A kind of environment-friendly type terpolymer EP rubber and paracril are also with closed pore second time of foaming material and preparation method thereof
Technical field
The present invention relates to a kind of environment-friendly type terpolymer EP rubber EPDM and paracril NBR also with closed pore second time of foaming material and preparation method thereof.
Background technology
Terpolymer EP rubber EPDM is ethene, propylene and the unsaturated the 3rd monomeric multipolymer; Be a kind of high saturation rubber; Have performances such as excellent heat-resisting, anti-ozone, acid and alkali-resistance, Weather-resistant, antifatigue, anti tear, can be under-60 ℃~135 ℃ conditions life-time service, be widely used in fields such as automobile industry, construction industry, electric wire and polymer modification; Its molecular chain is essentially the aliphatics saturated chain; Lack reactive group and polar substitution group, so vulcanization rate is slower, oil-proofness and binding property are relatively poor.
Paracril has characteristics such as good oil-proofness, wear resistance, cohesive strength, compression set are little, mechanical property height, but its Weather-resistant and ozone resistance are relatively poor.
Rubber and elastomeric material also can improve the mechanical property of rubber with modification, improve the processing characteristics and the application performance of single rubber kind, and be not only effectively simple, and economical.
The present invention selects EPDM and NBR and uses; Can improve performances such as the ozone resistance, weather of NBR, performance such as low temperature resistant and dielectric; Also can better improve the performance of technical process of EPDM rubber, NBR rubber can be given the better oil-proofness of EPDM, binding property and reduce cost.When researching and developing and making these closed cell foamed materials, make every effort to reduce the halogens content in the material simultaneously, make it to become environmentally friendly machine, also do not find the report of the secondary closed cell foamed material of relevant environment-friendly type terpolymer EP rubber and paracril and usefulness at present.
Summary of the invention
The object of the present invention is to provide a kind of environment-friendly type terpolymer EP rubber and paracril also with closed pore second time of foaming material and preparation method thereof; The invention solves terpolymer EP rubber and paracril blended rubber performance and reduce cost, improve performances such as the ozone resistance, weather of NBR, performance such as low temperature resistant and dielectric; And overcome the higher shortcoming of content of halogen in the existing foam material.
In order to achieve the above object, technical scheme of the present invention is:
A kind of environment-friendly type terpolymer EP rubber EPDM and paracril NBR and with closed pore second time of foaming material are formed by the preparation of raw material of following weight part: terpolymer EP rubber 60~120; Paracril 27~36; 8~15 parts of carbon blacks; 10~15 parts in the strong powder of magnesium; 15~35 parts of U.S.'s carclazytes; 10~15 parts of softening oils; 2~3 parts of whipping agents; 1.5~2 parts of sulphur promotor; 4~6 parts in zinc oxide; 1.5~2.5 parts of Triple Pressed Stearic Acid.
Preferred weight part proportioning of said raw material is: terpolymer EP rubber 75; Paracril 30; 12 parts of carbon blacks; 12 parts in the strong powder of magnesium; 22 parts of U.S.'s carclazytes; 12 parts of softening oils; 2.5 parts of whipping agents; 1.7 parts of sulphur promotor; 5 parts in zinc oxide; 2 parts of Triple Pressed Stearic Acid.
A kind of environment-friendly type terpolymer EP rubber EPDM and paracril NBR are also with closed pore second time of foaming preparation methods, and may further comprise the steps: (1) is with the banburying of above-mentioned weight part raw materials mix; (2) heat refining slice; (3) extrude filter glue; Closed pore foaming in (4) first apotypes; Closed pore foaming, steady shape in (5) second apotypes, then the second time of foaming body is cooled to room temperature and obtains finished product.
Said step is preferably following:
(1) banburying:
The strong powder of magnesium of the carbon black of A, the terpolymer EP rubber with above-mentioned weight part, paracril, 1/2 proportional quantity, 1/2 proportional quantity, softening oil, U.S.'s carclazyte drop in the Banbury mixer and form epoxy glue;
B, the zinc oxide of above-mentioned weight part, Triple Pressed Stearic Acid are dropped in the Banbury mixer and epoxy glue kneading 1~2min;
The strong powder of the magnesium of C, the carbon black that will be left 1/2 proportional quantity, 1/2 proportional quantity drops into kneading 1-2min in the Banbury mixer;
D, the whipping agent of above-mentioned weight part, sulphur promotor are dropped in the Banbury mixer kneading 8~10min that pressurizes then, weight pressure 4~6Kg;
E, the banburying built-in temperature is controlled at 105~110 ℃ when mixing;
F, binder removal, cooling;
(2) heat refining, slice:
Sizing material after mixing is dropped into heat refining in 18 cun opening rubber mixing machines; And parked 12 hours with thickness 5-8mm slice cooling; And then drop in another 18 cun opening rubber mixing machines and play the triangle bag, turn refining and drop into again for two or three times in 18 cun opening rubber mixing machines with 8-15mm thickness slice, slitting;
(3) extrude filter glue:
The film that the slice slitting is good drops in the forcing machine and extrudes filter glue, is extruded into the glue embryo, and the speed of forcing machine is 550 rev/mins; The outlet of extruder temperature is controlled to be 40-60 ℃;
Closed pore foaming in (4) first apotypes:
The glue embryo extruded cut off to weigh to deliver to carry out closed pore foaming first time in first vulcanizer, 1300 tons of sulfide stresses, the sulfur foam time is 45 minutes, the sulfur foam temperature is 134 ± 5 ℃, obtains foam material cooling for the first time and carries out the processing of light face;
The closed pore steady shape typing of foaming in (5) second apotypes:
Foam is delivered to and is carried out the foaming sulfuration typing second time in second vulcanizer for the first time; 1300 tons of sulfide stresses; Curing time 25-45 minute; 160 ± 5 ℃ of sulfide stress temperature, for the second time the foam cool to room temperature obtains halogen-free environment-friendly type terpolymer EP rubber and paracril also with secondary closed cell foamed material finished product then.
The invention has the beneficial effects as follows: the invention solves terpolymer EP rubber and paracril blended rubber performance and reduce cost, improve performances such as the ozone resistance, weather of NBR, performance such as low temperature resistant and dielectric, compliance with environmental protection requirements; And overcome the higher shortcoming of content of halogen in the existing foam material, and detect through SGS, meet the new standard REACH of European Union.
Embodiment
Specific embodiments more of the present invention below are provided, understand the present invention to help further, but protection scope of the present invention are not limited in these embodiment.
Embodiment 1
The present embodiment prescription is as shown in table 1, and EPDM is that terpolymer EP rubber, NBR are paracril.The preparation method of present embodiment raw material is following:
(1) banburying
A, EPDM, NBR, 1/2 proportional quantity carbon black, the strong powder of 1/2 proportional quantity magnesium, softening oil KN4006, U.S.'s carclazyte dropped in the Banbury mixer by the weight part shown in the table 1 form epoxy glue.
B, zinc oxide, Triple Pressed Stearic Acid 1801 are pressed the weight part shown in the table 1 drop in the Banbury mixer and epoxy glue kneading 1-2min.
C. will be left the carbon black of 1/2 proportional quantity, the interior kneading 1-2min of the strong powder input of magnesium Banbury mixer of 1/2 proportional quantity.
D, with whipping agent OBSH,, sulphur promotor EG-4 presses the weight part shown in the table 1 and drops in the Banbury mixer, the kneading 8-10min that pressurizes then, weight pressure 5KG.
E, the banburying built-in temperature is controlled at 105-110 ℃ when mixing.
F, binder removal cooling.
(2) heat refining, slice
Sizing material after mixing is dropped into heat refining in 18 cun opening rubber mixing machines; And parked 12 hours with thickness 5-8mm slice cooling; And then drop in another 18 cun opening rubber mixing machines and play the triangle bag, turn refining and twice or thrice drop into again in 18 cun opening rubber mixing machines with 8-15mm thickness slice, slitting.
(3) extrude filter glue
Film that the slice slitting is good drops in the model 250 model forcing machine and extrudes filter glue, is extruded into the glue embryo, the outlet of extruder temperature is controlled to be 40-60 ℃, and rotating speed is 550 rev/mins.
Closed pore foaming in (4) first apotypes
The glue embryo extruded cut off to weigh to deliver to carry out first time closed pore in the vulcanizing press (Taiwan benefit high yield) and foam; 1300 tons of sulfide stresses; The sulfur foam time is 45 minutes, and the sulfur foam temperature is 134 ± 5 ℃, obtains foam material cooling for the first time and carries out the processing of light face.
The closed pore steady shape typing of foaming in (5) second apotypes
With the first time foam deliver to and carry out the foaming sulfuration typing second time in 1300 tons the vulcanizing press; 1300 tons of sulfide stresses; Curing time 25-45 minute; 160 ± 5 ℃ of sulfide stress temperature, the foam cool to room temperature obtains halogen-free environment-friendly type EPDM/NBR also with secondary closed cell foamed material finished product for the second time then.
The halogen-free environment-friendly type terpolymer EP rubber of gained of the present invention and paracril are also as shown in table 2 with secondary closed cell foamed material physicals test result.Present embodiment halogen-free environment-friendly type EPDM and NBR are also as shown in table 3 with secondary closed cell foamed material SGS halogens test report.
The EPDM of present embodiment and NBR also make through rational prescription and preparation technology with rubber and to have good anti-ozone; Ageing-resistant characteristic and the performance of good oil resistant, anti-solvent and chemical-resistant reagent is arranged; Visible by last two parts of examining reports; The halogen-free environment-friendly type EPDM of manufacturing of the present invention and NBR also detect with the halogens in the secondary closed cell foamed material and all do not detect, and meet the new standard REACH of European Union.Reach the needed environmental requirement of material, and the tensile strength of this material is high, tear resistance is good.Can be widely used in using in the severe rugged environment condition.Have good social benefit and economic benefit.
Embodiment 2
The present embodiment prescription is as shown in table 4, and EPDM is that terpolymer EP rubber, NBR are paracril.The preparation method of present embodiment foam material is with embodiment 1.
The halogen-free environment-friendly type terpolymer EP rubber of gained of the present invention and paracril are also also as shown in table 2 with secondary closed cell foamed material physicals test result.Present embodiment halogen-free environment-friendly type EPDM and NBR are also also as shown in table 3 with secondary closed cell foamed material SGS halogens test report.
The EPDM of present embodiment and NBR also make through rational prescription and preparation technology with rubber and to have good anti-ozone; Ageing-resistant characteristic and the performance of good oil resistant, anti-solvent and chemical-resistant reagent is arranged; Visible by last two parts of examining reports; The halogen-free environment-friendly type EPDM of manufacturing of the present invention and NBR also detect with the halogens in the secondary closed cell foamed material and all do not detect, and meet the new standard REACH of European Union.Reach the needed environmental requirement of material, and the tensile strength of this material is high, tear resistance is good.Can be widely used in using in the severe rugged environment condition.Have good social benefit and economic benefit.
Embodiment 3
The present embodiment prescription is as shown in table 5, and EPDM is that terpolymer EP rubber, NBR are paracril.The preparation method of present embodiment foam material is with embodiment 1.
The halogen-free environment-friendly type terpolymer EP rubber of gained of the present invention and paracril are also also as shown in table 2 with secondary closed cell foamed material physicals test result.Present embodiment halogen-free environment-friendly type EPDM and NBR are also also as shown in table 3 with secondary closed cell foamed material SGS halogens test report.
The EPDM of present embodiment and NBR also make through rational prescription and preparation technology with rubber and to have good anti-ozone; Ageing-resistant characteristic and the performance of good oil resistant, anti-solvent and chemical-resistant reagent is arranged; Visible by last two parts of examining reports; The halogen-free environment-friendly type EPDM of manufacturing of the present invention and NBR also detect with the halogens in the secondary closed cell foamed material and all do not detect, and meet the new standard REACH of European Union.Reach the needed environmental requirement of material, and the tensile strength of this material is high, tear resistance is good.Can be widely used in using in the severe rugged environment condition.Have good social benefit and economic benefit.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Table 1 (annotate: each raw material by weight)
Table 2
Table 3
Test event |
Unit |
Test result |
MDL |
Limit value |
Cadmium (Cd) |
mg/kg |
N.D |
2 |
100 |
Plumbous (Pb) |
mg/kg |
N.D |
2 |
1000 |
Mercury (Hg) |
mg/kg |
N.D |
2 |
1000 |
Basic soln extraction sexavalent chrome |
mg/kg |
N.D |
2 |
1000 |
PBBs (PBBS) sum |
mg/kg |
N.D |
|
1000 |
Single bromo biphenyl |
mg/kg |
N.D |
5 |
|
'-dibromobiphenyl |
mg/kg |
N.D |
5 |
|
Three bromo biphenyls |
mg/kg |
N.D |
5 |
|
Tetrabromo biphenyl |
mg/kg |
N.D |
5 |
|
Pentabromo-biphenyl |
mg/kg |
N.D |
5 |
|
Hexabromobiphenyl |
mg/kg |
N.D |
5 |
|
Seven bromo biphenyls |
mg/kg |
N.D |
5 |
|
Octabromo-diphenyl |
mg/kg |
N.D |
5 |
|
Nine bromo biphenyls |
mg/kg |
N.D |
5 |
|
Decabromodiphenyl |
mg/kg |
N.D |
5 |
|
PBDE (PBDES) sum |
mg/kg |
N.D |
|
1000 |
Single dibromodiphenyl ether |
mg/kg |
N.D |
5 |
|
Dibromodiphenyl ether |
mg/kg |
N.D |
5 |
|
Three dibromodiphenyl ethers |
mg/kg |
N.D |
5 |
|
Tetrabromodiphenyl ether |
mg/kg |
N.D |
5 |
|
Pentabromodiphenyl oxide |
mg/kg |
N.D |
5 |
|
The hexabromo phenyl ether |
mg/kg |
N.D |
5 |
|
Seven dibromodiphenyl ethers |
mg/kg |
N.D |
5 |
|
Octabromodiphenyl ether |
mg/kg |
N.D |
5 |
|
Nine dibromodiphenyl ethers |
mg/kg |
N.D |
5 |
|
Two ethers of ten bromines |
mg/kg |
N.D |
5 |
|
(note: 1.mg/kg=PPM; 2.N.D=the end detect (<MDL); 3.MDL=the method detectability)
Table 4 (annotate: each raw material by weight)
Table 5 (annotate: each raw material by weight)