linking agent, strengthening agent is raw material, by following steps, prepares:
Raw material is mixed, be processed into flaky material, be then cut into certain size and put into closed mold and heat-treat foaming, obtain foam sheet;
It is characterized in that: described strengthening agent is Graphene.
As preferably, each component and the parts by weight thereof of described raw material are as follows:
100 parts, silicon rubber, 1~5 part of whipping agent, 1~5 part of frothing aid, 1~10 part of linking agent, 1~20 part of strengthening agent.
As preferably, in described raw material, the parts by weight of strengthening agent are 2~15 parts, more preferably 3~10 parts, and more preferably 4~8 parts.
Described silicon rubber comprises one or more in trifluoropropyl siloxane, nitrile silicone rubber, dimethyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl silicone rubber, ethyl silicon rubber and phenylene silicone rubber.
Described whipping agent comprises sodium bicarbonate, volatile salt, bicarbonate of ammonia, sodium borohydride, Diisopropyl azodicarboxylate (AIBN), Cellmic C 121 (AC), N, N-dinitrosopentamethlyene tetramine (H), N, N '-dimethyl-N, N '-dinitroso is to benzene (DMDNTA), benzol sulfohydrazide (BSH), 4,4 '-OBSH (OBSH), 3,3 '-disulfonyl hydrazide sulfobenzide, 1, one or more in 3-benzene disulfohydrazide, p-toluene sulfonylsemicarbazide, benzene sulfonamido urea, trihydrazinotriazine etc.
Described frothing aid comprises one or more in urea, thanomin, stearic acid, lauric acid, Whitfield's ointment, phenylformic acid, lead stearate, potassium aluminium sulfate, tetramethylolmethane, glycerol etc.
Described linking agent comprises dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), 2,5-dimethyl 2,5-di-t-butyl peroxy hexane (DBPMH), 2, any one in 4-dichloro dibenzoyl peroxide (DCBP), peroxidized t-butyl perbenzoate (TBPB), peroxidation di tert butyl carbonate (DTBP) etc.
The method that mixture is processed into sheet is not limit, and comprises extrusion method, opens the sheet method etc. that is smelt.
The mode that described thermal treatment is foamed is not limit, and comprises and adopts the mode of baking oven, drying tunnel or vulcanizing press to realize.
Tool of the present invention has the following advantages:
Existing invention generally adopts silicon-dioxide, calcium carbonate, carbon black, zinc oxide, aluminum oxide etc. to carry out reinforcement to silicon rubber foam, but the problem such as ubiquity add-on is many, difficulty of processing is large, reinforcement efficiency is low.
In sum, the present invention is when preparing silicon rubber foam material, adopt Graphene as strengthening agent, because Graphene has high specific surface area, therefore only need add a small amount of Graphene just can greatly improve the mechanical stretch intensity of silicon rubber foam material, thereby it is high to efficiently solve in the existing technology of preparing silicon rubber foam material existing strengthening agent content, the problem that silicon rubber foam intensity is little.In addition, preparation method provided by the invention is simple for process, to equipment require low, can utilize existing installation to produce completely, prepared silicon rubber foam has except having advantages of general silicon rubber foam, for example light weight, heat insulation, impact resistance good, outside the advantage such as the good and chemical stability of high and low temperature resistance is good, also has excellent mechanical stretch intensity.
 
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played to any restriction effect.
Embodiment 1:
(1) preparation raw material, each component and the parts by weight thereof of raw material are as follows:
Methyl vinyl silicone rubber: 100 parts
Graphene: 3 parts
Blowing agent AC: 3 parts
Zinc oxide: 3 parts
Crosslinking agent B PO:1 part
(2) by join raw material add high-speed mixer to mix; Mixture is placed in to mill, opens the mixture sheet material that refining obtains thickness 3mm; Mixture sheet material is put into closed mold, and heat-treat with vulcanizing press, obtain silicon rubber foam plate.
The above-mentioned silicon rubber foam plate making is carried out to mechanical test, and test result is: high tensile measurement shows: this silicon rubber foam plate density is 310g/L; Permanent compression set is 2.5%; Through universal tensile testing machine test, its tensile strength is 1.23MPa.
Embodiment 2:
(1) preparation raw material, each component and the parts by weight thereof of raw material are as follows:
Methyl vinyl silicone rubber: 100 parts
Graphene: 3 parts
Whipping agent sodium bicarbonate: 3 parts
Citric acid: 3 parts
Crosslink agent DCP: 2 parts
(2) by join raw material add high-speed mixer to mix; Mixture is placed in to mill, opens the mixture sheet material that refining obtains thickness 3mm; Mixture sheet material is put into closed mold, and heat-treat with vulcanizing press, obtain silicon rubber foam plate.
The above-mentioned silicon rubber foam plate making is carried out to mechanical test, and test result is: high tensile measurement shows: this silicon rubber foam plate density is 300g/L; Permanent compression set is 2.1%; Through universal tensile testing machine test, its tensile strength is 1.35MPa.
Embodiment 3:
(1) preparation raw material, each component and the parts by weight thereof of raw material are as follows:
Methyl vinyl silicone rubber: 70 parts, methyl phenyl silicone rubber: 30 parts
Graphene: 3 parts
Blowing agent AC: 3 parts
Tetramethylolmethane: 3 parts
Crosslink agent DCP: 2 parts
(2) by join raw material add high-speed mixer to mix; Mixture is placed in to mill, opens the mixture sheet material that refining obtains thickness 3mm; Mixture sheet material is put into closed mold, and heat-treat with vulcanizing press, obtain silicon rubber foam plate.
The above-mentioned silicon rubber foam plate making is carried out to mechanical test, and test result is: high tensile measurement shows: this silicon rubber foam plate density is 290g/L; Permanent compression set is for being 2.1%; Through universal tensile testing machine test, its tensile strength is 1.33MPa.
Embodiment 4:
(1) preparation raw material, each component and the parts by weight thereof of raw material are as follows:
Methyl vinyl silicone rubber: 100 parts
Graphene: 5 parts
Whipping agent sodium bicarbonate: 3 parts
Citric acid: 3 parts
Crosslink agent DCP: 2 parts
(2) by join raw material add high-speed mixer to mix; Mixture is placed in to mill, opens the mixture sheet material that refining obtains thickness 3mm; Mixture sheet material is put into closed mold, and heat-treat with vulcanizing press, obtain silicon rubber foam plate.
The above-mentioned silicon rubber foam plate making is carried out to mechanical test, and test result is: high tensile measurement shows: this silicon rubber foam plate density is 295g/L; Permanent compression set is for being 2.2%; Through universal tensile testing machine test, its tensile strength is 1.98MPa.
Embodiment 5:
In the present embodiment, raw material and preparation method are substantially the same manner as Example 1, and difference is that Graphene consumption is 0 parts by weight.
The silicon rubber foam plate making is tested through universal tensile testing machine, and its tensile strength is 0.78MPa.
Embodiment 6:
In the present embodiment, raw material and preparation method are substantially the same manner as Example 1, and difference is that Graphene consumption is 5 parts by weight.
The silicon rubber foam plate making is tested through universal tensile testing machine, and its tensile strength is 1.98MPa.
Embodiment 7:
In the present embodiment, raw material and preparation method are substantially the same manner as Example 1, and difference is that Graphene consumption is 7 parts by weight.
The silicon rubber foam plate making is tested through universal tensile testing machine, and its tensile strength is 2.51MPa.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any modifications of making within the scope of principle of the present invention, supplement or similar fashion substitutes etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a preparation method with the silicon rubber foam material of high tensile, take silicon rubber, whipping agent, frothing aid, linking agent, strengthening agent is raw material, by following steps, prepares:
Raw material is mixed, be processed into flaky material, be then cut into certain size and put into closed mold and heat-treat foaming, obtain foam sheet;
It is characterized in that: described strengthening agent is Graphene.
2. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, is characterized in that: each component and the parts by weight thereof of described raw material are as follows:
100 parts, silicon rubber, 1~5 part of whipping agent, 1~5 part of frothing aid, 1~10 part of linking agent, 1~20 part of strengthening agent.
3. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, is characterized in that: in described raw material, the parts by weight of strengthening agent are 2~15 parts.
4. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, is characterized in that: in described raw material, the parts by weight of strengthening agent are 3~10 parts, is preferably 4~8 parts.
5. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, it is characterized in that: described whipping agent comprises sodium bicarbonate, volatile salt, bicarbonate of ammonia, sodium borohydride, Diisopropyl azodicarboxylate (AIBN), Cellmic C 121 (AC), N, N-dinitrosopentamethlyene tetramine (H), N, N '-dimethyl-N, N '-dinitroso is to benzene (DMDNTA), benzol sulfohydrazide (BSH), 4, 4 '-OBSH (OBSH), 3, 3 '-disulfonyl hydrazide sulfobenzide, 1, 3-benzene disulfohydrazide, p-toluene sulfonylsemicarbazide, benzene sulfonamido urea, one or more in trihydrazinotriazine.
6. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, is characterized in that: described frothing aid comprises one or more in urea, thanomin, stearic acid, lauric acid, Whitfield's ointment, phenylformic acid, lead stearate, potassium aluminium sulfate, tetramethylolmethane, glycerol.
7. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, it is characterized in that: described linking agent comprises dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), 2,5-dimethyl 2,5-di-t-butyl peroxy hexane (DBPMH), 2, any one in 4-dichloro dibenzoyl peroxide (DCBP), peroxidized t-butyl perbenzoate (TBPB), peroxidation di tert butyl carbonate (DTBP).
8. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, is characterized in that: the method that described mixture is processed into sheet comprises extrusion method, opens the sheet method that is smelt.
9. the preparation method with the silicon rubber foam material of high tensile as claimed in claim 1, is characterized in that: described thermal treatment is foamed and adopted the mode of baking oven, drying tunnel or vulcanizing press to realize.
10. the preparation method of the silicon rubber foam material with high tensile as described in arbitrary claim in claim 1 to 9, is characterized in that: its tensile strength more than 1.0MPa, more than being optimized for 1.2MPa, 1.3~2.8MPa more preferably.
CN201410273779.4A 2014-06-18 2014-06-18 Preparation method of silicon rubber foam material with high tensile strength Pending CN104017369A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104387776A (en) * 2014-10-28 2015-03-04 中国科学院宁波材料技术与工程研究所 Preparation method of antistatic and flame-retardant silicon rubber foam material
CN106566259A (en) * 2016-11-07 2017-04-19 山东非金属材料研究所 Silicone rubber foaming material and preparation method thereof
CN106832962A (en) * 2016-12-30 2017-06-13 安徽凌宇电缆科技有限公司 A kind of anti-aging cable insulation layer formula of high temperature resistant
CN107722629A (en) * 2017-11-03 2018-02-23 安徽潜隆机电科技有限公司 A kind of coaxial radio-frequency foamed cable crust containing modified antibacterial graphene
CN108977105A (en) * 2018-07-11 2018-12-11 薛向东 A kind of preparation method of heat-conducting silica gel sheet
CN114571815A (en) * 2022-03-10 2022-06-03 浙江葆润应用材料有限公司 Multi-layer fireproof PCM composite material for battery pack
CN115321526A (en) * 2022-08-24 2022-11-11 湖南镕锂新材料科技有限公司 Preparation method and application of graphene precursor slurry

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CN102093718A (en) * 2010-11-19 2011-06-15 四川大学 Method for preparing silicone rubber foam material with low density and high opening rate

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104387776A (en) * 2014-10-28 2015-03-04 中国科学院宁波材料技术与工程研究所 Preparation method of antistatic and flame-retardant silicon rubber foam material
CN106566259A (en) * 2016-11-07 2017-04-19 山东非金属材料研究所 Silicone rubber foaming material and preparation method thereof
CN106832962A (en) * 2016-12-30 2017-06-13 安徽凌宇电缆科技有限公司 A kind of anti-aging cable insulation layer formula of high temperature resistant
CN107722629A (en) * 2017-11-03 2018-02-23 安徽潜隆机电科技有限公司 A kind of coaxial radio-frequency foamed cable crust containing modified antibacterial graphene
CN108977105A (en) * 2018-07-11 2018-12-11 薛向东 A kind of preparation method of heat-conducting silica gel sheet
CN114571815A (en) * 2022-03-10 2022-06-03 浙江葆润应用材料有限公司 Multi-layer fireproof PCM composite material for battery pack
CN115321526A (en) * 2022-08-24 2022-11-11 湖南镕锂新材料科技有限公司 Preparation method and application of graphene precursor slurry
CN115321526B (en) * 2022-08-24 2023-12-19 湖南镕锂新材料科技有限公司 Preparation method and application of graphene precursor slurry

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Application publication date: 20140903