CN117511221A - Impact hardening composite material and preparation method thereof - Google Patents
Impact hardening composite material and preparation method thereof Download PDFInfo
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- CN117511221A CN117511221A CN202311526905.8A CN202311526905A CN117511221A CN 117511221 A CN117511221 A CN 117511221A CN 202311526905 A CN202311526905 A CN 202311526905A CN 117511221 A CN117511221 A CN 117511221A
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 56
- -1 polysiloxane Polymers 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 229910052796 boron Inorganic materials 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- ZFMOJHVRFMOIGF-UHFFFAOYSA-N 2,4,6-trimethoxy-1,3,5,2,4,6-trioxatriborinane Chemical compound COB1OB(OC)OB(OC)O1 ZFMOJHVRFMOIGF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 32
- 235000012239 silicon dioxide Nutrition 0.000 description 22
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 20
- 239000012975 dibutyltin dilaurate Substances 0.000 description 20
- YYXFJSDMOVHLMJ-UHFFFAOYSA-N (4-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(O)C=C1 YYXFJSDMOVHLMJ-UHFFFAOYSA-N 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 12
- 239000005267 main chain polymer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000003938 response to stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 190000008236 carboplatin Chemical group 0.000 description 1
- 229960004562 carboplatin Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- ORRNVHHOEJMPDQ-UHFFFAOYSA-N ethoxy-hydroxy-dimethoxysilane Chemical group CCO[Si](O)(OC)OC ORRNVHHOEJMPDQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses an impact hardening composite material and a preparation method thereof, relating to the technical field of high polymer materials, wherein the method comprises the following steps: step 1, uniformly mixing polysiloxane with active groups, a boron-containing compound and a reinforcing filler to obtain a masterbatch, and dividing the masterbatch into two parts; step 2, adding a cross-linking agent into one part of master batch, and uniformly mixing to obtain a component A; step 3, adding the catalyst into another masterbatch, and uniformly mixing to obtain a component B; and 4, uniformly mixing the component A and the component B, heating to 80-160 ℃, and reacting for 2-12 hours at the stirring speed of 15 r/min to obtain the impact hardening composite material. The composite material prepared by the invention not only has good impact hardening property, but also has good dimensional stability under quasi-static state. The end group of the composite material is provided with an active polar group, and has good bonding performance with the substrate. The preparation process is simple and is beneficial to industrialized mass production.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to the technical field of impact hardening composite materials and a preparation method thereof.
Background
The intelligent protective material can be in a soft and light natural state in normal practice, but can be quickly hardened when being subjected to external force, and can absorb a large amount of energy, so that the high-efficiency protection of an external force receptor is realized, and therefore, the intelligent protective material is always a focus of attention. From inorganic rigid materials (such as cement, metal materials and the like) to high-strength high-molecular fibers (such as ultra-high molecular weight polyethylene, kevlar fibers and the like), porous foam materials and damping materials (such as polyurethane, crosslinked rubber and the like), the intelligent protective material makes great contribution to human beings in the protective field. In 2005, the united states armon laboratory pushed "liquid armor" manufactured using Shear-Thickening Fluid (STF) technology, which first turned the ideal smart protective material into reality. The STF technology utilizes inorganic nano particles dispersed in a fluid phase to generate aggregation under the action of external force shearing, so that the viscosity of the fluid is suddenly increased, and the effective protection of an external force receptor is realized.
Impact hardening materials (Impact Hardening Polymer, IHP) are a class of non-Newtonian fluid materials that have been rapidly developed in recent years, including the dilatant materials (Di latant mater ials) of the American Dow Corning company, the Armourge materials and D3O materials of the United kingdom, the G-Form materials of the United states, and the like, all rely on the impact hardening properties provided by the structural design of the materials to impart smart response characteristics to the protective materials. Under low shear conditions, the material exhibits an extremely low elastic modulus, whereas at a particular shear frequency range, the material modulus rapidly rises by several orders of magnitude, imparting to the material impact hardening characteristics. And the prior patent discloses the following techniques:
patent publication No. CN108070044B entitled "impact-hardening gel Material and method for preparing same" discloses the following: the gel material provided by the invention is prepared from the following raw materials in parts by weight: 5 to 30 parts of acrylamide monomer, 0.01 to 0.08 part of cross-linking agent, 10 to 30 parts of water, 0.01 to 0.25 part of photoinitiator, 5 to 25 parts of polysiloxane modifier and 0.2 to 5 parts of organic solvent; the polysiloxane modifier is a polymer formed by the polymerization reaction of a polysiloxane matrix; the polysiloxane matrix is selected from one or more of diamino terminated polydimethylsiloxane, vinyl hydroxyl terminated polydimethylsiloxane, vinyl amino terminated polydimethylsiloxane, hydrogen radical hydroxyl terminated polydimethylsiloxane, hydrogen radical amino terminated polydimethylsiloxane and vinyl hydrogen terminated polydimethylsiloxane. The gel material provided by the invention has excellent mechanical property and impact hardening property, and endows the gel material with low-temperature non-freezing property.
Patent publication No. CN108047468B entitled "impact-hardening gel Material and method for preparing same" discloses the following: the invention mixes the main chain oligomer with the structure shown in the formula (I), the chain extender and the boron-containing compound for reaction to obtain a first heavy polymer system. The invention also adopts a branched chain oligomer with a structure shown in a formula (I I), and the branched chain oligomer reacts with a chemical crosslinking agent to obtain a branched and crosslinked structure, so that a second heavy network is formed. The invention utilizes the first heavy polymer system to provide stress response characteristics, and further introduces a second heavy crosslinked network to endow the material with dimensional stability and better mechanical properties. The catalyst is used for the radical reaction between the branched polymer chain added in the second reaction process and the cross-linking agent, so as to obtain a constant cross-linking structure. The interpenetrating structure can improve the elastic modulus and the dimensional stability of the material. Therefore, the prepared impact hardening material has better self stability and mechanical strength, and simultaneously has better impact hardening performance.
However, the patent publication No. CN108070044B discloses that an impact hardening gel is prepared by adopting a photo-curing mode, but the mechanical property of the gel is poor. The patent with publication No. CN108047468B adopts a multi-crosslinking network to prepare an impact hardening material, and the final reactant terminal group of the material is not active and has no adhesiveness although the mechanical property of the material is improved to a certain extent.
How to solve the above problems is the direction of effort of those skilled in the art.
Disclosure of Invention
The invention aims at: in order to solve the technical problems, the invention provides an impact hardening composite material and a preparation method thereof. The impact hardening composite material and the preparation method thereof have the characteristics of stress response, good mechanical strength and good adhesion.
The invention adopts the following technical scheme for realizing the purposes:
in one aspect, the present invention provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 And X 2 Independently selected from alkoxy, epoxy;
X 3 is alkyl or benzyl;
n is 10 to 50000.
In one embodiment, the cross-linking agent is one or more of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, or tetramethoxysilane.
In one embodiment, the catalyst is one of a platinum catalyst or an organotin catalyst.
In one embodiment, the boron-containing compound is one or more of boric acid, tetrahydroxydiborane, parahydroxyphenylboric acid, trimethoxyboroxine.
In one embodiment, the reinforcing filler is one or more of silica, calcium carbonate, or silica fume;
another aspect of the present invention provides a method for preparing an impact-hardening composite material, using the above-mentioned impact-hardening composite material, comprising the steps of:
step 1, uniformly mixing polysiloxane with active groups, a boron-containing compound and a reinforcing filler to obtain a masterbatch, and dividing the masterbatch into two parts;
step 2, adding a cross-linking agent into one part of master batch, and uniformly mixing to obtain a component A;
step 3, adding the catalyst into another masterbatch, and uniformly mixing to obtain a component B;
step 4, uniformly mixing the component A and the component B, heating to 80-160 ℃, and reacting for 2-12 hours at a stirring speed of 15 r/min to obtain an impact hardening composite material;
in one embodiment, the mass ratio of the polysiloxane with active groups, the boron-containing compound and the reinforcing filler is 60 to 100: 1-5:5-30;
in one embodiment, the mass ratio of masterbatch to cross-linking agent is 66-136:1-5;
in one embodiment, the mass ratio of masterbatch to catalyst is 66-136: 0.1 to 0.5;
in one embodiment, the mass ratio of masterbatch A to masterbatch B is 1-100:1-100.
The beneficial effects of the invention are as follows:
1. the impact hardening composite material has 3 crosslinking modes, wherein the first crosslinking mode is physical crosslinking between a polymer and a filler, the second crosslinking mode is dynamic covalent bond crosslinking between an intermediate product silicon hydroxyl group and a boron hydroxyl group, and the third crosslinking mode is covalent bond crosslinking between the intermediate product silicon hydroxyl group and a crosslinking agent alkoxy group; physical crosslinking and covalent bond crosslinking can inhibit cold flow, so that the stability of the shape and the size of the material is ensured; the dynamic covalent bond cross-linking between the intermediate silicon hydroxyl groups and boron hydroxyl groups provides impact hardening properties to the composite material.
2. Because the reaction adopted by the invention can remain alkoxy and epoxy, the impact hardening composite material has good adhesion when being compounded with materials such as high-strength polymer fibers and the like.
3. The impact hardening material obtained by the invention not only can inhibit cold flow, but also has good adhesion, and has better stability and service life with bulletproof armor prepared by compounding high-strength fibers such as ultra-high molecular weight polyethylene, kevller fibers and the like.
4. The preparation process is simple and is beneficial to industrialized mass production.
Drawings
Fig. 1 is a graph of storage modulus as a function of frequency for some of the examples (example 1, example 3, example 5, example 7).
FIG. 2 is a graph of the effect of boron hydroxyl to reactive end group ratio (r value) on storage modulus for some examples.
Fig. 3 is an infrared spectrum of a portion of the composite materials of examples (example 2, example 4, example 6, example 8).
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In describing embodiments of the present invention, it should be noted that the directions or positional relationships indicated by the terms "inner", "outer", "upper", etc. are directions or positional relationships based on those shown in the drawings, or those that are conventionally put in place when the inventive product is used, are merely for convenience of description and simplification of description, and are not indicative or implying that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Example 1
As shown in fig. 1 to 3, the present embodiment provides an impact-hardening composite material including the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=50, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, polysiloxane (X) with active groups and having a structure shown in formula (1) 1 、X 2 Is epoxy, n=50, x 3 Alkyl) 60g, 5g of p-hydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B;
and 4, finally, putting 1g of the component A and 33.1g of the component B into an internal mixer, heating to 80 ℃, stirring at a speed of 15 revolutions per minute, and reacting for 12 hours to obtain the impact hardening composite material.
Example 2
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, polysiloxane (X) with active groups and having a structure shown in formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B;
and 4, putting 1g of the component A and 33.1g of the component B into an internal mixer, heating to 80 ℃, stirring at a speed of 15 revolutions per minute, and reacting for 12 hours to obtain the impact hardening composite material.
Example 3
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is tetrahydroxydiborane.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, placing 60g of main chain polymer (X1 and X2 are epoxy groups, n=5000 and X3 is alkyl) with a structure shown in a formula (1), 1g of tetrahydroxy diborane and 5g of silicon dioxide into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Example 4
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is an epoxy group，n＝5000,X 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silica micropowder;
the preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon micropowder are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Example 5
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is methyltrimethoxysiloxane.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide.
The preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, placing 33g of master batch and 1g of methyltrimethoxysilane into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Example 6
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is a carboplatin catalyst.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide.
The preparation method of the composite material comprises the following steps:
step 1, placing 60g of main chain polymer (X1 and X2 are epoxy groups, n=5000 and X3 is alkyl) with a structure shown in a formula (1), 1g of parahydroxyphenylboric acid and 5g of silicon dioxide into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, placing 33g of master batch and 0.1g of Karster platinum catalyst into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Example 7
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain a 33.1 component B; finally, 33.1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Example 8
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; and finally, putting 34g of the component A and 0.34g of the component B into an internal mixer, heating to 80 ℃, stirring at a speed of 15 revolutions per minute, and reacting for 12 hours to obtain the impact hardening composite material.
Example 9
This example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are put into an internal mixer, heated to 160 ℃, stirred at 15 revolutions per minute, and reacted for 2 hours to obtain the impact hardening composite material.
Comparative example 1
This comparative example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Comparative example 2
This comparative example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is alkyl, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The catalyst is dibutyl tin dilaurate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, a main chain polymer (X) having a structure represented by the formula (1) 1 、X 2 Is alkyl, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, putting 33g of master batch and 0.1g of dibutyltin dilaurate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 33.1g of component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
Comparative example 3
This comparative example provides an impact-hardened composite comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 、X 2 Is epoxy, n=5000, x 3 Is alkyl.
The cross-linking agent is ethyl orthosilicate.
The boron-containing compound is p-hydroxyphenylboric acid.
The reinforcing filler is silicon dioxide;
the preparation method of the composite material comprises the following steps:
step 1, the compound is represented by the formula (1)Backbone Polymer of Structure (X) 1 、X 2 Is epoxy, n=5000, x 3 Alkyl) 60g, 1g of parahydroxyphenylboric acid and 5g of silicon dioxide are put into an internal mixer and uniformly mixed at the speed of 15 r/min at room temperature to obtain 66g of master batch;
step 2, putting 33g of master batch and 1g of ethyl orthosilicate into an internal mixer, and uniformly mixing at a speed of 15 revolutions per minute at room temperature to obtain 34g of component A;
step 3, uniformly mixing 33g of the masterbatch in an internal mixer at a speed of 15 revolutions per minute at room temperature to obtain 33g of a component B; finally, 1g of the component A and 33.1g of the component B are placed into an internal mixer, heated to 80 ℃, stirred at 15 revolutions per minute, and reacted for 12 hours to obtain the impact hardening composite material.
The impact-hardened composites obtained in examples 1 to 9 and comparative examples 1 to 3 were tested for physical properties using the following criteria:
testing the peel strength of the impact hardening composite material on the stainless steel plate by adopting a test method of the peel strength of the GB/T2792-2014 adhesive tape;
the impact-hardened composite was tested for storage modulus dependence on frequency using the oscillation mode of the rheometer.
TABLE 1 physical Property test results
As is clear from the above examples, the present invention has not only impact hardening properties but also good adhesion properties by constructing an impact-hardened composite material containing dynamic boron-oxygen bonds and active end groups.
Claims (10)
1. An impact-hardened composite material comprising the following components: polysiloxane with active groups, a cross-linking agent, a catalyst, a boron-containing compound and a reinforcing filler; the polysiloxane with active groups has a structure shown as a formula (1):
wherein X is 1 And X 2 Independently selected from alkoxy, epoxy;
X 3 is alkyl or benzyl;
n is 10 to 50000.
2. An impact-cured composite material as claimed in claim 1, wherein the cross-linking agent is one or more of ethyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane or tetramethoxysilane.
3. An impact-hardened composite according to claim 1, wherein the catalyst is one of a platinum catalyst or an organotin catalyst.
4. An impact-hardening composite material according to claim 1, wherein the boron-containing compound is one or more of boric acid, tetrahydroxydiborane, parahydroxyphenylboric acid, trimethoxyboroxine.
5. An impact-hardening composite material according to claim 1, wherein the reinforcing filler is one or more of silica, calcium carbonate or silica micropowder.
6. A method of producing an impact-hardened composite material using the seed impact-hardened composite material according to any one of claims 1 to 5, comprising the steps of:
step 1, uniformly mixing polysiloxane with active groups, a boron-containing compound and a reinforcing filler to obtain a masterbatch, and dividing the masterbatch into two parts;
step 2, adding a cross-linking agent into one part of master batch, and uniformly mixing to obtain a component A;
step 3, adding the catalyst into another masterbatch, and uniformly mixing to obtain a component B;
and 4, uniformly mixing the component A and the component B, heating to 80-160 ℃, and reacting for 2-12 hours at the stirring speed of 15 r/min to obtain the impact hardening composite material.
7. The method for producing an impact-hardening composite material according to claim 6, wherein the mass ratio of the reactive group-containing polysiloxane, the boron-containing compound and the reinforcing filler is 60 to 100: 1-5:5-30.
8. The method for producing an impact-hardening composite material according to claim 6, wherein the mass ratio of the masterbatch to the crosslinking agent is 66 to 136:1 to 5.
9. The method for preparing an impact-hardening composite material according to claim 6, wherein the mass ratio of the masterbatch to the catalyst is 66-136: 0.1 to 0.5.
10. The method for producing an impact-hardening composite material according to claim 6, wherein the mass ratio of the masterbatch A to the masterbatch B is 1 to 100:1 to 100.
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