CN111548705A - Titanium nano polymer resin and preparation method and application thereof - Google Patents
Titanium nano polymer resin and preparation method and application thereof Download PDFInfo
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- CN111548705A CN111548705A CN202010507489.7A CN202010507489A CN111548705A CN 111548705 A CN111548705 A CN 111548705A CN 202010507489 A CN202010507489 A CN 202010507489A CN 111548705 A CN111548705 A CN 111548705A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000010936 titanium Substances 0.000 title claims abstract description 76
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 76
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 35
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 25
- 238000005260 corrosion Methods 0.000 claims description 24
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 230000007797 corrosion Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920002959 polymer blend Polymers 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 230000005764 inhibitory process Effects 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- -1 titanium hydride Chemical compound 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 239000013535 sea water Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 241000544076 Whipplea modesta Species 0.000 claims description 2
- 229920001222 biopolymer Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 description 17
- 239000003973 paint Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 8
- 239000002861 polymer material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a titanium nano polymer resin and a preparation method and application thereof. The resin is prepared from the following components in parts by weight: 100 parts of resin, 5-15 parts of solvent-free titanium nano polymer, 0.3-0.5 part of anti-settling agent, 0.3-0.5 part of dispersant and 0.3-0.5g of defoaming agent; the solvent-free titanium nano polymer is prepared from the following components in parts by weight: 100 parts of titanium powder, 5-10 parts of a crushing agent, 5-10 parts of a pulverization-assisting agent and 1000 parts of a solvent-free carrier.
Description
Technical Field
The invention relates to the technical field of soft substances, in particular to titanium nano polymer resin and a preparation method and application thereof.
Background
With the progress of science and technology, nano materials will play more and more important roles. The micro-nano metal is an important content in the nano material and plays an important role in advanced polymer materials. The metal nano material replaces metal short fibers, metal sheets and metal coarse powder filler, and has a huge application prospect, and the application of the metal nano filler not only obviously improves the mechanical property of a high polymer material by using coarser metal powder, but also endows a plurality of new properties. The nano metal polymer material not only has the performance of common high polymer materials, but also has the functions of conductivity, wear resistance, interference resistance, radiation protection, invisibility and the like, also has a plurality of potential functions and has huge development potential. Therefore, in recent years, metal nano materials have been greatly developed in the fields of electronics, communication, military, national defense and the like.
The same as other nano materials, the dispersion technology is still a great obstacle to the application of the metal nano materials, and the dispersion methods are various, wherein the preparation of the micro-nano metal material with self-dispersion performance can greatly simplify the difficulty in application. Has great significance for popularizing the industrial application of the micro-nano metal polymer composite material.
As is known, the polymer material has an unlimited application prospect in the fields of national defense, war industry, aerospace, petrochemical industry, civil life and the like. The liquid epoxy resin in the advanced polymer material is one of the most widely applied resins, and the emergence of a novel resin requires more than 20 years to be widely applied in industry.
The inventor of the present invention has carried out a series of studies on a preparation method, a preparation apparatus, an application, and the like of a metal soft substance. The applied patents are granted, such as a CN00209258.1 titanium-based nano metal powder grinding device, a CN00105672.7 titanium-based nano metal powder manufacturing method, CN00132108.0 titanium nano polymer paint and CN03153420.1 a novel titanium nano polymer anticorrosion and antiscale water injection oil pipe.
Disclosure of Invention
The present invention is directed to the solution of the problems found in the above studies and further improvements in performance. Compared with CN03153420.1 a new titanium nanometer polymer anticorrosion antiscale water injection oil pipe, the paint contains solvent and common titanium nanometer metal powder, the resin of the invention does not need solvent, including solvent-free titanium nanometer polymer prepared by solvent-free carrier, the solvent-free titanium nanometer polymer obtains unexpected effect on the performance of resin modification. The present invention is based on this finding.
According to 40 years of research on titanium nano materials by the inventor, the application range of the epoxy resin can be remarkably expanded by modifying the epoxy resin with a novel nano material, and the modified epoxy resin can also be used as a novel epoxy resin. The novel epoxy resin is an advanced high polymer material.
The invention aims to modify epoxy resin by utilizing a titanium nano polymer to obtain a novel advanced high polymer resin, namely the titanium nano polymer resin.
The first aspect of the invention provides a titanium nano polymer resin, which is prepared from the following components in parts by weight:
100 parts of resin, 5-15 parts of solvent-free titanium nano polymer, 0.3-0.5 part of anti-settling agent, 0.3-0.5 part of dispersant and 0.3-0.5g of defoaming agent;
the solvent-free titanium nano polymer is prepared from the following components in parts by weight:
100 parts of titanium powder, 5-10 parts of a crushing agent, 5-10 parts of a pulverization-assisting agent and 1000 parts of a solvent-free carrier.
In some embodiments, the titanium powder is selected from one or more of titanium sponge powder, titanium hydride powder, and alloyed titanium powder.
In some embodiments, the size reducing agent is selected from one or more of an epoxy resin and a sulfur-containing rubber.
The epoxy resin is a low molecular weight epoxy resin with a molecular weight of less than 500. The modification effect of the solvent-free titanium nano polymer on the epoxy resin with the molecular weight of more than 700 is obviously reduced.
In some embodiments, the pulverization assisting agent is selected from one or more of a silicon coupling agent and a titanium coupling agent.
In some embodiments, the solvent-free carrier is selected from one or more of a crosslinker, an epoxy resin reactive diluent.
In some embodiments, the anti-settling agent used is selected from one or more of the group consisting of humate 202P, bentonite, and specialty white carbon.
The grinding aid and the solvent-free carrier not only influence the grinding effect in the preparation of the solvent-free titanium nano polymer mixture, such as the grinding time under the same conditions, but also influence the performance, particularly the corrosion resistance, of the finally obtained titanium nano polymer resin. Wherein, the combination of silicon coupling agent, epoxy resin reactive diluent and bentonite is preferred.
In some embodiments, the dispersant is selected from one or more of BYK163, BYK170, BYK 190.
In some embodiments, the antifoaming agent is selected from one or more of modesty 6800, BYK085, BYK 1790.
The dispersing agent and the defoaming agent not only affect the stability of the finally obtained titanium nano polymer resin, but also affect the scale inhibition performance of the finally obtained titanium nano polymer resin. Among them, BYK163 and BYK085 are preferably combined in a 1:1 weight ratio.
A second aspect of the present invention provides a method for preparing a titanium nano-polymer resin according to the first aspect, comprising the steps of:
s01, mixing titanium powder with a crushing agent, a grinding aid and a solvent-free carrier, and grinding to obtain a solvent-free titanium nano polymer mixture;
s02, mixing the solvent-free titanium nano polymer mixture with resin, an anti-settling agent, a dispersing agent and a defoaming agent, and carrying out colloid treatment to obtain titanium nano polymer resin;
preferably, the colloidization treatment is carried out in a high-efficiency high-energy dispersion machine;
preferably, the milling is carried out in a ball mill, preferably in a high-energy planetary ball mill pot.
In some embodiments, the solvent-free titanium nano polymer mixture is mixed with a resin, an anti-settling agent, a dispersing agent and an antifoaming agent during the colloidization treatment, wherein the parts of the resin, the anti-settling agent, the dispersing agent and the antifoaming agent are determined by the following steps:
firstly, constructing sample data;
mixing resins, anti-settling agents, dispersing agents and defoaming agents in different parts with the solvent-free titanium nano polymer mixture, and controlling the mixture in the same suitable environment during mixing to form n mixed records, wherein the n mixed records form a corresponding matrix M, each row of the matrix M is provided with n 4 columns, each row of the matrix M represents one record, the first column of the matrix M represents the part of the first material resin, the second column of the matrix M represents the part of the second material anti-settling agent, the third column of the matrix M represents the part of the third material dispersing agent, and the fourth column of the matrix M represents the part of the fourth material defoaming agent;
then, calculating the loss amount of each material by using a formula (1) for the matrix M;
in the above formula (1), Qiα is the loss of the ith column of the matrix M, i.e., the loss of the ith materialijValues representing the ith row and jth column of the matrix M, αitA value representing the ith row and the tth column of the matrix M, wherein T is the weight of the solvent-free titanium nano polymer mixture, ln () is a logarithm taking a natural constant e as a base, and i is 1,2,3 and 4; j is 1,2, …, n, n is the total number of rows of matrix M;
then, calculating the adjusting coefficient of each column of information according to the formula (2);
in the above formula (2), wiThe adjustment coefficient of the ith column of the matrix M is the adjustment coefficient of the ith material, and lg is the logarithm with the base of 10;
finally, calculating the amount of each material according to the formula (3);
in the above formula (3), MiThe quantity in column i of matrix M, i.e. the quantity of material i ═ 1,2,3,4, M solved by equation (3)1、M2、M3、M4The weight ratio of the resin, the anti-settling agent, the dispersing agent and the defoaming agent is determined.
Determining the parts of the resin, the anti-settling agent, the dispersing agent and the defoaming agent by using the technology, scientifically obtaining the parts of the resin, the anti-settling agent, the dispersing agent and the defoaming agent according to test record data, and simultaneously calculating the information loss amount of each material by using a formula (1), wherein the larger the information loss of the material is, the larger the obtained value is, the smaller the coefficient value of the regulating coefficient after calculation is, so that the regulating coefficient can be well regulated according to the information loss amount; the adjustment coefficient is solved by using the formula (2), and is determined according to the relation between data, so that the objectivity of the adjustment coefficient is strong, the extra introduction amount required for determining the coefficient is not increased, and a strong mathematical theoretical basis is provided; when the formula (3) is used for the weight of each material, not only the adjusting coefficient in the matrix is considered, but also the weight of each record in the record when the matrix is constructed is considered, and the matrix construction is a subjective judgment method by artificially judging the data composition when the yield of the titanium nano polymer resin is high, so that the formula (3) fully considers subjective factors and objective calculation, and the obtained result is more scientific and convincing.
The third aspect of the invention provides the application of the titanium nano polymer resin in scale inhibition, corrosion resistance, adhesion to aluminum alloy and seawater resistance.
In some embodiments, the applications include the manufacture of heat exchanger coatings and scale inhibition coatings, the manufacture of heavy duty corrosion protection coatings, the manufacture of aluminum alloy corrosion protection coatings, the manufacture of marine coatings.
The invention has the beneficial effects that:
in the invention, the solvent-free titanium nano polymer has obviously better modification effect on resin than common titanium powder.
The resin of the invention has many new functions which are not possessed by the original resin, such as an anti-scaling function, a high corrosion resistance function, a temperature resistance, an excellent seawater resistance function and an excellent oil resistance function, and the resin can be directly used for preparing heavy anti-corrosion paint.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
In the following examples and comparative examples, parallel tests of the same operation were conducted unless otherwise specified. The purity of the titanium sponge powder is 99.4 percent and the purity of the titanium sponge powder is 120-200 meshes. The high-efficiency high-energy dispersion machine is an ESJ-500 type high-speed dispersion machine and is purchased from Shanghai Yile electromechanical equipment Limited company. The molecular weights of novolac epoxy resin F51, epoxy resin E51, and rubber 121 are all below 500.
Example 1
A, taking 100g of titanium sponge powder, 5g of a crushing agent (novolac epoxy resin F51), 5g of a co-crushing agent (silicon coupling agent) and 500g of a solvent-free carrier (crosslinking agent triallyl isocyanurate), stirring and mixing, putting into a high-energy planetary ball mill charging bucket, and grinding for 4 hours to obtain a solvent-free titanium nano polymer;
and B, taking epoxy resin E51100 g, adding 5g of the solvent-free titanium nano polymer obtained in the step A, 0.3g of an anti-settling agent (a modest 202P), 0.3g of a dispersing agent (A-10) and 0.3g of a defoaming agent (a modest 6800), and then carrying out colloidization treatment by using a high-efficiency high-energy dispersing machine to obtain the titanium nano polymer resin.
Example 2
A, taking 100g of titanium hydride powder, 8g of a crushing agent (epoxy resin E51), 8g of a co-crushing agent (titanium coupling agent) and 600g of a solvent-free carrier (phenyl glycidyl ether), stirring and mixing, putting into a high-energy planetary ball mill charging bucket, and grinding for 5 hours to obtain a solvent-free titanium nano polymer;
and B, taking epoxy resin E44100 g, adding 8g of the solvent-free titanium nano polymer obtained in the step A, 0.5g of an anti-settling agent (a humble 202P), 0.3g of a dispersant (BYK170) and 0.5g of a defoaming agent (BYK1790), and then carrying out colloidization treatment by using a high-efficiency high-energy dispersion machine to obtain the titanium nano polymer resin.
Example 3
A, taking 100g of alloy titanium powder, 5g of a grinding agent (rubber 121), 3g of a co-grinding agent (silicon coupling agent) and 800g of a solvent-free carrier (active diluent 660A), stirring and mixing, putting into a high-energy planetary ball mill charging bucket, and grinding for 4 hours to obtain a solvent-free titanium nano polymer;
and B, taking epoxy resin F44100g, adding 10g of the solvent-free titanium nano polymer obtained in the step A, 0.8g of anti-settling agent (white carbon black), 0.3g of dispersing agent (HT-5083) and 0.5g of defoaming agent (moderate 6800), and then carrying out colloid treatment by adopting a high-efficiency high-energy dispersing machine to obtain the titanium nano polymer resin.
Comparative example 1
The difference from the embodiment 1 is that the sponge titanium powder is directly crushed in the step A without adding a crushing agent, a grinding aid and a solvent-free carrier; and directly adding the crushed product obtained in the step A into the step B.
The application range of the titanium nano polymer resin is as follows:
as a novel epoxy resin, the epoxy resin can be used as heavy anti-corrosion coating, glass fiber reinforced plastic binder, waterproof coating and marine anti-corrosion coating.
The main characteristics are as follows:
the scale inhibitor has a scale inhibiting function, and can be used for manufacturing heat exchanger coatings and scale inhibiting coatings;
secondly, the corrosion resistance of the epoxy resin is obviously improved, and heavy anti-corrosion paint can be manufactured;
the adhesion force with the aluminum alloy is good, and the aluminum alloy anticorrosive paint can be manufactured;
fourthly, the coating has excellent seawater resistance and can be used for manufacturing marine coatings.
Specific practical examples are listed for evidence:
example 1 anti-fouling coating Material
Taking 550g of the titanium nano polymer resin obtained in the example 1, 110g of plasticizer polysulfide rubber, 100g of filler talcum powder, 20g of mixed auxiliary agent and 220g of mixed solvent, and performing high-speed dispersion, sanding and filtration to obtain a component A, wherein the component B is 110g of phenolic aldehyde amine and 190g of mixed solvent; b is 5:1, preparing and using. The scale inhibition performance is as follows:
1. determination of fouling factor of the resin coating
Adopting FJ corrosion and scaling monitor, controlling the flow velocity to be 0.5m/s and the test medium at the most easily scaling temperature of the industrial water of 60 ℃: total hardness 272.8mg/l (as CaCO 3); total alkalinity of 279.0mg/l (as CaCO 3); calcium 193.4mg/l (as CaCO 3); chlorine 28mg/l (in CI); the pH value is 7.01. Fouling deposition rates and fouling coefficients of the titanium nano-polymer resin coatings were determined and the results are shown in table 1.
TABLE 1 Scale inhibition Properties of titanium biopolymer resin coatings
The fouling deposition rate of the anti-corrosion and anti-fouling coating prepared from the titanium nano polymer resin obtained in example 1 is only 1/70 of stainless steel, and the fouling coefficient is 1/33 of the stainless steel, which is far lower than the good grade of the national standard.
By adopting the same formula and replacing the resin with the titanium nano polymer resin obtained in the comparative example 1, the fouling deposition rate of the prepared anti-corrosion and anti-scaling coating is far less than that of the examples 1-3. The scale inhibition and modification effects of the solvent-free titanium nano polymer on the resin are superior to those of titanium powder.
2. The anti-scaling performance of the titanium nano polymer resin coating, the epoxy resin coating and the Ni-P plating coating is compared and shown in the table 2.
TABLE 2 comparison of the antifouling Properties of the coating layers
| Serial number | Coating layer | Scale inhibition rate/%) | Film thickness/. mu.m |
| 1 | Titanium nano polymer coating | 50.69 | 40 |
| 2 | Epoxy resin coating | 31.25 | 40 |
| 3 | Electroless plating of Ni-P alloys | 37.50 | 20 |
As can be seen from the data in the table, the anti-scaling performance of the titanium nano polymer resin paint obtained in example 1 is much higher than that of other two common coating samples, and the anti-scaling performance is better.
Example 2 taking 570g of the titanium nano polymer resin obtained in example 1, 90g of dibutyl phthalate, 100g of mica powder, 50g of quartz powder and 170g of mixed solvent, dispersing at high speed and grinding to obtain a component A; the component B is 650180 g +20g of mixed solvent of polyamide; when used, A and B are 5: 1. The coating of the paint has the following corrosion resistance:
1. general corrosion resistance
Chemical reagent resistance and corrosion resistance test results
| Medium and concentration | Temperature of | Time h | Surface state | Corrosion resistance |
| H2SO4 30％ | 25 | 5000 | Without change | Stabilization |
| HNO3 10％ | 25 | 5000 | Without change | Stabilization |
| NaOH 10％ | 25 | 5000 | Without change | Stabilization |
| HCl 10％ | 25 | 5000 | Without change | Stabilization |
| NaCl 3.5％ | 25 | 5000 | Without change | Stabilization |
2. Comparison with the corrosion resistance of novolac epoxy resin
| Contrast item | Titanium nano polymer resin paint | Epoxy phenolic aldehyde anticorrosive paint |
| 30％H2S04 | 4320h without discoloration, bubbling, wrinkling, peeling, rusting | Rusty spot appears after soaking for 400h |
| 10％NaOH | No occurrence of phenomena of discoloration, bubbling, wrinkling, falling off, rusting and the like after 6000h | The paint film falls off after soaking for 600h |
| 10％NaOH | No occurrence of phenomena of discoloration, bubbling, wrinkling, falling off, rusting and the like after 2000h | Spraying for 300h and then dischargingRusty spot |
| Results | Is very good | In general |
The anti-corrosion paint film of the paint has good acid, alkali and salt spray resistance, and is obviously superior to epoxy phenolic aldehyde anti-corrosion paint.
And also. And by adopting the same formula, the resin is replaced by the titanium nano polymer resin obtained in the comparative example 1, and the corrosion resistance of the coating of the prepared coating is obviously reduced.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The titanium nano polymer resin is prepared from the following components in parts by weight:
100 parts of resin, 5-15 parts of solvent-free titanium nano polymer, 0.3-0.5 part of anti-settling agent, 0.3-0.5 part of dispersant and 0.3-0.5g of defoaming agent;
the solvent-free titanium nano polymer is prepared from the following components in parts by weight:
100 parts of titanium powder, 5-10 parts of a crushing agent, 5-10 parts of a pulverization-assisting agent and 1000 parts of a solvent-free carrier.
2. The metal soft mass according to claim 1, wherein the titanium powder is selected from one or more of titanium sponge powder, titanium hydride powder and alloy titanium powder.
3. The titanium nano-polymer resin according to claim 1 or 2, wherein the pulverizing agent is selected from one or more of epoxy resin and sulfur-containing rubber.
4. The titanium nano-polymer resin according to any one of claims 1 to 3, wherein the pulverization assisting agent is selected from one or more of a silicon coupling agent and a titanium coupling agent.
5. The titanium biopolymer resin of any one of claims 1-4, wherein the solvent-free carrier is selected from one or more of a crosslinker, an epoxy reactive diluent.
6. The titanium nano-polymer resin according to any one of claims 1 to 5, wherein the anti-settling agent is selected from one or more of the group consisting of humate 202P, bentonite, and specialty white carbon black.
7. The titanium nano-polymer resin according to any one of claims 1 to 6, wherein the dispersing agent is selected from one or more of BYK163, BYK170, BYK 190;
and/or the antifoaming agent is selected from one or more of modesty 6800, BYK085, BYK 1790.
8. A method for preparing a titanium nano-polymer resin according to any one of claims 1 to 7, comprising the steps of:
s01, mixing titanium powder with a crushing agent, a grinding aid and a solvent-free carrier, and grinding to obtain a solvent-free titanium nano polymer mixture;
s02, mixing the solvent-free titanium nano polymer mixture with resin, an anti-settling agent, a dispersing agent and a defoaming agent, and carrying out colloid treatment to obtain titanium nano polymer resin;
preferably, the colloidization treatment is carried out in a high-efficiency high-energy dispersion machine;
preferably, the milling is carried out in a ball mill, preferably in a high-energy planetary ball mill pot.
9. The method according to claim 8, wherein the solvent-free titanium nano polymer mixture is mixed with resin, anti-settling agent, dispersant and defoaming agent during the colloidization treatment, wherein the parts of the resin, the anti-settling agent, the dispersant and the defoaming agent are determined according to the following steps:
firstly, constructing sample data;
mixing resins, anti-settling agents, dispersing agents and defoaming agents in different parts with the solvent-free titanium nano polymer mixture, and controlling the mixture in the same suitable environment during mixing to form n mixed records, wherein the n mixed records form a corresponding matrix M, each row of the matrix M is provided with n 4 columns, each row of the matrix M represents one record, the first column of the matrix M represents the part of the first material resin, the second column of the matrix M represents the part of the second material anti-settling agent, the third column of the matrix M represents the part of the third material dispersing agent, and the fourth column of the matrix M represents the part of the fourth material defoaming agent;
then, calculating the loss amount of each material by using a formula (1) for the matrix M;
in the above formula (1), Qiα is the loss of the ith column of the matrix M, i.e., the loss of the ith materialijValues representing the ith row and jth column of the matrix M, αitA value representing the ith row and the tth column of the matrix M, wherein T is the weight of the solvent-free titanium nano polymer mixture, ln () is a logarithm taking a natural constant e as a base, and i is 1,2,3 and 4; j is 1,2, …, n, n is the total number of rows of matrix M;
then, calculating the adjusting coefficient of each column of information according to the formula (2);
in the above formula (2), wiThe adjustment coefficient of the ith column of the matrix M is the adjustment coefficient of the ith material, and lg is the logarithm with the base of 10;
finally, calculating the amount of each material according to the formula (3);
in the above formula (3), MiThe quantity in column i of matrix M, i.e. the quantity of material i ═ 1,2,3,4, M solved by equation (3)1、M2、M3、M4The weight ratio of the resin, the anti-settling agent, the dispersing agent and the defoaming agent is determined.
10. The use of the titanium nano polymer resin according to any one of claims 1 to 7 for scale inhibition, corrosion resistance, adhesion to aluminum alloys, and seawater resistance;
preferably, the applications include the manufacture of heat exchanger coatings and scale inhibition coatings, the manufacture of heavy duty corrosion protection coatings, the manufacture of aluminium alloy corrosion protection coatings, the manufacture of marine coatings.
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| CN112980329A (en) * | 2021-02-26 | 2021-06-18 | 山东福源节能环保工程有限公司 | Flue polymer composite anticorrosive paint formula |
| CN113198707A (en) * | 2021-05-13 | 2021-08-03 | 云南云天化红磷化工有限公司 | Method for repairing surface of flow passage component of phosphogypsum slurry pump |
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