CN105199120A - Method for preparing basic magnesium sulfate whisker/natural latex composite latex film - Google Patents
Method for preparing basic magnesium sulfate whisker/natural latex composite latex film Download PDFInfo
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- CN105199120A CN105199120A CN201510576412.4A CN201510576412A CN105199120A CN 105199120 A CN105199120 A CN 105199120A CN 201510576412 A CN201510576412 A CN 201510576412A CN 105199120 A CN105199120 A CN 105199120A
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- magnesium sulfate
- crystal whisker
- sulfate crystal
- alkali magnesium
- latex
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Abstract
The invention discloses a method for preparing a basic magnesium sulfate whisker/natural latex composite latex film. The method comprises the following steps of performing surface treatment on a basic magnesium sulfate whisker: performing modification treatment on the basic magnesium sulfate whisker, and performing ultrasonic dispersion and emulsion grafting polymerization to prepare PMMA (polymethyl methacrylate)-basic magnesium sulfate whisker particles; blending PMMA-basic magnesium sulfate whisker dispersion obtained by ultrasonic dispersion and MMA (methyl methacrylate) modified natural latex by adopting an emulsion-blending wet process, and performing direct film laying to prepare the basic magnesium sulfate whisker/natural latex composite latex film. According to the method, high performance such as higher structural integrity, mechanical strength approximate to theoretical strength of interatomic valence bond force and far stronger than that of various granular fillers which are commonly used at present, high length-diameter ratio and high heat resistance and flame retardance of the basic magnesium sulfate whisker is utilized, so that the comprehensive performance of the composite latex film is enhanced, and the prepared basic magnesium sulfate whisker/natural latex composite latex film is high in performance.
Description
Technical field
The present invention relates to the preparation method of natural rubber latex composite latex film, particularly
oneplant the preparation method of alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
Background technology
Natural rubber latex has excellent over-all properties, and its wet gel strength is high, film forming properties good, be easy to sulfuration, and resulting product also has excellent characteristic, and higher intensity, longer elongation and less creep, therefore by widespread production medical material etc.But because other non-rubber component in environment and natural rubber latex are on the impact of latex product, cause the variability of the tear-resistant performance of latex product, wear resisting property, corrosion resistance nature etc. large, it is limited to some extent in application.Along with the high speed development of medical level now and to people to preventing AIDS, the consciousness of the Ebola virus of tuberculosis and outburst in the recent period improves constantly, the demand of the medical latex product such as latex examination gloves, medical gloves and condom sharply rises, also more and more higher to the requirement of its quality.Therefore the requirement not meeting social development just must improve the performance of Natural Rubber Latex Products, prepares low cost, high performance environmental type latex product.
Whisker is a kind of single crystal fibre material, because its crystalline structure is more complete, its physical strength is similar to the theoretical strength of valence link power between atom, considerably beyond the various particulate fillers of a large amount of use at present, simultaneously whisker has the large feature of length-to-diameter ratio, because of but a kind of filamentary material preparing fiber reinforced composite of good mechanical performance.The research team of the author once strengthened natural rubber latex compound cutan conducted a preliminary study calcium carbonate crystal whisker, four acicular type zinc oxide crystal whisker, achieved certain achievement.Calcium carbonate crystal whisker has suitable vast scale to be hydrolyzed due to surface carbon acid ion, particle surface is caused to become hydrophilic oleophobic because there is a large amount of hydroxyls, be difficult to dispersed in organic medium, and there is no bonding force between base-material, easily cause boundary defect, and when calcium carbonate particles is dry, surface hydroxyl interacts and forms hydrogen bond, rely on hydrogen bond action between particle and mutually assemble, thus forming the shortcoming of hard aggregation.Four acicular type zinc oxide crystal whisker is in machining process, and the space four needle-like crystalline structure of as easy as rolling off a log its distinctive uniqueness destroyed, causes its peculiar space four needle-like to have the premium properties brought can not give full play in glued membrane.Therefore research team's consideration alkali magnesium sulfate crystal whisker of the author replaces calcium carbonate crystal whisker, four acicular type zinc oxide crystal whisker to improve the performance of composite latex film.
Alkali magnesium sulfate crystal whisker is a kind of inexpensive, that whiteness is high micron order novel single crystal fibre shape strongthener, has very excellent physical and mechanical property.Compared with conventional mineral filler, have filling capacity strong, strongthener reprocessing cycle ability is strong, affects the characteristics such as little to latex film tone.Rely on the high strength of self, high-modulus and produce enhancement in system simultaneously, and be micron order, agglomeration is few, is easy to dispersion, thus likely in large quantities for improving the mechanical property of polymer composites.Meanwhile, alkali magnesium sulfate crystal whisker molecule, due to the existence of crystal water, makes it in the process of burning, dehydration reaction occur, and absorbs a large amount of heat energy thus the temperature of reduction matrix material.The water vapour generated can dilute flame-zone reaction gas concentration, can absorb smog again, thus plays effect that is fire-retardant and that eliminate smoke.But alkali magnesium sulfate crystal whisker surface hydrophilic oleophobic property, it is made to be difficult in organic medium dispersed, and bonding force is weak between matrix, easily cause boundary defect, cause natural rubber latex composite latex film not reach desirable performance, so surface modification must be carried out to magnesium sulfate crystal whisker, improve the wettability between organic base-material and bonding force, give full play to the effect of whisker, and then improve the performance of composite latex film.
The author once went to prepare calcium carbonate crystal whisker/natural rubber latex composite latex film and four acicular type zinc oxide crystal whisker/natural rubber latex composite latex film with traditional " emulsion blending " wet processing.Though than traditional dry process, the labor force of input and the energy reduce, and environmental protection more.But on operating procedure, there is a lot of unstable, the various Synergist S-421 95 dispersions that such as traditional " emulsion blending " wet processing need add.Synergist S-421 95 dispersion manufacture process bothers very much, and interpolation consumption is relative and latex amount is little, and its amount wayward, easily causes error large.Synergist S-421 95 is when blended with latex, and for temperature, the time, the requirement of the techniques such as stir speed (S.S.) is high, easily causes the reunion of latex.Technique can Synergist S-421 95 of a great variety, when formulation, also need to consider between often kind of Synergist S-421 95, Synergist S-421 95 and packing material, when Synergist S-421 95 is blended with latex, generation can chemical reaction thus cause latex reunion or degradation.The probing into of feasibility of Synergist S-421 95 formula gropes also to bring trouble to the experiment property grasped." emulsion blending " of the present invention wet processing is different from traditional wet processing, utilize similar dissolve mutually theory, by MMA in alkali magnesium sulfate crystal whisker grafting modified for silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane (AC_FAS), blended with the natural rubber latex of MMA modification, direct plastic film mulch obtains alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.This method is without the need to adding Synergist S-421 95 dispersion, workable, efficient simple than conventional wet of its technique.And so far, not yet have people to go filled natural latex to prepare composite latex film with MMA-whisker particle.
Summary of the invention
The object of the present invention is to provide a kind of method adopting " emulsion blending " wet processing to prepare high-performance alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
In order to reach above-mentioned purpose, solution of the present invention is:
Prepare a method for alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film, its step is as follows:
The first step, the surface treatment of alkali magnesium sulfate crystal whisker: stirred by the slip heating in water bath of alkali magnesium sulfate crystal whisker, adds the 10ml ethanol solution of 5% (per-cent relative to alkali magnesium sulfate crystal whisker quality) silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane gradually at 80 DEG C.Alkali magnesium sulfate crystal whisker filtered while hot after modification, filtration cakes torrefaction, obtains modification alkali magnesium sulfate crystal whisker product.Modified alkali magnesium sulfate crystal whisker, through ultrasonic disperse, obtains alkali magnesium sulfate crystal whisker dispersion liquid.In alkali magnesium sulfate crystal whisker dispersion liquid, add emulsifier sodium lauryl sulfate and initiator ammonium persulfate.When temperature reaches 75 DEG C, after within 10 seconds, the speed of one slowly instills methyl methacrylate MMA monomer, carry out emulsion grafting polymerization.Carry out suction filtration, washing after completion of the reaction, dry obtained polymetylmethacrylate-alkali magnesium sulfate crystal whisker particle.
Second step, the preparation of alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film: in natural rubber latex, intensification limit, limit adds initiator TBHP after stirring and adding MMA, oleic acid, continues to heat up to stir and adds activator TEPA, the natural rubber latex of PMMA in obtained grafting.By blended for the natural rubber latex of PMMA on the PMMA-alkali magnesium sulfate crystal whisker dispersion liquid that disperses through ultrasonic wave and grafting, under stirring at constant temperature water bath 40 DEG C, obtained compounded latex.The sheet glass with frame is poured into, drying and forming-film under room temperature after being filtered by compounded latex.Then dry after dried compound cutan drip washing, obtained alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
If directly added in natural rubber latex by PMMA-alkali magnesium sulfate crystal whisker particle, then PMMA-alkali magnesium sulfate crystal whisker particle then well can not disperse in natural rubber latex, poor stability, easily causes the reunion of latex.According to traditional technology, in PMMA-alkali magnesium sulfate crystal whisker particle/natural rubber latex system, add various Synergist S-421 95 dispersion allow whisker particle be able to good dispersion, improve the system stability of compounded latex.But Synergist S-421 95 dispersion manufacture process bothers very much, and interpolation consumption is relative and latex amount is little, and its amount wayward, easily causes error large.Synergist S-421 95 is when blended with latex, and for temperature, the time, the requirement of the techniques such as stir speed (S.S.) is high, easily causes the reunion of latex.Technique can Synergist S-421 95 of a great variety, when formulation, also need to consider between often kind of Synergist S-421 95, Synergist S-421 95 and packing material, when Synergist S-421 95 is blended with latex, generation can chemical reaction thus cause latex reunion or degradation.The probing into of feasibility of Synergist S-421 95 formula gropes also to bring trouble to the experiment property grasped." emulsion blending " of the present invention wet processing is compared with traditional wet processing, efficiently simple to operate, utilize similar dissolve mutually theory, by PMMA in natural rubber latex grafting, allow PMMA-alkali magnesium sulfate crystal whisker particle natural rubber latex of PMMA in grafting evenly better disperse, improve the stability of compounded latex system.
Described alkali magnesium sulfate crystal whisker, diameter D<1.0 μm, average length L: 20-40 μm, length-to-diameter ratio L/D>30, consumption is 1-8 part.
The concentrated natural latex of described natural rubber latex obtained by para ruber, total solid content is about 60%.
Described surface treatment agent is silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane (AC_FAS).
After adopting such scheme, key of the present invention is to carry out surface modification with silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane (AC_FAS) to alkali magnesium sulfate crystal whisker, adopt MMA emulsion by in-situ to be polymerized coated method again and carry out grafting to by modified alkali magnesium sulfate crystal whisker, obtain PMMA-alkali magnesium sulfate crystal whisker particle.Finally adopt the wet processing of " emulsion blending " by the PMMA-alkali magnesium sulfate crystal whisker dispersion liquid disperseed through ultrasonic wave and use the natural rubber latex of MMA modification blended, direct plastic film mulch obtains alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
The present invention not only as the strongthener of natural rubber latex composite latex film, can also can be used as a kind of heat-stable material and the halogen-free flame retardants of natural rubber latex composite latex film using alkali magnesium sulfate crystal whisker simultaneously, and its thermal stability and flame retardant properties are improved.Present method utilizes alkali magnesium sulfate crystal whisker crystalline structure more complete, its physical strength is similar to the theoretical strength of valence link power between atom, considerably beyond various particulate fillers conventional at present, and its length-to-diameter ratio is large, there is the premium propertiess such as good thermotolerance and flame retardant resistance, to strengthen the over-all properties of composite latex film, prepare high performance alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
Embodiment
The surface modification of alkali magnesium sulfate crystal whisker:
The alkali magnesium sulfate crystal whisker of 21.7g is added in the distilled water of 250ml, bath temperature 80 DEG C, stirring velocity is stir 50min under 800r/min, and adds the 10ml ethanol solution of 5% (per-cent relative to alkali magnesium sulfate crystal whisker quality) silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane (AC_FAS) gradually.Alkali magnesium sulfate crystal whisker filtered while hot after modification, filter cake, 85 DEG C of dryings 2 hours, obtains modification alkali magnesium sulfate crystal whisker product.Modified alkali magnesium sulfate crystal whisker, through ultrasonic disperse, obtains alkali magnesium sulfate crystal whisker dispersion liquid.In there-necked flask, add alkali magnesium sulfate crystal whisker dispersion liquid, after add emulsifier sodium lauryl sulfate and initiator ammonium persulfate.When temperature reaches 75 DEG C, after within 10 seconds, the speed of one slowly instills MMA monomer, carry out emulsion grafting polymerization.Carry out suction filtration, washing after completion of the reaction, at 85 DEG C, dry obtained PMMA-alkali magnesium sulfate crystal whisker particle.
The preparation of alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film:
In there-necked flask, add natural rubber latex, intensification limit, limit adds MMA, oleic acid limit adds initiator TBHP after stirring 135min, continues intensification stirring and reaches temperature 60 C, add activator TEPA, the natural rubber latex of PMMA in isothermal reaction obtained grafting in 3 hours.The wet processing of " emulsion blending ", by blended for the natural rubber latex of PMMA on the PMMA-alkali magnesium sulfate crystal whisker dispersion liquid that disperses through ultrasonic wave and grafting, stirs 24h constant temperature water bath 40 DEG C, obtained compounded latex.The sheet glass with frame is poured into, drying and forming-film under room temperature after being filtered by compounded latex.Then dry after dried compound cutan drip washing, obtained alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
The alkali magnesium sulfate crystal whisker that the present invention obtains/natural rubber latex composite latex film, has following unusual effect:
300% stress at definite elongation brings up to 1.44Mpa by 1.18Mpa,
Tensile strength brings up to 32.67Mpa by 22.35Mpa,
Tear strength brings up to 55.9KN/m by 37.69KN/m.
The composite emulsion membrane process using the method to prepare is simple, cost is low, has more wide application prospect.
Claims (4)
1. prepare a method for alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film, it is characterized in that step is as follows:
The first step, the surface treatment of alkali magnesium sulfate crystal whisker: stirred by the slip heating in water bath of alkali magnesium sulfate crystal whisker, adds the 10ml ethanol solution of the silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane relative to alkali magnesium sulfate crystal whisker quality 5% gradually at 80 DEG C; Alkali magnesium sulfate crystal whisker filtered while hot after modification, filtration cakes torrefaction, obtains modification alkali magnesium sulfate crystal whisker product; Modified alkali magnesium sulfate crystal whisker, through ultrasonic disperse, obtains alkali magnesium sulfate crystal whisker dispersion liquid; In alkali magnesium sulfate crystal whisker dispersion liquid, add emulsifier sodium lauryl sulfate and initiator ammonium persulfate; When temperature reaches 75 DEG C, after within 10 seconds, the speed of one slowly instills methyl methacrylate MMA monomer, carry out emulsion grafting polymerization; Carry out suction filtration, washing after completion of the reaction, dry obtained polymetylmethacrylate-alkali magnesium sulfate crystal whisker particle;
Second step, the preparation of alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film: in natural rubber latex, intensification limit, limit adds initiator TBHP after stirring and adding MMA, oleic acid, continues to heat up to stir and adds activator TEPA, the natural rubber latex of PMMA in obtained grafting; By blended for the natural rubber latex of PMMA on the PMMA-alkali magnesium sulfate crystal whisker dispersion liquid that disperses through ultrasonic wave and grafting, under stirring at constant temperature water bath 40 DEG C, obtained compounded latex; The sheet glass with frame is poured into, drying and forming-film under room temperature after being filtered by compounded latex; Then dry after dried compound cutan drip washing, obtained alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film.
2. a kind of method preparing alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film according to claim 1, it is characterized in that: described alkali magnesium sulfate crystal whisker, diameter D<1.0 μm, average length L: 20-40 μm, length-to-diameter ratio L/D>30, consumption is 1-8 part.
3. a kind of method preparing alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film according to claim 1, is characterized in that: the concentrated natural latex of described natural rubber latex obtained by para ruber, total solid content is about 60%.
4. a kind of method preparing alkali magnesium sulfate crystal whisker/natural rubber latex composite latex film according to claim 1, is characterized in that: described surface treatment agent is silane coupling agent 17 fluorine certain herbaceous plants with big flowers ethyl triethoxy silicane alkane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663283A (en) * | 2017-10-18 | 2018-02-06 | 龙岩学院 | The preparation method of beta-type silicon carbide whisker/Nano chitosan high intensity antibacterial latex film |
| CN107739449A (en) * | 2017-10-25 | 2018-02-27 | 龙岩学院 | The preparation method of alkali magnesium sulfate crystal whisker/military latex film of potassium titanate crystal whisker/carboxylic acrylonitrile butadiene rubber latex |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536012A (en) * | 2003-04-07 | 2004-10-13 | 上海日之升新技术发展有限公司 | Magnesium solt whisker rein forced fire-resisting polypropylene composition |
| CN101508787A (en) * | 2009-03-10 | 2009-08-19 | 沈阳理工大学 | Method for reinforcing PP material capability with alkali magnesium sulfate crystal whisker and product thereof |
| CN103613811A (en) * | 2013-11-27 | 2014-03-05 | 沈阳化工大学 | Method for preparing reinforced chloroprene rubber by using light-burned powder alkali type magnesium salt whisker |
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2015
- 2015-09-11 CN CN201510576412.4A patent/CN105199120B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536012A (en) * | 2003-04-07 | 2004-10-13 | 上海日之升新技术发展有限公司 | Magnesium solt whisker rein forced fire-resisting polypropylene composition |
| CN101508787A (en) * | 2009-03-10 | 2009-08-19 | 沈阳理工大学 | Method for reinforcing PP material capability with alkali magnesium sulfate crystal whisker and product thereof |
| CN103613811A (en) * | 2013-11-27 | 2014-03-05 | 沈阳化工大学 | Method for preparing reinforced chloroprene rubber by using light-burned powder alkali type magnesium salt whisker |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663283A (en) * | 2017-10-18 | 2018-02-06 | 龙岩学院 | The preparation method of beta-type silicon carbide whisker/Nano chitosan high intensity antibacterial latex film |
| CN107739449A (en) * | 2017-10-25 | 2018-02-27 | 龙岩学院 | The preparation method of alkali magnesium sulfate crystal whisker/military latex film of potassium titanate crystal whisker/carboxylic acrylonitrile butadiene rubber latex |
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