CN1563181A - nano composite material of rubber/layer silicate and preparation method - Google Patents

nano composite material of rubber/layer silicate and preparation method Download PDF

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Publication number
CN1563181A
CN1563181A CN 200410026875 CN200410026875A CN1563181A CN 1563181 A CN1563181 A CN 1563181A CN 200410026875 CN200410026875 CN 200410026875 CN 200410026875 A CN200410026875 A CN 200410026875A CN 1563181 A CN1563181 A CN 1563181A
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rubber
monomer
composite material
silicate
initiator
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CN1322053C (en
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贾德民
罗远芳
刘岚
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

A rubber/layered silicate nanocomposite is prepared from rubber, organic modified-layered silicate monomer or mixed monomer and initiator. Its preparing process includes adding organic modified-layered silicate and reactable monomer in rubber mixing procedure or adding proper amount of initiator is necessary, realizing layer-insertion for layered silicate by home polymerization of monomer in course of rubber heating-valcanizing and simultaneously generating graft between rubber and mnonomer or same other chemical combination.

Description

A kind of rubber/lamellar silicate nanometer composite material and preparation method thereof
Technical field
The present invention relates to the nano composite material technical field, specifically relate to a kind of rubber/lamellar silicate nanometer composite material.The invention still further relates to the preparation method of this matrix material.
Background technology
The principal character of nano composite material (Nanocomposites) be a component in the compound system have at least one dimension with nano-scale (≤100nm) be evenly dispersed in the matrix of another component, be called hybrid materials or hybrid material (Hybrid materials) sometimes again.The Organic that polymkeric substance and some layered silicate are formed, its polymkeric substance forms even and firm combining with the inorganics with nano-scale laminate structure, the nanophase specific surface area is big, and phase spacing is little, there is special interaction, so its performance has the raising of highly significant than corresponding macroscopic view or micron order matrix material (for example, traditional Inorganic Fillers Filled polymer-modified), even qualitative leap appears, show brand-new performance or function.Since middle 1980s, the development of nano composite polymer/laminated silicate material has represented a wide path of improving current material performance and development novel material significantly.
Nano composite polymer/laminated silicate material has multiple preparation method, intercalation compounding wherein or claim to embed composite algorithm and at home and abroad study at most, tool use value and development prospect.This method is to utilize clay class layered silicate (if you would take off soil, kaolin etc.) have the characteristics of nano-lamellar structure, with between the help interposed layer of monomer by properties-correcting agent (as the quaternary ammonium salts cats product etc.), and carry out home position polymerization reaction, or macromole is at melt, solution, under the emulsion state, directly insert the interlayer of organic modified layered inorganic materials, finally obtaining complete isolating leafing nano composite material of nanometer lamella (Exifoliatednanocomposites) or interlamellar spacing is the intercalated nano-composite (Intercalatednanocomposites) of nano-scale.
Widely-used various layered inorganic fillers of rubber industry such as potter's clay, kaolin, talcum powder, mica powder etc., traditional rubber process can only make it to reach micron order disperses, and can not produce strengthening action to rubber usually.The development of polymer/laminated silicate intercalation nano compounding technology in recent years, making this class have the inorganic materials of nano-lamellar structure and rubber, to reach nano level compound, thereby make it to produce significant strengthening action, and can improve other performances of rubber simultaneously, as resistance to air loss, oil-proofness, flame retardant resistance, ageing resistance etc., this has just opened up a new research field for the development of rubber science and technology.
Prepare the rubber/lamellar silicate nanometer composite material by intercalation technique and can adopt several different methods, as the in-situ polymerization intercalated method of monomer, fluid rubber reaction graft process, mechanical mixing method, solution intercalation method, latex graft process etc.Wherein, though the in-situ polymerization intercalated method intercalation of monomer efficient is higher, technology is complicated, is difficult to control; There is the solvent contamination environmental problem in the solution intercalation method; The latex graft process is because the rubber latex particle is bigger, and major part surpasses the interlamellar spacing of organic modified sheet silicate, thus not high at the latex state with rubber particles form intercalation efficient, and in the difficult implementation of general rubber product source mill, influence it and apply; The mechanically milling graft process is that rubber and layered silicate are directly realized intercalation by mechanically milling, have that technology is simple, cost is low, can utilize advantages such as existing rubber processing and equipment carry out, but because molecular weight rubber is big, body viscosity is big, and the power of intercalation only is physical action, so macromole is difficult to realize good intercalation, disperse phase is generally the body of combining closely of multilayer clay crystal layer, phase farmland size is bigger, and a little less than the combination of interface, is physical action.
Summary of the invention
One object of the present invention is to provide a kind of rubber/lamellar silicate nanometer composite material with special construction and performance at the shortcoming of prior art existence.
Another object of the present invention is to provide the preparation method of this matrix material, this method combines mechanically milling with reacting phases such as chemical grafts, can bring into play simple, the advantages such as cost is low, easy enforcement of mechanically milling graft process technology, introduce chemical reaction again as intercalation power, overcome that interfacial interaction is weak, the inefficient shortcoming of intercalation, thereby improve the intercalation nano composite effect of rubber and layered silicate, further improve the performance of nano composite material.
For achieving the above object, the present invention has taked following technical scheme:
A kind of rubber/lamellar silicate nanometer composite material in weight part, comprises the material of following umber:
Rubber 100
Organic modified sheet silicate 0.5～50
Monomer or mix monomer 1～40
Initiator 0～3.0.
Described rubber is natural rubber or synthetic rubber;
Described organic modified sheet silicate is organic modification montmonrillonite or the wilkinite that interlayer contains C12～C18 alkyl, carbon-carbon double bond, epoxy group(ing), amido isoreactivity group.
Described monomer is the various monomers that contain unsaturated carbon-carbon double bond, as acrylic acid or the like or methacrylic monomer, acrylate or methacrylate, maleic anhydride and ester thereof, fumaric acid anhydride and ester thereof, it also can be two or more above-mentioned monomeric mixture, also comprise the monomer that can carry out polycondensation, as resorcin/formaldehyde donor (as hexamethylenetetramine, hexamethoxy methyl cyanuramide) etc.;
Described initiator is a radical polymerization initiator, as peroxide initiator and redox system thereof etc.
Preferred as technique scheme, above-mentioned rubber/lamellar silicate nanometer composite material in weight part, comprises the material of following umber:
Rubber 100
Organic modified sheet silicate 1～10
Monomer or mix monomer 1～30
Initiator 0～1.0.
Prepare the method for above-mentioned rubber/lamellar silicate nanometer composite material, comprise the steps:
(1) in rubber mixing process, by weight, in 100 parts of rubber, add organic modified sheet silicate of prescription part and the monomer that reacts or the mix monomer of prescription part, and the initiator that adds prescription part;
(2) in rubber baking process, monomer carries out home position polymerization reaction, realizes the intercalation to layered silicate, and monomer and rubber generation grafting or other Chemical bond make reactive intercal type rubber nano composite material simultaneously.
The routine techniques that related rubber mixing process and rubber baking process are all the present technique field in the inventive method, involved processing parameter is known in the art, the those skilled in the art in present technique field all can better grasp.
Compared with the prior art, the present invention has following beneficial effect:
(1) have the two advantage of in-situ monomer intercalation method and macromole graft process concurrently, intercalation effect is good, and combining between polymkeric substance and the layered silicate is strong, the excellent property of nano composite material;
(2) technology is simple, can utilize existing Rubber processing method and apparatus, easy operation control;
(3) need not use carbon black can obtain the reinforcing effect close, be specially adapted to light color, colour or transparent rubber goods, also can and use with carbon black with carbon black.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Select natural gum (NR) for use, prescription (mass ratio, down together) is as follows: NR 100, and the value of long chain alkyl ammonium salt modified montmorillonoid (HMMT) and Resorcinol and hexamethylenetetramine complex compound (RH) sees Table 1, are variable; (for example the meaning of NR/HMMT10/RH6 is that the mass ratio of NR: HMMT: RH is 100: 10: 6, and is as follows); Stearic acid 2, ZnO4, accelerant CZ 1.5, altax 0.5, antioxidant 4010NA 1.5, sulphur 1.5.Normal temperature is mixing in Ф 160 mills, vulcanizes on 25 tons of vulcanizing presses then, and curing temperature is 143 ℃.Table 1 has been listed NR/HMMT/RH reacting nano matrix material mechanical properties of vulcanizate.As seen from the table, after the NR/HMMT system added RH, its cross-linked rubber not only stress at definite elongation, tensile strength, tear strength obviously improved, and tensile yield also increases, and its every physical and mechanical properties index all significantly surpasses pure NR cross-linked rubber.This is owing to not only promoted the intercalation effect during formaldehyde in-situ polycondensation that the decomposition of Resorcinol and hexamethylenetetramine is emitted, and the resol and the rubber that generate produced Chemical bond such as grafting, co-crosslinking, improved dispersion and the interface combination of inorganic sheet in rubber matrix.
Table 1:NR/HMMT/RH mechanical properties of vulcanizate
300% is fixed Tensile strength Pull apart elongation Pull apart permanent Tear strength Hardness (Shao
Stretch stress/Mpa ????/MPa Rate/% Distortion % ??/KN/m Family name A)/degree
?NR ????1.36 ????16.70 ????800 ????6 ??28.72 ????30
?NR/HMMT10 ????1.62 ????19.44 ????750 ????10 ??26.74 ????32
?NR/HMMT10/RH4 ????1.85 ????24.48 ????900 ????16 ??33.34 ????32
?NR/HMMT10/RH6 ????2.11 ????26.34 ????900 ????18 ??35.72 ????34
?NR/HMMT10/RH10 ????2.81 ????25.34 ????450 ????32 ??38.34 ????59
?NR/HMMT10/RH20 ????3.34 ????22.51 ????400 ????20 ??43.71 ????63
?NR/HMMT2/RH10 ????1.75 ????20.26 ????700 ????12 ??28.36 ????33
?NR/HMMT5/RH10 ????2.54 ????26.88 ????800 ????18 ??36.90 ????50
?NR/HMMT30/RH10 ????5.74 ????15.31 ????320 ????20 ??49.28 ????78
?NR/HMMT50/RH10 ????6.43 ????13.24 ????230 ????16 ??47.31 ????82
Embodiment 2
Rubber is selected butadiene-acrylonitrile rubber (NBR) for use, and it is as follows to fill a prescription: NBR 100, and HMMT 10, and Resorcinol and hexamethylenetetramine complex compound (RH) are variable, stearic acid 2, ZnO4, accelerant CZ 1.5, altax 0.5, antioxidant 4010NA 1.5, sulphur 1.5.Mixing routinely in Ф 160 mills, on 25 tons of vulcanizing presses, vulcanize 160 ℃ of curing temperatures then.Utilize X-ray diffraction to measure the interlamellar spacing (d of layered silicate lamella 001Value) variation the results are shown in Table 2:
Table 2: the d of various materials 001Value
Material ??MMT ?HMMT ?NBR/HMMT ?NBR/HMMT/RH4 ?NBR/HMMT/RH8
d 001(nm) ??1.2 ?2.6 ?3.9 ?4.2 ?4.8
By table 2 as seen, the adding of RH makes the interlamellar spacing of polynite expand 4.2～4.8nm to.As seen RH has been inserted into the interlayer of polynite, has promoted the dispersion of montmorillonite layer.Table 3 has been listed the performance with the paracril/Nano composite material of montmorillonite modified of mechanically milling reaction graft process preparation, and every mechanical property of NBR/HMMT/RH system all is better than not adding the NBR/HMMT system of RH as can be seen.
Table 3: the performance of the paracril/Nano composite material of montmorillonite modified of mechanically milling grafting graft process preparation
300% stress at definite elongation/MPa Tensile strength/MPa Tensile yield/% Setafter break/% Tear strength/KN/m Hardness (Shao Shi A)/degree
?NBR ????2.23 ????2.77 ????360 ????4 ????10.40 ????50
?NBR/HMMT10 ????4.65 ????13.76 ????630 ????14 ????22.15 ????54
?NBR/HMMT10/RH4 ????6.22 ????15.41 ????640 ????16 ????26.34 ????54
?NBR/HMMT10/RH8 ????6.94 ????16.84 ????660 ????18 ????30.45 ????58
Embodiment 3
Rubber is selected butadiene-styrene rubber for use, and it is as follows to fill a prescription: SBR 100, and HMMT 10, resorcinol stearic acid eutectic (RS) variable, hexamethoxy methyl cyanuramide (RA) variable, ZnO4, stearic acid 2, sulphur 1.5, promotor 2.The mixing slice of mill normal temperature is vulcanized on vulcanizing press then, and cure conditions is 150 ℃ * sulfurizing time (min).The mechanical property of butadiene-styrene rubber/quaternary ammonium salt modified montmorillonoid system when table 2 is different RS/RA additions.The adding of RS/RA has the effect of certain reinforcement equally to butadiene-styrene rubber as can be seen, and particularly stress at definite elongation improves a lot, and has kept good elongation at break and tear strength.
Table 4: the mechanical property of butadiene-styrene rubber/quaternary ammonium salt modified montmorillonoid system during different RS/RA addition
300% stress at definite elongation/MPa Tensile strength/MPa Tensile yield/% Setafter break % Tear strength/KN/m Hardness (Shao Shi A)/degree
SBR ?1.67 ?2.08 ?340 ?6 ?10.11 ?30
SBR/HMMT10 ?3.14 ?9.61 ?480 ?10 ?17.28 ?34
SBR/HMMT10/RS2/RA2 ?5.56 ?13.85 ?540 ?10 ?28.20 ?38
SBR/HMMT10/RS3/RA3 ?6.83 ?16.62 ?580 ?16 ?32.28 ?42
Embodiment 4
Rubber is selected terpolymer EP rubber (EPDM) for use, it is as follows to fill a prescription: EPDM (EP33) 100, interlayer contains the modified montmorillonoid (EMMT) 8 of epoxy group(ing), glycidyl methacrylate (GMA) 5.0, and ZnO 5.0, stearic acid 1.0, antioxidant MB 1.0, anti-aging agent RD 1.0, paraffin oil 5.0, dicumyl peroxide (DCP, 40%) 5.0.Mixing routinely in mill, 162 ℃ of sulfurations on vulcanizing press.The adding of GMA has significantly improved the mechanical property of nano composite material as can be seen from Table 5.
Table 5: the mechanical property of the EPDM/EMMT/GMA nano composite material of mechanically milling reaction graft process preparation
300% is fixed Tensile strength Pull apart elongation Pull apart permanent Tear strength Hardness (Shao
Stretch stress/MPa /MPa Rate/% Distortion % /KN/m Family name A)/degree
?EPDM ?- ?4.84 ?280 ?6 ?20.8 ?50
?EPDM/EMMT6 ?6.78 ?15.7 ?480 ?10 ?37.8 ?68
?EPDM/EMMT6/GMA5 ?8.83 ?22.9 ?580 ?15 ?48.0 ?78
Embodiment 5:
Rubber is selected butadiene-acrylonitrile rubber for use, and it is as follows to fill a prescription: NBR 100, zinc methacrylate (ZDMA) 30, dicumyl peroxide (DCP) 1, the double bond containing modified montmorillonoid of HMMT or interlayer (USM) 8.Mixing in Ф 160 mills, on 25 tons of vulcanizing presses, vulcanize then, cure conditions is 170 ℃ * 10min.Table 6 has been listed NBR/ modified montmorillonoid/zinc methacrylate mechanical properties of vulcanizate.As can be seen from Table 6, HMMT/ZDMA and USM/ZDMA system have significant strengthening action to the NBR cross-linked rubber, performance index such as its stress at definite elongation, tensile strength, tensile yield and tear strength are not only all far above the pure glue cross-linked rubber of NBR, and are significantly higher than simple cross-linked rubber with the ZDMA modification.It is particularly remarkable that wherein interlayer contains the reinforcing effect of the modified montmorillonoid USM of unsaturated double-bond and ZDMA and usefulness.Since the in-situ polymerization intercalated effect of zinc methacrylate and with the grafting and the crosslinked action of rubber, strengthened combining of inorganic sheet and rubber macromolecule chain, promoted the dispersion of inorganic sheet in rubber matrix, well work in coordination with strengthening action thereby played.Its reinforcing effect reaches and has surpassed the level of 30 parts of N330 black-reinforceds.This system is light reinforcement system, cross-linked rubber even have translucent sense.
Table 6:NBR/ modified montmorillonoid/zinc methacrylate matrix material mechanical properties of vulcanizate
300% fixed stretching is pulled apart and is torn hardness (Shao forever
Pull apart and stretch
System is stretched stress intensity Bian Xingqiangdushi A of a specified duration)/
Long rate %
/ Mpa/MPa/% KN/m degree
NBR??????????????????2.34?????????2.91????380??????8?????????10.51????45
NBR/ZDMA(40)?????????/????????????21.17???260??????6?????????43.27????74
NBR/HMMT(8)/ZDMA(40)?12.48????????24.65???420??????8?????????56.04????72
NBR/USM(8)/ZDMA(40)??15.48????????26.15???520??????12????????57.46????74

Claims (3)

1, a kind of rubber/lamellar silicate nanometer composite material is characterized in that in weight part, comprises the material of following umber:
Rubber 100
Organic modified sheet silicate 0.5～50
Monomer or mix monomer 1～40
Initiator 0～3.0.
Described rubber is natural rubber or synthetic rubber;
Described organic modified sheet silicate is organic modification montmonrillonite or the wilkinite that interlayer contains C12～C18 alkyl, carbon-carbon double bond, epoxy group(ing), amido;
Described monomer is to contain the monomer that the monomer of unsaturated carbon-carbon double bond maybe can carry out polycondensation; Mix monomer is two or more described monomer mixture;
Described initiator is a radical polymerization initiator.
2, rubber/lamellar silicate nanometer composite material according to claim 1 is characterized in that in weight part, comprises the material of following umber:
Rubber 100
Organic modified sheet silicate 1～10
Monomer or mix monomer 1～30
Initiator 0～1.0.
3, the method for preparing the described rubber/lamellar silicate nanometer composite material of claim 1 is characterized in that comprising the steps:
(1), in rubber mixing process, by weight, in 100 parts of rubber, add 0.5～50 part organic modified sheet silicate and 1～40 part monomer that reacts or mix monomer, and add 0～3.0 part initiator;
(2), in rubber baking process, monomer carries out home position polymerization reaction, realizes the intercalation to layered silicate, monomer and rubber generation grafting or other Chemical bond make reactive intercal type rubber nano composite material simultaneously.
CNB2004100268755A 2004-04-16 2004-04-16 nano composite material of rubber/layer silicate and preparation method Expired - Fee Related CN1322053C (en)

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Cited By (5)

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CN102863824A (en) * 2012-08-25 2013-01-09 华南理工大学 Method for preparing unsaturated carboxylic zinc salt functionalized graphene
CN107501656A (en) * 2017-10-17 2017-12-22 高产明 A kind of preparation method of the wear-resisting nitrile rubber of conduction
CN111315786A (en) * 2017-10-31 2020-06-19 株式会社普利司通 Rubber vulcanization method using eutectic mixture
CN116200018A (en) * 2022-12-22 2023-06-02 江南大学 Flame-retardant polymer prepared based on modified bentonite and application thereof
CN117327374A (en) * 2023-12-01 2024-01-02 饭田（佛山）橡塑有限公司 Reinforcing film for automobile and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1194998C (en) * 2002-08-20 2005-03-30 华南理工大学 Nano-class rubber-laminated inorganic substance composition and its preparing process
CN1425712A (en) * 2003-01-09 2003-06-25 上海交通大学 Triple ethylene-propylene rubber/montmorillonoid peeling nano composite material and its preparing method

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102863824A (en) * 2012-08-25 2013-01-09 华南理工大学 Method for preparing unsaturated carboxylic zinc salt functionalized graphene
CN107501656A (en) * 2017-10-17 2017-12-22 高产明 A kind of preparation method of the wear-resisting nitrile rubber of conduction
CN111315786A (en) * 2017-10-31 2020-06-19 株式会社普利司通 Rubber vulcanization method using eutectic mixture
EP3704162A4 (en) * 2017-10-31 2021-08-11 Bridgestone Corporation Rubber vulcanization processes employing an eutectic mixture
CN111315786B (en) * 2017-10-31 2022-08-19 株式会社普利司通 Rubber vulcanization method using eutectic mixture
US11667774B2 (en) 2017-10-31 2023-06-06 Bridgestone Corporation Rubber vulcanization processes employing an eutectic mixture
CN116200018A (en) * 2022-12-22 2023-06-02 江南大学 Flame-retardant polymer prepared based on modified bentonite and application thereof
CN116200018B (en) * 2022-12-22 2024-03-26 江南大学 Flame-retardant polymer prepared based on modified bentonite and application thereof
CN117327374A (en) * 2023-12-01 2024-01-02 饭田（佛山）橡塑有限公司 Reinforcing film for automobile and preparation method thereof
CN117327374B (en) * 2023-12-01 2024-02-20 饭田（佛山）橡塑有限公司 Reinforcing film for automobile and preparation method thereof

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