CN102153794A - Method for preparing polymer/clay nano-composite - Google Patents
Method for preparing polymer/clay nano-composite Download PDFInfo
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Abstract
The invention relates to a method for preparing polymer/clay nano-composite by using epoxidized natural rubber latex as compatilizer of clay and a polymer. On the one hand, an epoxidized natural rubber molecular chain is inserted between clay layers to be subjected to chemical reaction with the clay layers, and the on the other hand, unsaturated double bonds in epoxidized natural rubber and the matrix polymer can be subjected to crosslinking reaction. The effect of dispersing the clay in the matrix polymer can be improved and the interaction between the clay and the matrix polymer can be enhanced by using the bridging function of the epoxidized natural rubber latex, and the high-performance polymer/clay nano-composite is prepared. The prepared polymer/clay nano-composite has excellent physical and mechanical properties and greatly improved dynamic mechanical properties.
Description
Technical field
The present invention relates to the preparation method of polymer based nanocomposites.Specifically, the present invention relates to a kind of nanometer lamella and be dispersed in method in the polymkeric substance clay.
Background technology
Traditional strengthening agent has carbon black, white carbon black and lime carbonate etc. in the polymkeric substance, and carbon black occupies dominant position always in rubber industry.Wherein the size of the primary partical of carbon black and white carbon black is very little, composite materials property excellence prepared therefrom.Yet also there are many important disadvantages in they, and are big as processing pollution; Long processing time, mixing energy consumption is big; High level carbon black generally has better synthesis reinforcement ability than white carbon black, thereby more is usually used in rubber industry, but the black of goods can't change; The two is all difficult gives rubber item higher hardness, better the saturating performance of gasproof etc.; To the dependency of tar and oil, the sooty resource scarcity, price rises.White carbon black can not replace carbon black fully, and price is more expensive, and as using the silane coupling agent surface treatment, price is higher.Though lime carbonate is cheap, be difficult for giving birth to heat, poor to the strengthening action of rubber, reduce cost through being often used as extender.Therefore, the development trend of novel strengthening agent is to have good processing properties and better synthesis reinforcement ability, preferably light filler, and price is low.And clay has caused people's extensive attention as a kind of novel strengthening agent.
Clay is a kind of natural stratiform silicate inorganic material with nano-lamellar structure, because it has particular structure, the source is easily, price is low, thus the preparation of composite nano polymer/clay material with use in especially be subject to people's attention.Polymkeric substance and clay make characteristics such as material has light specific gravity, good heat resistance, barrier height, ageing resistance is good, flame retardant resistance is good nanoscale compound.
The composite nano polymer/clay material preparation method has monomer reaction in intercalation technique, macromole fusion intercalation technology, macromole solution intercalation technology and macromole emulsion intercalation technology etc.Monomer reaction in intercalation technique can obtain the exfoliated clay composite material of high-performance, but organic intercalation agent and clay are had higher technical requirements, and the industrialization of in-situ inserted polymerization technique investment is big, and the cycle is long, is difficult for applying.And the matrix material of melt intercalated method preparation is the intercal type matrix material usually, is more difficult to get the clay composite material of peeling off fully.The solution intercalation technology will be used a large amount of solvents, and contaminate environment is recycled difficulty, causes cost to rise.And the emulsion intercalation technology all has the advantage of the emulsion form of oneself based on most of rubber, be a kind of simple to operate, cost is low, widely applicable, be easy to industrialized method.
Because the surface and the interlayer of clay have the intensive wetting ability, be difficult in the organic polymer matrix, realize that nano level disperses, thereby must at first carry out organically-modifiedly clay, make interlayer surface be hydrophobicity, be beneficial between the polymer interposed layer, realize nano combined.
At present, organically-modified method research mainly concentrates on wet-process modified and the solid phase modification to clay, and properties-correcting agent mainly concentrates on organic amine, organic quaternary ammonium salt and coupling agent.The wet-process modified of clay is earlier clay dispersion to be formed suspension in water, add properties-correcting agent again and carry out ion-exchanged, filter then, wash, dry, series of processes such as grind, sieve, complex process, equipment is huge, and starting material and energy consumption are big, makes the cost of organic clay further increase, cause environmental pollution simultaneously, thereby have a strong impact on clay applying in polymkeric substance.And that the solid phase method of modifying of clay has is simple, need not water or advantages such as solvent, non-environmental-pollution, but this method need be used a certain amount of organic modifiers and coupling agent, and organic modifiers and coupling agent modification efficiency be not very high.Organic amine, organic quaternary ammonium salt class modifier modification clay are to utilize ion-exchange to be inserted into the interlayer of clay, make interlamellar spacing increase, but this type of properties-correcting agent can not and clay layer and base rubber between react, so the gained performance of composites can not get increasing substantially.
Therefore, also need provide at present a kind of and can significantly improve the dispersiveness of clay in polymeric matrix and the preparation method of the composite nano polymer/clay material of energy-and time-economizing, non-environmental-pollution.
Summary of the invention
The present invention is directed to the problem that exists among the organically-modified and composite nano polymer/clay material preparation method of above-mentioned clay, propose a kind of preparation method of composite nano polymer/clay material.
Specifically, the present invention be by epoxy natural rubber as the dispersion compatilizer between clay and the polymkeric substance, on the one hand, epoxy natural rubber molecular chain intercalation between clay layer and and clay layer generation chemical reaction; On the other hand, between unsaturated double-bond and the matrix polymer crosslinking reaction can take place in the epoxy natural rubber.Utilize the bridge linking effect of epoxidized natural latex, improve the dispersion effect of clay in matrix polymer, strengthen the interaction between clay and the matrix polymer, preparation high-performance polymer/clay nanocomposites.
The object of the invention is achieved through the following technical solutions.
A kind of preparation method of composite nano polymer/clay material may further comprise the steps:
(1) clay dispersion is formed the slurry of 0.2 ~ 20%wt in water, preferred 1-15%.Add epoxidized natural latex, stir, obtain clay dispersion;
(2) stirring joins above-mentioned clay dispersion in the polymer emulsion down, after mixing, and flocculation, washing, drying, thus obtain composite nano polymer/clay material;
Described polymer emulsion is one or both in rubber latex or the plastics with emulsion form;
The consumption of described raw material is as follows in parts by weight:
1 ~ 40 part of clay;
1 ~ 30 part of epoxidized natural latex weight by dry rubber;
100 parts of polymer emulsion weight by dry rubber.
Described clay is natural or the synthetic laminated clay, for example terre verte, polynite, kaolin, illite, attapulgite, sepiolite, vermiculite or hydromica, and preferably polynite in this experiment comprises its natural or Physical Processing product.
What described epoxidized natural latex was that epoxidation level is 10 ~ 55%, total solids level is 10 ~ 30%wt prepares epoxidized natural latex by the emulsus epoxy natural rubber of epoxidation reaction preparation or by natural rubber latex by epoxidation reaction by natural rubber.
Described rubber latex is natural rubber latex, styrene-butadiene latex, nitrile rubber, carboxylic styrene butadiene latex, chloroprene rubber latex or elastic polyurethane precursor emulsion.
Described plastics with emulsion form are polyvinyl chloride emulsion, polyacrylate dispersion, polyvinyl acetate emulsion or EVA emulsion.
The described properties-correcting agent that clay dispersion is added in water time of step (1), the weight percent that described properties-correcting agent accounts for clay is 1% ~ 15%; Described properties-correcting agent is silane coupling agent, phthalate ester coupling agent or interface modifier.
The described dispersive of step (1) applies ultrasonic wave to slurry simultaneously.
The described blended of step (2) applies ultrasonic wave to mixed solution simultaneously.
Described flocculation is flocculation agent flocculation, freezing flocculation, high speed centrifugation flocculation or machinery flocculation.
Present method does not have special requirement to polymer emulsion yet, can be natural rubber latex, can be synthetic rubber latex yet, and kind is not limit, and the latex solid content is not limit.As natural rubber latex, styrene-butadiene latex, nitrile rubber, carboxylic styrene butadiene latex, chloroprene rubber latex, or the like; Or the plastics with emulsion form, as polyvinyl chloride emulsion, polyacrylate dispersion, polyvinyl acetate emulsion, EVA emulsion etc., also can use the mixed solution of two or more emulsion.
Can also in water, during suspended dispersed, can add a certain amount of silane coupling agent or phthalate ester coupling agent at clay among the present invention, or other interface modifiers; When clay disperses in water and clay water suspension when mixing, can promote to disperse and mix with ultrasonication with polymer emulsion.
Described flocculation is to add flocculation agent such as electrolyte solution, organic slat solution, polyelectrolyte solution or adopt freezing flocculation, high speed centrifugation flocculation and machinery flocculation.
The present invention does not have special requirement to used flocculation agent, but different different according to employed matrix polymer latex type uses latex needed flocculation agent when industrialization is condensed of respective type just can.But as the natural rubber latex working concentration is 10%(weight) calcium chloride solution, but paracril latex working concentration is a 2%(weight) hydrochloric acid soln; but the styrene butadiene rubber latex working concentration is a 5%(weight) octadecyl trimethyl ammonium chloride solution, but the polyvinyl chloride emulsion working concentration is about 10% (weight) sodium chloride solution.
Compared with prior art, the present invention has the following advantages:
(1) need in the conventional clay organic modification process to loose with large quantity of moisture, also need dry, operation such as grind, sieve, cause complex process, starting material and energy consumption are big, cost is high, contaminate environment, be unfavorable for promoting the use of.The present invention's and preparation process matrix material organically-modified clay is integrated, need not simplify technology through organic modification in advance, saves cost, modification efficiency height, the composite property excellence of preparation.
(2) the present invention prepares the method for composite nano polymer/clay material, and technology is simple, cost is low, production process is pollution-free.With the composite nano polymer/clay material that this method makes, both can directly add various Synergist S-421 95s carry out mixing, also can with the rubber or the plastic blend of other type, or with other fillers such as strengthening agent carbon black, white carbon black and lime carbonate, potter's clay and use.
(3) because clay layer is scattered in the matrix as toughener in advance equably, produce significant reinforcing effect, thereby can not add or add less carbon black, thereby significantly reduce the environmental pollution that causes owing to dust from flying in the rubber mixing process, reduce mixing time simultaneously, reduce mixing energy consumption.This sizing material is also fine to the wedging of other Synergist S-421 95s.
The composite nano polymer/clay material that the present invention is prepared confirms through X-ray diffraction (XRD), and fractionated polymer subchain intercalation causes the clay layer spacing to increase between clay layer; Mechanics Performance Testing shows that indexs such as the tensile strength of matrix material, stress at definite elongation, tear strength all have improvement in various degree; The DMA test shows, the dynamic properties of matrix material has obtained increasing substantially.
Description of drawings
Fig. 1 is the XRD figure of SBR and matrix material thereof.
Embodiment
Embodiment 1:
Earlier 8 parts of commercially available polynites are added and carry out dispersed with stirring in the entry, the polynite solid content is controlled at 2%(weight); Adding 8 parts of weight by dry rubber epoxidation levels in above-mentioned montmorillonite suspension liquid is 25%, and total solids level is a 25%(weight) epoxidized natural latex, dispersed with stirring prepares the polynite dispersion; Again above-mentioned polynite dispersion being added 100 parts of weight by dry rubber total solid contents is 60%(weight) the natural rubber latex Ruzhong mix, use 10%(weight then) calcium chloride solution flocculate.Throw out is washed to neutrality, in 80 ℃ of vacuum drying ovens, dries to constant weight, obtain the NR/ENR/MMT nano composite material.This matrix material is added various Synergist S-421 95s by rubber compounding commonly used carry out mixing and sulfuration, the physical and mechanical properties of NR sees Table 1.By table 1 as seen, the comprehensive mechanical property of NR/ENR/MMT matrix material is good.
Table 1
Annotate: rubber unvulcanizate prescription: NR100, stearic acid 2, zinc oxide 5, promotor 1.5, anti-aging agent 1, sulphur 1.5.143 ℃ * T90 of cure conditions.
Embodiment 2:
Earlier 40 parts of commercially available polynites are added in the entry and stir, the polynite solid content is controlled at 5%(weight); Adding 25 parts of weight by dry rubber epoxidation levels in above-mentioned montmorillonite suspension liquid is 30%, and total solids level is 25% epoxidized natural latex, and dispersed with stirring prepares the polynite dispersion; Again above-mentioned polynite dispersion is added 100 parts of weight by dry rubber total solid contents and be in 20% the styrene butadiene rubber latex and mix, flocculate with 5% octadecyl trimethyl ammonium chloride solution then.Throw out is washed to neutrality, in 80 ℃ of vacuum drying ovens, dries to constant weight, obtain the SBR/ENR/MMT nano composite material.This matrix material is added various Synergist S-421 95s by rubber compounding commonly used carry out mixing and sulfuration, the tensile strength of gained cross-linked rubber is 18.5MPa, and tensile yield is 460%.Matrix material is carried out the XRD test result as shown in Figure 1, as seen from Figure 1, cheating engaging layer pitch enlargement in SBR/ENR/MMT (mass ratio the is 100/25/40) matrix material has arrived 4.8nm, interlamellar spacing 1.5nm than polynite in SBR/MMT (mass ratio the is 100/40) matrix material is much bigger, illustrate, successfully get intercalation between montmorillonite layer with fractionated polymer subchain in the matrix material of this method preparation.
Embodiment 3:
Earlier 20 parts of commercially available polynites are added in the entry and stir, add 1 part of silane coupling agent KH560 simultaneously, wherein the polynite solid content is controlled at 10%(weight); Adding 10 parts of (weight by dry rubber) epoxidation levels in above-mentioned montmorillonite suspension liquid is 15%, and total solids level is 10% epoxidized natural latex, and dispersed with stirring prepares the polynite dispersion; Again above-mentioned polynite dispersion is added 100 parts of weight by dry rubber paracril latex and carboxylic styrene butadiene latex epoxy glue Ruzhong mixes, wherein to contain the solid content of 50 parts of weight by dry rubber be that the solid content of 20% paracril latex and 50 parts of weight by dry rubber is 20% carboxylic styrene butadiene latex in the epoxy glue Ruzhong.Use 2%(weight then) hydrochloric acid soln flocculate, throw out is washed to neutrality, in 80 ℃ of vacuum drying ovens, dry to constant weight, obtain nano composite material.This matrix material is added various Synergist S-421 95s by rubber compounding commonly used carry out mixing and sulfuration, gained cross-linked rubber tensile strength is 26.7MP, and tensile yield is 570%.
Embodiment 4:
Earlier 10 parts of commercially available polynites are added in the entry and stir, the polynite solid content is controlled at 15%(weight); Adding 5 parts of weight by dry rubber epoxidation levels in above-mentioned montmorillonite suspension liquid is 25%, and total solids level is 25% epoxidized natural latex, mixes, and loads ultrasonic wave simultaneously 30 minutes, preparation polynite dispersion; Again above-mentioned polynite dispersion is added 100 parts of weight by dry rubber total solid contents and is 60% natural rubber latex Ruzhong and mix, use 10%(weight then) calcium acetate solution flocculate.Throw out is washed to neutrality, in 80 ℃ of vacuum drying ovens, dries to constant weight, get the NR/ENR/MMT nano composite material.Matrix material is carried out the dynamic properties analytical test, the DMA result of NR and matrix material thereof is as shown in table 2, as shown in Table 2, compare with NR, the anti-slippery of NR/ENR/MMT matrix material has obtained increasing substantially, rolling resistance also has decline by a relatively large margin simultaneously, and overall dynamic properties is good.
Table 2
Embodiment 5:
Earlier 8 parts of commercially available polynites are added in the entry and stir, the polynite solid content is controlled at 10%(weight); Adding 2 parts of weight by dry rubber epoxidation levels in above-mentioned montmorillonite suspension liquid is 25%, and total solids level is 10% epoxidized natural latex, and dispersed with stirring prepares the polynite dispersion; Again above-mentioned polynite dispersion is added 100 parts to mix in siccative paracril latex and the polyvinyl chloride emulsion mixed emulsion, wherein to contain the solid content of 70 parts of weight by dry rubber be that paracril latex and 30 parts of solid contents in siccative of 20% are 40% polyvinyl chloride emulsion in the epoxy glue Ruzhong.Product is washed to neutrality through the high speed centrifugation breakdown of emulsion with throw out, dries to constant weight in 80 ℃ of vacuum drying ovens, obtains nano composite material.This matrix material is added various Synergist S-421 95s by prescription commonly used carry out mixing and sulfuration, gained matrix material 300% stress at definite elongation is 6.3 MPa, and tensile strength is 20.7MPa, and tensile yield is 490%, and tear strength is 35.6kNm
-1, shore a hardness is 58 degree.
Claims (9)
1. the preparation method of a composite nano polymer/clay material is characterized in that, may further comprise the steps:
(1) clay dispersion is formed the slurry of 0.2 ~ 20%wt in water, add epoxidized natural latex, stir, obtain clay dispersion;
(2) stirring joins above-mentioned clay dispersion in the polymer emulsion down, after mixing, and flocculation, washing, drying, thus obtain composite nano polymer/clay material;
Described polymer emulsion is one or both in rubber latex or the plastics with emulsion form;
The consumption of described raw material is as follows in parts by weight:
1 ~ 40 part of clay;
1 ~ 30 part of epoxidized natural latex weight by dry rubber;
100 parts of polymer emulsion weight by dry rubber.
2. preparation method according to claim 1 is characterized in that, described clay is natural or synthetic terre verte, polynite, kaolin, illite, attapulgite, sepiolite, vermiculite or hydromica laminated clay.
3. preparation method according to claim 1 is characterized in that, described epoxidized natural latex is that epoxidation level is 10 ~ 55%, total solids level is emulsus epoxy natural rubber or the epoxidized natural latex of 10 ~ 30%wt.
4. preparation method according to claim 1 is characterized in that, described rubber latex is natural rubber latex, styrene-butadiene latex, nitrile rubber, carboxylic styrene butadiene latex, chloroprene rubber latex or elastic polyurethane precursor emulsion.
5. preparation method according to claim 1 is characterized in that, described plastics with emulsion form are polyvinyl chloride emulsion, polyacrylate dispersion, polyvinyl acetate emulsion or EVA emulsion.
6. preparation method according to claim 1 is characterized in that, step (1) is described also to comprise adding properties-correcting agent with clay dispersion in water, and the weight percent that described properties-correcting agent accounts for clay is 1% ~ 15%; Described properties-correcting agent is silane coupling agent, phthalate ester coupling agent or interface modifier.
7. preparation method according to claim 1 is characterized in that, the described dispersive of step (1) applies ultrasonic wave to slurry simultaneously.
8. preparation method according to claim 1 is characterized in that, the described blended of step (2) applies ultrasonic wave to mixed solution simultaneously.
9. preparation method according to claim 1 is characterized in that: described flocculation is flocculation agent flocculation, freezing flocculation, high speed centrifugation flocculation or machinery flocculation.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589005A (en) * | 2013-10-17 | 2014-02-19 | 中科纳达控股有限公司 | Preparation method of illite/montmorillonite mixed-layer clay/natural rubber compounded rubber |
| CN105733047A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Nitrile rubber/attapulgite nano composite material, vulcanized rubber and preparation method thereof |
| CN106118117A (en) * | 2016-07-12 | 2016-11-16 | 广西南宁桂尔创环保科技有限公司 | A kind of 3D prints and uses plastics clay material |
| CN106432804A (en) * | 2016-11-08 | 2017-02-22 | 承德人和矿业有限责任公司 | Illite powder reinforcer, preparation method thereof and rubber containing reinforcer |
| CN107099062A (en) * | 2017-04-26 | 2017-08-29 | 无锡永高新材料科技有限公司 | A kind of nano composite material of vermiculite and natural rubber and preparation method thereof |
| CN107746481A (en) * | 2017-09-16 | 2018-03-02 | 南京工程学院 | A kind of NR latex/clay organic aerogel composite and preparation method thereof |
| CN108976577A (en) * | 2018-06-04 | 2018-12-11 | 合肥谦尧建筑装饰工程有限公司 | A kind of amendatory artificial sliver of tensile strength and preparation method thereof |
| CN110511454A (en) * | 2019-09-12 | 2019-11-29 | 中国热带农业科学院农产品加工研究所 | A kind of ageing-resistant natural rubber and preparation method thereof, ageing-resistant natural rubber vulcanized rubber and preparation method thereof |
| CN111171392A (en) * | 2020-01-17 | 2020-05-19 | 青岛科技大学 | Preparation method of white carbon black/natural rubber composite material |
| CN111286093A (en) * | 2020-02-12 | 2020-06-16 | 江苏瑞京科技发展有限公司 | Composition for producing medical gloves and application thereof |
| CN111546555A (en) * | 2020-05-18 | 2020-08-18 | 中国热带农业科学院农产品加工研究所 | Preparation method of natural latex tube |
| CN112080051A (en) * | 2020-09-29 | 2020-12-15 | 昕中和成都胶业有限公司 | Special rubber composition with high damping ratio and preparation method and application thereof |
| CN114213558A (en) * | 2021-11-12 | 2022-03-22 | 青岛科技大学 | Application of montmorillonite as flocculant of natural latex and flocculation method |
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| CN1238353A (en) * | 1998-06-04 | 1999-12-15 | 北京化工大学 | Process for preparing clay-rubber nm-class composite material |
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| CN103589005A (en) * | 2013-10-17 | 2014-02-19 | 中科纳达控股有限公司 | Preparation method of illite/montmorillonite mixed-layer clay/natural rubber compounded rubber |
| CN103589005B (en) * | 2013-10-17 | 2014-09-03 | 中科纳达控股有限公司 | Preparation method of illite/montmorillonite mixed-layer clay/natural rubber compounded rubber |
| CN105733047A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Nitrile rubber/attapulgite nano composite material, vulcanized rubber and preparation method thereof |
| CN106118117A (en) * | 2016-07-12 | 2016-11-16 | 广西南宁桂尔创环保科技有限公司 | A kind of 3D prints and uses plastics clay material |
| CN106432804A (en) * | 2016-11-08 | 2017-02-22 | 承德人和矿业有限责任公司 | Illite powder reinforcer, preparation method thereof and rubber containing reinforcer |
| CN107099062A (en) * | 2017-04-26 | 2017-08-29 | 无锡永高新材料科技有限公司 | A kind of nano composite material of vermiculite and natural rubber and preparation method thereof |
| CN107746481A (en) * | 2017-09-16 | 2018-03-02 | 南京工程学院 | A kind of NR latex/clay organic aerogel composite and preparation method thereof |
| CN108976577A (en) * | 2018-06-04 | 2018-12-11 | 合肥谦尧建筑装饰工程有限公司 | A kind of amendatory artificial sliver of tensile strength and preparation method thereof |
| CN110511454A (en) * | 2019-09-12 | 2019-11-29 | 中国热带农业科学院农产品加工研究所 | A kind of ageing-resistant natural rubber and preparation method thereof, ageing-resistant natural rubber vulcanized rubber and preparation method thereof |
| CN110511454B (en) * | 2019-09-12 | 2021-06-22 | 中国热带农业科学院农产品加工研究所 | Anti-aging natural rubber and preparation method thereof, anti-aging natural rubber vulcanized rubber and preparation method thereof |
| CN111171392A (en) * | 2020-01-17 | 2020-05-19 | 青岛科技大学 | Preparation method of white carbon black/natural rubber composite material |
| CN111286093A (en) * | 2020-02-12 | 2020-06-16 | 江苏瑞京科技发展有限公司 | Composition for producing medical gloves and application thereof |
| CN111546555A (en) * | 2020-05-18 | 2020-08-18 | 中国热带农业科学院农产品加工研究所 | Preparation method of natural latex tube |
| CN112080051A (en) * | 2020-09-29 | 2020-12-15 | 昕中和成都胶业有限公司 | Special rubber composition with high damping ratio and preparation method and application thereof |
| CN112080051B (en) * | 2020-09-29 | 2022-08-05 | 昕中和成都胶业有限公司 | Special rubber composition with high damping ratio and preparation method and application thereof |
| CN114213558A (en) * | 2021-11-12 | 2022-03-22 | 青岛科技大学 | Application of montmorillonite as flocculant of natural latex and flocculation method |
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Application publication date: 20110817 |