CN104987621A - Antibiosis aging-resistant polyvinyl chloride material and preparation method thereof - Google Patents
Antibiosis aging-resistant polyvinyl chloride material and preparation method thereof Download PDFInfo
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- CN104987621A CN104987621A CN201510413828.4A CN201510413828A CN104987621A CN 104987621 A CN104987621 A CN 104987621A CN 201510413828 A CN201510413828 A CN 201510413828A CN 104987621 A CN104987621 A CN 104987621A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides an antibiosis aging-resistant polyvinyl chloride material, of which a formula comprises raw materials in percentage by weight: 70-90 percent of polyvinyl chloride, 3-6 percent of plant source extract, 6-20 percent of nano loess, 0.7-2.5 percent of epoxy pomegranate seed oil, and 0.3-1.5 percent of octadecyl 2-hydroxyethyl amine oxide. The above raw materials are reasonably compounded through multiple machining means, synergistic interaction is realized, and the polyvinyl chloride material is endowed with multiple effects of natural antibiosis, mildew proofing, antioxidation, UV resistance, far infrared health care and the like, and a product prepared from the polyvinyl chloride material is wide in antibiotic spectrum, strong in bacteriostatic ability and durable in antibiosis effect. The aging resistance and mechanical properties are more excellent, and the material has no color change, deformation and cracking after being exposed for a long term in the sun, and is long in service life. Meanwhile, due to an infrared effect, actions of self cleaning, environment air purifying and peculiar smell eliminating are realized, the material is favorable for human health and environment-friendly and the application range of the polyvinyl chloride is greatly expanded.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically relate to a kind of antibiotic aging-resistant pvc material and preparation method thereof.
Background technology
The thermoplastic resin that polyvinyl chloride (PVC) is polymerized under the effect of initiator by vinylchlorid, be the homopolymer of chloroethene, ryuron and vinyl chloride copolymer are referred to as vinyl chloride resin.Because of its have nonflammable, chemical proofing is high, electrical insulation capability good, physical and chemical performance is stable, the advantage such as cheap, there is very consequence in the industrial production, be widely used in the fields such as industry, agricultural, traffic, building, telecommunications, household electrical appliance, furniture, packaging and health care.Also be applied to and the goods such as the tubing of human body close contact, infusion bag, oxygen mask, toy, footwear, pipeline, food product pack, film.But polyvinyl chloride is very sensitive for environment, especially fast light oxidative aging is poor, and many polrvinyl chloride products are easily aging when outdoor application, become fragile or efflorescence, even embrittlement, affect its use properties.Simultaneously because polyvinyl chloride does not have germ resistance, its goods are with after for some time, and surface can become dirty, grows the harmful microorganisms such as various bacterium, mould, fungi.Special more easily breeding when the objective condition such as temperature, humidity is suitable for spreads harmful microorganism, different people's contacts will cause cross infection, become bacterial contamination source and pathophoresis source, harm is brought to the healthy of people, limit the range of application of polyvinyl chloride to a certain extent.
Because above-mentioned factor, in recent years, lot of domestic and international scholar had been devoted to research and develop the polyvinyl chloride with antibacterial, achieved certain achievement.Through retrieval, the antiseptic-germicide at present for polyvinyl chloride is mainly divided into inorganic, organic and natural three major types by structure.Inorganic antiseptic adopts the metal ions such as silver, zinc, copper to be antiseptic-germicide, with porous, inorganic non-metallic material such as phosphoric acid salt, wilkinite, zeolites for carrier obtains, there is antimicrobial efficiency high, thermotolerance is strong, but easily oxidation stain and antibacterial ability is reduced and even lost efficacy, mechanical property significantly declines, and consumption is relatively large, cost is high, marketing difficulty.Organic antibacterial agent comprises quaternary ammonium salts, imidazoles, pyridines, organo-metallic class etc., although germ-killing efficiency is higher, addition is less, but poor heat resistance, easily separates out, and toxicity is larger, not only Durability of antimicrobial effect is short, and be absorbed by the body, can cause very large potential hazard to HUMAN HEALTH, practical value is not high.By comparison, natural antibacterial agent extracts from plant, animal or biology, its wide material sources, cost is low, there is safety non-toxic, antimicrobial efficiency is high, thermotolerance is good, colour stability is good, not easily produce resistance and advantages of environment protection, therefore its application and research is more and more subject to people's attention.But natural antibacterial agent normally extracts and forms from a kind of plant, animal or biology, and antimicrobial component is single, narrow antimicrobial spectrum, poor compatibility between itself and polyvinyl chloride, easy generation is reunited, is disperseed the problems such as uneven, and in use antimicrobial component is easily separated out, and antibacterial effect can not be lasting.In addition, existing antiseptic-germicide can not have antibiotic aging-resistant and nourishing function concurrently simultaneously, in order to reach the ageing-resistant index needed for polrvinyl chloride product, usually adopts the method for blending and modifying in polyethylene, to add oxidation inhibitor to improve its ageing-resistant performance.But known oxidation inhibitor mostly is the micromolecular compound of certain toxicity, has under sunlight, oxygen and heat effect gradually to the trend that polrvinyl chloride product surface is separated out, exist and easily lost efficacy and hygienic safety hidden danger.
Therefore, work out one and possess that natural antibacterial is ageing-resistant simultaneously, health care and mechanical property, and effect is lasting, the pvc material of long service life seems particularly important.
Summary of the invention
Object of the present invention is just to provide a kind of nano-loess load Extracts from Plant Recourses and is evenly distributed in PVC base system antibiotic aging-resistant pvc material making various bioactivators synergy and preparation method thereof as antiseptic-germicide, to solve prior art Problems existing.
To achieve these goals, the present invention is achieved by the following technical solutions: the ageing-resistant pvc material of a kind of natural antibacterial, by weight percentage, its composition of raw materials consists of: polyvinyl chloride 70 ~ 90%, Extracts from Plant Recourses 3 ~ 6%, nano-loess 6 ~ 20%, epoxy granada seed oil 0.7 ~ 2.5%, octadecyl dihydroxy ethyl amine oxide 0.3 ~ 1.5%; Described Extracts from Plant Recourses be by the emblic cotyledon of weight percentage 25 ~ 35%, 35 ~ 55% Leaf of Betel Pepper and 20 ~ 30% Malus doumeri Leaf extract obtained, its preparation method comprises the following steps:
1. Extracts from Plant Recourses is prepared: take fresh by formula, without the emblic cotyledon rotted, Leaf of Betel Pepper, Malus doumeri Leaf impurity elimination respectively, clean, dry, mixing, be ground into 50 ~ 80 order fragments, put into refiner, add the water being equivalent to fragment weight 6 ~ 15 times, homogenate, squeezing, obtain pressed liquor and press residue, press residue is with 40 ~ 75 DEG C of hot water extraction 2 times, each 1 ~ 3h, merge 2 vat liquors to mix with pressed liquor, whizzer is adopted to carry out solid-liquid separation, collect filtrate and cross D101 macroporous adsorptive resins, first wash with water, discard water lotion, be the ethanolic soln wash-out of 35 ~ 70wt% again by concentration, collect alcohol eluen, concentrating under reduced pressure, spraying dry, obtain Extracts from Plant Recourses,
2. nano-loess is prepared: the loess powder gathering certainweight is broken to particle diameter≤100 order, adding the concentration being equivalent to loess weight 6 ~ 12 times is the sulphuric acid soln of 0.5 ~ 30wt%, control reacting liquid pH value between 4.5 ~ 6, stirring reaction 30 ~ 60min at 80 ~ 90 DEG C, cool the temperature to 50 ~ 65 DEG C, adding the concentration accounting for loess weight 0.3 ~ 5% is again the formaldehyde solution of 10 ~ 45wt%, stirring reaction 1 ~ 3h, and filtration, filter cake deionized water wash are checked without SO to bariumchloride
4 2-, bake at 150 ~ 200 DEG C to water content≤1.5%, be milled to particle diameter 1200 ~ 2500 order with ceramic bead grinding machine, obtain the nano-loess of white;
3. prepare epoxy granada seed oil: gather full, without the Semen Granati of going mouldy, dry, pulverize, pass through supercritical CO
2the method of extracting obtains granada seed oil and drops in reactor, add 732 resins accounting for granada seed oil weight 0.3% ~ 15%, be heated to 35 ~ 50 DEG C, being added dropwise to the concentration accounting for granada seed oil weight 0.5 ~ 1.2 times is while stirring the hydrogen peroxide of 30 ~ 60wt%, after dropwising, be warmed up to 60 ~ 70 DEG C, stirring reaction 30 ~ 50min, is washed till neutrality with deionized water, removes water layer after leaving standstill, underpressure distillation, obtains epoxy granada seed oil;
4. take nano-loess by formula, add deionized water with the solid-liquid weight ratio of 1: 6 ~ 25, then add the polyvinylpyrrolidone accounting for nano-loess weight 3 ~ 5%, at 70 ~ 85 DEG C, stir 0.5 ~ 3h, form stable and uniform colloidal solution; Then the Extracts from Plant Recourses by formula ratio is dissolved in deionized water, solid-liquid weight ratio is made to be 1: 3, add in above-mentioned colloidal solution after the octadecyl dihydroxy ethyl amine oxide adding formula ratio is again uniformly mixed, be heated to 65 ~ 80 DEG C, stir 1 ~ 3h, centrifugal, the vacuum-drying at 95 DEG C of gained solids, pulverize, obtain plant-sourced/loess complex antimicrobials;
5. take epoxy granada seed oil by formula, adding triphenylphosphate and controlling its weight ratio is 1: 0.7, is stirred to fully fusing and mixes, obtain Preblend at 60 ~ 75 DEG C;
6. polyvinyl chloride is taken by formula, send in high-speed mixer, add step Preblend 5. to mix, add step plant-sourced 4./loess complex antimicrobials again, at 80 ~ 95 DEG C, mixing 1 ~ 5min under 350 ~ 500r/min, send into cooling mixing machine, at 30 ~ 50 DEG C, mixing 3 ~ 10min under 80 ~ 150r/min, send into twin screw extruder melt blending extruding pelletization, processing temperature is 100 ~ 150 DEG C, obtains antibiotic aging-resistant pvc material.
Formula given by aforesaid method ensures that the present invention produces the basic recipe of desired effect, it is technological core of the present invention, but in actual applications, completely can on the basis of the present invention's formula, coupling agent, softening agent, compatilizer, tinting material etc. are added according to various needs, these all belong to general knowledge well known in the art, as long as and control suitably, also to have a negative impact to the present invention.
Polyvinyl chloride in above-mentioned raw materials formula can adopt various polyvinyl chloride of the prior art, as universal polyvinyl chloride (PVC) RESINS, polychloroethylene with high polymerization degree resin, crosslinked pvc resin etc.
Emblic cotyledon in above-mentioned raw materials formula is the leaf of Euphorbiaceae (Euphorbiaceae) Leafflower defoliation small arbor phyllanthus emblica (phyllanthus emblica L), sweet, the micro-hardship of its taste, cool in nature; Have clearing heat and detoxicating, inducing diuresis and reducing edema, effect of clearing damp diuresis.Be rich in the chemical compositions such as flavones, Anthraquinones, Polyphenols, tonka bean camphor, triterpenes, alkaloid, steroidal, tannin, gallic acid, lactones, cardiac glycoside, there is antimicrobial antiphlogistic, antitumor, anti-oxidant isoreactivity [Zhong Yining, " research of emblic cotyledon active chemical and antitumor action thereof " Chengdu University of Traditional Chinese Medicine 2006 grades of doctor's Diplomarbeit].Pharmacological research shows, Extracts from Leaves of Phyllanthus emblica L all has restraining effect [Zhong Zhenguo etc., " research of Extracts from Leaves of Phyllanthus emblica L Antimicrobial test " " Chinese medicinal materials " the 3rd phase in 2008] to intestinal bacteria, streptococcus aureus sensitive strain, staphylococcus aureus resistance strain, Candida albicans, Salmonella typhi, klebsiella pneumoniae, alpha streptococcus, beta streptococcus.
Above-mentioned raw materials formula Zhong Leaf of Betel Pepper, also known as betel, Betel leaf etc., for the leaf of piperaceae Zhi Wu Betel sauce, its compound structure type comprises aldehyde, acid, ester, phenol, alkene, aromatic hydrocarbon and (ring) alkane, main containing 2-methoxyl group-5-tolyl aldehyde, chavicol acetic ester, isoeugenol, chavicol, γ-cadinene, Eugenol, the volatile components such as acetyl isoeugenol and multiple total free aminoacids, xitix, oxysuccinic acid, oxalic acid, glucose, fructose, maltose, glucuronic acid and calcium, iron, zinc, manganese, the trace elements such as strontium, there are stronger anti-oxidant activity and good health value [Yin Zhenhua etc., " HS-SPME-GC-MS Fen Xi Leaf of Betel Pepper volatile component " " research and development of natural products " 10 phases in 2012].Modern pharmacology research shows, Piper betel extract has stronger anti-oxidant activity, inhibitory or killing effect [Liang Hui etc., " the anti-oxidant and bacteriostatic activity of Piper betel extract is studied " " Yunnan traditional Chinese medicine magazine " 2011 (5): 57] is all had to gamboge coccus, intestinal bacteria, proteus vulgaris, streptococcus aureus, Pseudomonas aeruginosa, Buddhist Shigella flexneri.
Malus doumeri Leaf in above-mentioned raw materials formula is the leaf of rosaceous plant Chinese pear-leaved crabapple Malus asiaticaNakai, be rich in the trace elements such as organic acid, flavonoid, Polyphenols, tannin class, terpene, steroid, saponins, vitamins C, vitamin-E, amino acid and selenium, zinc, fluorine, copper, iron, there is antibacterial, anti-oxidant, antitumor, anti-ageing multiple efficacies of waiting for a long time preferably.The master thesis that Lu Jing delivers compares systematic research to the chemical composition of Malus doumeri Leaf and physiologically active, result display extraction and isolation from Malus doumeri Leaf obtains β-sitosterol, daucosterol, Oleanolic Acid, ursolic acid, chrysin, phlorizin, the compounds such as trifloroside, to streptococcus aureus, intestinal bacteria, Bacillus subtilus, aspergillus niger, Mucor, rhodotorula and cereuisiae fermentum all have restraining effect, and Scavenging activity the strongest [" separation of Malus doumeri Leaf chemical composition and the antibacterial of extract thereof to DPPH free radical, anti-oxidant activity is studied " " University Of Chongqing " 2014 grades of master thesis].
From published bibliographical information, although it is more ripe to have antibacterial, anti-oxidant research to the biologically active substance of emblic cotyledon, Leaf of Betel Pepper, Malus doumeri Leaf both at home and abroad, but using the biologically active substance of emblic cotyledon, Leaf of Betel Pepper, Malus doumeri Leaf by its formula rate of appropriate variable and nano-loess compound as antiseptic-germicide add in polyvinyl chloride there is the ageing-resistant and nourishing function of natural antibacterial while promote the report that mechanical property yet there are no correlative study at home and abroad, also have no suitability for industrialized production.
The present invention is by emblic cotyledon, Leaf of Betel Pepper, the composite use of Malus doumeri Leaf three kind of plant source extract, effect is complementary, can the advantage of each biologically active substance be played to greatest extent and its inferior position is reduced to minimum level, compound is carried out on this basis with nano-loess, make various bioactivators synergy and play antibiotic aging-resistant mechanism better, not give only some new characteristics of antimicrobial component, have also obtained uvioresistant, radical-scavenging activity and health-care effect.Well compensate for the deficiency that natural antibacterial agent composition is single, narrow antimicrobial spectrum, antibacterial ability are weak, for polyvinyl chloride have the ageing-resistant and nourishing function of natural antibacterial concurrently while promote mechanical property and propose new method.Those skilled in the art can not determine this component and proportioning easily according to prior art, can not expect and embody creativeness of the present invention by the technique effect that Extracts from Plant Recourses in the present invention and nano-loess act synergistically and bring.
Epoxy granada seed oil in above-mentioned raw materials formula, it is the vegetables oil extracted from Punicaceae plant pomegranate seeds, containing lipid acid, Mierocrystalline cellulose, crude protein, total reducing sugar, Stigmasterol, volatile oil, flavones, osajin, phenols, steroid etc., wherein fatty acid content enriches, mainly contain palmitinic acid, linolic acid, oleic acid, stearic acid, Trichosanoic acid eicosenoic acid, eicosanoic acid and Trichosanoic acid three alkene isomer, there is anticancer change, antiviral, anti-oxidant, [the beautiful Chinese mugwort of A Yigu is closed wheat and carries for the effects such as reducing blood-fat and stronger Antioxidation in vitro, the extraction of granada seed oil and the research northwest pharmaceutical journal of Antioxidation in vitro the 1st phase in 2011 thereof].
Nano-loess in above-mentioned raw materials formula is natural loess modified product, and Natural Resources in China is enriched, reserves the first in the world.Various places loess composition transfer is little, and it is primarily of detrital mineral, clay mineral and carbonate minerals composition, and quartz, feldspar and the mica group content in detrital mineral accounts for 80% of detrital mineral, with a small amount of hornblende, pistacite, chlorite, magnetite etc.; Clay mineral comprises illite, montmorillonite, kaolinite, pyrrhosiderite etc.Chemical composition is with SiO
2preponderating, is secondly Al
2o
3, CaO, be Fe again
2o
3, MgO, K
2o, Na
2o, FeO, TiO
2, MnO and organic impurity etc., due to the existence of these organic impuritys, loess color is usually in light yellow, lark or tawny etc., but because of the microvoid structure of its uniqueness, specific surface area is large, bulk density is little, the characteristics such as pore volume is large, not only there is exquisiteness, loose, light weight, porous, water-absorbent strong and the physical property of Heat stability is good, also there is good adsorptive power and larger cation exchange capacity [Sha Aimin etc., " composition of opinion loess cation exchange capacity and character " " Xian Institute of Highway journal " the 4th phase in 1994].Detected by modern science and technology, containing catalase, diphenol oxidase, multitudinous carbohydrase, Guang enzyme isoreactivity material in loess, there is effect of purification, removing toxic substances, can not only the perching of anti-bacteria, mould etc., and can also be releasing far infrared and cut off electromagnetic radiation.Record in supplement to the Herbal, loess and human body have good consistency, can be used as medicine.Decoct water treatment children's scaring, poisoning proved recipe at useful loess for a long time among the people, also can cure burn, have directly and the effect of indirect treatment the many diseases of thread.It has been applied to environmental protection, building materials, makeup and medicine and other fields, but nano-loess load Extracts from Plant Recourses is added in PVC base system the correlative study of preparing antibiotic aging-resistant pvc material as antiseptic-germicide has no report.
The present inventor utilizes the specific surface area of loess large just, multi-cellular structure and good adsorptivity, the feature such as thermostability and dispersion suspension, played the high-affinity between loess and Extracts from Plant Recourses simultaneously, by octadecyl dihydroxy ethyl amine oxide and positively charged ion, nonionic, zwitter-ion has the feature of good compatibleness, co-induction Extracts from Plant Recourses is worked in coordination with and is expanded the interlayer structure of loess, thus make Extracts from Plant Recourses more easily be intercalation among the interlayer structure of loess, form nano level plant-sourced/loess complex antimicrobials, this complex antimicrobials and epoxy granada seed oil, polyvinyl chloride under melting condition with common intercalated form, plant-sourced/loess complex antimicrobials is made to be dispersed in PVC base system, obtain antibiotic aging-resistant pvc material.Contriver is surprised to find that, has good synergistic effect between epoxy granada seed oil and triphenylphosphate by thermal treatment, not only increases antibiotic aging-resistant ability and the health-care effect of pvc material.And make wetting ability loess lamella be dispersed in PVC base system with nano-grade size, produce good interfacial bond property, effectively reduce internal friction between polyvinyl chloride molecular chain, prevent the possibility that it is reunited.Improve melting rate and the melt deformability of polyvinyl chloride, reduce melt viscosity and improve plasticizing capacity, its surface tissue changes, and mechanical property and processing characteristics are promoted simultaneously.Efficiently solve natural antibacterial agent in PVC base system median surface incompatible, easy generation reunite and disperse uneven problem.
The present inventor unexpectedly finds, SiO in loess
2content is high, and in the loess micropore after acidifying, acidity increases, and loses water of constitution through baking, in removing micropore, impurity is comparatively thorough, produces a large amount of spaces, changes the crystalline structure of inorganic impurity simultaneously and activate, strengthen the ability of impurity with acid-respons itself, obtain the SiO that purity is high, porous grain is thin
2, its surface and internal surface of hole are distributed with a large amount of silicone hydroxyl (-Si-OH), and these silicone hydroxyl in aqueous dissociation go out H
+, surface exhibits goes out certain electronegativity, is a kind of excellent chelation group, nucleophilic reaction group.And octadecyl dihydroxy ethyl amine oxide is a kind of amphoterics, can dissolve each other to greatest extent with stone extracts, and by the generation synergistic function that attracts each other, both obtain the electric charge needed while working in coordination with and expanding the interlayer structure of nano-loess, thus Extracts from Plant Recourses is incorporated between loess formation, the as easy as rolling off a log inside penetrating into loess lamella, make Extracts from Plant Recourses be carried on the homogeneity of nano-loess and stability significantly improves, show the collaborative antibiotic aging-resistant ability that is added and health-care effect.The antimicrobial component well overcoming existing natural antibacterial agent is single, and narrow antimicrobial spectrum is easily separated out, the unendurable defect of antibacterial effect.Its mechanism is, when Extracts from Plant Recourses spreads in PVC base system, due to polyvinyl chloride, nano-loess, Extracts from Plant Recourses, epoxy granada seed oil, the performance of octadecyl dihydroxy ethyl amine oxide is carried out combination and is formed a kind of limited system, the Extracts from Plant Recourses inserted in this system is made to be bound between the lamella of loess, the rotation of molecule, the motion of translation and segment is all subject to very large constraint, Extracts from Plant Recourses cannot be spread by straight line, define effective physical barriers, cause Extracts from Plant Recourses precipitation rate pining down and slow down precipitation rate by loess lamella, extend antibiotic aging-resistant timeliness, when the Extracts from Plant Recourses concentration on polrvinyl chloride product surface reduces, can by the mutually continuous migration certainly to surface of PVC base system, thus the continuous dynamic embellishment realized dynamic interface, control Extracts from Plant Recourses precipitation rate.And because Activities of Some Plants source extract is supported on loess inside, therefore after the Extracts from Plant Recourses on loess surface is separated out, the Extracts from Plant Recourses of its inside can be separated out continuously under the effect of concentration gradient, reaches good slow release effect.Goods still can keep good antibiotic aging-resistant, health care and mechanical property after using the long period.
The present invention is by the processing means of the raw materials such as polyvinyl chloride, loess, emblic cotyledon, Leaf of Betel Pepper, Malus doumeri Leaf, Semen Granati, octadecyl dihydroxy ethyl amine oxide by number of ways, rationally composite, synergy, obtain a kind of pvc material having natural antibacterial, mildew-resistant, anti-oxidant, uvioresistant and far infrared health care concurrently, for the manufacture of polrvinyl chloride product, not only has a broad antifungal spectrum, bacteriostasis are strong for they, do not produce resistance, not easily separate out, durable antibacterial effect.And there is excellent ageing-resistant and mechanical energy, long-term exposure in the sunlight, nondiscoloration, indeformable, not embrittlement, long service life.Meanwhile, far-infrared radiation effect also can play self-cleaning, cleaning ambient air, eliminates the effect of peculiar smell, is beneficial to HUMAN HEALTH and environmental friendliness.And complex antimicrobials raw material of the present invention is taken from natural, Environmental Safety, with low cost.
Pvc material of the present invention may be used for the polrvinyl chloride product of any routine, for example prepare food product pack, container, pipeline, toy, basketball, gloves, footwear, tubing, infusion bag, oxygen mask, film etc., greatly extend the range of application of polyvinyl chloride material, contain huge society, ecology and economic benefit.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.But these embodiments are only limitted to illustrate that the present invention and being not used in limits the scope of the invention.
Embodiment one
1. raw material prepares:
1. Extracts from Plant Recourses is prepared: take fresh, without the emblic cotyledon 30kg rotted, Leaf of Betel Pepper 45kg, Malus doumeri Leaf 25kg impurity elimination respectively, clean, dry, mixing, be ground into 60 order fragments, put into refiner, add the water being equivalent to fragment weight 10 times, homogenate, squeezing, obtain pressed liquor and press residue, press residue is with 60 DEG C of hot water extraction 2 times, each 1.5h, merge 2 vat liquors to mix with pressed liquor, whizzer is adopted to carry out solid-liquid separation, collect filtrate and cross D101 macroporous adsorptive resins, first wash with water, discard water lotion, be the ethanolic soln wash-out of 50wt% again by concentration, collect alcohol eluen, concentrating under reduced pressure, spraying dry, obtain Extracts from Plant Recourses,
2. nano-loess is prepared: the loess powder gathering certainweight is broken to particle diameter≤100 order, adding the concentration being equivalent to loess weight 7 times is the sulphuric acid soln of 0.5 ~ 30wt%, controlling reacting liquid pH value is 5, stirring reaction 50min at 80 DEG C, cool the temperature to 50 DEG C, adding the concentration accounting for loess weight 1.2% is again the formaldehyde solution of 20wt%, stirring reaction 2h, and filtration, filter cake deionized water wash are checked without SO to bariumchloride
4 2-, bake at 150 DEG C to water content≤1.5%, be milled to particle diameter 2000 order with ceramic bead grinding machine, obtain the nano-loess of white;
3. prepare epoxy granada seed oil: gather full, without the Semen Granati of going mouldy, dry, pulverize, pass through supercritical CO
2the method of extracting obtains granada seed oil and drops in reactor, add 732 resins accounting for granada seed oil weight 3.5%, be heated to 40 DEG C, being added dropwise to the concentration accounting for granada seed oil weight 0.8 times is while stirring the hydrogen peroxide of 50wt%, after dropwising, be warmed up to 65 DEG C, stirring reaction 20min, is washed till neutrality with deionized water, removes water layer after leaving standstill, underpressure distillation, obtains epoxy granada seed oil;
2. composition of raw materials:
Polychloroethylene with high polymerization degree resin 78.6kg, Extracts from Plant Recourses 3.5kg, nano-loess 16kg, epoxy granada seed oil 1.2kg, octadecyl dihydroxy ethyl amine oxide 0.7kg.
3. preparation process:
1. take nano-loess 16kg, add deionized water 240kg, add polyvinylpyrrolidone 0.56kg, at 75 DEG C, stir 1.5h, form stable and uniform colloidal solution;
2. taking Extracts from Plant Recourses 3.5kg is dissolved in 10.5kg deionized water, adding after octadecyl dihydroxy ethyl amine oxide 0.7kg is uniformly mixed adds in step colloidal solution 1. again, be heated to 75 DEG C, stir 2h, centrifugal, the vacuum-drying at 95 DEG C of gained solids, pulverizes, obtains plant-sourced/loess complex antimicrobials;
3. take epoxy granada seed oil 1.2kg, add triphenylphosphate 0.84kg, at 70 DEG C, be stirred to fully fusing and mix, obtaining Preblend;
4. polychloroethylene with high polymerization degree resin 78.6kg is taken, send in high-speed mixer, add step Preblend 3. to mix, add step plant-sourced 2./loess complex antimicrobials again, 90 DEG C, mix 3min under 450r/min, send into cooling mixing machine, 35 DEG C, mix 5min under 120r/min, send into twin screw extruder melt blending extruding pelletization, processing temperature is 100 ~ 150 DEG C, obtains antibiotic aging-resistant pvc material.
Embodiment two
1. raw material prepares:
1. Extracts from Plant Recourses is prepared: take fresh, without the emblic cotyledon 25kg rotted, Leaf of Betel Pepper 55kg, Malus doumeri Leaf 20kg impurity elimination respectively, clean, dry, mixing, be ground into 80 order fragments, put into refiner, add the water being equivalent to fragment weight 12 times, homogenate, squeezing, obtain pressed liquor and press residue, press residue is with 70 DEG C of hot water extraction 2 times, each 2h, merge 2 vat liquors to mix with pressed liquor, whizzer is adopted to carry out solid-liquid separation, collect filtrate and cross D101 macroporous adsorptive resins, first wash with water, discard water lotion, be the ethanolic soln wash-out of 60wt% again by concentration, collect alcohol eluen, concentrating under reduced pressure, spraying dry, obtain Extracts from Plant Recourses,
2. nano-loess is prepared: the loess powder gathering certainweight is broken to particle diameter≤100 order, adding the concentration being equivalent to loess weight 10 times is the sulphuric acid soln of 0.5 ~ 30wt%, controlling reacting liquid pH value is 4.5, stirring reaction 30min at 90 DEG C, cool the temperature to 60 DEG C, adding the concentration accounting for loess weight 2.5% is again the formaldehyde solution of 10wt%, stirring reaction 3h, and filtration, filter cake deionized water wash are checked without SO to bariumchloride
4 2-, bake at 180 DEG C to water content≤1.5%, be milled to particle diameter 1500 order with ceramic bead grinding machine, obtain the nano-loess of white;
3. prepare epoxy granada seed oil: gather full, without the Semen Granati of going mouldy, dry, pulverize, pass through supercritical CO
2the method of extracting obtains granada seed oil and drops in reactor, add 732 resins accounting for granada seed oil weight 0.3% ~ 15%, be heated to 35 ~ 50 DEG C, being added dropwise to the concentration accounting for granada seed oil weight 0.5 ~ 1.2 times is while stirring the hydrogen peroxide of 30 ~ 60wt%, after dropwising, be warmed up to 60 ~ 70 DEG C, stirring reaction 30min, is washed till neutrality with deionized water, removes water layer after leaving standstill, underpressure distillation, obtains epoxy granada seed oil;
2. composition of raw materials:
Crosslinked pvc resin 75kg, Extracts from Plant Recourses 4.5kg, nano-loess 18kg, epoxy granada seed oil 1.6kg, octadecyl dihydroxy ethyl amine oxide 0.9kg.
3. preparation process:
1. take nano-loess 18kg, add deionized water 324kg, add polyvinylpyrrolidone 0.72kg, at 75 DEG C, stir 2h, form stable and uniform colloidal solution;
2. taking Extracts from Plant Recourses 4.5kg is dissolved in 13.5kg deionized water, adding after octadecyl dihydroxy ethyl amine oxide 0.9kg is uniformly mixed adds in step colloidal solution 1. again, be heated to 65 DEG C, stir 3h, centrifugal, the vacuum-drying at 95 DEG C of gained solids, pulverizes, obtains plant-sourced/loess complex antimicrobials;
3. take epoxy granada seed oil 1.6kg, add triphenylphosphate 1.12kg, at 75 DEG C, be stirred to fully fusing and mix, obtaining Preblend;
4. crosslinked pvc resin 75kg is taken, send in high-speed mixer, add step Preblend 3. to mix, add step plant-sourced 2./loess complex antimicrobials again, 85 DEG C, mix 5min under 350r/min, send into cooling mixing machine, 50 DEG C, mix 8min under 100r/min, send into twin screw extruder melt blending extruding pelletization, processing temperature is 100 ~ 150 DEG C, obtains antibiotic aging-resistant pvc material.
Claims (1)
1. an antibiotic aging-resistant pvc material, it is characterized in that, by weight percentage, its composition of raw materials consists of: polyvinyl chloride 70 ~ 90%, Extracts from Plant Recourses 3 ~ 6%, nano-loess 6 ~ 20%, epoxy granada seed oil 0.7 ~ 2.5%, octadecyl dihydroxy ethyl amine oxide 0.3 ~ 1.5%; Described Extracts from Plant Recourses be by the emblic cotyledon of weight percentage 25 ~ 35%, 35 ~ 55% Leaf of Betel Pepper and 20 ~ 30% Malus doumeri Leaf extract obtained, its preparation method comprises the following steps:
1. Extracts from Plant Recourses is prepared: take fresh by formula, without the emblic cotyledon rotted, Leaf of Betel Pepper, Malus doumeri Leaf impurity elimination respectively, clean, dry, mixing, be ground into 50 ~ 80 order fragments, put into refiner, add the water being equivalent to fragment weight 6 ~ 15 times, homogenate, squeezing, obtain pressed liquor and press residue, press residue is with 40 ~ 75 DEG C of hot water extraction 2 times, each 1 ~ 3h, merge 2 vat liquors to mix with pressed liquor, whizzer is adopted to carry out solid-liquid separation, collect filtrate and cross D101 macroporous adsorptive resins, first wash with water, discard water lotion, be the ethanolic soln wash-out of 35 ~ 70wt% again by concentration, collect alcohol eluen, concentrating under reduced pressure, spraying dry, obtain Extracts from Plant Recourses,
2. nano-loess is prepared: the loess powder gathering certainweight is broken to particle diameter≤100 order, adding the concentration being equivalent to loess weight 6 ~ 12 times is the sulphuric acid soln of 0.5 ~ 30wt%, control reacting liquid pH value between 4.5 ~ 6, stirring reaction 30 ~ 60min at 80 ~ 90 DEG C, cool the temperature to 50 ~ 65 DEG C, adding the concentration accounting for loess weight 0.3 ~ 5% is again the formaldehyde solution of 10 ~ 45wt%, stirring reaction 1 ~ 3h, and filtration, filter cake deionized water wash are checked without SO to bariumchloride
4 2-, bake at 150 ~ 200 DEG C to water content≤1.5%, be milled to particle diameter 1200 ~ 2500 order with ceramic bead grinding machine, obtain the nano-loess of white;
3. prepare epoxy granada seed oil: gather full, without the Semen Granati of going mouldy, dry, pulverize, pass through supercritical CO
2the method of extracting obtains granada seed oil and drops in reactor, add 732 resins accounting for granada seed oil weight 0.3% ~ 15%, be heated to 35 ~ 50 DEG C, being added dropwise to the concentration accounting for granada seed oil weight 0.5 ~ 1.2 times is while stirring the hydrogen peroxide of 30 ~ 60wt%, after dropwising, be warmed up to 60 ~ 70 DEG C, stirring reaction 30 ~ 50min, is washed till neutrality with deionized water, removes water layer after leaving standstill, underpressure distillation, obtains epoxy granada seed oil;
4. take nano-loess by formula, add deionized water with the solid-liquid weight ratio of 1: 6 ~ 25, then add the polyvinylpyrrolidone accounting for nano-loess weight 3 ~ 5%, at 70 ~ 85 DEG C, stir 0.5 ~ 3h, form stable and uniform colloidal solution; Then the Extracts from Plant Recourses by formula ratio is dissolved in deionized water, solid-liquid weight ratio is made to be 1: 3, add in above-mentioned colloidal solution after the octadecyl dihydroxy ethyl amine oxide adding formula ratio is again uniformly mixed, be heated to 65 ~ 80 DEG C, stir 1 ~ 3h, centrifugal, the vacuum-drying at 95 DEG C of gained solids, pulverize, obtain plant-sourced/loess complex antimicrobials;
5. take epoxy granada seed oil by formula, adding triphenylphosphate and controlling its weight ratio is 1: 0.7, is stirred to fully fusing and mixes, obtain Preblend at 60 ~ 75 DEG C;
6. polyvinyl chloride is taken by formula, send in high-speed mixer, add step Preblend 5. to mix, add step plant-sourced 4./loess complex antimicrobials again, at 80 ~ 95 DEG C, mixing 1 ~ 5min under 350 ~ 500r/min, send into cooling mixing machine, at 30 ~ 50 DEG C, mixing 3 ~ 10min under 80 ~ 150r/min, send into twin screw extruder melt blending extruding pelletization, processing temperature is 100 ~ 150 DEG C, obtains antibiotic aging-resistant pvc material.
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| CN105331005A (en) * | 2015-11-13 | 2016-02-17 | 吴江市风尚鞋厂 | Antibacterial and stretch-proof PVC shoe sole material and preparation method thereof |
| CN106675240A (en) * | 2016-12-14 | 2017-05-17 | 刘兴旺 | Environment-friendly metal protective coating |
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