CN113308089A - Preparation method of high-whiteness and high-toughness epoxy resin composite material - Google Patents
Preparation method of high-whiteness and high-toughness epoxy resin composite material Download PDFInfo
- Publication number
- CN113308089A CN113308089A CN202110704746.0A CN202110704746A CN113308089A CN 113308089 A CN113308089 A CN 113308089A CN 202110704746 A CN202110704746 A CN 202110704746A CN 113308089 A CN113308089 A CN 113308089A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- preparation
- composite material
- whiteness
- epoxy
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 76
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- -1 polysiloxane Polymers 0.000 claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 30
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 13
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-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
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000012745 toughening agent Substances 0.000 abstract description 5
- 238000004100 electronic packaging Methods 0.000 abstract description 3
- 239000000675 fabric finishing Substances 0.000 abstract description 2
- 238000009962 finishing (textile) Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 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 8
- 229920001400 block copolymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 6
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 2
- 238000009435 building construction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 230000003442 weekly effect Effects 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
- C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本发明公开一种高白度、韧性环氧树脂复合材料的制备方法，属于聚合物复合材料领域。该方法是在环氧树脂组合物中加入液体织物整理剂—环氧基封端型聚醚聚硅氧烷作为增韧剂，然后加入固化剂，固化反应得到环氧树脂复合材料。本发明可以通过调节环氧基封端型聚醚聚硅氧烷中聚硅氧烷和聚醚链段的长度来控制在环氧树脂中形成纳米相的尺寸，从而实现对环氧树脂增韧效果的调控，制备方法液‑液共混，由于纳米分相作用，体系明显增白增稠，从而能制备出高白度的环氧树脂复合材料。本发明方法操作简单，绿色环保，能大规模生产，因而在建筑材料、航空航天和电子封装等领域有广泛的应用前景。
The invention discloses a preparation method of a high whiteness and toughness epoxy resin composite material, which belongs to the field of polymer composite materials. In the method, a liquid fabric finishing agent-epoxy group-terminated polyether polysiloxane is added to the epoxy resin composition as a toughening agent, then a curing agent is added, and the epoxy resin composite material is obtained by curing reaction. The present invention can control the size of the nano-phase formed in the epoxy resin by adjusting the length of the polysiloxane and the polyether segment in the epoxy-terminated polyether polysiloxane, thereby realizing the toughening of the epoxy resin The control of the effect, the preparation method of liquid-liquid blending, due to the nano-phase separation effect, the system is obviously whitened and thickened, so that high whiteness epoxy resin composite materials can be prepared. The method of the invention is simple to operate, green and environmentally friendly, and can be mass-produced, so it has wide application prospects in the fields of building materials, aerospace, electronic packaging and the like.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a preparation method of a high-whiteness and high-toughness epoxy resin composite material.
Background
Epoxy resins are widely used in the fields of electronic packaging, building construction, aerospace, and the like because of their good mechanical strength, adhesion, electrical insulation, acid and alkali resistance, processability, and the like. However, the three-dimensional epoxy resin after curing has high structural crosslinking density, high surface energy and large curing internal stress, so that the product is brittle and easy to crack in long-term use, and the application of the epoxy resin is limited due to the defects. Therefore, toughening modification of epoxy resins has been an important research topic in the epoxy resin industry.
The toughening means commonly used in epoxy resins is to incorporate elastomers, thermoplastic polymers, amphiphilic block copolymers, nanofillers, core-shell nanoparticles, etc. (Domun, et al. nanoscales 2015,7, 10294-. Among them, amphiphilic block copolymers can significantly improve toughness of epoxy resins at low contents without significantly affecting glass transition temperature and other properties, and are good tougheners for epoxy resins, and many types of block copolymers have been synthesized and used for toughening epoxy resins (Lipic, et al.j.am.chem.soc.1998,120, 8963-8970; Guo, et al.macromolecular 2002, Zhou, et al.polym.chem.2020,11, 3615-3626). Huang Yajiang and the like use chain segments which do not react with epoxy resin, such as polystyrene, polypropylene oxide, polybutadiene and the like, and chain segments which react with the epoxy resin, such as polymethacrylic acid, polyglycidyl methacrylate and the like, to form a block copolymer toughened epoxy resin, so that a good effect is achieved (Huang Yajiang, Tang soldier and the like, a reinforced toughening agent, a toughened epoxy resin composite material and a preparation method thereof, CN 107459612A). Among them, the silicone chains are also used to prepare block copolymers for toughening epoxy resins due to their good flexibility and poor compatibility with epoxy resins. The weekly patent application discloses that a triblock copolymer is prepared by taking Polydimethylsiloxane (PDMS) as a middle block and Polycaprolactam (PCL) as two side blocks, and is used for toughening epoxy resin, so that a remarkable effect is achieved (the weekly patent application discloses Song Ning, and the like, a triblock copolymer based on an anion ring-opening polymerization mechanism and a preparation method, CN 111763324A).
However, the block copolymer toughened epoxy resin still has some problems to be improved. First, most of the existing block copolymers are solid, and organic solvents are generally required to be added for dissolution and dispersion when the block copolymers are mixed with epoxy resin, so that the process is complicated, the energy consumption is high, the efficiency is low, and the environment is polluted. Secondly, most of the existing block copolymers are still synthesized in laboratories and are not produced in large quantities, so that the industrial production of toughened epoxy resin is difficult.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to provide a preparation method of an epoxy resin composite material with high whiteness and toughness, the preparation method adopts a commercially available liquid fabric finishing agent, namely epoxy-terminated polyether polysiloxane, as a toughening agent, and the size of a nanophase formed in epoxy resin can be controlled by adjusting the lengths of polysiloxane and polyether chain segments, so that the toughening effect of the epoxy resin is adjusted and controlled.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a high-whiteness and high-toughness epoxy resin composite material comprises the following steps:
1) epoxy terminated polyether polysiloxane is added into epoxy resin and stirred at high speed for 30-40 min to obtain white slurry mixture.
2) And adding a curing agent into the white slurry mixture, stirring at a high speed for 10-15 minutes, vacuumizing, removing bubbles, pouring the obtained epoxy resin mixture into a mold, and carrying out curing reaction to obtain the high-whiteness and high-toughness epoxy resin composite material.
The epoxy-terminated polyether polysiloxane is colorless transparent or light yellow transparent liquid, and the viscosity is 200-20000 cP.
The midblock in the epoxy-terminated polyether polysiloxane structure is one or more copolymers of polydimethylsiloxane, polymethylphenylsiloxane, polymethylethylsiloxane and polyethylphenylsiloxane. The molecular weight of the midblock is 300-15000 g/mol.
Two side blocks in the epoxy terminated polyether polysiloxane structure are one or two copolymers of polyoxyethylene ether and polyoxyethylene oxypropylene ether. The molecular weight of the two side blocks is 200-3000 g/mol.
The end group in the epoxy terminated polyether polysiloxane structure is an epoxy group.
The epoxy resin is liquid epoxy resin, and specifically is one or a combination of more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and aliphatic epoxy resin.
The curing agent is one or a combination of several of polyether amine, aliphatic amine, alicyclic amine, aromatic amine, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride and polythiol.
The epoxy resin mixture comprises the following components in parts by weight: epoxy resin: 100 parts by mass; epoxy-terminated polyether polysiloxane: 2-200 parts by mass; a curing agent; 10 to 120 parts by mass.
The curing reaction is heating curing step by step, the curing temperature of the first stage is 20-140 ℃, and the curing time is 30-90 minutes; the curing temperature of the second stage is 60-180 ℃, and the time is 60-300 minutes.
By adopting the technical scheme, the invention has the following beneficial effects: 1) the toughening agent adopted by the invention is a commercially available block copolymer-epoxy terminated polyether polysiloxane, the extremely large flexibility of the organic silicon-oxygen chain structure has an obvious toughening effect on the epoxy resin, and the system nanometer component caused by the extremely large compatibility difference of the toughening agent and the epoxy resin has an obvious whitening and thickening effect on the epoxy resin. Meanwhile, the chain length in the block structure is adjusted, so that the whitening, thickening and toughening effects of the epoxy resin can be adjusted and controlled; 2) the preparation method of the invention adopts liquid-liquid mixing, has simple process, no organic solvent, green and environmental protection, and can meet the requirement of industrial production; 3) the epoxy resin composite material prepared by the invention has high whiteness and high toughness, and has great application value in the fields of electronic packaging, building construction, aerospace and the like.
Drawings
FIG. 1 shows the chemical structure of epoxy-terminated polyether polysiloxane.
FIG. 2 is a picture of the appearance of the epoxy resin materials obtained in the examples and comparative examples.
FIG. 3 is a sectional scanning electron microscope image of the epoxy resin materials obtained in example 1 and comparative example 1.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
10 parts by mass of epoxy terminated polyether polysiloxane (polydimethylsiloxane segment: 3000g/mol, epoxy polyether segment: 500g/mol) with the molecular weight of 4000g/mol are added into 100 parts by mass of bisphenol A epoxy resin (bisphenol A glycidyl ether), after stirring at high speed for 30 minutes, 25 parts by mass of curing agent polyether amine D230 is added, and stirring at high speed is continued for 10 minutes. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing at 25 ℃ for 1 hour, heating to 60 ℃ and curing for 4 hours to prepare the epoxy resin composite material.
Comparative example 1
To 100 parts by mass of bisphenol a epoxy resin (bisphenol a glycidyl ether), 25 parts by mass of curing agent polyetheramine D230 was added and stirred at high speed for 10 minutes. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing at 25 ℃ for 1 hour, heating to 60 ℃ and curing for 4 hours to obtain the epoxy resin cured product.
Example 2
20 parts by mass of epoxy terminated polyether polysiloxane with a molecular weight of 5000g/mol (polydimethylsiloxane chain segment: 4000g/mol, epoxy polyether chain segment: 500g/mol) is added into 100 parts by mass of bisphenol A epoxy resin (bisphenol A glycidyl ether), after stirring at high speed for 30 minutes, 85 parts by mass of curing agent methylhexahydrophthalic anhydride and 1.5 parts by mass of 2, 4, 6-tris (dimethylaminomethyl) phenol are added, and stirring at high speed is continued for 10 minutes. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 1.5 hours at 110 ℃, heating to 160 ℃ and curing for 4 hours to prepare the epoxy resin composite material.
Comparative example 2
To 100 parts by mass of bisphenol a epoxy resin (bisphenol a glycidyl ether), 85 parts by mass of a curing agent methylhexahydrophthalic anhydride and 1.5 parts by mass of 2, 4, 6-tris (dimethylaminomethyl) phenol were added, and the mixture was stirred at high speed for 10 minutes. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing at 110 ℃ for 1.5 hours, heating to 160 ℃ and curing for 4 hours to obtain the epoxy resin cured product.
Example 3
25 parts by mass of epoxy terminated polyether polysiloxane having a molecular weight of 8700g/mol (polydimethylsiloxane segment: 7700g/mol, epoxy polyether segment: 500g/mol) was added to 100 parts by mass of bisphenol A epoxy resin (bisphenol A glycidyl ether), stirred at high speed for 30 minutes, added with 24.5 parts by mass of curing agent diethyltoluenediamine, and stirred at high speed for 10 minutes. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing at 110 ℃ for 1 hour, heating to 180 ℃ and curing for 2 hours to prepare the epoxy resin composite material.
Comparative example 3
To 100 parts by mass of bisphenol a epoxy resin (bisphenol a glycidyl ether), 24.5 parts by mass of a curing agent diethyltoluenediamine was added, and the mixture was stirred at high speed for 10 minutes. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing at 110 ℃ for 1 hour, heating to 180 ℃ and curing for 2 hours to obtain the epoxy resin cured product.
In order to better illustrate the effects of the present invention, examples and comparative examples were tested. The impact strength test is carried out according to the ASTM D6110-2017 standard, the tensile test is carried out according to the ASTM D638-10 standard, and the whiteness test is carried out according to the GB 2913-1982 standard. As can be seen from Table 1, the addition of the epoxy-terminated polyether polysiloxane not only significantly improves the impact strength and elongation at break of the epoxy resin, but also illustrates the significant improvement in toughness when the fracture type of the epoxy resin is changed from brittle fracture to ductile fracture in FIG. 3. Meanwhile, the epoxy terminated polyether polysiloxane enables the epoxy resin to still present high whiteness, so that the epoxy resin composite material prepared by the invention can be proved to have excellent performances of high whiteness and high toughness.
TABLE 1 results of performance test of examples and comparative examples
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (9)
1. A preparation method of a high-whiteness and high-toughness epoxy resin composite material is characterized by comprising the following steps:
1) adding epoxy group end-capped polyether polysiloxane into epoxy resin, and uniformly stirring to obtain a mixture;
2) and adding a curing agent into the mixture, uniformly stirring, vacuumizing, removing bubbles, pouring the obtained epoxy resin mixture into a mold, and carrying out curing reaction to obtain the high-whiteness and high-toughness epoxy resin composite material.
2. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the viscosity of the epoxy-terminated polyether polysiloxane is 200-20000 cP.
3. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the epoxy-terminated polyether polysiloxane structure is characterized in that the midblock is one or more of polydimethylsiloxane, polymethylphenylsiloxane, polymethylethylsiloxane and polyethylphenylsiloxane, and the molecular weight of the midblock is 300-15000 g/mol.
4. The method for preparing the high-whiteness and high-toughness epoxy resin composite material according to the claims 1 and 2, wherein the method comprises the following steps: two side blocks in the epoxy terminated polyether polysiloxane structure are one or two copolymers of polyoxyethylene ether and polyoxyethylene oxypropylene ether, and the molecular weight of the two side blocks is 200-3000 g/mol.
5. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the end group in the epoxy terminated polyether polysiloxane structure is an epoxy group.
6. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the epoxy resin is liquid epoxy resin, and the liquid epoxy resin is one or a combination of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and aliphatic epoxy resin.
7. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the curing agent is one or a combination of several of polyether amine, aliphatic amine, alicyclic amine, aromatic amine, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride and polythiol.
8. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the epoxy resin mixture comprises the following components in parts by weight: epoxy resin: 100 parts by mass; epoxy-terminated polyether polysiloxane: 2-200 parts by mass; a curing agent; 10 to 120 parts by mass.
9. The preparation method of the high-whiteness and high-toughness epoxy resin composite material according to claim 1, wherein the preparation method comprises the following steps: the curing reaction is heating curing step by step, the curing temperature of the first stage is 20-140 ℃, and the curing time is 30-90 minutes; the curing temperature of the second stage is 60-180 ℃, and the time is 60-300 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110704746.0A CN113308089A (en) | 2021-06-24 | 2021-06-24 | Preparation method of high-whiteness and high-toughness epoxy resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110704746.0A CN113308089A (en) | 2021-06-24 | 2021-06-24 | Preparation method of high-whiteness and high-toughness epoxy resin composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113308089A true CN113308089A (en) | 2021-08-27 |
Family
ID=77380328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110704746.0A Pending CN113308089A (en) | 2021-06-24 | 2021-06-24 | Preparation method of high-whiteness and high-toughness epoxy resin composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113308089A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881051A (en) * | 2021-11-05 | 2022-01-04 | 无锡东润电子材料科技有限公司 | Preparation method and application of multifunctional toughening agent for epoxy resin |
| CN114316516A (en) * | 2021-12-31 | 2022-04-12 | 广州惠利电子材料有限公司 | Formula and preparation method of toughened epoxy resin |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279257A (en) * | 1999-06-30 | 2001-01-10 | 中国科学院化学研究所 | Polysiloxane modified epoxy resin composition |
| CN105237776A (en) * | 2014-07-10 | 2016-01-13 | 广州市延广化学工业有限公司 | Synthetic method for super-soft hydrophilic polyester silicone oil and epoxy active polyester intermediate thereof |
| CN107129578A (en) * | 2017-06-21 | 2017-09-05 | 唐山三友硅业有限责任公司 | The preparation method of network structure amino-modified silicone oil finishing agent |
| CN108117835A (en) * | 2018-02-15 | 2018-06-05 | 湖南辰砾新材料有限公司 | A kind of chromium-free fingerprint-resistant environmental protection coating material and preparation method thereof |
| US20200291188A1 (en) * | 2019-03-13 | 2020-09-17 | Ele' Corporation | Epoxy-functionalized polyorganosiloxane toughener |
| US20200377670A1 (en) * | 2017-05-31 | 2020-12-03 | Toray Industries, Inc. | Block copolymer and method of producing same, epoxy resin composition and cured product thereof, and semiconductor encapsulating material |
| CN112391841A (en) * | 2020-11-16 | 2021-02-23 | 宁波丹盈服饰有限公司 | Method for manufacturing anti-wrinkle fabric |
-
2021
- 2021-06-24 CN CN202110704746.0A patent/CN113308089A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279257A (en) * | 1999-06-30 | 2001-01-10 | 中国科学院化学研究所 | Polysiloxane modified epoxy resin composition |
| CN105237776A (en) * | 2014-07-10 | 2016-01-13 | 广州市延广化学工业有限公司 | Synthetic method for super-soft hydrophilic polyester silicone oil and epoxy active polyester intermediate thereof |
| US20200377670A1 (en) * | 2017-05-31 | 2020-12-03 | Toray Industries, Inc. | Block copolymer and method of producing same, epoxy resin composition and cured product thereof, and semiconductor encapsulating material |
| CN107129578A (en) * | 2017-06-21 | 2017-09-05 | 唐山三友硅业有限责任公司 | The preparation method of network structure amino-modified silicone oil finishing agent |
| CN108117835A (en) * | 2018-02-15 | 2018-06-05 | 湖南辰砾新材料有限公司 | A kind of chromium-free fingerprint-resistant environmental protection coating material and preparation method thereof |
| US20200291188A1 (en) * | 2019-03-13 | 2020-09-17 | Ele' Corporation | Epoxy-functionalized polyorganosiloxane toughener |
| CN112391841A (en) * | 2020-11-16 | 2021-02-23 | 宁波丹盈服饰有限公司 | Method for manufacturing anti-wrinkle fabric |
Non-Patent Citations (2)
| Title |
|---|
| 孙秀武等: "聚醚接枝聚硅氧烷共聚物改进环氧树脂表面性能的研究", 《应用化学》 * |
| 段志豪 等: "线性双端环氧基FB-450聚醚硅氧烷的合成", 《印染》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881051A (en) * | 2021-11-05 | 2022-01-04 | 无锡东润电子材料科技有限公司 | Preparation method and application of multifunctional toughening agent for epoxy resin |
| CN114316516A (en) * | 2021-12-31 | 2022-04-12 | 广州惠利电子材料有限公司 | Formula and preparation method of toughened epoxy resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2387683C2 (en) | Epoxide resins reinforced with amphiphilic block-copolymer | |
| JP5259397B2 (en) | Reinforced composition | |
| CN106281174B (en) | A kind of high tenacity, impact resistance, high flexibility epoxy pouring sealant and preparation method thereof | |
| CN109265922B (en) | A kind of high toughness autocatalytic epoxy resin and preparation method thereof | |
| CN113308089A (en) | Preparation method of high-whiteness and high-toughness epoxy resin composite material | |
| CN113201207B (en) | A kind of preparation method of high toughness, high strength carbon nanotube/epoxy resin composite material | |
| CN112980372B (en) | Adhesive and preparation method thereof | |
| CN103497311A (en) | Expoxy resin polyamine curing agent and waterborne epoxy curing agent emulsion | |
| CN112745501A (en) | Dendritic toughening curing agent, and preparation method and application thereof | |
| CN107325490A (en) | A kind of RTM shapings two grades of method for toughening of high temperature tough epoxy resin system | |
| CN108504041A (en) | A kind of epoxy resin/poly ion liquid composite material and preparation method | |
| CN103304960B (en) | A kind of preparation method of two-arch tunnel POSS-epoxy modified resin | |
| Zhao et al. | Morphology and properties of nanostructured epoxy blends toughened with epoxidized carboxyl-terminated liquid rubber | |
| CN109694551A (en) | A kind of preparation method of the high-performance epoxy composite material with particular nanostructure | |
| CN113683777A (en) | Preparation method of epoxy-terminated hyperbranched polyether sulfone and application of epoxy-terminated hyperbranched polyether sulfone in salt spray-resistant epoxy resin | |
| CN107955333A (en) | A kind of activeness and quietness type ring epoxy resin composition | |
| CN109679282A (en) | A kind of high-strength high-toughness epoxy composite material with particular nanostructure | |
| CN109705312A (en) | A kind of high temperature resistant epoxy resin based on bifunctional POSS and its preparation and application | |
| CN111004472B (en) | Epoxy resin prepolymer with phase-splitting structure and preparation method and application thereof | |
| CN109628038A (en) | A kind of novel building modified epoxide resin adhesive and preparation method thereof | |
| CN113817289A (en) | High-toughness transparent alicyclic epoxy resin composition | |
| Meijer et al. | Processing of thermoplastic polymers using reactive solvents | |
| CN105482373B (en) | A kind of method of epoxy terminated polystyrene oligomer Toughening Modification of Epoxy | |
| CN108659527B (en) | High-strength glass fiber composite material and preparation method thereof | |
| CN109385045B (en) | Medium-temperature cured high-toughness epoxy resin 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210827 |