CN109912800A - A kind of preparation method for the heat-resisting liquid silastic improving intensity and interfacial adhesion - Google Patents
A kind of preparation method for the heat-resisting liquid silastic improving intensity and interfacial adhesion Download PDFInfo
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- CN109912800A CN109912800A CN201810899068.6A CN201810899068A CN109912800A CN 109912800 A CN109912800 A CN 109912800A CN 201810899068 A CN201810899068 A CN 201810899068A CN 109912800 A CN109912800 A CN 109912800A
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- liquid silastic
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- epoxy resin
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- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 229920000260 silastic Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 58
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000012467 final product Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- -1 Methyl Hydrogen Chemical compound 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000004945 silicone rubber Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- MJULMZZKFYNTHK-UHFFFAOYSA-N ethenyl(phenyl)silicon Chemical compound C=C[Si]C1=CC=CC=C1 MJULMZZKFYNTHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical group [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 150000003376 silicon Chemical class 0.000 abstract description 9
- 238000010010 raising Methods 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 28
- 239000002131 composite material Substances 0.000 description 24
- 238000006731 degradation reaction Methods 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides the preparation methods of a kind of improvement intensity and the heat-resisting liquid silastic of interfacial adhesion, it is the following steps are included: under the conditions of (1) is existing for the catalyst B, up to prepolymer after taking bisphenol A type epoxy resin to react at 100 DEG C with silane coupling agent；(2) weigh prepolymer, liquid silastic stirs evenly, add curing agent and catalyst A and be uniformly mixed, deaeration solidifies to obtain the final product.The present invention is related to angle from molecular structure, by the modified silicon rubber for selecting specific raw material to be prepared, realizes and increases substantially the intensity of silicon rubber in the case where few additive (tensile strength raising reaches 0.83MPa, improves 162% compared with pure sample；160%) and elongation at break (elongation at break reaches 268%, improves about 2 times compared with pure sample) adhesive property 0.81MPa improves compared with pure sample, i.e., improves the rigidity and toughness of material simultaneously, that has widened liquid silicon rubber material uses field.
Description
Technical field
The present invention relates to a kind of preparation methods of the improved heat resistant type liquid silastic of molecular chain structure, and in particular to a kind of
Improve the preparation method of the heat-resisting liquid silastic of intensity and interfacial adhesion.
Background technique
Silicon rubber alternately forms its main chain, organic group (such as methyl, ethyl, vinyl, benzene by silicon oxygen bond (Si-O)
Base, trifluoro propyl etc.) form a kind of line style polysiloxane of its side group.Due to structure and the particularity of composition, silicon rubber
Material integrates the characteristic and function of inorganic matter and organic matter, the superiority that cannot be provided simultaneously with many other materials
Can, such as brilliant resistant of high or low temperature, excellent oil resistant, solvent resistant, resistance to ultraviolet, radiation resistance, good resistance to ag(e)ing are excellent
Electrical insulating property and chemical stability and physiological inertia etc., thus aerospace, electrical, electronics, chemical industry, instrument, automobile,
The industry such as machinery and health care, daily life every field have been widely used.But since silicon rubber is intermolecular
Intermolecular force is small, very poor for modified Mechanical Properties of Silicone Rubber, basic without actual use value, seriously constrains silicon rubber
The application of glue product.
Currently, the method for modifying of silicon rubber mainly has addition filler, graft modification is carried out to silicon rubber main chain, with other height
Molecular material blending, copolymerization etc..And there is some unavoidable scarce for fiber and inorganic filler enhancing silicon rubber composite material
Point, such as: 1, most of inorganic filler surface all has active group, there is interaction between inorganic particulate, cause its
Dispersion in silicon rubber is relatively difficult, is easy to happen reunion in intrinsic silicon, thus under will lead to the mechanical property of composite material
Drop；2, inorganic filler is introduced into silicon rubber, and the viscosity of its sizing material can be made to increase sharply, as additive amount constantly increases, nothing
The dispersion of machine particle becomes extremely difficult, and machine-shaping also can be extremely difficult；3, the introducing of inorganic filler can greatly improve silicon
The mechanical property and hot property of rubber matrix, but adhesive property to silicon rubber composite material and surface property do not improve.And
Individual surface is modified, for example will form one layer of fragile silica nonwoven fabric from filaments in silastic surface after plasma modification, changes
Silicon rubber after property will lose its hydrophilic nmature in a short time.Silicon rubber modification can be improved with other macromolecules
The shortcomings that stating, currently, having no the report that bisphenol A epoxide resin is used for modified liquid silicon rubber.
Summary of the invention
The purpose of the present invention is to provide the preparations of a kind of improvement intensity and the heat-resisting liquid silastic of interfacial adhesion
Method, it the following steps are included:
(1) existing for the catalyst B under the conditions of, after taking bisphenol A type epoxy resin to react at 100 DEG C with silane coupling agent
Up to prepolymer；
(2) weigh prepolymer, liquid silastic stirs evenly, add curing agent and catalyst A and be uniformly mixed, deaeration,
Solidify to obtain the final product.
Further, in step (1), the molar ratio of the bisphenol A type epoxy resin and silane coupling agent is 1~3:1, excellent
It is selected as 1:1；The mass ratio of the epoxy resin and catalyst B are 434~1305:1.
Further, in step (1), the bisphenol A type epoxy resin is E44, E51, E20；The silane coupling agent is
SCA-L,A-172；The catalyst B is tetraisopropyl titanate, dibutyl tin dilaurate, butyl titanate.
Further, in step (1), the time of the reaction is 4~10h, preferably 4h.
Further, in step (2), the liquid silastic, prepolymer, curing agent, catalyst A weight proportion are as follows:
90~110:7~15:3:0.2.
Further, the weight proportion of the liquid silastic, prepolymer, curing agent, catalyst A are as follows: 100:10:3:
0.2。
Further, in step (2), the liquid silastic is methyl vinyl silicone rubber, phenyl vinyl silicon rubber；
The curing agent is Methyl Hydrogen Polysiloxane Fluid；The catalyst A is chloroplatinic acid, palladium catalyst.
Further, in step (2), the cured temperature is 95~110 DEG C, preferably 100 DEG C.
Further, in step (2), the cured time is 2~3h, preferably 2h.
The present invention is related to angle from molecular structure, by the silicon rubber for selecting specific raw material to be prepared, realizes
The intensity of silicon rubber is greatly improved in the case where extremely low additive amount, and (tensile strength raising reaches 0.83MPa, compared with pure sample
Improve 162%；Adhesive property 0.81MPa, compared with pure sample improve 160%) and elongation at break (elongation at break reaches 268%, compared with
Pure sample improves about 2 times), i.e., the rigidity and toughness of composite material are improved simultaneously, avoids brittle fracture, have greatly been widened multiple
Condensation material uses field and prolongs its service life.Its heat resistance remains at higher level simultaneously, residual in 800 DEG C of heat
It weighs to 53.53%, and synthesis technology is simple, handling ease, the time is short, and step is few, has a vast market application prospect.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is the internal standard infrared spectrum of obtained prepolymer (EK) under the conditions of differential responses.
Fig. 2 is profile scanning Electronic Speculum (SEM) figure × 500:(a that quenches of silicon rubber compound system) silicon rubber pure sample, (b) 4-
40,(c)4-80,(d)4-120,(e)7-40,(f)7-80,(g)7-120,(h)10-40,(i)10-80,(j)10-120。
Fig. 3 is silicon rubber compound system in N2The TG (a) and DTG (b) curve that atmosphere measures.
Fig. 4 is silicon rubber compound system in N2Atmosphere thermal degradation infrared spectrum.
Fig. 5 is the infrared analysis spectrogram of (TGA, nitrogen) carbon residue after the test of 4-120 silastic material heat analysis.
Fig. 6 is the influence for being different prepolymers to silicon rubber compound system tensile strength and elongation at break.
Fig. 7 is the result figure of different prepolymer modified silicon rubber compound system adhesive properties.
Specific embodiment
Embodiment 1, epoxy resin modification of the present invention liquid silastic preparation
One, the preparation method of the liquid silastic of epoxy resin modification of the present invention
1 experimental raw
The preparation of 2 bisphenol A type epoxy resins-silane coupling agent performed polymer
It is 1 that molar ratio is sequentially added into the three-necked flask equipped with thermometer, mechanical agitator and reflux condenser device:
1 epoxy resin (E44,50g) and silane coupling agent (SCA-L, 13.04g) is passed through inert gas and drains air in device, rises
Temperature is to 100 DEG C and keeps constant, and starting stirring is uniformly mixed mixture.By the time and the catalyst that change prepolymerization reaction
9 groups of different head products are made respectively, head product are taken out, and wash away it with methanol for (tetraisopropyl titanate) dosage (being shown in Table 1)
The middle complete silane coupling agent of unreacted, then removes methanol, obtains prepolymer (EK).
1 bisphenol A epoxide resin of table-silane coupling agent prepolymer formulation table
The preparation of 3 EK- liquid silastics
According to the proportion of table 2, the liquid silastic of corrresponding quality is weighed in 250ml beaker, and EK prepolymer is added
10phr, stirred the mixture under the conditions of 100 DEG C uniformly, be cooled to room temperature, be subsequently added into curing agent (Methyl Hydrogen Polysiloxane Fluid) and
Catalyst (H2PtCl6·6H2O), progress deaeration processing in normal-temperature vacuum baking oven is put it into after mixing.To deaeration technique
After the completion, it is poured and is cast from Teflon mould, be put into convection oven, solidify 2h at 100 DEG C.After curing completely, will
It is taken out in sample from mould, it is stand-by to be cut into batten.
The formula table of 2 bisphenol A type epoxy resin modified liquid silicon rubber of table
Note: phr indicates the mass fraction contained in every 100 parts of silicon rubber
Two, the nature examination of the liquid silastic of epoxy resin modification of the present invention
(1) infrared spectroscopy (FTIR) test and analysis of prepolymer
The 570 type Fourier Transform Infrared Spectrometer of Nicolet produced using Nicolet company, the U.S., institute's sample are
Viscous liquid is directly applied to KBr on piece and carries out examination of infrared spectrum, and scanning range is 400~4000cm-1。
Fig. 1 is the internal standard infrared spectrum of prepolymer (EK) obtained under the conditions of differential responses, in spectrogram, 3509cm-1It is hydroxyl
The characteristic absorption peak of base, 1210-1050cm-1The absorption peak at place is the characteristic absorption peak of Si-O-Si, 913cm-1For epoxy group
Characteristic absorption peak.Spectrogram is with phenyl (the characteristic absorption peak 1607cm in epoxy molecule-1) it is used as reference group, by hydroxyl
Base as calibration group, reaction front and back hydroxyl absorbance and phenyl absorbance ratio can quantitative analysis hydroxy radical content variation,
It is listed in table 3, numerical value is smaller, and hydroxyl consumption is more, illustrates that the extent of reaction is more complete.
Table 3 differential responses condition prepolymer (EK) internal standard numerical tabular
As known from Table 3, obtained numerical value differs greatly under the conditions of differential responses, illustrates the degree of each prepolymerization reaction all
It is different.
(2) sem test and analysis
Batten after solidification first carries out brittle failure in liquid nitrogen, then its section is placed in vacuum after the metal spraying of surface, uses type
Number be JEOL JSM5900LV scanning electron microscope (Japan Electronics Corporation), observe the internal microstructure of sample, accelerate
Voltage is 5.0kV.
Fig. 2 is the SEM figure of the section of quenching of pure silicon glue and its compound system, and Fig. 2 is the SEM figure after matrix solidifies, You Tuke
Know, the section of quenching of pure sample is smooth；Fig. 2 (b)-(j) is that the SEM of modified silicon rubber system schemes, as seen from the figure, modified multiple
The rough surface out-of-flatness of zoarium system, there is typical " island " phase separation structure, and epoxy resin prepolymer is dispersed in continuously in " island " shape
Silicone rubber matrix phase in, and dispersed phase distribution is uneven, and size is inhomogenous.For under the same reaction time, prepolymerization reaction is urged
Agent dosage increases, and the dispersed phase of performed polymer in the base is smaller, illustrates that increasing catalyst amount facilitates mentioning for the extent of reaction
It is high；In situation identical for catalyst amount, the reaction time increases, and the dispersed phase of performed polymer in the base is smaller, and explanation is prolonged
The long reaction time facilitates the raising of the extent of reaction.
(3) thermogravimetric (TGA) test and analysis
Using the hot weightless instrument for the model Q 600 that TA company, the U.S. produces, weighs the cured sample of 5~10mg and be placed in heat
In the crucible of weightless instrument, temperature elevating range is 30~800 DEG C, and heating rate is 10 DEG C/min, and nitrogen atmosphere, specific gas flow rate is
60mL/min。
Fig. 3 is the silicon rubber compound system curve that thermal weight loss percentage and weight loss rate vary with temperature under nitrogen atmosphere
Figure.Table 4 lists the relevant thermal stability parameter of silicon rubber compound system, including temperature of initial decomposition (T5%), maximum heat point
The heat solved at the corresponding temperature (Tmax) of rate and 800 DEG C is residual heavy.
From the figure 3, it may be seen that pure silicone rubber has three rank degradation processes under heat treatment: 1) random scission causes its degree of polymerization to drop
Low, the rearrangement of silicon oxygen bond forms low molecule ring aggressiveness；2) the ring aggressiveness formed can acceleration molecular main chain degradation, and from figure
At smaller ring aggressiveness；3) at higher temperatures, side chain is broken, and forms the organic gas such as methane.The following institute of its mechanism of degradation
Show.And identical three ranks degradation process is also presented in modified silicon rubber compound system, illustrates that performed polymer, which is added, not to be changed again
The degradation period of condensation material, what the weightlessness of composite material mainly or by the structure destruction of silicon rubber strand itself was determined.
Degradation rate of the silicon rubber compound system after high temperature (700 DEG C) is gradually reduced, and heat drop solution curve is closer to pure silicone rubber warm
Degradation curve, show be added performed polymer do not have a significant effect its at high temperature at charcoal so that the degradation carbon residue of compound system
Retained.
4 silicon rubber compound system N of table2The thermal stability relevant parameter of atmosphere
As shown in Table 4, the introducing of performed polymer causes the temperature of initial decomposition (T5%) of compound system to decline, can from Fig. 3 (b)
To see, the degradation peak temperature of first stage shifts to an earlier date, and is learnt by Fig. 4, and it is complete to be primarily due to unreacted in epoxy resin
Hydroxyl group be mutually dehydrated and epoxy resin molecule chain break itself, cause composite material is weightless in this stage to increase rapidly
Add；Secondly, the second stage degradation peak temperature of compound system is also declined compared to pure sample, as shown in figure 4, silicon rubber is compound
The degradation of material second stage is mainly that its strand is broken by rearrangement reaction under dynamic conditions, formation Si-O-Si,
C-O (aryl ether) ,-CH2(cycloalkane) ,-CH3The small molecule that equal small molecule structures, hydroxyl group and the first degradation period are formed
Structure can then promote the degradation of silicon rubber compound system in this stage, form smaller ring aggressiveness, so that its weightlessness continues to increase
Add.From Fig. 3 (b), it can be seen that, silicon rubber compound system is almost consistent in the degradation peak temperature and pure sample of phase III, but its
Degradation rate is bigger than pure sample, and the degradation peak region of pure sample is bigger than compound system, the result is that this stage pure sample and silicon rubber
The weightlessness of compound system is almost the same.It is learnt from Fig. 4, emerging absorption peak 863cm-1For the characteristic absorption peak of Si-C, explanation
It is in the degradation in this stage and noted earlier consistent.Epoxy resin is introduced into so that rigid phenyl ring content increases in compound system,
The composite material that exists for of phenyl ring is degraded into charcoal at high temperature and provides " carbon source " very rich, so that the residuals generated
Surface compact, and the silica species generated with silicon oxygen chain degradation are combined together, and generate SiC class high temperature resistant substance, because
The carbon residue of this compound system is retained.
(4) infrared spectroscopy (FTIR) test and analysis of carbon residue
Fig. 5 is the infrared analysis spectrogram of (TGA, nitrogen) carbon residue after the test of 4-120 silastic material heat analysis.It can by figure
Know, 3415cm-1、1633cm-1、784cm-1The characteristic absorption peak at place belongs to the appearance of SiO2,1034cm-1It is Si-O-Si structure
Characteristic absorption peak, 1275cm-1Absorption peak is the characteristic absorption peak of C-O-C structure, 1367cm-1Then belong to the bending of-C-H
Vibration absorption peak, 2185cm-1Absorption peak is the characteristic absorption peak of remaining Si -- H bond.As a result the heat of silicon rubber composite material is proved
Mechanism of degradation is consistent with the above.
(5) Mechanics Performance Testing and analysis
Fig. 6 is influence of the different prepolymers to silicon rubber compound system tensile strength and elongation at break.It can be seen by Fig. 6
To: the tensile strength of modified silicon rubber composite material has different degrees of promotion compared to pure sample, in the same reaction time
Under condition control, increase catalyst amount, the tensile strength of composite material is bigger.Particularly, it is 4h when the prepolymerization reaction time, urges
When agent dosage is 120 μ l, prepared prepolymer composite material tensile strength reaches 0.83MPa, improves about 162% compared with pure sample.
From Fig. 6 also it can be seen that: be added performed polymer after, the elongation at break of silicon rubber compound system shows change similar with tensile strength
Law.It is 7h when the prepolymerization reaction time, when catalyst amount is 120 μ l, prepared prepolymer fracture of composite materials elongation
Reach 268%, improves about 2 times compared with pure sample.
(6) adhesive property
Fig. 7 is the result figure of different prepolymer modified silicon rubber compound system adhesive properties.As seen from the figure, unmodified silicon rubber
The adhesive strength of glue is lower, is 0.31MPa, is primarily due to the presence of not no polar group in the forging of silicon oxygen chain, with substrate it
Between adhesive force it is poor.And siloxanes segment is nonpolarity, and between each other without strand active force, intensity is lower.And it is modified
The adhesive strength of silicon rubber compound system all obtain the raisings of different amplitudes compared to pure sample.Especially 4-120 compound system
Shear strength is even more to have reached 0.81MPa, improves 160% compared with pure sample, failure mode is interfacial failure.Composite material is cut
Shearing stress is mainly determined by two aspect factors: 1) cohesion between composite material and aluminium sheet substrate；2) composite material itself is strong
Degree.If the cohesion between composite material and aluminium sheet substrate is greater than the intensity of composite material itself, material is drawn by the external world
Happens is that cohesional failure when power；If the cohesion between composite material and aluminium sheet substrate is less than the strong of composite material itself
Degree, then happens is that interfacial failure when material is by external tensile force.On the one hand epoxy resin modification silicon rubber passes through increase system
In polar group increase the adhesive force between composite material and aluminium sheet substrate, on the other hand increased by the introducing of rigid phenyl ring
The intensity of compound system, to improve the tensile-sbear strength of modified silicon rubber composite material.Epoxy resin is added in silicon rubber,
System polar group increases, and the friction clamping between aluminium sheet increases；Co-crosslinking between prepolymer and matrix forms densification
The epoxy molecule chain of rigidity is not only introduced into system by three-dimensional crosslinked network, but also is enhanced between prepolymer and matrix
Compatibility, make its dispersion in the base more evenly, dispersed phase size is smaller, and the intensity of composite material is significantly increased.Therefore,
The adhesive strength of modified silicon rubber compound system improves.
To sum up, the present invention is related to angle from molecular structure, the silicon rubber being prepared by the specific raw material of selection,
Realize be greatly improved in the case where extremely low additive amount silicon rubber intensity (tensile strength raising reaches 0.83MPa, compared with
Pure sample improves 162%；Adhesive property 0.81MPa, compared with pure sample raising, 160%) (elongation at break reaches with elongation at break
268%, about 2 times are improved compared with pure sample), i.e., the rigidity and toughness of composite material are improved simultaneously, avoid brittle fracture, greatly
Using field and prolonging its service life for composite material is widened.Its heat resistance remains at higher level simultaneously,
800 DEG C of heat are residual to weigh to 53.53%, and synthesis technology is simple, and handling ease, the time is short, and step is few, has a vast market
Application prospect.
Claims (9)
1. a kind of preparation method for the heat-resisting liquid silastic for improving intensity and interfacial adhesion, it is characterised in that: it includes
Following steps:
(1) existing for the catalyst B under the conditions of, after taking bisphenol A type epoxy resin to react at 100 DEG C with silane coupling agent to obtain the final product
Prepolymer；
(2) weigh prepolymer, liquid silastic stirs evenly, add curing agent and catalyst A and be uniformly mixed, deaeration, solidification
To obtain the final product.
2. according to the method described in claim 1, it is characterized by: in step (1), the bisphenol A type epoxy resin and silane
The molar ratio of coupling agent is 1~3:1, preferably 1:1；The mass ratio of the bisphenol A type epoxy resin and catalyst B is 434~
1305:1。
3. method according to claim 1 or 2, it is characterised in that: in step (1), the bisphenol A type epoxy resin is
E44,E51,E20；The silane coupling agent is SCA-L, A-172；The catalyst B is tetraisopropyl titanate, tin dilaurate two
Butyl tin, butyl titanate.
4. described in any item methods according to claim 1~3, it is characterised in that: in step (1), the time of the reaction is 4
~10h, preferably 4h.
5. method according to any one of claims 1 to 4, it is characterised in that: the liquid silastic, pre- in step (2)
Polymers, curing agent, catalyst A weight proportion are as follows: 90~110:7~15:3:0.2.
6. according to the method described in claim 5, it is characterized by: the liquid silastic, prepolymer, curing agent, catalyst A
Weight proportion are as follows: 100:10:3:0.2.
7. described in any item methods according to claim 1~6, it is characterised in that: in step (2), the liquid silastic is
Methyl vinyl silicone rubber, phenyl vinyl silicon rubber；The curing agent is Methyl Hydrogen Polysiloxane Fluid；The catalyst A is chlordene
Platinic acid, palladium catalyst.
8. described in any item methods according to claim 1~7, it is characterised in that: in step (2), the cured temperature is
95~110 DEG C, preferably 100 DEG C.
9. described in any item methods according to claim 1~8, it is characterised in that: in step (2), the cured time is 2
~3h, preferably 2h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009097013A (en) * | 2007-09-27 | 2009-05-07 | Hitachi Chem Co Ltd | Liquid resin composition for sealing, electronic component device and wafer level chip-size package |
| CN105255438A (en) * | 2015-11-17 | 2016-01-20 | 湖北回天新材料股份有限公司 | Bisphenol a epoxy resin modified room temperature vulcanized silicone rubber and preparation method thereof |
| CN106046386A (en) * | 2016-08-08 | 2016-10-26 | 四川大学 | Epoxy resin-organosilicon polymer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009097013A (en) * | 2007-09-27 | 2009-05-07 | Hitachi Chem Co Ltd | Liquid resin composition for sealing, electronic component device and wafer level chip-size package |
| CN105255438A (en) * | 2015-11-17 | 2016-01-20 | 湖北回天新材料股份有限公司 | Bisphenol a epoxy resin modified room temperature vulcanized silicone rubber and preparation method thereof |
| CN106046386A (en) * | 2016-08-08 | 2016-10-26 | 四川大学 | Epoxy resin-organosilicon polymer and preparation method and application thereof |
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