CN111205599B - High-strength high-light-transmittance epoxy resin composition and preparation method thereof - Google Patents
High-strength high-light-transmittance epoxy resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN111205599B CN111205599B CN202010180360.XA CN202010180360A CN111205599B CN 111205599 B CN111205599 B CN 111205599B CN 202010180360 A CN202010180360 A CN 202010180360A CN 111205599 B CN111205599 B CN 111205599B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- composition according
- formula
- silane coupling
- 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 110
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 110
- 238000002834 transmittance Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title claims description 38
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 41
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003607 modifier Substances 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- -1 handicrafts Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GMEMZXVKMVBEGX-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;trimethoxy(propyl)silane Chemical compound C1OC1COCC1CO1.CCC[Si](OC)(OC)OC GMEMZXVKMVBEGX-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- XEZQDUHEOQUYAL-UHFFFAOYSA-N C(C1CO1)CCCO[Si](OC)(OC)CCC Chemical compound C(C1CO1)CCCO[Si](OC)(OC)CCC XEZQDUHEOQUYAL-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparation method of high-strength and high-transparency epoxy resin, wherein a novel nitrogen-containing heterocyclic silane coupling agent is adopted as a filler modifier, and the nitrogen-containing heterocyclic silane has the advantages of high reaction activity and good compatibility with epoxy resin, can remarkably improve the mechanical strength of the epoxy resin by the filler, can improve the light transmittance of the epoxy resin, and can be applied to the field with higher requirements on the mechanical strength and the light transmittance of the epoxy resin.
Description
Technical Field
The invention relates to a preparation method of epoxy resin, in particular to a high-strength high-light-transmission epoxy resin composition and a preparation method thereof.
Technical Field
Epoxy resins have good adhesion and mechanical strength, and thus are widely used in the fields of automobiles, electronics, electrical appliances, and the like. In order to further improve the application properties such as mechanical strength of the epoxy resin, a large number of documents report methods of adding additives such as inorganic fillers, but the compatibility of the inorganic fillers and the epoxy resin is poor, and performance defects are easily caused, and the compatibility of the inorganic fillers and the epoxy resin is often required to be improved by a silane coupling agent.
The silane coupling agents reported in the literature include: aminopropyltriethoxysilane, glycidylethylpropyltrimethoxysilane, and the like. General-purpose silane coupling agents have been widely used in the field of epoxy resins, and various methods have been reported in the literature for enhancing the properties of epoxy resins.
Patent CN 109467679 discloses a method for preparing epoxy resin, which uses benzoxazine resin and phenolic resin as epoxy resin curing agent after mixing, and the product has higher glass transition temperature and bending strength, but the cured epoxy resin is opaque solid. Patent CN 106674901 provides a method for preparing high-strength epoxy resin, which uses toughening of nitrile rubber and reinforcement of carbon fiber to achieve the purpose of preparing high-strength epoxy resin, but needs to use more silane coupling agent. Patent CN 107652607 provides a method for preparing nano-metal or metal oxide particles by using a chemical coprecipitation method, so as to improve the strength of epoxy resin, but the process is complex and difficult to implement.
In addition, the literature reports various methods for improving the strength of epoxy resin, such as organosilicon modified epoxy resin, glass fiber reinforced epoxy resin, etc., but some application fields, such as high-end glass fiber reinforced plastic field, require epoxy resin to have better light transmittance in addition to the requirement on the strength of epoxy resin, and the above patents do not mention the problem of epoxy resin transparency. Therefore, in order to expand the application fields, it is necessary to prepare an epoxy resin having both high strength and good light transmittance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the epoxy resin composition with high strength and high light transmission, the preparation method of the epoxy resin composition is simple, the compatibility of the epoxy resin and the filler is improved by using a novel silane coupling agent, and the mechanical strength and the light transmission of a cured product of the epoxy resin composition are improved.
The invention realizes the aim through the following technical scheme:
a high-strength and high-light-transmittance epoxy resin composition comprises a component A and a component B, wherein the component A contains epoxy resin, inorganic filler and a silane coupling agent shown in a formula (I), and the component B contains a curing agent; preferably, the epoxy resin composition comprises the following components in parts by weight:
the component A comprises:
5-80 parts of epoxy resin
30-80 parts of inorganic filler
0.5-2 parts of silane coupling agent
And B component:
1-20 parts of a curing agent.
In the epoxy resin composition, the structural formula of the silane coupling agent is shown as the formula (I):
wherein R is1、R2Identical or different, respectively represent saturated or unsaturated hydrocarbon radicals of C1-C6; preferably, R1、R2Respectively represent methyl, ethyl and propyl; more preferably, R1、R2Represents a methyl group.
In the epoxy resin composition of the present invention, the method for preparing the silane coupling agent of formula (I) comprises:
adding ethylenediamine into the trapping agent, heating to reflux, slowly dropwise adding silane shown as a structural formula (II) into a reaction system, continuously reacting for a period of time after dropwise adding, removing ammonium salt through filtering after the reaction is finished, and distilling to obtain a target product, namely a silane coupling agent (I);
in the formula (II), R1、R2The silane of formula (II) is most preferably chloromethyldimethylchlorosilane, as previously described for formula (I).
In the preparation method of the silane coupling agent, the molar ratio of the ethylenediamine to the silane with the structural formula (II) is preferably 0.5-5, more preferably 0.8-2, and the time for continuing the reaction after the completion of the dropwise addition of the silane with the structural formula (II) is preferably 2-12 hours, preferably 3-6 hours.
In the preparation method of the silane coupling agent, the trapping agent is triethylamine and/or pyridine, preferably triethylamine; preferably, the scavenger is used in an amount of 2 to 10 times, preferably 3 to 5 times, the molar amount of the silane of formula (II).
In the prior art, silane coupling agents commonly used in epoxy resin systems are aminopropyltriethoxysilane, glycidyl ether propyl trimethoxysilane and the like, and the principle of increasing the compatibility between epoxy resin and a filler is as follows: on one hand, trimethoxy or triethoxy of the silane coupling agent reacts with hydroxyl on the surface of the filler to form a new chemical bond; on the other hand, the amino or epoxy group of the silane coupling agent reacts with the epoxy resin to enhance the interaction between the epoxy resin and the filler, thereby improving the modification effect of the filler on the epoxy resin. However, the conventional silane coupling agent needs further hydrolysis by water to achieve the best coupling effect, and the presence of water causes the dosage of the silane coupling agent to be higher and the effect to be deviated.
The action principle of the aminopropyltriethoxysilane modified epoxy resin and the filler shows that the novel silane coupling agent adopted by the invention has a silicon nitrogen bond with higher activity, can quickly and effectively modify the surface of the filler, and can quickly perform coupling modification even on the surface of the dry filler; the novel silane coupling agent generates ethylenediamine propyl after modifying the surface of the filler, and has more active groups to interact with epoxy resin. The treatment effect between the filler and the epoxy resin is improved by improving the reactivity of the silane coupling agent, the transparency of the cured epoxy resin can be obviously modified, and the using amount of the silane coupling agent is reduced.
In the epoxy resin composition of the present invention, preferably, the amount of the silane coupling agent is 1 to 6% of the amount of the inorganic filler; more preferably, the amount of the silane coupling agent is 2 to 5% of the amount of the inorganic filler.
In the epoxy resin composition of the present invention, the epoxy resin is not particularly limited, and may be, for example, one or more selected from bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, o-cresol novolac epoxy resin, naphthalene type epoxy resin, and the like; preferably, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and o-cresol formaldehyde epoxy resin.
In the epoxy resin composition of the present invention, the inorganic filler is preferably selected from fumed silica.
In the epoxy resin composition of the present invention, preferably, the curing agent is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, hexamethylenediamine, isophoronediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and diaminodiphenylsulfone; more preferably, the curing agent is selected from one or more of diethylenetriamine, triethylenetetramine, isophoronediamine and diaminodiphenylsulfone.
The preparation process of the epoxy resin composition is simple, for example: mixing inorganic filler with silane coupling agent, and treating at 60-150 deg.C (such as 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C); the treatment time is 0.5-6h (for example, 1h, 2h, 3h, 4h, 5h, 6 h); then adding epoxy resin and mixing uniformly to obtain the component A.
When in use, the component A and the component B are uniformly mixed at a certain temperature, preferably room temperature, and then cured under certain curing conditions to obtain a cured product, wherein the curing conditions can be determined by a person skilled in the art according to actual needs, such as 20-150 ℃/1-10 h.
The epoxy resin composition can be applied to high-end glass fiber reinforced plastics, handicrafts, glass adhesives and the like.
The invention has the beneficial effects that:
1. a novel silane coupling agent is adopted, so that the treatment effect between the filler and the epoxy resin is improved, the transparency of a cured epoxy resin is obviously improved, and the using amount of the silane coupling agent is reduced;
2. the cured product of the epoxy resin composition after curing has good transparency and high strength, the bending strength is more than 100MPa, and the transmittance is more than 80%.
Drawings
FIG. 1 is the HNMR nuclear magnetic spectrum of the product of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In examples and comparative examples, methods for testing flexural strength of cured epoxy resin: the bending property of the plastic is determined according to GB/T9341-2008; glass transition temperature test method: testing by using a differential scanning calorimeter; the transmittance test method comprises the following steps: and testing by using a haze meter.
In the examples, the E44, E51 epoxy resins were from south channel star composites, inc;
k150 and K200 fumed silica are from Cabot corporation;
ethylenediamine, triethylamine, diethylenetriamine, isophoronediamine and aminopropyltrimethoxysilane are from the company Aladdin reagent, Inc.
Example 1
480g of ethylenediamine (8mol) and 1010g of triethylamine (10mol) are added into a reaction flask, and the temperature is raised to reflux; slowly dripping 572g of chloromethyl dimethylchlorosilane (4mol) into the reaction flask within 2h, and continuing the reaction for 4h after finishing dripping; after the completion of the reaction, the amine salt formed was removed by filtration, and then distilled under reduced pressure at 87 ℃ under 5kPa to obtain the silane coupling agent (I), and the nuclear magnetic analysis is shown in FIG. 1.
Example 2
The epoxy resin composition formula comprises:
10g of E51 epoxy resin, 2g of isophorone diamine curing agent, 30g of K150 fumed silica and 0.5g of silane coupling agent (I).
The preparation process of the condensate comprises the following steps:
adding fumed silica into a high-speed stirrer, heating to 80 ℃, removing water in vacuum, adding a silane coupling agent, mixing for 30min to obtain modified fumed silica, adding epoxy resin, and continuously mixing for 30min to obtain a component A; and mixing the component A with a curing agent (component B), and curing at the speed of 80 ℃/2h +100 ℃/1h +120 ℃/2h to obtain a product.
Example 3
The epoxy resin composition formula comprises:
50g of E44 epoxy resin, 4g of diethylenetriamine curing agent, 80g of K200 fumed silica and 1g of silane coupling agent (I).
The preparation process of the condensate comprises the following steps:
adding fumed silica into a high-speed stirrer, heating to 80 ℃, removing water in vacuum, adding a silane coupling agent, mixing for 60min to obtain modified fumed silica, adding epoxy resin, and continuously mixing for 30min to obtain a component A; and mixing the component A with a curing agent (component B), and curing at 80 ℃/2h +100 ℃/1h to obtain a product.
Example 4
The epoxy resin composition formula comprises:
80g of E51 epoxy resin, 7g of diethylenetriamine curing agent, 70g of K200 fumed silica and 2g of silane coupling agent (I).
The preparation process of the condensate comprises the following steps:
adding fumed silica into a high-speed stirrer, heating to 80 ℃, removing water in vacuum, adding a silane coupling agent, mixing for 30min to obtain modified fumed silica, adding epoxy resin, and continuously mixing for 30min to obtain a component A; and mixing the component A with a curing agent (component B), and curing at 80 ℃/2h +100 ℃/1h to obtain a product.
Comparative example 1
The epoxy resin composition formula comprises:
50g of E51 epoxy resin, 5g of diethylenetriamine curing agent, 80g of K150 fumed silica and 5g of aminopropyltrimethoxysilane.
The preparation process of the condensate comprises the following steps:
adding fumed silica into a high-speed stirrer, heating to 80 ℃, removing water in vacuum, adding a silane coupling agent, mixing for 30min to obtain modified fumed silica, adding epoxy resin, and continuously mixing for 30min to obtain a component A; and mixing the component A with a curing agent (component B), and curing at 80 ℃/2h +100 ℃/1h to obtain a product.
The results of the performance test of the epoxy resin cured products of examples and comparative examples are shown in Table 1.
TABLE 1 epoxy resin cured product Performance test results
| Examples | Glass transition temperature of | Bending strength MPa | Light transmittance% |
| Example 2 | 112 | 113 | 82 |
| Example 3 | 105 | 125 | 90 |
| Example 4 | 109 | 121 | 86 |
| Comparative example 1 | 103 | 79 | 20 |
As can be seen from Table 1, the novel silane coupling agent is used as a filler modifier instead of traditional aminopropyltrimethoxysilane, so that the improvement effect of the filler on epoxy resin can be obviously improved, the dosage of the coupling agent is reduced, the bending strength of the cured epoxy resin can be improved by more than 20-30%, and the light transmittance is obviously improved.
Claims (17)
1. A high-strength and high-light-transmittance epoxy resin composition is characterized by comprising an epoxy resin, an inorganic filler, a silane coupling agent shown in a formula (I) and an optional curing agent;
wherein R is1、R2The same or different, are respectively selected from saturated hydrocarbon groups of C1-C6.
2. The epoxy resin composition of claim 1, wherein R is1、R2Are respectively selected from methyl, ethyl and propyl.
3. The epoxy resin composition of claim 2, wherein R is1、R2Represents a methyl group.
4. The epoxy resin composition according to claim 1, wherein the epoxy resin composition comprises the following components in parts by weight:
the component A comprises:
5-80 parts of epoxy resin
30-80 parts of inorganic filler
0.5-2 parts of silane coupling agent
And B component:
1-20 parts of a curing agent.
5. The epoxy resin composition according to claim 4, wherein the silane coupling agent is used in an amount of 1 to 6 wt% based on the amount of the inorganic filler.
6. The epoxy resin composition according to any one of claims 1 to 5, wherein the silane coupling agent is prepared by a method comprising: adding ethylenediamine into a trapping agent, heating to reflux, slowly adding silane shown as a formula (II) into a reaction system, continuing to react for a period of time after the addition is finished, filtering after the reaction is finished, and distilling to obtain a target product, wherein the trapping agent is triethylamine and/or pyridine;
7. the epoxy resin composition according to claim 6, wherein the molar ratio of ethylenediamine to the silane represented by the formula (II) is 0.5 to 5; the time for continuing the reaction after the silane shown in the formula (II) is added is 2-12 h.
8. The epoxy resin composition according to claim 7, wherein the molar ratio of ethylenediamine to the silane represented by the formula (II) is 0.8 to 2; the time for continuing the reaction after the silane shown in the formula (II) is added is 3-6 h.
9. The epoxy resin composition according to claim 6, wherein the scavenger is triethylamine; the amount of the scavenger used is 2 to 10 times the molar amount of the silane represented by the formula (II).
10. The epoxy resin composition according to claim 9, wherein the amount of the scavenger is 3 to 5 times the molar amount of the silane represented by the formula (II).
11. The epoxy resin composition according to any one of claims 1 to 5, wherein the epoxy resin comprises one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, o-cresol novolac epoxy resin, naphthalene type epoxy resin.
12. The epoxy resin composition of claim 11, wherein the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, and o-cresol novolac epoxy resin.
13. The epoxy resin composition according to any one of claims 1 to 5, wherein the inorganic filler is selected from fumed silica.
14. The epoxy resin composition according to any one of claims 1 to 5, wherein the curing agent is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, hexamethylenediamine, isophoronediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and diaminodiphenylsulfone.
15. The epoxy resin composition of claim 14, wherein the curing agent is selected from one or more of diethylenetriamine, triethylenetetramine, isophoronediamine, and diaminodiphenylsulfone.
16. A process for preparing the epoxy resin composition of any one of claims 1-15 comprising: mixing an inorganic filler and a silane coupling agent, then performing high-temperature treatment, and then adding epoxy resin and uniformly mixing to obtain a component A; when in use, the component A and the curing agent are uniformly mixed and cured under certain curing conditions to obtain a cured product.
17. The method according to claim 16, wherein the treatment temperature is 60-150 ℃ and the treatment time is 0.5-6 h; the curing condition is 20-150 ℃/1-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010180360.XA CN111205599B (en) | 2020-03-16 | 2020-03-16 | High-strength high-light-transmittance epoxy resin composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010180360.XA CN111205599B (en) | 2020-03-16 | 2020-03-16 | High-strength high-light-transmittance epoxy resin composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111205599A CN111205599A (en) | 2020-05-29 |
| CN111205599B true CN111205599B (en) | 2022-04-22 |
Family
ID=70787134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010180360.XA Active CN111205599B (en) | 2020-03-16 | 2020-03-16 | High-strength high-light-transmittance epoxy resin composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111205599B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232440B (en) * | 2022-07-22 | 2023-06-09 | 中科威禾科技(肇庆)股份有限公司 | High-light-transmittance epoxy resin composite board and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1058711A (en) * | 1959-01-17 | 1967-02-15 | Bayer Ag | Sila-piperazines |
| WO2010134339A1 (en) * | 2009-05-20 | 2010-11-25 | 株式会社ブリヂストン | Process for production of silane coupling agent |
| CN103468095A (en) * | 2013-07-23 | 2013-12-25 | 江苏博特新材料有限公司 | Silane coupling agent-modified epoxy resin, and preparation method and application thereof |
-
2020
- 2020-03-16 CN CN202010180360.XA patent/CN111205599B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1058711A (en) * | 1959-01-17 | 1967-02-15 | Bayer Ag | Sila-piperazines |
| WO2010134339A1 (en) * | 2009-05-20 | 2010-11-25 | 株式会社ブリヂストン | Process for production of silane coupling agent |
| CN103468095A (en) * | 2013-07-23 | 2013-12-25 | 江苏博特新材料有限公司 | Silane coupling agent-modified epoxy resin, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111205599A (en) | 2020-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3258477A (en) | Acryloxyalkylsilanes and compositions thereof | |
| CN109851759B (en) | Organic silicon modified epoxy resin, preparation method thereof and organic silicon modified epoxy resin adhesive | |
| KR101582158B1 (en) | Inorganic fiber reinforced organic-inorganic hybrid cationic exchange membrane with high dimensional stability and high thermal resistance and method for manufacturing the same | |
| CN104610521B (en) | silane-modified phenolic resin and preparation method thereof | |
| CN105315437A (en) | Nonionic self-emulsifying waterborne epoxy curing agent and preparation method thereof | |
| EP0012835A2 (en) | Ambient temperature curable hydroxyl containing polymer/silicon compositions | |
| CN112500553B (en) | Waterborne epoxy back-screen adhesive curing agent, preparation method thereof and back-screen adhesive | |
| CN109265922B (en) | A kind of high toughness autocatalytic epoxy resin and preparation method thereof | |
| CN101665571B (en) | Polyphenyl methyl siloxane modified epoxy resin and preparation method of high-performance electronic packaging material thereof | |
| CN111205599B (en) | High-strength high-light-transmittance epoxy resin composition and preparation method thereof | |
| CN118955873A (en) | Monoalkylated diamines for epoxy formulations: New hardeners for epoxy systems | |
| CN109749129A (en) | A kind of multi-functional silane coupling agent and its preparation method and application | |
| CN111793215B (en) | Modified organopolysiloxane, preparation method and application thereof | |
| CN109439245B (en) | Two-component epoxy interface adhesive and preparation method thereof | |
| CN106758242B (en) | A kind of surface modified castor fiber and its preparation method and application | |
| CN109836557B (en) | A kind of toughening hydrophobic epoxy resin and preparation method thereof | |
| KR101222502B1 (en) | Silicone-Epoxy-Vinyl Resin Useful for Dispersion and Coupling of Fillers and Method of Producing the Same | |
| JPH04220422A (en) | Epoxy resin, resin composition containing same, and cured article prepared from the composition | |
| CN110815619B (en) | Method for producing epoxy resin-based composite material by using ultrasonic mixing | |
| CN104650788A (en) | Caulking adhesive with favorable retractility and preparation method thereof | |
| CN109439246B (en) | Two-component epoxy structural adhesive and preparation method thereof | |
| CN117946404A (en) | Water-based epoxy curing agent with salt spray resistance, and preparation method and application thereof | |
| CN103540286B (en) | Machine brush-manufacturing adhesive and preparation method thereof | |
| CN102060978A (en) | Pyridine polyether ionic liquid toughened epoxy resin and preparation method thereof | |
| CN113637330A (en) | High-strength modified epoxy resin plate and preparation method 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 |