CN104893218A - Mold-proof semisolid composite system - Google Patents
Mold-proof semisolid composite system Download PDFInfo
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- CN104893218A CN104893218A CN201510381244.3A CN201510381244A CN104893218A CN 104893218 A CN104893218 A CN 104893218A CN 201510381244 A CN201510381244 A CN 201510381244A CN 104893218 A CN104893218 A CN 104893218A
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Abstract
The invention relates to a mold-proof semisolid composite system. The mold-proof semisolid composite system is prepared by using active filler, polydimethylsiloxane, trimethylsiloxysilicate, sodium lauryl sulfate, sodium alga acid, astaxanthin, diethyl phosphite, acrylic resin prepolymer and 1,3-propylene glycol. The mold-proof semisolid composite system disclosed by the invention has the advantages that the components are reasonable, the compatibility between the components is good, the prepared mold-proof semisolid composite system has good oxidation resistance and adhesive performance and especially has excellent mold-proof performance and heat-resistant performance, and the demands of the development and application of the mold-proof semisolid composite system are satisfied.
Description
Technical field
The invention belongs to advanced composite material technical field, be specifically related to a kind of mildew-resistant semi-solid bonding system, there is good cementability and mildew resistance.
Background technology
Mould is a trivial name of filamentous fungus, meaning and mouldy fungi, is often referred to those mycelium more flourishing and don't produce the fungi of large-scale sporophore.Their often raised growth breedings under the weather of humidity, grow the mycelium of macroscopic thread, velvet-like or spider web, have stronger land natural disposition, under field conditions (factors), often cause going mouldy and the fungal disease of plant of food, industrial and agricultural products.Increasingly extensive along with leatherware use range, the increase year by year of China's leather export volume, eliminates that problem that leather goes mouldy is more aobvious gives prominence to; Along with the increase of the old degree in house, the wall in house easily becomes damp and generation is gone mouldy, and mouldyly will produce bacterium and virus, unpleasant and healthy very unfavorable for human body of taste.At present for the terms of settlement of this situation, not very effective.
Various plasthetics is full of in modern life ever-changing environment, simple to basic people's livelihood articles for use, such as various people's livelihood plastic casing, consumption electronic products plastic parts, all kinds of electric wire insulating material etc., plastic cement in use becomes easily infected by and grows multiple-microorganism, and such as polyvinyl chloride (PVC) electronic material is in dampness, very easily mouldy and grow multiple malignant bacteria, harm is brought to the healthy of people.Antibacterial and mouldproof modification is carried out, to reach antibacterial and mouldproof effect for plastic material.Antibacterial polyvinyl chloride is that a class possesses antibacterial and type material that is bactericidal property, keeping the clean of material self, reducing the cross infection occurred because using plasthetics.
The microorganism of erosion material has bacterium, mould, yeast and algae, for resin system, if endanger larger microbial host bacterium and mould, the material that can be used as antibacterial mildew inhibitor has a lot, is mainly divided into the large class of organic antibacterial agent, inorganic antiseptic, natural antibacterial agent and polymer antibacterial agent 4.Inorganic antiseptic utilizes the sterilization of the metal ions such as silver, zinc, copper, titanium or bacteriostasis and an obtained class antiseptic-germicide, good heat resistance, broad-spectrum antimicrobial, and validity period is long, toxicity is low, does not produce resistance; But easy to change, preparation difficulty, more weak to mould restraint.What organic antibacterial agent was conventional has halogenide, organotin, isothiazole, pyridine metal-salt, imidazolone, aldehyde compound, quaternary ammonium salt etc., and sterilization speed is fast, and easy to process, colour stability is good, and anti-mold effect is good; But poor heat resistance, and be easy to produce biology drug resistance.Natural antibacterial agent mainly contains chitosan class, and thermotolerance is poor, and application is restricted.Polymer antibacterial agent is the macromolecular material with certain anti-microbial property of simulation natural polymer antiseptic-germicide synthesis, prepares more difficult.
Because resin system is not containing solvent, be made up of components such as resin, filler, additives, after antibacterial mildew inhibitor adds, require have good consistency not cause the change of material color, smell and stability with each component, and temperature when can withstand resin system solidification, and the crosslinking curing not affecting resin system does not affect the performance of film.The main light of antibacterial mildew inhibitor, heat impact and colorific change, antibacterial and mouldproof resin system will stand the storing temperature of more than 180 DEG C, so topmost influence factor is the heat in curing of coating process.Thermostability to increase and to reduce thermostability poor in resin system construction process along with the consumption of antibacterial mildew inhibitor, often can run into the problem of consistency, and the incompatible or poor compatibility of if tree resin system, will produce the various problems such as shrinkage cavity, loss of gloss, pin hole.
Select must consider the many factors such as antibacterial, mildew-resistant, biology drug resistance, fungicidal spectrum during antibacterial mildew inhibitor, inorganic/organic composite system can reach this requirement.
Summary of the invention
The object of this invention is to provide a kind of mildew-resistant semi-solid bonding system, it has excellent fungicidal properties, and good cementability.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of mildew-resistant semi-solid bonding system, is obtained by the raw material of following weight part:
Acrylic resin prepolymer 100 parts
Active filler 8 ~ 15 parts
Polydimethylsiloxane 25 ~ 32 parts
Trimethylsiloxysilicates 6 ~ 8 parts
Sodium alginate 11 ~ 17 parts
Astaxanthin 2 ~ 5 parts
Lauryl alcohol sodium sulfovinate 8 ~ 10 parts
1,3-PD 15 ~ 26 parts
Phosphonous acid diethyl ester 4 ~ 7 parts
Described active filler is prepared by with under type: add in graphene oxide water solution by the ytterbium nitrate aqueous solution, stirs 40 minutes, and then in 170 DEG C of reactions 16 hours, naturally cooling, obtains solid after centrifugal; Dry, be active filler;
Described acrylic resin prepolymer is formed through reacting by monofunctional acrylates's ester monomer and nitrogenous vinyl monomer.
In the present invention, the molecular weight of described acrylic resin prepolymer is 10500-50000, and molecular weight distribution is 1.2 ~ 1.3; Described monofunctional acrylates's ester monomer is methyl methacrylate, ethyl propenoate, n-butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, 2-(thiophenyl) ethyl propylene acid esters, 2-(p-cumyl-phenoxy group)-hexyl olefin(e) acid ester etc.; The structural formula of described nitrogenous vinyl monomer is:
。
In the present invention, monofunctional acrylates's ester monomer and nitrogenous vinyl monomer react form acrylic resin prepolymer time, the mol ratio of monofunctional acrylates's ester monomer and nitrogenous vinyl monomer is 1: 1.5.This is not simple in order to react completely, and the conventional means slightly improving a certain material rate adopted, but the mol ratio of creationary setting monofunctional acrylates's ester monomer and nitrogenous vinyl monomer, vinyl major part on nitrogenous vinyl monomer is cross-linked with the vinyl on monofunctional acrylates's ester monomer, also have part can form ehter bond with hydroxyl simultaneously, while increasing prepolymer cross-link intensity further, give again prepolymer certain snappiness, with this prepolymer for matrix resin, for bonding, when solidifying, ductility is good, cure shrinkage is suitable, certain toughness is had after solidification.
Acrylic resin prepolymer of the present invention retains all fragrant heterocycles of monomer and alkane group, and after fragrant heterocycle resin system solidification, the filling of cross-linking density, improves the intensity of material; Also play the effect of coupling, not only can with the hydroxyl reaction of filling surface, increase system internal bond strength, can also biochemical coupled action anti-with substrate surface, the reactive force formed is much larger than physical adsorption power, due to the generation of chemical bond, substantially increase the adhesiveproperties of whole system, ensure adhesive effect.
In the present invention, organic object is the primary bond composition of matrix material, and the pre-polymerization degree of prepolymer has material impact for the organic-inorganic consistency of composite material exhibits, in particular concerns the cementability of material; Pre-polymerization degree is low causes material cured speed comparatively slow, is unfavorable for the raising of system cross-linking density, and high resin system is not good to the wettability of inorganic filler, causes the many defects of system.Organic-compound system of the present invention not only has the function of effectively solidification, and high temperature, low temperature, still well bonding under wet environment.
In the present invention, the mass ratio of ytterbium nitrate and graphene oxide is 1: 1.3.
Preferably, described mildew-resistant semi-solid bonding system is obtained by the raw material of following weight part:
Acrylic resin prepolymer 100 parts
Active filler 9 ~ 13 parts
Polydimethylsiloxane 26 ~ 30 parts
Trimethylsiloxysilicates 6 ~ 8 parts
Sodium alginate 13 ~ 15 parts
Astaxanthin 2 ~ 5 parts
Lauryl alcohol sodium sulfovinate 8 ~ 10 parts
1,3-PD 18 ~ 24 parts
Phosphonous acid diethyl ester 4 ~ 7 parts.
In the present invention, active filler, polydimethylsiloxane, trimethylsiloxysilicates are mixed, obtains mixture; Successively lauryl alcohol sodium sulfovinate, sodium alginate, astaxanthin are added in mixture, stir 1 ~ 2 hour, then add phosphonous acid diethyl ester, stir 2 ~ 3 hours in 50 ~ 60 DEG C; Finally add acrylic resin prepolymer, 1,3-PD, stir 3 ~ 5 hours in 80 ~ 90 DEG C, obtain mildew-resistant semi-solid bonding system.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. mildew-resistant semi-solid bonding system composition disclosed by the invention rationally, between each component, consistency is good, prepare mildew-resistant semi-solid bonding system thus, there is good oxidation-resistance, adhesiveproperties, there is excellent fungicidal properties and crocking resistance especially, meet the development and application of mildew-resistant semi-solid bonding system.
2. in preparation mildew-resistant semi-solid bonding system raw material disclosed by the invention, raw material is simple and easy to get, without the need to the complex reaction of prior art, the mildew-resistant semi-solid bonding system of preparation has excellent fungicidal properties, system solidification effect is good, time mould on making moist, active filler on the one hand, particularly ytterbium nitrate/Graphene increases the fungicidal properties of system, between many organism, reaction is formed on the other hand, and form stable mildew-resistant molecular bonding structure, mildew-resistant stability is strong, to the sterilizing rate of common bacteria more than 99%, anti-protein adsorption rate reaches 92%; Achieve beyond thought effect; And avoid anti-fungus material bad adhesion in prior art, the unabiding defect of effect.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
First benzoyl peroxide (for 3% of Acrylic Acid Monomer quality) and dioxane are added in reactor, be heated to backflow, then 10mol monofunctional acrylates ester monomer, the nitrogenous vinyl monomer of 15mol is added, back flow reaction, then be cooled to 60 DEG C, vacuum removes solvent, finally adds hydramine (for 5% of Acrylic Acid Monomer quality), column chromatography obtains thermosetting acrylic resin prepolymer, and it is water-soluble.
100g ytterbium nitrate is added to the water and obtains the ytterbium nitrate aqueous solution, 130g graphene oxide is added to the water and obtains adding in graphene oxide water solution, the ytterbium nitrate aqueous solution is added in graphene oxide water solution, stir 40 minutes, then in 170 DEG C of reactions 16 hours, naturally cooling, obtains solid after centrifugal; Dry, be active filler.
Embodiment one
9g active filler, 26g polydimethylsiloxane, 6g trimethylsiloxysilicates are mixed, obtains mixture; Successively 8g lauryl alcohol sodium sulfovinate, 10g sodium alginate, 5g astaxanthin are added in mixture, stir 1 hour, then add 7g phosphonous acid diethyl ester, stir 2 hours in 50 DEG C; Finally add 100g acrylic resin prepolymer, 18g1, ammediol, stir 3 hours in 90 DEG C, obtain mildew-resistant semi-solid bonding system.
Embodiment two
13g active filler, 30g polydimethylsiloxane, 6g trimethylsiloxysilicates are mixed, obtains mixture; Successively 9g lauryl alcohol sodium sulfovinate, 14g sodium alginate, 4g astaxanthin are added in mixture, stir 2 hours, then add 6g phosphonous acid diethyl ester, stir 2 hours in 50 DEG C; Finally add 100g acrylic resin prepolymer, 23g1, ammediol, stir 3 hours in 80 DEG C, obtain mildew-resistant semi-solid bonding system.
Embodiment three
12g active filler, 28g polydimethylsiloxane, 8g trimethylsiloxysilicates are mixed, obtains mixture; Successively 10g lauryl alcohol sodium sulfovinate, 13g sodium alginate, 4g astaxanthin are added in mixture, stir 1 hour, then add 6g phosphonous acid diethyl ester, stir 3 hours in 50 DEG C; Finally add 100g acrylic resin prepolymer, 24g1, ammediol, stir 5 hours in 90 DEG C, obtain mildew-resistant semi-solid bonding system.
Embodiment four
8g active filler, 25g polydimethylsiloxane, 8g trimethylsiloxysilicates are mixed, obtains mixture; Successively 10g lauryl alcohol sodium sulfovinate, 17g sodium alginate, 5g astaxanthin are added in mixture, stir 2 hours, then add 6g phosphonous acid diethyl ester, stir 2.5 hours in 505 DEG C; Finally add 100g acrylic resin prepolymer, 26g1, ammediol, stir 4 hours in 90 DEG C, obtain mildew-resistant semi-solid bonding system.
Embodiment five
15g active filler, 32g polydimethylsiloxane, 6g trimethylsiloxysilicates are mixed, obtains mixture; Successively 10g lauryl alcohol sodium sulfovinate, 15g sodium alginate, 5g astaxanthin are added in mixture, stir 1.5 hours, then add 6g phosphonous acid diethyl ester, stir 3 hours in 55 DEG C; Finally add 100g acrylic resin prepolymer, 25g1, ammediol, stir 4 hours in 85 DEG C, obtain mildew-resistant semi-solid bonding system.
Comparative example one
32g polydimethylsiloxane, 6g trimethylsiloxysilicates are mixed, obtains mixture; Successively 10g lauryl alcohol sodium sulfovinate, 15g sodium alginate are added in mixture, stir 1.5 hours, then add 6g phosphonous acid diethyl ester, stir 3 hours in 55 DEG C; Finally add 100g acrylic resin prepolymer, 25g1, ammediol, stir 4 hours in 85 DEG C, obtain mildew-resistant semi-solid bonding system.
Comparative example two
25g polydimethylsiloxane, 8g trimethylsiloxysilicates are mixed, obtains mixture; Successively 17g sodium alginate, 5g astaxanthin are added in mixture, stir 2 hours, then add 6g phosphonous acid diethyl ester, stir 2.5 hours in 50 DEG C; Finally add 100g acrylic resin prepolymer, 26g1, ammediol, stir 4 hours in 90 DEG C, obtain mildew-resistant semi-solid bonding system.
Performance test
Utilize dimension card thermal distortion instrument test heat-drawn wire (CTE/ DEG C); Liquid crystal type balance weight impact testing machine is utilized to test shock strength (α/KJ/m
2); Utilize 3M 600 adhesive tape, drawing coating test sticking power; Hot weightless instrument is utilized to test temperature of initial decomposition (T
0/ DEG C); The sterilizing rate of the said products to intestinal bacteria (A), streptococcus aureus (B) is tested with identification method in adopting according to " disinfection technology standard "; Ultraviolet spectrophotometer is utilized to test the anti-protein adsorption rate (C) of the said products.
The performance test results of above-mentioned mildew-resistant semi-solid bonding system is in table 1.
The performance of table 1 solid gums
| CTE | α | Sticking power | A | B | C | |
| Embodiment one | 155 | 3.7 | >5B | 99.2% | 99.8% | 92.2% |
| Embodiment two | 151 | 3.6 | >5B | 99.1% | 99.2% | 91.9% |
| Embodiment three | 149 | 3.8 | >5B | 99.3% | 99.4% | 92.5% |
| Embodiment four | 150 | 3.5 | >5B | 99.2% | 99.6% | 93.2% |
| Embodiment five | 153 | 3.7 | >5B | 99.4% | 99.2% | 92.7% |
| Comparative example one | 120 | 2.7 | 4B | 75.3% | 68.2% | 53.2% |
| Comparative example two | 118 | 1.8 | 4B | 68.8% | 67.2% | 64.5% |
To sum up, mildew-resistant semi-solid state system composition disclosed by the invention rationally, between each component, consistency is good, prepare mildew-resistant semi-solid bonding system thus, there is good oxidation-resistance, adhesiveproperties, there is excellent fungicidal properties, resistance toheat especially, meet the development and application of mildew-resistant semi-solid bonding system.
Claims (7)
1. a mildew-resistant semi-solid bonding system, is characterized in that: obtained by the raw material of following weight part:
Acrylic resin prepolymer 100 parts
Active filler 8 ~ 15 parts
Polydimethylsiloxane 25 ~ 32 parts
Trimethylsiloxysilicates 6 ~ 8 parts
Sodium alginate 11 ~ 17 parts
Astaxanthin 2 ~ 5 parts
Lauryl alcohol sodium sulfovinate 8 ~ 10 parts
1,3-PD 15 ~ 26 parts
Phosphonous acid diethyl ester 4 ~ 7 parts
Described active filler is prepared by with under type: add in graphene oxide water solution by the ytterbium nitrate aqueous solution, stirs 40 minutes, and then in 170 DEG C of reactions 16 hours, naturally cooling, obtains solid after centrifugal; Dry, be active filler;
Described acrylic resin prepolymer is formed through reacting by monofunctional acrylates's ester monomer and nitrogenous vinyl monomer.
2. mildew-resistant semi-solid bonding system according to claim 1, is characterized in that: the molecular weight of described acrylic resin prepolymer is 10500-50000, and molecular weight distribution is 1.2 ~ 1.3.
3. mildew-resistant semi-solid bonding system according to claim 2, is characterized in that: described monofunctional acrylates's ester monomer is methyl methacrylate, ethyl propenoate, n-butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, 2-(thiophenyl) ethyl propylene acid esters, 2-(p-cumyl-phenoxy group)-hexyl olefin(e) acid ester.
4. mildew-resistant semi-solid bonding system according to claim 1, is characterized in that: the structural formula of described vinyl monomer is
.
5. mildew-resistant semi-solid bonding system according to claim 1, it is characterized in that: monofunctional acrylates's ester monomer and nitrogenous vinyl monomer react form acrylic resin prepolymer time, the mol ratio of monofunctional acrylates's ester monomer and nitrogenous vinyl monomer is 1: 1.5.
6. mildew-resistant semi-solid bonding system according to claim 1, is characterized in that: the mass ratio of described ytterbium nitrate and graphene oxide is 1: 1.3.
7. mildew-resistant semi-solid bonding system according to claim 1, is characterized in that: described mildew-resistant semi-solid bonding system is obtained by the raw material of following weight part:
Acrylic resin prepolymer 100 parts
Active filler 9 ~ 13 parts
Polydimethylsiloxane 26 ~ 30 parts
Trimethylsiloxysilicates 6 ~ 8 parts
Sodium alginate 13 ~ 15 parts
Astaxanthin 2 ~ 5 parts
Lauryl alcohol sodium sulfovinate 8 ~ 10 parts
1,3-PD 18 ~ 24 parts
Phosphonous acid diethyl ester 4 ~ 7 parts.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111804A (en) * | 2015-09-15 | 2015-12-02 | 苏州凯欧曼新材料科技有限公司 | Magnetic paste-like compound system |
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2015
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| JPS6268833A (en) * | 1985-09-20 | 1987-03-28 | Showa Denko Kk | Polyethylene based composition and molded article thereof |
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| CN1699492A (en) * | 2005-07-11 | 2005-11-23 | 大连轻工业学院 | Photo-curable conductive adhesive and method for making same |
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| CN105111804A (en) * | 2015-09-15 | 2015-12-02 | 苏州凯欧曼新材料科技有限公司 | Magnetic paste-like compound system |
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Application publication date: 20150909 |