CN101440140B - Preparation of exfoliated chloroprene rubber / vermiculite nano composite material by emulsion polymerization - Google Patents
Preparation of exfoliated chloroprene rubber / vermiculite nano composite material by emulsion polymerization Download PDFInfo
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- CN101440140B CN101440140B CN2008101808922A CN200810180892A CN101440140B CN 101440140 B CN101440140 B CN 101440140B CN 2008101808922 A CN2008101808922 A CN 2008101808922A CN 200810180892 A CN200810180892 A CN 200810180892A CN 101440140 B CN101440140 B CN 101440140B
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- vermiculite
- composite material
- chloroprene rubber
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- rubber
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Abstract
The invention discloses a method for preparing exfoliated chloroprene rubber/vermiculite nano-composites, in particular a method for preparing exfoliated chloroprene rubber /vermiculite nano-composites by using vermiculite not subjected to organification, taking 2-chloro-1,3-butadiene as a raw material and adopting a in-situ intercalative polymerization method in an emulsion system.
Description
Technical field
The present invention relates to a kind of exfoliated chloroprene rubber/vermiculite nano composite material and preparation method thereof, be particularly related to vermiculite and 2-chloro-1 that utilization does not organise and handles, 3-divinyl small molecules carries out in-situ inserted polyreaction in emulsion system, prepare the method for exfoliated chloroprene rubber/vermiculite nano composite material.
Background technology
Nano composite polymer/laminated silicate material is to be that external phase, phyllosilicate nano lamella are a class advanced composite material of disperse phase with the polymkeric substance.Because the thickness of this nanometer lamella is one to several nanometers, width and length are that hundreds of arrives several thousand nanometer (QiZongNengs, Shang Wenyu, the nano composite polymer/laminated silicate material theory and practice, Chemical Industry Press, 2002:3-14), so the nanoparticle specific surface area in this material structure is big, the surface energy height, can make macromolecular material show brand-new performance or function, thereby be better than general polymerization thing material in performance and application facet, become the focus of current polymer materials fundamental research and Application and Development research, and polyethylene, the laminated nm-silicate composite material of polypropylene and polymeric amide has been realized suitability for industrialized production.
At present, intercalation compound in the most frequently used layer silicate mineral be montmorillonite.Compare with montmorillonite, performances such as heat insulation, low temperature resistant, fire-retardant, the suction of vermiculite, sound absorption are more excellent, have higher net negative charge simultaneously, so polymkeric substance/vermiculite nano composite material is compared with polymkeric substance/montmorillonite nano-composite material and is had more good performance.
Chloroprene rubber is widely used at industry fields such as automotive industry, light industry, construction industries.And the mechanical property, thermotolerance, winter hardiness, flame retardant resistance, static resistance etc. that further improve chloroprene rubber are significant for the range of application that enlarges chloroprene rubber.
About the modification of chloroprene rubber, carried out the research of each side both at home and abroad.Wherein the development of nano composite polymer/laminated silicate material is the focus of studying in recent years for the performance of improving rubber provides new approach.(intercalation compounding prepares the research [J] of paracril/clay nanocomposites as Wang Li of University Of Qingdao etc., New Chemical Materials, 2004 (2): 13-51) adopt the intercalation compounding technology to prepare mechanical property and the flame retardant resistance that paracril/clay nanocomposites improves rubber; (the preparation method of clay-rubber nm-class composite material [P] such as Zhang Liqun, China Patent No. 98101496.8, on June 4th, 1998 filed an application) macromole inserts the clay mineral interlayer that organises and handle in emulsion system, and then preparation clay mineral/SBR matrix material, thereby the mechanical property and the barrier property of raising rubber.
According to domestic and international science and technology look into newly (novelty assessment report numbering: 20061100100005) and recent literature retrieval show, at present existing researchist is a raw material with the chloroprene rubber and the laminar silicic acid of handling that organises, prepare the chloroprene rubber/montmorillonite matrix material by blending method, prepare non-exfoliated chloroprene rubber latex/clay nanocomposites by the blend coagulation method, and there is the researchist to prepare a series of chlorinated polymers (as poly-2-chloro-1 by melt intercalated method, the 3-divinyl, polyvinyl chloride, chlorinated polyvinyl chloride etc.)/clay nanocomposites, this seminar is by solution intercalation method chloroprene rubber, montmorillonite and the vermiculite of handling that organise is raw material, prepares chloroprene rubber/montmorillonite nano-composite material and Duprene rubber/vermicultie namo composite material.But at home and abroad there is no the report for preparing exfoliated chloroprene rubber/vermiculite nano composite material about the vermiculite that uses the processing that do not organise by emulsion polymerization so far.
Summary of the invention
The purpose of this invention is to provide a kind ofly, organise and prepare the method for exfoliated chloroprene rubber/vermiculite nano composite material under the condition of technology saving vermiculite from the chlorbutadiene monomer.
Particularly, the invention provides a kind ofly by using the vermiculite of handling without organising, is raw material with the chlorbutadiene monomer in emulsion system, adopts in-situ inserted polymerization to prepare the method for exfoliated chloroprene rubber/vermiculite nano composite material.
The inventor finds after deliberation, in emulsion system, 2-chloro-1,3-divinyl small molecules and initiator can more successfully be inserted between vermiculite layers, and at the interlayer polymerization reaction take place, vermiculite layers spacing support is big so that layer is destructurized and peel off, and vermiculite is evenly dispersed in the matrix of chloroprene rubber rubber with the form of nanometer fragment as a result.Then, by treatment process known in the art, as plasticate, mixing and sulfuration etc., handle and make exfoliated chloroprene rubber/vermiculite nano composite material.
As a preferred implementation for preparing the method for exfoliated chloroprene rubber/vermiculite nano composite material of the present invention, may further comprise the steps:
A. purifying vermiculite
B. emulsion method prepares chloroprene rubber rubber/vermiculite nano composite material: will prepare in advance by 2-chloro-1, the gained vermiculite joins in the reactor simultaneously in the water of being made up of emulsifying agent, sodium hydroxide and water of the oil phase that 3-divinylic monomer, Dodecyl Mercaptan and emulsifying agent are formed, preparation in advance and the steps A, and stirring makes the three-phase thorough mixing; Be warming up to 30～38 ℃ and add initiator, stir and make its thorough mixing; Further heat up constant temperature to 40～58 ℃, stirring reaction 3～8h, cooling, washing, dry chloroprene rubber rubber/vermiculite nano composite material;
C. prepare Duprene rubber/vermicultie namo composite material: with the chloroprene rubber rubber/vermiculite nano composite material of gained among the step B plasticate, mixing and the sulfuration, obtain Duprene rubber/vermicultie namo composite material.
In step B, the oil phase composition is preferably chlorbutadiene: molecular weight regulator: emulsifying agent=100: 0.1～5: 1～10; The water composition is preferably emulsifying agent: sodium hydroxide: water=1～5: 1～10: 50～800; The vermiculite consumption is preferably 1～10 part, and initiator amount is preferably 0.5～5 part, and described part all is mass parts.Wherein, used emulsifying agent can be a rosin in the oil phase, and the used emulsifying agent of aqueous phase can be sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or petroleum sodium sulfonate.
In step B, the temperature that adds initiator can be 30～38 ℃.
In step C, plasticate, mixing and sulfurized material proportion is preferably: gained chloroprene rubber rubber/vermiculite nano composite material among 100 parts of step B, 0.3～8 part of ZnO, 0.3～8 parts of MgO, 0.2～5 parts of stearic acid, 0.2～2NA-22, described part all is mass parts.
In step C, curing temperature preferably is controlled between 120 ℃～180 ℃; Curing time is preferably 20～60min.
According to the present invention, the vermiculite of selecting net negative charge height, aspect excellent performance such as heat insulation, fire-retardant for use is as dispersed substance.
With regard to chemical ingredients, vermiculite is the moisture layer silicate mineral of a class, its theoretical construct formula be (Mg, Ca)
0.3-4.5(H
2O)
n{ (Mg, Fe
3+, Al)
3[(Si, Al)
4O
10] (OH)
2.The complex chemical composition of vermiculite is changeable, Al in the tetrahedral sheet
3+, Fe
3+Replacing Si is the major cause that layer charge produces, and the compensation of electric charge is mainly by the interlayer cation compensation.For common magnesium base vermiculite, interlayer cation is with Mg
2+Be main, also Ca can be arranged
2+, Na
+, K
+, (H
3O)
+, Rb can also be arranged
+, Cs
+, Li
+, Ba
2+Deng.The charge number of its unit chemical formula is between 0.6～0.9, and than 0.2～0.6 height of montmorillonite, this makes vermiculite show more particular performances with respect to montmorillonite, as thermotolerance, sound insulation, water-absorbent etc.
With regard to crystalline structure, vermiculite is an oblique system, and crystalline structure is 2: 1 (TOT) types, the C of common magnesium base vermiculite
0=1.5nm, as shown in Figure 1.
In the vermiculite tetrahedral sheet, the organic monomer that exists for of exchangeable cation enters in emulsion system condition is provided between vermiculite layers, and the positively charged ion of interlayer mainly contains Mg
2+, Ca
2+, Na
+, K
+Deng positively charged ion, its ionic exchange capacity (CEC) is preferably 80～120meq/100g at 50～200meq/100g.Used vermiculite particle diameter required 200 mesh sieves.
The present invention is a raw material with technical grade chlorbutadiene monomer.
The initiator that uses among the present invention is selected from one or more superoxide of benzoyl peroxide, ammonium persulphate and Potassium Persulphate etc.
The emulsifying agent that uses among the present invention is selected from one or more of sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate and rosin etc.
Use Dodecyl Mercaptan as molecular weight regulator among the present invention; Use sodium hydroxide as alkalinity regulator.
The vulcanizing agent that sulfidation is used among the present invention is zinc oxide and magnesium oxide, and promotor is NA-22, and tenderizer is a stearic acid.
What the present invention obtained is W type (exfoliated) Duprene rubber/vermicultie namo composite material, and its form is sheet or block, and outward appearance is creamy white to beige or light brown.
The processing that layered silicate must be organised of existing preparation chloroprene rubber/laminated nm-silicate composite material technology (solution intercalation method, melt intercalated method etc.), this will cause complex production process, the product cost height.And the present invention directly uses the vermiculite of handling without organising, with chlorbutadiene be monomer in emulsion system, employing in-situ monomer intercalation polymerization is prepared and is peeled off chloroprene rubber rubber/vermiculite nano composite material; Adopt and the processing of chloroprene rubber rubber, the identical processing method of sulfuration, made exfoliated chloroprene rubber/vermiculite nano composite material.
Description of drawings
Fig. 1: vermiculite crystalline structure synoptic diagram.
Fig. 2: the XRD figure of chloroprene rubber rubber/vermiculite nano composite material and vermiculite.
Wherein: the XRD figure of a-chloroprene rubber rubber/vermiculite nano composite material;
The XRD figure of b-vermiculite.
Fig. 3: the XRD figure of sulfuration back Duprene rubber/vermicultie namo composite material and chloroprene rubber/vermiculite matrix material vermiculite.
Wherein: a-sulfuration back Duprene rubber/vermicultie namo composite material,
The XRD figure of b-chloroprene rubber and vermiculite blend.
Fig. 4: the TEM figure of sulfuration back Duprene rubber/vermicultie namo composite material.
Embodiment
Embodiment below in conjunction with the inventive method specifically describes the present invention.
1. purifying vermiculite.
The purifying vermiculite adopts settlement separate method, takes by weighing a certain amount of vermiculite and distilled water and is made into suspension, and " concentration " is 5～20g/L, be preferably 10g/L, left standstill 5～15 hours after stirring half an hour fast, preferred 8 hours, then take out 10 centimetres of supernatant liquids with inner height with siphonage, with the supernatant liquid centrifugation, remove distilled water, with the vermiculite that obtains under 30～80 ℃, preferred 50 ℃ of oven dry down, levigate mistake 200 mesh sieves get pure vermiculite sample.
2. chloroprene rubber rubber/vermiculite nano composite material preparation
(1) with 0.1～10, preferred 0.2～7 part of vermiculite is dispersed in 10～500 parts of water and obtains A liquid.
(2) 100 parts of chlorbutadiene, 0.1～5 part of Dodecyl Mercaptan, 1～6 part of rosin blending and stirring are evenly obtained oil phase component B liquid.
(3) with 1～4 part of petroleum sodium sulfonate, 0.1～5 part of sodium hydroxide, 10～500 parts of water blending and stirring evenly obtain water component C liquid.
(4) A liquid, B liquid and C liquid are put into there-necked flask simultaneously, fully mix, form stable emulsion system, be warmed up to 30～38 ℃, add 0.5～5 part of initiator and stir; Be warmed up to 40～50 ℃ again, constant temperature stirring reaction 3～8h, cooling, breakdown of emulsion, washing, the dry chloroprene rubber rubber/vermiculite nano composite material that gets carry out analysis and characterization with XRD characterization test method to sample, the results are shown in Figure 2.
3. preparation Duprene rubber/vermicultie namo composite material
In weight part, be the prescription of sample in 100 parts of ratios that contain the chloroprene rubber rubber/vermiculite nano composite material of 1～10% vermiculite, 0.4～8 part of ZnO, 0.3～8 part of MgO, 0.2～5 part of stearic acid, 0.2～2 part of NA-22.Then, " open refining, mixing on 150 * 300 mixing rolls (open); left standstill 15～30 hours; on 600 * 600100T QLB vulcanizer, vulcanize at last; curing temperature is controlled between 120 ℃～200 ℃; curing time is 20～40 minutes, finally obtain W type sulfuration Duprene rubber/vermicultie namo composite material respectively 6.
By adopting XRD, TEM characterization test method, confirm that obtained structures of samples is an exfoliated chloroprene rubber/vermiculite nano composite material, sees Fig. 3 and Fig. 4.
Particularly, when carrying out analysis and characterization, use the D/max-rA type to change the target X-ray diffractometer, continuous sweep, and Cu target K alpha-ray (λ=0.154nm), tube voltage 40kV, tube current 100mA, 2 °/min of sweep velocity, 1.5～30 ° of test angle (2 θ) scopes, the changing conditions of vermiculite structure in the mensuration gained matrix material; Using the H-800 of Hitachi transmission electron microscope simultaneously, is under the 200KV condition at acceleration voltage, and sample through cryoultramicrotome, is measured the pattern of vermiculite in the matrix material.
A among Fig. 3 is the XRD figure line of the Duprene rubber/vermicultie namo composite material after the sulfuration, the a figure line shows that the Duprene rubber/vermicultie namo composite material XRD figure after the sulfuration does not have charateristic avsorption band, the structure irregularity or the destruction of the vermiculite in the Duprene rubber/vermicultie namo composite material of sulfuration back are described, the stratiform vermiculite may be present in the matrix of vulcanized rubber with the form of peeling off lamella.B among Fig. 3 is the XRD figure of vermiculite and chloroprene rubber intermingling material, and the b figure line exists high-intensity vermiculite characteristic peak, and this shows that vermiculite is dispersed in the chloroprene rubber with complete former laminate structure.
From the transmission electron microscope picture of Fig. 4 as can be seen, have a lot " black line ", " thin slices " in the chloroprene rubber matrix, this illustrates that clearly vermiculite exists with the form of peeling off lamella, and is dispersed in the chloroprene rubber matrix, and this and XRD result match.The bonding interface of vermiculite lamella and rubber matrix is fuzzy in the picture simultaneously, illustrates that there is good effect on the vermiculite surface with rubber molecule, thereby is that the mechanical property that improves rubber is laid a good foundation.
Embodiment
Embodiment 1: the preparation of chloroprene rubber rubber/vermiculite nano composite material
(1) adopts settlement separate method purifying vermiculite, take by weighing a certain amount of vermiculite and distilled water and be made into suspension, " concentration " is 10g/L, left standstill 8 hours after stirring half an hour fast, then take out 10 centimetres of supernatant liquids, the supernatant liquid centrifugation with inner height with siphonage, remove distilled water, the vermiculite that obtains is dry under 50 ℃, and levigate mistake 200 mesh sieves get pure vermiculite sample.
(2) with blend (the 3g vermiculite is dispersed in the 300g water), oil phase (chlorbutadiene 100g, the Dodecyl Mercaptan 1.0g of vermiculite and water, rosin 4.0g), water (petroleum sodium sulfonate 2.5g, sodium hydroxide 1.0g, water 200g) put into there-necked flask simultaneously, stir and make the three-phase thorough mixing; Be warmed up to 30 ± 2 ℃, add Potassium Persulphate 4g, stir; Be warmed up to 40 ± 2 ℃ again, constant temperature stirring reaction 5h, cooling, breakdown of emulsion, washing, the dry chloroprene rubber rubber/vermiculite nano composite material that gets.
(3) this matrix material is pressed table 1 prescription batching, then, " open refining, mixing on 150 * 300 mixing rolls (open); left standstill 24 hours; vulcanize at last on 600 * 600100T QLB vulcanizer; curing temperature is controlled at 170 ℃, curing time is 30 minutes, finally obtains W type sulfuration Duprene rubber/vermicultie namo composite material respectively 6.
Table 1: sulfurizing formula
Embodiment 2: the preparation of Duprene rubber/vermicultie namo composite material
(1) the vermiculite purifying is with embodiment 1.
(2) with blend (the 6g vermiculite is dispersed in the 400g water), oil phase (chlorbutadiene 100g, the Dodecyl Mercaptan 1.0g of vermiculite and water, rosin 4.0g), water (sodium laurylsulfonate 4.5g, sodium hydroxide 1.0g, water 200g) put into there-necked flask simultaneously, stir and make the three-phase thorough mixing; Be warmed up to 35 ± 2 ℃ and add Potassium Persulphate 4g, stir; Be warmed up to 45 ± 2 ℃ again, constant temperature stirring reaction 5h, cooling, breakdown of emulsion, washing, the dry chloroprene rubber rubber/vermiculite nano composite material that gets.
(3) prescription of chloroprene rubber rubber/vermiculite nano composite material, plasticate, mixing and the sulfuration with embodiment 1.
Claims (4)
1. one kind is adopted in-situ inserted polymerization to prepare the method for exfoliated chloroprene rubber/vermiculite nano composite material in emulsion system by using without the vermiculite of handling that organises, and may further comprise the steps:
A. without the purifying vermiculite that organises and handle;
B. use emulsion method to prepare exfoliated chloroprene rubber rubber/vermiculite nano composite material: will prepare in advance by 2-chloro-1, the oil phase that 3-divinylic monomer, Dodecyl Mercaptan and emulsifying agent are formed, the purifying vermiculite of gained joins in the reactor simultaneously in the water of being made up of emulsifying agent, sodium hydroxid and water of preparation in advance and the steps A, and stirring makes the three-phase thorough mixing; Add initiator when being warming up to 30～38 ℃, stir and make its thorough mixing; Further be warming up to 40～58 ℃, constant temperature stirring reaction 3～8h, cooling, washing, the dry chloroprene rubber rubber/vermiculite nano composite material that gets;
C. prepare exfoliated chloroprene rubber/vermiculite nano composite material: with the chloroprene rubber rubber/vermiculite nano composite material of gained among the step B plasticate, mixing and the sulfuration, curing temperature is controlled between 120～180 ℃, and curing time is that 20～60min obtains exfoliated chloroprene rubber/vermiculite nano composite material.
2. according to the method described in the claim 1, it is characterized in that, quality proportioning raw materials used among the step B is as follows: 100 parts of chlorbutadiene monomers, 0.1～10 part of vermiculite, 0.1～5 part of Dodecyl Mercaptan, 1～10 part of emulsifying agent of oil phase, 1～10 part of emulsifying agent of water, 0.1～5 part of sodium hydroxid, 20～1000 parts in water, 0.5～5 part of initiator.
3. according to the method described in the claim 1, it is characterized in that quality proportioning raw materials used among the step C is as follows: gained exfoliated chloroprene rubber rubber/vermiculite nano composite material among 100 parts of step B, 0.3～8 parts of ZnO, 0.3～8 parts of MgO, 0.2～5 part of stearic acid, 0.2～2NA-22.
4. according to the described method of claim 3, it is characterized in that described initiator is to be selected from a kind of in benzoyl peroxide, ammonium persulphate and the Potassium Persulphate.
5. according to the described method of claim 3, it is characterized in that described oil phase emulsifying agent is a rosin, water is selected from sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate or petroleum sodium sulfonate with emulsifying agent.
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| CN101580562B (en) * | 2009-06-11 | 2010-12-08 | 山西合成橡胶集团有限责任公司 | High transformation rate preparation method of chloroprene rubber with high rotary viscosity |
| CN105837878A (en) * | 2016-04-27 | 2016-08-10 | 柳州申通汽车科技有限公司 | Porous sound-insulating material and preparation method thereof |
| CN106117661B (en) * | 2016-06-28 | 2017-12-22 | 温州市环球汽车衬垫有限公司 | A kind of preparation method of lightweight broad-band sound-absorbing material |
| CN114133627B (en) * | 2021-12-02 | 2023-10-20 | 亚士防水科技(滁州)有限公司 | Hydrophobically modified expanded vermiculite and preparation method thereof, modified rubber asphalt and preparation method and application thereof |
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