CN109608889B - POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof - Google Patents
POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof Download PDFInfo
- Publication number
- CN109608889B CN109608889B CN201811426293.4A CN201811426293A CN109608889B CN 109608889 B CN109608889 B CN 109608889B CN 201811426293 A CN201811426293 A CN 201811426293A CN 109608889 B CN109608889 B CN 109608889B
- Authority
- CN
- China
- Prior art keywords
- poss
- hollow glass
- modified
- epoxy resin
- modified high
- 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
- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000007787 solid Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 40
- 239000004005 microsphere Substances 0.000 claims abstract description 40
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011324 bead Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 238000000465 moulding Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims 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 claims description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 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
- 238000003756 stirring Methods 0.000 claims description 4
- 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 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 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 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- -1 isooctyl Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A POSS modified high-toughness solid buoyancy material and a preparation method thereof are provided, the solid buoyancy material comprises an epoxy resin matrix modified by POSS and a hollow glass bead filler modified by POSS and dispersed in the matrix; the POSS for modifying the epoxy resin contains an epoxy group capable of carrying out copolymerization reaction with the resin, and the POSS for modifying the hollow glass microspheres contains trisilicon hydroxyl capable of carrying out chemical bonding with the surfaces of the hollow glass microspheres. The method overcomes the defect that the traditional flexibilizer can not be uniformly dispersed and is easy to agglomerate in the buoyancy material, the POSS with epoxy groups is uniformly dispersed in a polymer network in a mode of copolymerization with matrix resin, the nano effect of POSS particles is exerted, the dispersibility and compatibility of the hollow glass microspheres in the resin matrix are improved, the solid buoyancy material has higher toughness, the elongation at break (material toughness) reaches 6-8%, and the density is as low as 0.45-0.6g/cm3The compression strength is 25-50MPa, and the water absorption is not more than 1%.
Description
Technical Field
The invention relates to a solid buoyancy material for a marine environment, in particular to a POSS modified high-toughness solid buoyancy material and a preparation method thereof.
Background
The solid buoyancy material is an important marine special engineering material, is one of essential materials for deep sea development, and plays a key role in improving the effective load of marine development equipment and realizing suspension positioning. At present, most of solid buoyancy materials belong to brittle materials, are easily damaged when being collided or impacted in the underwater use process, need to be repaired or even replaced regularly, and influence the working efficiency of ocean development equipment. Therefore, the large-scale popularization and application of the solid buoyancy material in the ocean field needs to solve the toughness problem preferentially.
The toughening method of the solid buoyancy material reported at present mainly focuses on the following two aspects:
the Chinese patent CN 103172975 improves the toughness of the solid buoyancy material by adding ultra-high molecular weight polyethylene microparticles grafted by irradiation maleic anhydride. Chinese patent CN 103937165 describes a method for improving the toughness of solid buoyancy material by using semi-interpenetrating network and reinforced dopamine coated aramid fiber. Because the existing methods for adding the toughening particles and the toughening fibers are simple mechanical blending and are difficult to uniformly disperse in a resin system containing hollow microspheres, the actual improvement effect of toughness is not obvious.
Chinese patent CN 104164057 describes a method for improving the toughness of a solid buoyancy material by adopting a composite epoxy resin system and liquid carboxyl-terminated butadiene-acrylonitrile rubber. Chinese patent CN 108314808 describes a method for improving the toughness of a buoyancy material by using vulcanized liquid rubber as a matrix. Because the toughening effects of the two methods are positively correlated with the content of the rubber phase, and the rubber phase is too large, the defects of low strength and high density are caused, so that the actual toughening is less.
Disclosure of Invention
The invention aims to solve the technical problem that the traditional toughening agent cannot be uniformly dispersed in a buoyancy material, and provides a POSS modified high-toughness solid buoyancy material and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a POSS modified high-toughness solid buoyancy material comprises an epoxy resin matrix modified by POSS and a hollow glass bead filler modified by POSS and dispersed in the matrix; the POSS for modifying the epoxy resin contains an epoxy group capable of carrying out copolymerization reaction with the resin, and the POSS for modifying the hollow glass microspheres contains trisilicon hydroxyl capable of carrying out chemical bonding with the surfaces of the hollow glass microspheres.
The POSS for modifying the epoxy resin is one of heptaisooctyl monoepoxy POSS, heptaisobutyl monoepoxy POSS and heptaphenyl monoepoxy POSS.
The POSS for modifying the hollow glass beads is one of heptaisooctyl trisilicon hydroxyl POSS or heptaphenyl trisilicon hydroxyl POSS.
The weight ratio of the epoxy resin to the hollow glass bead is 5: 1-1: 1.
the solid buoyancy material is also added with a curing agent and an accelerant, wherein the dosage of the curing agent is 20-100% of the type of the epoxy resin, and the dosage of the accelerant is not more than 1% of the weight of the epoxy resin.
The curing agent is one of methyl tetrahydrophthalic anhydride, methyl nadic anhydride, isophorone diamine, diamino diphenyl sulfone and polyether amine D230; the promoter is one of 2-ethyl-4-methylimidazole, 2-methylimidazole and DMP-30.
The average grain diameter of the hollow glass microspheres is 45-60 microns.
A preparation method of a POSS modified high-toughness solid buoyancy material comprises the following steps:
(1) and dissolving POSS containing trisilicon hydroxyl capable of chemically bonding with the surface of the hollow glass microsphere in an ethanol solution, adding the hollow glass microsphere for uniform dispersion, filtering and drying to prepare the POSS surface modified hollow glass microsphere for later use.
(2) And dissolving POSS (polyhedral oligomeric silsesquioxane) containing an epoxy group capable of carrying out copolymerization reaction with resin by using tetrahydrofuran, then adding into the epoxy resin, mixing and stirring, and obtaining a POSS modified epoxy resin matrix after the tetrahydrofuran solvent is completely volatilized for later use.
(3) And (3) adding a curing agent and an accelerator into the POSS modified epoxy resin matrix prepared in the step (2), uniformly mixing, adding the POSS surface modified hollow glass microspheres prepared in the step (1) into the mixture, and uniformly mixing.
(4) And (4) injecting the mixture obtained in the step (3) into a mold, and curing at a certain temperature after pressure molding to obtain the POSS modified high-toughness solid buoyancy material.
After the mixture is injected into a mold for pressure molding, the mixture is cured for not less than 48 hours at the temperature of 80-120 ℃, and after the blank is demolded, the mixture is cured for not less than 24 hours again at the temperature of 120-160 ℃.
The pressure of the pressure molding is 5-20 MPa.
The invention has the beneficial effects that: the POSS is short for cage type polysilsesquioxane (polysilsesquioxane), is an organic-inorganic hybrid nano material, has a hollow cage type structure consisting of Si-O-Si as an inner core, and is provided with organic groups on the periphery. Because the inorganic core is coated by organic groups, the compatibility of the inorganic core and a resin matrix is better, and active functional groups on the surface can be polymerized into a polymer network in a chemical bond form. Meanwhile, the cage structure can be self-assembled in the resin matrix to form nanoclusters, and the resin matrix has an obvious toughening effect.
The POSS containing different reaction functional groups is utilized to respectively carry out synergistic modification on the buoyancy material resin matrix and the hollow glass microspheres, so that the defect that the traditional toughening agent cannot be uniformly dispersed in the buoyancy material and is easy to agglomerate is overcome, and the POSS with epoxy groups is uniformly dispersed in the polymer network in a mode of copolymerization with the matrix resin. Meanwhile, the surface of the hollow glass microsphere is modified by using the nano macromolecular POSS similar to the functional group of the traditional silane coupling agent, so that the nano effect of POSS particles is fully exerted, and the dispersibility and compatibility of the hollow glass microsphere in a resin matrix are improved. The solid buoyancy material has higher toughness, the elongation at break (material toughness) reaches 6 to 8 percent, and the density of the solid buoyancy material is as low as 0.45 to 0.6g/cm3The compression strength is 25-50MPa, and the water absorption is not more than 1%.
Detailed Description
The following description specifically describes the embodiments of the present invention with reference to specific examples.
The high-toughness solid buoyancy material takes POSS modified epoxy resin as matrix resin and POSS modified hollow glass beads as fillers. POSS containing different reaction functional groups is utilized to respectively carry out synergistic modification on the buoyancy material resin matrix and the hollow glass microspheres, so that the hollow glass microspheres are uniformly dispersed in the matrix resin.
The POSS for modifying the epoxy resin contains an epoxy group capable of carrying out copolymerization reaction with the resin, and is a fully condensed POSS for improving the toughness of the buoyancy material by using a volume effect. One of heptaisooctyl monoepoxy POSS, heptaisobutyl monoepoxy POSS and heptaphenyl monoepoxy POSS can be selected. The general structural formula is as follows:
wherein R is isooctyl, isobutyl or phenyl.
The POSS for modifying the hollow glass microspheres is a semi-condensed POSS which not only contains trisilicon hydroxyl capable of chemically bonding with the surfaces of the hollow glass microspheres, but also contains organic groups with good compatibility with matrix resin. The POSS can improve the binding force between the surface of the hollow glass microsphere and the epoxy resin matrix to improve the integral toughness of the buoyancy material. One of heptaisooctyl trisilicyl hydroxyl POSS or heptaphenyl trisilicyl hydroxyl POSS can be selected. The general structural formula is as follows:
wherein R is isooctyl or phenyl.
POSS with epoxy groups is uniformly dispersed in a polymer network in a copolymerization mode with matrix resin, and meanwhile, the surfaces of the hollow glass microspheres are uniformly dispersed in the matrix resin after POSS modification, wherein the used epoxy resin is bisphenol A type epoxy resin and can adopt one of the trademarks of E44, E51 and E54. The hollow glass beads are used for reducing the overall density of the buoyancy material, and the average particle size of the hollow glass beads is 45-60 micrometers, and the density of the hollow glass beads is 0.15-0.37g/cm3And one of the hollow glass microspheres with the compressive strength of 2-25 MPa. For example, the K series or S series from 3M company, the Q-Cel series from Philadelphia Quartz.
The epoxy resin and the hollow glass bead are arranged according to a certain proportion, the density of the solid buoyancy material can be adjusted, and the weight ratio of the epoxy resin to the hollow glass bead can be 5: 1-1: 1.
And a curing agent and an accelerator are also added into the solid buoyancy material, wherein the curing agent is an acid anhydride or amine curing agent matched with the epoxy resin. One of methyl tetrahydrophthalic anhydride MeTHPA, methyl nadic anhydride MNA, isophorone diamine IPDA, diamino diphenyl sulfone DDS and polyether amine D230 can be selected. The accelerator is imidazole or amine accelerator matched with the acid anhydride or amine curing agent. One of 2-ethyl-4-methylimidazole, 2-methylimidazole and DMP-30 can be selected.
The amount of the curing agent is 20-100% of the epoxy resin, and the amount of the accelerator is not more than 1% of the weight of the epoxy resin.
A preparation method of a POSS modified high-toughness solid buoyancy material comprises the following steps:
(1) dissolving a certain amount of hollow glass microsphere for surface modification in an ethanol solution by using POSS, then adding a proper amount of hollow glass microsphere into the solution, mechanically stirring at the rotating speed of 20rpm/min at 50 ℃ for 1h, ultrasonically dispersing for 10min, and then performing suction filtration, drying and sieving to obtain the POSS surface modified hollow glass microsphere for later use.
(2) And dissolving a certain amount of POSS for modifying epoxy resin with tetrahydrofuran, adding into the epoxy resin, mechanically stirring at the rotating speed of 10rpm/min for 4 hours at the temperature of 80 ℃, and obtaining the POSS modified epoxy resin matrix after the tetrahydrofuran solvent is completely volatilized for later use.
(3) And (3) adding a curing agent and an accelerator into the POSS modified epoxy resin matrix prepared in the step (2), uniformly mixing, adding the POSS surface modified hollow glass microspheres prepared in the step (1), uniformly mixing at a rotating speed of 25-50r/min, and defoaming in vacuum to obtain a raw material mixture for later use.
(4) Injecting the raw material mixture in the step (3) into a stainless steel die coated with a release agent, molding under the pressure of 5-20MPa, curing at the temperature of 80-120 ℃ for not less than 48h after molding, and demolding to obtain a blank.
And (3) re-curing the obtained blank at the temperature of 120-160 ℃ for not less than 24h, and naturally cooling the cured blank to obtain the POSS modified high-toughness solid buoyancy material product.
In the above method, the step (1) and the step (2) are not in sequence, and can also be carried out simultaneously.
Example 1
According to the mass percentage, 100 parts of bisphenol A epoxy resin E44 is modified by 10 parts of heptaisooctyl monoepoxy POSS for modifying the epoxy resin according to the method; 30 parts of S15 hollow glass microspheres from 3M company are modified by 10 parts of heptaisooctyltrisiloxanehydroxyPOSS for surface modification of the hollow glass microspheres. The prepared POSS modified epoxy resin matrix and POSS surface modified hollow glass microspheres are mixed with 90 parts of methyl tetrahydrophthalic anhydride (MeTHPA) and 0.5 part of 2-ethyl-4-methylimidazole according to the method to prepare a POSS modified high-toughness solid buoyancy material product.
Example 2
According to the mass percentage, 100 parts of bisphenol A epoxy resin E51 is modified by 10 parts of heptaisobutyl monoepoxy POSS for modifying the epoxy resin according to the method; 35 parts of K20 hollow glass microspheres from 3M company were modified with 10 parts of heptaisooctyltrisiloxanehydroxyPOSS for surface modification of the hollow glass microspheres. The prepared POSS modified epoxy resin matrix and POSS surface modified hollow glass microspheres are mixed with 23 parts of isophorone diamine IPDA and 0.2 part of DMP-30 according to the method to prepare the POSS modified high-toughness solid buoyancy material product.
Example 3
According to the mass percentage, 100 parts of bisphenol A epoxy resin E54 is modified by 10 parts of heptaphenyl monoepoxy POSS for modifying the epoxy resin according to the method; 40 parts of K25 hollow glass microspheres from 3M company are modified with 10 parts of heptaphenyltrisilico hydroxyl POSS for modifying the surfaces of the hollow glass microspheres. The prepared POSS modified epoxy resin matrix and POSS surface modified hollow glass microspheres are mixed with 32 parts of polyetheramine D230 and 0.3 part of DMP-30 according to the method to prepare the POSS modified high-toughness solid buoyancy material product.
Comparative example
Taking 100 parts of bisphenol A epoxy resin E44 according to mass percentage; 30 parts of S15 hollow glass microspheres from 3M company were taken. A solid buoyant product without POSS modification was made by mixing 90 parts of MeTHPA, methyltetrahydrophthalic anhydride, 0.5 parts of 2-ethyl-4-methylimidazole, as in example 1.
The POSS modified high-toughness solid buoyancy material obtained in the embodiment of the invention and the solid buoyancy material prepared in the comparative example are subjected to various performance tests, and the test results are as follows:
the foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A POSS modified high-toughness solid buoyancy material is characterized in that: the POSS modified hollow glass microsphere filler comprises an epoxy resin matrix modified by POSS and a hollow glass microsphere filler dispersed in the matrix and modified by POSS; the POSS for modifying the hollow glass beads contains trisilicon hydroxyl which can be chemically bonded with the surfaces of the hollow glass beads, and also contains organic groups compatible with matrix resin.
2. A POSS modified high toughness solid buoyant material according to claim 1 wherein: the POSS for modifying the epoxy resin is one of heptaisooctyl monoepoxy POSS, heptaisobutyl monoepoxy POSS and heptaphenyl monoepoxy POSS.
3. A POSS modified high toughness solid buoyant material according to claim 1 wherein: the POSS for modifying the hollow glass beads is one of heptaisooctyl trisilicon hydroxyl POSS or heptaphenyl trisilicon hydroxyl POSS.
4. A POSS modified high toughness solid buoyant material according to claim 1 wherein: the weight ratio of the epoxy resin to the hollow glass bead is 5: 1-1: 1.
5. a POSS modified high toughness solid buoyant material according to claim 1 wherein: the solid buoyancy material is also added with a curing agent and an accelerant, wherein the dosage of the curing agent is 20-100% of the weight of the epoxy resin, and the dosage of the accelerant is not more than 1% of the weight of the epoxy resin.
6. A POSS modified high tenacity solid buoyant material according to claim 5 wherein: the curing agent is one of methyl tetrahydrophthalic anhydride, methyl nadic anhydride, isophorone diamine, diamino diphenyl sulfone and polyether amine D230; the promoter is one of 2-ethyl-4-methylimidazole, 2-methylimidazole and DMP-30.
7. A POSS modified high toughness solid buoyant material according to claim 1 wherein: the average grain diameter of the hollow glass beads is 45-60 microns.
8. A preparation method of a POSS modified high-toughness solid buoyancy material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving semi-condensed POSS (polyhedral oligomeric silsesquioxane) which contains trisilicon hydroxyl capable of chemically bonding with the surfaces of the hollow glass microspheres and also contains organic groups compatible with matrix resin in an ethanol solution, adding the hollow glass microspheres for uniform dispersion, filtering and drying to prepare POSS surface modified hollow glass microspheres for later use;
(2) dissolving POSS (polyhedral oligomeric silsesquioxane) containing an epoxy group capable of carrying out copolymerization reaction with resin by using tetrahydrofuran, then adding the dissolved POSS into the epoxy resin, mixing and stirring, and obtaining a POSS-modified epoxy resin matrix for later use after the tetrahydrofuran solvent is completely volatilized;
(3) adding a curing agent and an accelerator into the POSS modified epoxy resin matrix prepared in the step (2), uniformly mixing, adding the POSS surface modified hollow glass beads prepared in the step (1) into the mixture, and uniformly mixing;
(4) and (4) injecting the mixture obtained in the step (3) into a mold, and curing at a certain temperature after pressure molding to obtain the POSS modified high-toughness solid buoyancy material.
9. The method for preparing a POSS modified high tenacity solid buoyant material of claim 8 wherein: after the mixture is injected into a mold for pressure molding, the mixture is cured for not less than 48 hours at the temperature of 80-120 ℃, and after the blank is demolded, the mixture is cured for not less than 24 hours again at the temperature of 120-160 ℃.
10. A method of making a POSS modified high tenacity solid buoyant material according to claim 8 or 9 wherein: the pressure of the pressure molding is 5-20 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811426293.4A CN109608889B (en) | 2018-11-27 | 2018-11-27 | POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811426293.4A CN109608889B (en) | 2018-11-27 | 2018-11-27 | POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109608889A CN109608889A (en) | 2019-04-12 |
| CN109608889B true CN109608889B (en) | 2021-04-02 |
Family
ID=66004831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811426293.4A Active CN109608889B (en) | 2018-11-27 | 2018-11-27 | POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109608889B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174031B (en) * | 2021-06-10 | 2023-01-03 | 哈尔滨工程大学 | Internal toughening nanoparticle curing agent, epoxy resin matrix and preparation method of internal toughening nanoparticle curing agent |
| CN115948080B (en) * | 2022-12-27 | 2023-10-20 | 海南电网有限责任公司文昌供电局 | Insulating glove and preparation method thereof |
| CN116285809A (en) * | 2023-02-06 | 2023-06-23 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | A kind of lightweight high-adhesive underwater epoxy grouting material and its preparation method |
| CN120157993A (en) * | 2025-05-20 | 2025-06-17 | 赣州恒信塑业有限公司 | High-temperature-resistant PP bar and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824206A (en) * | 2010-04-28 | 2010-09-08 | 清华大学深圳研究生院 | Ultra-high-strength buoyancy material and preparation method thereof |
| EP2412771A3 (en) * | 2010-07-27 | 2012-03-07 | United Technologies Corporation | Composite article having protective coating |
| CN102372734A (en) * | 2010-08-24 | 2012-03-14 | 江南大学 | Synthesis of novel nano hybrid reinforcing agent containing POSS |
| CN103865235A (en) * | 2014-02-13 | 2014-06-18 | 甘肃康博丝特新材料有限责任公司 | Solid buoyancy material with high impact strength and preparation method thereof |
| CN105924904A (en) * | 2016-06-26 | 2016-09-07 | 吴迪 | Preparation method for solid buoyancy material |
-
2018
- 2018-11-27 CN CN201811426293.4A patent/CN109608889B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824206A (en) * | 2010-04-28 | 2010-09-08 | 清华大学深圳研究生院 | Ultra-high-strength buoyancy material and preparation method thereof |
| EP2412771A3 (en) * | 2010-07-27 | 2012-03-07 | United Technologies Corporation | Composite article having protective coating |
| CN102372734A (en) * | 2010-08-24 | 2012-03-14 | 江南大学 | Synthesis of novel nano hybrid reinforcing agent containing POSS |
| CN103865235A (en) * | 2014-02-13 | 2014-06-18 | 甘肃康博丝特新材料有限责任公司 | Solid buoyancy material with high impact strength and preparation method thereof |
| CN105924904A (en) * | 2016-06-26 | 2016-09-07 | 吴迪 | Preparation method for solid buoyancy material |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and Characterization of Three Phase Epoxy Syntactic Foam Filled With Carbon Fiber Reinforced Hollow Epoxy Macrospheres and Hollow Glass Microspheres;Xinfeng Wu等;《Polymer Composites》;20140901;第37卷(第2期);497-502 * |
| 空心玻璃微珠表面改性对固体浮力材料性能影响研究;王鹏;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180315(第3期);B020-9 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109608889A (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608889B (en) | POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof | |
| CN106543647B (en) | A kind of high tenacity, low temperature resistant resin matrix and preparation method thereof | |
| CN105670223B (en) | Epoxy resin composition for wind turbine blade and composite material | |
| CN101186796A (en) | A kind of preparation method of epoxy resin adhesive | |
| CN107459819B (en) | Medium-temperature cured cyanate ester resin and preparation method and application thereof | |
| CN102924690A (en) | Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof | |
| CN105907040B (en) | Composition epoxy resin that a kind of suitable low temperature uses and preparation method thereof | |
| CN103865237B (en) | A kind of High-strength solid buoyancy material and preparation method thereof | |
| CN110740997A (en) | Epoxy resin system for composite materials | |
| CN103865238B (en) | A kind of deep-sea High-strength solid buoyancy material and preparation method thereof | |
| CN103694637B (en) | A kind of High-tenacity vacuum slow epoxy resin for wind power blade and preparation method thereof | |
| CN116640457B (en) | Modified asphalt for waterproof coiled material and preparation method thereof | |
| CN109836970B (en) | High-impermeability graphene modified epoxy coating liquid composition and preparation method thereof | |
| CN114605697B (en) | Low-density high-strength buoyancy material and preparation method thereof | |
| CN1213084C (en) | Preparation method and application of modified double maleimide resin | |
| CN111172762B (en) | Nano-reinforced environment-friendly impregnation system for fiber surface treatment and preparation method thereof | |
| CN119570199A (en) | Degradable epoxy resin system material and its use, body, composite material and recycling method | |
| CN113773611B (en) | Vacuum infusion epoxy resin composite material for wind power blade and preparation method thereof | |
| CN106867202A (en) | A kind of composition epoxy resin | |
| CN107474772B (en) | Epoxy glue for protecting end part of wind power motor stator and preparation method thereof | |
| CN117467246B (en) | Carbon fiber/glass fiber reinforced epoxy resin composite material and preparation method thereof | |
| CN112409758A (en) | Solid buoyancy material and preparation method and application thereof | |
| CN103937167B (en) | Solid buoyancy material of a kind of anti-marine attaching organism and preparation method thereof | |
| CN114409959B (en) | A kind of organic-inorganic hybrid high-performance resin toughening agent and preparation method thereof | |
| CN108329656A (en) | A kind of high tenacity solid buoyancy material and preparation method thereof containing elastic microsphere |
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 |