CN107118351B - Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application - Google Patents
Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application Download PDFInfo
- Publication number
- CN107118351B CN107118351B CN201710347999.0A CN201710347999A CN107118351B CN 107118351 B CN107118351 B CN 107118351B CN 201710347999 A CN201710347999 A CN 201710347999A CN 107118351 B CN107118351 B CN 107118351B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- silsesquioxane
- deck
- modification agent
- double
- 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.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 92
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 45
- 230000004048 modification Effects 0.000 title claims abstract description 36
- 238000012986 modification Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000006735 epoxidation reaction Methods 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims description 2
- 244000223014 Syzygium aromaticum Species 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000010792 warming Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- 150000002924 oxiranes Chemical class 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- -1 siloxanes Chemical class 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 2
- 239000005770 Eugenol Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930189110 naamine Natural products 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of double-deck silsesquioxane epoxy resin modification agent, and structural formula such as following formula (I) or (II) are shown, and in formula, n is selected from 1~20 integer, and R is selected fromOrThe invention also discloses the preparation method of the bilayer silsesquioxane epoxy resin modification agent and the applications in modified epoxy.
Description
Technical field
The present invention relates to epoxy resin application fields, and in particular to it is a kind of bilayer the agent of silsesquioxane epoxy resin modification and
Preparation method and application.
Background technique
Epoxy resin has excellent mechanical performance, electric property and adhesive property and is widely used in structure composite material
The fields such as material, electronic semi-conductor's encapsulation, adhesive.But epoxy resin, since internal stress is big, ontology is more crisp, wet-hot aging performance
Poor, fracture toughness and impact strength shortcoming largely limit its application.Therefore to the toughening modifying of epoxy resin and
Moisture-proof heat modification has very important significance to epoxy resin using tool.
For the toughening problem of epoxy resin, many correlation techniques are developed.Research shows that using long-chain thermoplasticity
Resin, nanoparticle and organo-silicon compound etc. carry out toughening modifying, and effect is obvious.Such as 104725782 A of Publication No. CN
Chinese patent discloses a kind of preparation method of nano-rubber epoxy resin toughener.This method passes through nano-rubber particle and its
His auxiliary agent has obtained a kind of modest viscosity after the techniques such as pre-dispersed, finely divided, infiltration cladding and ultrasonication, has been easily dispersed
Plasticized modifier.The Chinese patent of 105906814 A of Patent No. CN uses a kind of polyethers of epoxy terminated group as ring
The toughener of oxygen resin.But since the presence of long-chain polyether, the glass transition temperature of epoxy resin drastically reduce, being applied to can
Certain influence can be generated.
Organosilicon has many advantages, such as that good thermal stability, weatherability, high and low temperature resistance are good, molecular flexibility is good, in ring
Introducing organosilicon energy is epoxy resin toughened well in oxygen resin and makes moderate progress to its comprehensive performance.Such as Publication No. CN
The Chinese patent of 1560106 A discloses a kind of preparation method of modifying epoxy resin by organosilicon, effectively increases epoxy resin
Toughness and water resistance.But carry out preparing toughener since this method directlys adopt chlorosilane, possible residual organochlorine may
It can have a certain impact to the electric property of epoxy packages glue.And the glass transition temperature of usually organosilicon is very low, introduces organosilicon
The glass transition temperature of epoxy resin may be largely effected on, so that the application range to epoxy resin has an impact.
Silsesquioxane is the organosilicon/inorganic nano-hybrid material on a kind of real molecular level, and molecular structure is by Si-
The side chain composition that the main chain and organic group that O-Si is formed are formed.Currently, someone's report is using silsesquioxane to asphalt mixtures modified by epoxy resin
Rouge is modified, especially more with the research of cage-type silsesquioxane (POSS).
As 102492116 A of Publication No. CN Chinese patent literature in disclose a kind of epoxy resin and polyhedron cage
Type silsesquioxane nano hybridization material, the hybrid material are by γ-(2,3- the third oxygen of epoxy) propyl trimethoxy eight cage modle times
Half siloxanes is added in epoxy resin as nanoparticle, under curing agent effect, octa-epoxy POSS and epoxy resin hair
Raw cross-linking reaction forms network cross-linked structure so that octa-epoxy POSS monomer is introduced into epoxy resin structural.Preparation
Obtained hybrid material shows extremely low dielectric constant and dielectric loss value.But due to the rigid structure of octa-epoxy POSS,
While heat resistance, the mechanical performance for improving hybrid material, the toughness of hybrid material is often reduced.
Summary of the invention
The invention discloses a kind of double-deck silsesquioxane epoxy resin modification agent, are applied in epoxy resin,
While not influencing the glass transition temperature of epoxy resin, its toughness and wet-hot aging performance can be improved.
Specific technical solution is as follows:
A kind of bilayer silsesquioxane epoxy resin modification agent, structural formula such as following formula (I) or (II) are shown:
In above formula, n is selected from 1~20 integer, and R is selected from
Compared to other types of silsesquioxane, bilayer silsesquioxane epoxy resin modification agent prepared by the present invention
Epoxide number is 0.2~0.3mol/100g, has multiple epoxy groups in molecular structure, effectively can disperse and be reacted to
In epoxy-resin systems；On the other hand, the double-deck silsesquioxane structure in structure is in flexible characteristic, can effectively improve modification
The toughness of epoxy resin.
The invention discloses the preparation methods of the above-mentioned double-deck silsesquioxane epoxy resin modification agent.
Shown in the structural formula such as formula (I) of the double-deck silsesquioxane epoxy resin modification agent, preparation method includes such as
Lower step:
Using the hydrogeneous double-deck silsesquioxane and allyl bisphenol A epoxide resin as raw material, silicon is carried out under the action of catalyst
Addition reaction of hydrogen, then post-treated obtain；
Shown in the structural formula such as formula (II) of the double-deck silsesquioxane epoxy resin modification agent, preparation method includes such as
Lower step:
Using the hydrogeneous double-deck silsesquioxane and allyl bisphenol A epoxide resin as raw material, silicon is carried out under the action of catalyst
Addition reaction of hydrogen is added into the product after hydrosilylation and closes object progress end capping reaction containing double bond epoxidation, then after
Reason obtains.
Preferably, the mass ratio of the hydrogeneous double-deck silsesquioxane and allyl bisphenol A epoxide resin be 1:0.5~
2；
The catalyst is selected from catalyst made from platonic, such as chloroplatinic acid, Karst catalyst, platinum dioxide；
The temperature of the hydrosilylation be 70~90 DEG C, the time be 12~for 24 hours.
Preferably, described closes object selected from allyl glycidyl ether, cloves phenolic group glycidol containing double bond epoxidation
Ether etc..
Preferably, the post-processing includes vacuum distillation.
Preferably, the hydrogeneous double-deck silsesquioxane the preparation method is as follows:
A, phenyltrimethoxysila,e, sodium hydroxide, water are mixed, after back flow reaction, obtains intermediate production through filtration drying
Object；
The molar ratio of the phenyltrimethoxysila,e, sodium hydroxide and water is 4:2:5；
B, the obtained intermediate product of step A and triethylamine are dissolved in tetrahydrofuran solvent, are cooled to 0 DEG C hereinafter, logical
Simultaneously dimethyl dichlorosilane (DMCS) is added in nitrogen, after ice-water bath reaction, then post-treated obtains the hydrogeneous double-deck silsesquioxane；
The molar ratio of the intermediate product, triethylamine and dimethyl dichlorosilane (DMCS) is 1:1:2.
Preferably, the preparation process of the allyl bisphenol A epoxide resin is as follows:
Will a certain proportion of epoxychloropropane, allyl bisphenol-A and benzyltriethylammoinium chloride mix after be warming up to 60~
80℃.Sodium hydrate aqueous solution is slowly added under drying nitrogen protection, 1~5h is then reacted, after being warming up to 100~120 DEG C
Moisture in system is removed, is then cooled to 50~70 DEG C, 10~15h of sustained response.By the distillation washing of obtained product
It washs to neutrality, and distills out excessive epoxychloropropane to get the allyl bisphenol A epoxide resin is arrived.
The molar ratio of the epoxychloropropane, allyl bisphenol-A and benzyltriethylammoinium chloride is 1:0.05~0.1:
0.02~0.03.
The invention discloses the applications of the double-deck silsesquioxane epoxy resin modification agent, and steps are as follows:
Epoxy resin, curing agent and the double-deck silsesquioxane epoxy resin modification agent are dispersed in organic solvent
In, after heating removes organic solvent, then carry out curing process.
Preferably, the double-deck silsesquioxane epoxy resin modification agent, n value is selected from 1 or 2.It is found through experiment that
When n value is selected from above range, which can be effectively dispersed in epoxy resin, and to the water resistance of epoxy resin
Energy, mechanical property and toughness etc. all have clear improvement.
Preferably, the epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type ring
At least one of oxygen resin；
The curing agent is selected from 4,4 '-diaminodiphenyl-methane and/or 3,3 '-diaminodiphenyl-methane.
Compared with prior art, the present invention has the advantage that
The present invention has synthesized a kind of novel double-deck silsesquioxane epoxy resin modification agent, has in molecular structure more
A epoxy group can effectively disperse and be reacted in epoxy-resin systems；On the other hand, the double-deck silsesquioxane in structure
Alkyl structure is in flexible characteristic, can effectively improve the toughness of modified epoxy；Therefore it can be used as modifying agent applied to epoxy
The modification field of resin, compared to other types of silsesquioxane, it has the characteristics that good dispersion, molecular flexibility are good,
While not influencing the glass transition temperature of epoxy resin, its toughness and wet-hot aging performance can be improved.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance silicon spectrum of the double-deck silsesquioxane epoxy resin modification agent prepared by embodiment 1；
Fig. 2 is the nuclear magnetic resonance spectroscopy of the double-deck silsesquioxane epoxy resin modification agent prepared by embodiment 1；
Fig. 3 is the nuclear magnetic resonance silicon spectrum of the double-deck silsesquioxane epoxy resin modification agent prepared by embodiment 3；
Fig. 4 is the nuclear magnetic resonance spectroscopy of the double-deck silsesquioxane epoxy resin modification agent prepared by embodiment 3.
Specific embodiment
Below with reference to specific implementation case, the present invention is described further, but protection scope of the present invention and not only limits
In this:
In following embodiment, hydrogeneous bilayer silsesquioxane and allyl bisphenol A epoxide resin use identical preparation work
Skill, specific as follows:
The preparation process of hydrogeneous bilayer silsesquioxane is by phenyltrimethoxysila,e, sodium hydroxide, water according to certain
Ratio mixing, filters after reacting 4h as solvent refluxing using isopropanol and is dried to obtain DDSQ-Na；Wherein phenyl trimethoxy silicon
Alkane, sodium hydroxide, water molar ratio are 4:2:5.By DDSQ-Na and triethylamine, in the case where tetrahydrofuran is solvent, ice-water bath is cooled to 0
DEG C hereinafter, logical nitrogen and being slowly added to dimethyl dichlorosilane (DMCS), ice-water bath reacts 1h, can be prepared by hydrogeneous double-deck times after post treatment
Half siloxanes；Wherein DDSQ-Na, triethylamine and dimethyl dichlorosilane (DMCS) molar ratio are 1:1:2；Aftertreatment technology is successively to carry out water
Wash, salt pickling, saturated sodium bicarbonate are washed, and are washed three times, washed three times and be dried in vacuo with 100ml methanol again after distillation and produced
Object.
Allyl bisphenol A epoxide resin preparation process is epoxychloropropane, the allyl for being 1:0.05:0.02 by molar ratio
70 DEG C are warming up to after bisphenol-A and benzyltriethylammoinium chloride mixing.20% sodium hydrate aqueous solution is delayed under drying nitrogen protection
It is slow to be added, 2h is then reacted, 110 DEG C is warming up to and is removed the moisture in system using water segregator, be then cooled to 60 DEG C, continue
React 10h or more.Obtained product is washed with distilled water to neutrality, and distills out excessive epoxychloropropane to get alkene is arrived
Propyl bisphenol A epoxide resin.
Embodiment 1
10g allyl bisphenol A epoxide resin and the Karst 0.14g catalyst (50ppm) are added in 100ml toluene,
It is warming up to 75 DEG C under nitrogen protection, will then be dissolved in the hydrogeneous double-deck silsesquioxane of the 14.4g in 100ml toluene and delay in 2h
It is slow to be added, the reaction was continued after being added dropwise to complete 12h.Vacuum distillation removing solvent can be obtained the double-deck silsesquioxane epoxy resin and change
Property agent, be denoted as EPDDSQ-1, n value is 1 (Formulas I type).
The silicon that the present embodiment prepares product is composed and hydrogen spectrum is as shown in Figure 1, 2 respectively, and determines it by titration epoxide number
Epoxide number in molecular structure is 2.01mmol/g.
By 50g E51 epoxy resin, 18.5g DDS epoxy curing agent and 3.45g EPDDSQ-1 dissolve at 50 DEG C
It is uniformly dispersed in acetone, solvent then is removed in vacuum at 90 DEG C, is poured and is cast from steel die, it is small in 140 DEG C of solidifications 2
When, solidify 2 hours at 160 DEG C, solidifies 2 hours at 180 DEG C.The sample bubble-free of demoulding, appearance transparent no significant defect.Sample
Performance be listed in the table below in 1.
Embodiment 2
10g allyl bisphenol A epoxide resin and the Karst 0.14g catalyst (50ppm) are added in 100ml toluene,
It is warming up to 75 DEG C under nitrogen protection, will then be dissolved in the hydrogeneous double-deck silsesquioxane of the 19.2g in 100ml toluene and delay in 2h
It is slow to be added, the reaction was continued after being added dropwise to complete 12h.Vacuum distillation, which removes solvent, can be obtained product EPDDSQ2, and n value is 2 (Formulas I
Type), epoxide number 1.68mmol/g.
By 50g E51 epoxy resin, 18.5g DDS epoxy curing agent and 3.45g EPDDSQ2 dissolve at 50 DEG C
It is uniformly dispersed in acetone, solvent then is removed in vacuum at 90 DEG C, is poured and is cast from steel die, it is small in 140 DEG C of solidifications 2
When, solidify 2 hours at 160 DEG C, solidifies 2 hours at 180 DEG C.The sample bubble-free of demoulding, appearance transparent no significant defect.Sample
Performance be listed in the table below in 1.
Embodiment 3
10g allyl bisphenol A epoxide resin and the Karst 0.14g catalyst (50ppm) are added in 100ml toluene,
It is warming up to 75 DEG C under nitrogen protection, will then be dissolved in the hydrogeneous double-deck silsesquioxane of the 57.6g in 100ml toluene and delay in 2h
It is slow to be added, the reaction was continued after being added dropwise to complete 12h.0.63g allyl glycidyl ether is then added and reacts 6h.Vacuum distillation removes
Unreacted allyl glycidyl ether and solvent is gone to can be obtained product EPDDSQ3, n value is 1 (Formula II type, R group is in formula), epoxide number 1.35mmol/g.
The silicon that the present embodiment prepares product is composed and hydrogen spectrum is as shown in Figures 3 and 4 respectively.
By 50g E51 epoxy resin, 18.5g DDS epoxy curing agent and 3.45g EPDDSQ3 dissolve at 50 DEG C
It is uniformly dispersed in acetone, solvent then is removed in vacuum at 90 DEG C, is poured and is cast from steel die, it is small in 140 DEG C of solidifications 2
When, solidify 2 hours at 160 DEG C, solidifies 2 hours at 180 DEG C.The sample bubble-free of demoulding, appearance transparent no significant defect.Sample
Performance be listed in the table below in 1.
Embodiment 4
10g allyl bisphenol A epoxide resin and the Karst 0.14g catalyst (50ppm) are added in 100ml toluene,
It is warming up to 75 DEG C under nitrogen protection, then slowly adds the hydrogeneous double-deck silsesquioxane of the 57.6g being dissolved in toluene in 2h
Enter, the reaction was continued 12h after being added dropwise to complete.1.2g eugenol glycidol ether is then added and reacts 6h.Vacuum distillation removes not
The eugenol glycidol ether and solvent of reaction can be obtained product EPDDSQ4, and n value is 1 (Formula II type, R group is in formula), epoxide number 1.26mmol/g.
By 50g E51 epoxy resin, 18.5g DDS epoxy curing agent and 3.45g EPDDSQ4 dissolve at 50 DEG C
It is uniformly dispersed in acetone, solvent then is removed in vacuum at 90 DEG C, is poured and is cast from steel die, it is small in 140 DEG C of solidifications 2
When, solidify 2 hours at 160 DEG C, solidifies 2 hours at 180 DEG C.The sample bubble-free of demoulding, appearance transparent no significant defect.Sample
Performance be listed in the table below in 1.
Comparative example
By 50g E51 epoxy resin, 18.5g DDS epoxy curing agent, which is dissolved in acetone at 50 DEG C, to be dispersed
It is even, solvent then is removed in vacuum at 90 DEG C, is poured and is cast from steel die, solidifies 2 hours at 140 DEG C, solidifies at 160 DEG C
2 hours, solidify 2 hours at 180 DEG C.The sample bubble-free of demoulding, appearance transparent no significant defect.The performance of sample is listed in the table below
In 1.
Table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Tensile strength (MPa) | 89.6 | 93.5 | 88.3 | 89.9 | 58.3 |
| Impact strength (kJ/m2) | 25.6 | 29.6 | 26.3 | 26.5 | 13.9 |
| Glass transition temperature (DEG C) | 162 | 163 | 163 | 167 | 169 |
| Fracture toughness (Mpam1/2) | 1.14 | 1.22 | 1.09 | 1.08 | 0.65 |
| Water absorption rate (23 DEG C, %) | 1.1 | 0.8 | 0.9 | 0.8 | 2.6 |
| Water absorption rate (100 DEG C, %) | 1.5 | 1.2 | 1.3 | 1.2 | 3.5 |
As it can be seen from table 1 after the double-deck silsesquioxane epoxy resin modification agent is added, with unmodified epoxy resin phase
Than tensile strength, impact strength and the fracture toughness of epoxy resin are all significantly increased, and water absorption rate is substantially reduced.Vitrifying turns
Temperature is not decreased obviously, and has significantly been modified the comprehensive performance of epoxy resin.
Claims (9)
1. a kind of bilayer silsesquioxane epoxy resin modification agent, which is characterized in that structural formula such as following formula (I) or (II) are shown:
In above formula, n is selected from 1~20 integer, and R is selected from
2. a kind of preparation method of the double-deck silsesquioxane epoxy resin modification agent according to claim 1, feature exist
In shown in the structural formula such as formula (I) of the bilayer silsesquioxane epoxy resin modification agent, preparation method includes the following steps:
Using the hydrogeneous double-deck silsesquioxane and allyl bisphenol A epoxide resin as raw material, silicon hydrogen is carried out under the action of catalyst and is added
At reaction, then post-treated obtain；
Shown in the structural formula such as formula (II) of the bilayer silsesquioxane epoxy resin modification agent, preparation method includes following step
It is rapid:
Using the hydrogeneous double-deck silsesquioxane and allyl bisphenol A epoxide resin as raw material, silicon hydrogen is carried out under the action of catalyst and is added
At reaction, it is added into the product after hydrosilylation and contains double bond epoxidation conjunction object progress end capping reaction, then post-treated
It arrives.
3. the preparation method of bilayer silsesquioxane epoxy resin modification agent according to claim 2, which is characterized in that institute
The molar ratio for stating the hydrogeneous double-deck silsesquioxane and allyl bisphenol A epoxide resin is 1:0.5~2；
The catalyst is selected from catalyst made from platonic；
The temperature of the hydrosilylation be 70~90 DEG C, the time be 12~for 24 hours.
4. the preparation method of bilayer silsesquioxane epoxy resin modification agent according to claim 2, which is characterized in that institute
That states closes object selected from allyl glycidyl ether or cloves phenolic group glycidol ether containing double bond epoxidation.
5. the preparation method of bilayer silsesquioxane epoxy resin modification agent according to claim 2, which is characterized in that institute
The post-processing stated includes vacuum distillation.
6. the preparation method of bilayer silsesquioxane epoxy resin modification agent according to claim 2, which is characterized in that institute
State the hydrogeneous double-deck silsesquioxane the preparation method is as follows:
A, phenyltrimethoxysila,e, sodium hydroxide and water are mixed, after back flow reaction, obtains intermediate product through filtration drying；
The molar ratio of the phenyltrimethoxysila,e, sodium hydroxide and water is 4:2:5；
B, the obtained intermediate product of step A and triethylamine are dissolved in tetrahydrofuran solvent, are cooled to 0 DEG C hereinafter, logical nitrogen
And dimethyl dichlorosilane (DMCS) is added, after ice-water bath reaction, then post-treated obtain the hydrogeneous double-deck silsesquioxane；
The molar ratio of the intermediate product, triethylamine and dimethyl dichlorosilane (DMCS) is 1:1:2.
7. a kind of application of the double-deck silsesquioxane epoxy resin modification agent according to claim 1, which is characterized in that step
It is rapid as follows:
In organic solvent by epoxy resin, curing agent and the double-deck silsesquioxane epoxy resin modification agent dispersion, add
After heat removes organic solvent, then carry out curing process.
8. the application of bilayer silsesquioxane epoxy resin modification agent according to claim 7, which is characterized in that described
The double-deck silsesquioxane epoxy resin modification agent, n value are selected from 1 or 2.
9. the application of bilayer silsesquioxane epoxy resin modification agent according to claim 7, which is characterized in that described
Epoxy resin is selected from least one of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin；
The curing agent is selected from 4,4 '-diaminodiphenyl-methane and/or 3,3 '-diaminodiphenyl-methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347999.0A CN107118351B (en) | 2017-05-17 | 2017-05-17 | Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347999.0A CN107118351B (en) | 2017-05-17 | 2017-05-17 | Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107118351A CN107118351A (en) | 2017-09-01 |
| CN107118351B true CN107118351B (en) | 2019-07-30 |
Family
ID=59727130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710347999.0A Active CN107118351B (en) | 2017-05-17 | 2017-05-17 | Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107118351B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054016A (en) * | 2018-07-24 | 2018-12-21 | 西北工业大学 | One kind containing bicyclic oxygroup silsesquioxane cyanate hybrid resin and preparation method |
| CN109749087B (en) * | 2018-12-25 | 2021-03-19 | 陕西科技大学 | Semi-closed cage-shaped trifunctional epoxy ether POSS and preparation method thereof |
| CN110066493A (en) * | 2019-04-15 | 2019-07-30 | 浙江华正新材料股份有限公司 | A kind of halogen-free resin composition, prepreg and the laminate of low dielectric low dielectric loss |
| CN110724268B (en) * | 2019-11-07 | 2021-10-29 | 中国航空制造技术研究院 | Preparation method and application of bisphenol A type epoxy resin containing dimethyl siloxane suspension chain |
| CN110982078B (en) * | 2019-11-25 | 2022-05-20 | 江南大学 | Polysiloxane-containing multi-block polymer, composition prepared from same and preparation method of polysiloxane-containing multi-block polymer |
| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102449034A (en) * | 2009-06-02 | 2012-05-09 | Jnc株式会社 | Organic silicon compound, thermosetting composition containing said organic silicon compound, and sealing material for optical semiconductor |
-
2017
- 2017-05-17 CN CN201710347999.0A patent/CN107118351B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102449034A (en) * | 2009-06-02 | 2012-05-09 | Jnc株式会社 | Organic silicon compound, thermosetting composition containing said organic silicon compound, and sealing material for optical semiconductor |
Non-Patent Citations (1)
| Title |
|---|
| "笼型倍半硅氧烷增韧环氧树脂的机理研究;张增平，等;《绝缘材料》;20121231;第45卷(第3期);第41-42,46页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107118351A (en) | 2017-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107118351B (en) | Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application | |
| CN107353871B (en) | High-temperature-resistant bonding sealing silicone resin and preparation method thereof | |
| CN101724226B (en) | Modified hot setting resin and preparation method thereof | |
| CN104761872B (en) | A kind of modifying epoxy resin by organosilicon encapsulating material and preparation method thereof | |
| CN101260190B (en) | Multiple functionality degree polysiloxane coupling agent and preparation method thereof | |
| CN103665863B (en) | Containing the compositions of thermosetting resin of double-tower type epoxy silsesquioxane | |
| CN101717512B (en) | Method for preparing methyl phenyl vinyl silicone resin | |
| CN106866722B (en) | Benzocyclobutene-containing functionalized organosilicon compound and preparation method thereof | |
| CN108659471A (en) | A kind of light-cured resin and preparation method thereof that polyfunctionality POSS is modified | |
| CN107868647A (en) | A kind of silane modified polyether base rubber and its sulfydryl alkene addition preparation method | |
| CN101638517B (en) | Organosilicon resin composition | |
| CN111253575A (en) | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin | |
| CN110054779B (en) | Polysiloxane containing anhydride and preparation method and application thereof | |
| CN101974226A (en) | Flame-retardant bismaleimide resin and preparation method thereof | |
| CN111116869A (en) | Liquid epoxy group functionalized POSS modified epoxy resin and preparation method thereof | |
| CN110591288A (en) | Hyperbranched silicon-phosphorus synergistic flame retardant modified epoxy resin and preparation method thereof | |
| CN105254661A (en) | Cage-shaped oligomerization polyhedral silsesquioxane with eight phenolic hydroxyl groups and preparation method thereof | |
| CN102775614A (en) | Double-decker-shaped silsesquioxane-containing benzoxazine resin | |
| CN102504200A (en) | High-performance high-heat-resistance modified epoxy resin and preparation method and use thereof | |
| CN107814935B (en) | POSS-based organic-inorganic hybrid eight-arm epoxy resin and preparation method thereof | |
| CN103130982A (en) | Composite method and solidifying method of fluorine-containing high temperature resisting organosilicon epoxy resin | |
| CN106167621A (en) | Flame-retardant room temperature vulcanized liquid silicone rubber | |
| CN108659226B (en) | Preparation method and application of n-butyl terminated poly-bis-phenyl methyl silazane | |
| CN104086587A (en) | Preparation method for cage-type dec(glycidyl silsesquioxane) | |
| CN113004524B (en) | Epoxy-organic silicon resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |