CN101792559A - Rubber compound for rubber for coating chemical fiber bleaching rubber roll - Google Patents
Rubber compound for rubber for coating chemical fiber bleaching rubber roll Download PDFInfo
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Abstract
The invention relates to a rubber compound for a rubber for coating a chemical fiber bleaching rubber roll. The rubber compound comprises ethylene propylene diene monomer, white carbon black, paraffin oil, polymeric liquid plasticizers (such as oligomer esters, liquid ethylene propylene methylene and liquid high vinyl polybutadiene), sulfur, accelerating agents, dicumyl peroxide and other auxiliaries. The rubber compound has the characteristics of high hardness (the Shore A hardness is 90-95 degrees), white color, excellent bleaching liquid sodium hypochlorite resistance, good processability and suitability for covering and forming on a rubber roll extrusion and winding covering machine.
Description
Technical field
A kind of rubber compound for rubber for coating chemical fiber bleaching rubber roll of the present invention.
Background technology
Man-made fiber, particularly viscose staple fibre are bleached with SYNTHETIC OPTICAL WHITNER in postprocessing working procedures, to reach the effect that improves whiteness, improves visual appearance.SYNTHETIC OPTICAL WHITNER commonly used has hydrogen peroxide (hydrogen peroxide) and clorox, is higher than hydrogen peroxide with the finished product whiteness of sodium hypochlorite bleaching.
The staple fibre bleaching rubber roll that coats with sizing material of the present invention is used for viscose staple fibre refiner bleaching section, and the sodium hypochlorite solution principal constituent is a clorox, contains reactive chlorine 1-1.5g/L, pH 8-10.According to working conditions, require rubber roll to coat glue and be white, high rigidity (Shao Er A type hardness tester 90-95 degree), good anti-hypochlorite bleach fluidity energy is arranged.
Used common printer's roll, coating the sizing material that glue uses is natural rubber or natural rubber and styrene-butadiene rubber(SBR) blended rubber in the past, and anti-sodium hypochlorite bleaching fluidity can be bad, produce sclerosis in the use, shrink, work-ing life weak point.In used viscose staple fibre bleaching rubber roll, use well behaved terpolymer EP rubber of anti-clorox and chlorosulfonated polyethylene to make to coat glue, relatively, terpolymer EP rubber is preferably from the cost performance aspect.
But, the terpolymer EP rubber right and wrong are from the reinforcement rubber, and can not as natural rubber, styrene-butadiene rubber(SBR) or other dience rubbers, make vulcanizing agent and obtain the high rigidity cross-linked rubber with a large amount of Sulfurs, therefore to obtain the white sizing material of high rigidity (Shao Er A type hardness tester＞90 degree), need to add a large amount of light strengthening agent white carbon blacks, can only use a spot of softening agent again.Yet, mixing and processing is all very difficult because the mooney viscosity of sizing material is very high, particularly rubber roll coat glue extruding-be difficult to machine-shaping on the clad can shaper.
Can obtain white high rigidity rubber roll again in order to add white carbon black less as far as possible, existing technology is to use noncrosslinking thermoplasticity synthetic resins (for example high density polyethylene(HDPE), high styrene resin rubber master batch) or bridging property thermoset synthetic resin (for example resol) in sizing material, these resins have and increase hard effect, and can be used as processing aid mixing and extrude in improve processing property.But, though high-density polyethylene resin is good with the terpolymer EP rubber consistency, can be dispersed in well in the terpolymer EP rubber, and anti-clorox excellent property, yet it is complete saturated polymkeric substance, can not use sulfur vulcanization, the elasticity of cross-linked rubber is reduced and the compression set increase.In addition, high density polyethylene(HDPE) also can reduce the bond strength of sizing material and metal roller core.The high styrene resin rubber master batch is the blend of high styrene resin and styrene-butadiene rubber(SBR), and is not good with the consistency of terpolymer EP rubber, the anti-hypochlorous acid of prior reduction vulcanized rubber.In the terpolymer EP rubber sizing material, add line style (Novolac) resol,, form very hard product, the hardness of terpolymer EP rubber cross-linked rubber is increased greatly because it can be crosslinked by vulkacit H (vulkacit H).But the mooney viscosity of sizing material is very high, and resol and vulkacit H is dispersed very poor.Therefore, above-mentioned 3 kinds of synthetic resins are bleached rubber roll to preparation high rigidity terpolymer EP rubber and are not suitable for.
Data introduction [Rajan Vara is arranged, Christopher Grant, Christian Daniel.Rubber World, 2003,227 (5), 33], in the terpolymer EP rubber sizing material, add low polymerization degree, the liquid high vinyl polybutadiene resin of high-vinyl-content can be realized co-crosslinking by sulfur sulfide system with terpolymer EP rubber, and obviously reduce the mooney viscosity of sizing material and improve the hardness of cross-linked rubber. but this data only relates to carbon black-filled black terpolymer EP rubber sizing material, do not relate to the effect of liquid high vinyl polybutadiene resin, do not relate to the anti-sodium hypochlorite bleaching fluidity energy relevant yet with the chemical fiber bleaching rubber roll at the white terpolymer EP rubber sizing material of filling white carbon black.
Summary of the invention
The objective of the invention is to solve high rigidity terpolymer EP rubber sizing material, too high because of mooney viscosity, cause rubber roll to be difficult to the problem of moulding.A kind of hardness height (Shao Er A type hardness tester 90-95 degree) is provided, mooney viscosity is lower and can be used to extrude and twine the clad can moulding, have the sizing material that the chemical fiber bleaching rubber roll clad can glue of the good liquid of anti-the hypochlorite bleach is used.
The present invention is a kind of rubber compound for rubber for coating chemical fiber bleaching rubber roll, and it is formed and the quality proportioning is:
Terpolymer EP rubber 100
Zinc oxide 3-20
Magnesium oxide 0.5-15
Stearic acid 0.5-5
Anti-aging agent 1-4
Tackifying resin 2-10
White carbon black 60-90
Silane coupling agent 2-8
Titanium dioxide 5-30
Aggretion type liquid plasticizer 10-40
Paraffin oil 10-30
Sulfur 2-5
Promotor 3-7
Dicumyl peroxide 0.5-2
Above said terpolymer EP rubber be low mooney viscosity, the ENB type terpolymer EP rubber of wide molecular weight distribution: 1. Mitsui (Mitsui) EPT 4045, Mitsui petroleum chemistry company produces, 125 ℃ of mooney viscosity ML (1+4) be 29MU, ethylene content 54%, ENB content 8%, molecular weight distribution be wide; 2. Nordel (Luo Deer) IP 4725P, du pont company production, mooney viscosity ML (1+4) is 25MU, ethylene content 70%, ENB content 5%, wide molecular weight distribution for 125 ℃.
Above said tackifying resin be H-501 charcoal hydrogen resin (German D.O.G company) and SP 1077 alkyl phenolic resins [Sheng Laike specialization worker (Shanghai) Co., Ltd.].
Above said white carbon black be: 1. T-150 type precipitated silica, homemade; 2. A200 type thermal silica, German Degussa (Degussa) company produces.
Above said silane coupling agent be the Si-69[bis(3-triethoxy silylpropyl)tetrasulfide].
Above said titanium dioxide be Rutile type Titanium Dioxide.
Above said aggretion type liquid plasticizer be: 1. 12-I type oligomer ester, promptly tetramethyl-vinylformic acid two glycerol phthalic esters are homemade; 2. liquid ethylene propylene rubber Trilene (Te Lilin) CP80, ethene // propylene be than 43/57, viscosity-average molecular weight (M
v) 7200, U.S. lion board (Lion) company produces; 3. liquid high vinyl polybutadiene resin, trade(brand)name Ricon (Rui Kang) 153, contents of ethylene 85, number-average molecular weight (M
n) 4700, viscosity (45 ℃) 60000mPa.s, the U.S. husky Thomas (Sartomer) company produces.
Above said paraffin oil be high viscosity hydrogenation paraffin oil KP 6035, kinematic viscosity (100 ℃) 33-37mm
2/ s, Kelamayi petro-chemical corporation produces.
Above said other starting material are common commercial rubber ingredients.
Embodiment
Following examples are to explanation of the present invention, rather than limit the scope of the invention.
The sizing material physicals of following examples and Comparative Examples is measured by following test method: mooney viscosity is pressed GB/T123.1-2000, hardness and is pressed that GB/T 531-1999, tensile property press GB/T 528-1998, the liquid of anti-hypochlorite bleach fluidity can be pressed GB/T1690-2006.
Embodiment 1-3 and Comparative Examples l
The sizing compound formula of embodiment 1-3 and Comparative Examples 1 and various raw-material quality proportioning are listed in table 1.
Table 1
| Starting material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| Terpolymer EP rubber (4045) | ??100 | ??100 | ??100 | ??100 |
| Zinc oxide | ??10 | ??10 | ??10 | ??10 |
| Magnesium oxide | ??10 | ??10 | ??10 | ??10 |
| Stearic acid | ??3 | ??3 | ??3 | ??3 |
| Anti-aging agent (2246) | ??1.5 | ??1.5 | ??1.5 | ??1.5 |
| Tackifying resin (H-501) | ??3 | ??3 | ??3 | ??3 |
| Tackifying resin (SP 1077) | ??6 | ??6 | ??6 | ??6 |
| White carbon black (T-150) | ??80 | ??80 | ??50 | ??80 |
| White carbon black (A-200) | ??30 | |||
| Silane coupling agent (Si-69) | ??8 | ??8 | ??8 | ??8 |
| Titanium dioxide | ??20 | ??20 | ??20 | ??20 |
| Oligomer ester (12-I) | ??8 | ??8 | ??8 | |
| Liquid Ethylene Propylene Methylene (CP 80) | ??10 | ??20 | ||
| Paraffin oil (6035) | ??20 | ??20 | ??20 | ??20 |
| Captax | ??1.5 | ??1.5 | ??1.5 | ??1.5 |
| Starting material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| Altax | ??0.5 | ??0.5 | ??0.5 | ??0.5 |
| Accelerant B Z | ??1 | ??1 | ??1 | ??1 |
| TM monex TD | ??0.7 | ??0.7 | ??0.7 | ??0.7 |
| Sulfur | ??3 | ??3 | ??3 | ??3 |
| Dicumyl peroxide | ??0.8 | ??1.2 | ??1.6 |
The preparation technology of embodiment 1-3 and Comparative Examples 1 sizing material: the opening rubber mixing machine machine that will drop into 50-60 ℃ of roller temperature by the raw materials in sequence that prescription prepares carries out mixing.At first drop into the broken glue of terpolymer EP rubber rubber kneading, behind the continuous bag roller glue to be formed, the tackifying resin and the stearic acid that add zinc oxide, magnesium oxide, precomminution, staggered then powdery aniseed (white carbon black and titanium dioxide) and the fluent material (silane coupling agent, paraffin oil or oligomer ester or Liquid Ethylene Propylene Methylene) of adding, smash refining evenly, add promotor, Sulfur and/or dicumyl peroxide (mixing with a small amount of white carbon black in advance), smashing refining evenly, sheet under the thin-pass is parked standby.
The sizing material that makes prepares test piece, cure conditions on vulcanizing press: 150 ℃ * 90 minutes.The physical properties of rubber compound test result is listed in table 2.
Moulding and sulfuration: the sizing material for preparing is extruded adhesive tape continuously be wrapped in through sandblasting and having brushed on the roller core of Chemlok (Kai Muluoke) 205/238.The rubber roll base of forming is tightened with steel wire, in finishing sulfuration under 150～160 ℃ in the open steam vulcanization jar.After removing steel wire, grind on the roller stock surface, obtains the rubber roll finished product.The rubber roll base of forming is tightened with steel wire, in finishing sulfuration under 150～160 ℃ in the open steam vulcanization jar.After removing steel wire, grind on the roller stock surface, obtains the rubber roll finished product.
By the data of table 2 as seen, the mooney viscosity of Comparative Examples 1 sizing material is very high, and is mixing and extrude all difficulties, and autohension is relatively poor, can not implement to extrude to twine the clad can moulding.Embodiment 1 is after having added oligomer ester on the basis of Comparative Examples 1, and the mooney viscosity of sizing material obviously descends, and hardness does not have obvious increase, and tensile strength decreases, but mixing and extrude processing property and improve, sizing material viscosity increases, and more easily extrudes to twine the clad can moulding.But anti-hypochlorite bleach fluidity can have decline slightly.After adding Liquid Ethylene Propylene Methylene (embodiment 2), mooney viscosity descends, and hardness does not have big variation, can extrude smoothly and twine the clad can moulding, and anti-sodium hypochlorite bleaching agent performance is better than embodiment 1.Embodiment 3 usefulness thermal silicas substitute partly precipitated method white carbon black, and increase Liquid Ethylene Propylene Methylene consumption, the mooney viscosity of its sizing material further descends than embodiment 2 again, tensile strength increases, hardness is in target zone, mixing good with extrusion performance, smooth implementation is extruded on the clad can machine Overmolded at rubber roll.
Table 2
Embodiment 4
The sizing compound formula of embodiment 4 and various raw-material quality proportioning are as follows:
Terpolymer EP rubber (4725P) 100
Zinc oxide 10
Magnesium oxide 10
Stearic acid 3
Anti-aging agent (2246) 1.5
Tackifying resin (H-501) 3
Tackifying resin (SP1077) 6
White carbon black (T-150) 75
Silane coupling agent (Si-69) 6
Titanium dioxide 20
Oligomer ester (12-I) 8
Liquid polybutadiene resin (Ricon 153) 15
Paraffin oil (6035) 20
Accelerant CZ 1.6
Altax 0.5
Accelerant B Z 0.8
TM monex TD 0.7
Vulkacit D PTT 0.7
Sulfur 6
Dicumyl peroxide 0.8
The preparation technology of embodiment 4 sizing materials is identical with embodiment 1-3, difference: 1. opening rubber mixing machine roller temperature is 60-70 ℃; 2. fluent material is replaced with silane coupling agent, paraffin oil, oligomer ester and liquid polybutadiene resin.
The sizing material that makes prepares test piece, cure conditions on vulcanizing press: 150 ℃ * 90 minutes.The physical properties of rubber compound test result is listed in table 3.
Extruding of rubber roll is Wrapping formed identical with embodiment 1-3 with sulfuration process.
From the data of table 3 as seen, adopt the terpolymer EP rubber (4725P) of high ethylene content and the sizing material of liquid polybutadiene resin, mooney viscosity is lower, and the liquid polybutadiene resin helps processing mixing and play softening agent when extruding.And sulfur sulfide system can make it crosslinked when sulfuration, realizes co-crosslinking with terpolymer EP rubber, has improved the intensity of cross-linked rubber, has reduced the distortion of cross-linked rubber.Simultaneously, the sizing material of embodiment 4 has the performance of the good liquid of anti-the sodium hypochlorite bleaching.
Comparative Examples 2
The sizing compound formula of Comparative Examples 2 and various raw-material quality proportioning are as follows:
Terpolymer EP rubber (4725P) 100
High styrene resin rubber master batch (HS-860) 15
Zinc oxide 10
Magnesium oxide 10
Stearic acid 3
Anti-aging agent (2246) 1.5
Tackifying resin (H-501) 3
Tackifying resin (SP1077) 6
White carbon black (T-150) 75
Silane coupling agent (SI-69) 6
Titanium dioxide 20
Oligomer ester (12-I) 8
Paraffin oil (6035) 20
Accelerant CZ 1.6
Altax 0.5
Accelerant B Z 0.8
TM monex TD 0.7
Vulkacit D PTT 0.7
Sulfur 3
Above said high-phenylethylene rubber master batch be HS-860, Japanese auspicious father-in-law (Zeon) company produces.It is that the phenylethylene/butadiene mass ratio is 60/40 the high styrene resin and the latex coprecipitation thing of styrene-butadiene rubber(SBR) (SBR 1502), blend mass ratio 150/100, mooney viscosity ML (1+4) is that 55-70MU. can obviously increase the hardness of alkadiene vulcanized rubber owing to it for 100 ℃, is used as the rubber and plastic material of high rigidity roll cladding glue usually.
The preparation technology of Comparative Examples 2 sizing materials: 1. plasticate: the temperature control of opening rubber mixing machine roller is at 70-80 ℃, roll spacing 0.5mm, and with granular high-phenylethylene rubber master batch tablet forming, no particle is smooth to the surface is as the criterion, and descends sheet standby again; 2. close refining: 60-80 ℃ of opening rubber mixing machine roller temperature, roll spacing 3-4mm, behind the terpolymer EP rubber bag roller, add the high styrene resin rubber master batch sheet stock that has plastified, behind both mixings, adjust roll spacing, sheet is stand-by under the thin-pass; 3. mixing: good blended rubber drops into the opening rubber mixing machine machine of 50-60 ℃ of roller temperature will to close refining, behind the continuous bag roller glue to be formed, the tackifying resin and the stearic acid that add zinc oxide, magnesium oxide, precomminution, staggered then powdery aniseed (white carbon black and titanium dioxide) and the fluent material (silane coupling agent, paraffin oil, oligomer ester) of adding, smash refining evenly, add promotor, Sulfur, smash refining evenly, sheet under the thin-pass is parked standby.
The sizing material that makes prepares test piece, cure conditions on vulcanizing press: 150 ℃ * 90 minutes.The physical properties of rubber compound test result is listed in table 3.
Table 3
Extruding of rubber roll is Wrapping formed identical with embodiment 1-3 with sulfuration process.
By the data of table 3 as seen, the high styrene resin rubber master batch can effectively increase hardness, but the effect that reduces mooney viscosity is not as the liquid polybutadiene resin.And compare with embodiment 4, the intensity of Comparative Examples 2 is low, big, the liquid of anti-sodium hypochlorite bleaching poor performance of distortion.Comparative Examples 2 sizing materials can adopt extrudes that to twine the clad can machine Overmolded, but because of the bad high styrene resin of plasticizing is arranged in plasticating, and the consistency of it and terpolymer EP rubber is bad, close refining and mixing in be easy to generate and disperse badly, cause rubber roll finished surface generation defective through grinding.
Comparative Examples 3
The sizing compound formula of Comparative Examples 3 and various raw-material quality proportioning are as follows:
Chlorosulfonated polyethylene rubber (chlorosulfonated polyethylene 40) 100
Activated magnesia 10
Stearic acid 3
Antioxidant MB 2
White carbon black (T-150) 60
Silane coupling agent (Si-69) 6
Titanium dioxide 20
Epoxy soybean oil 12
Resins, epoxy (E-51) 18
Vulkacit D PTT 3
Altax 1
Tetramethylolmethane 3
The preparation technology of Comparative Examples 3 sizing materials: will drop into opening rubber mixing machine by the raw materials in sequence that prescription prepares and carry out mixing.Drop into the chlorosulfonated polyethylene rubber earlier, to smooth bag roller, add magnesium oxide, anti-aging agent, tetramethylolmethane then, alternately add powder (white carbon black and titanium dioxide, Si-69 allocates in the white carbon black in advance) and liquid material (epoxy soybean oil and Resins, epoxy) again, add promotor at last, smash refining evenly, sheet under the thin-pass, cooling is parked standby.
Moulding and sulfuration: the sizing material for preparing is extruded adhesive tape continuously be wrapped in through sandblasting and having brushed on the roller core of Chemlok (Kai Muluoke) 205/234B.The rubber roll base of forming is tightened with steel wire, in finishing sulfuration under 150～160 ℃ in the open steam vulcanization jar.After removing steel wire, grind on the roller stock surface, obtains the rubber roll finished product
The sizing material that makes prepares test piece, cure conditions on vulcanizing press: 150 ℃ * 90 minutes.The physical properties of rubber compound test result is as follows:
100 ℃ of mooney viscosity ML (1+4), MU 87
Shao Er A type hardness tester, degree 93
Tensile strength, MPa 16.1
Elongation rate of tensile failure, % 318
Break tension set, % 26
Anti-sodium hypochlorite bleaching fluidity energy
Volume change, %
60℃×24h????????????????????12.84
60℃×72h????????????????????20.48
60℃×168h???????????????????26.16
Mass change, %
60℃×24h????????????????????9.81
60℃×72h????????????????????15.08
60℃×168h???????????????????18.89
By top data as seen, the performance of the liquid of anti-sodium hypochlorite bleaching of Comparative Examples 3 sizing materials is than poor many of embodiment 1-4.The mooney viscosity height of this sizing material when extruding winding operation, is extruded difficulty, and the bad problem of incipient scorch and ply adhesion is arranged.
Claims (9)
1. rubber compound for rubber for coating chemical fiber bleaching rubber roll, it is formed and mass parts is:
Terpolymer EP rubber 100
Zinc oxide 3-20
Magnesium oxide 0.5-15
Stearic acid 0.5-5
Anti-aging agent 1-4
Tackifying resin 2-10
White carbon black 60-90
Silane coupling agent 2-8
Titanium dioxide 5-30
Aggretion type liquid plasticizer 10-40
Paraffin oil 10-30
Sulfur 2-5
Promotor 3-7
Dicumyl peroxide 0.5-2.
2. according to the sizing material of claim 1, it is characterized by the terpolymer EP rubber that the 3rd monomer is ethylidene norbornene (ENB) (EPDM), 125 ℃ of the mooney viscosity ML (1+4) of rubber are that 20-40MU, ENB content 4-10%, ethylene content 45-75%, molecular weight distribution are wide.
3. according to the sizing material of claim 1, the feature that it is characterized by used white carbon black is that the precipitated silica list is used or precipitated silica and thermal silica and usefulness.
4. according to the precipitated silica of claim 3, it is characterized by SiO
2Content＞92%, BET specific surface area 150-200m
2/ g, median size 10-15 μ m.
5. according to the thermal silica of claim 3, it is characterized by SiO
2Content＞99.8%, BET specific surface area 150-250m
2/ g, median size 10-20nm.
6. according to the sizing material of claim 1, it is characterized by used aggretion type liquid plasticizer is the low polymerization degree liquid polymers.
7. according to the aggretion type liquid plasticizer of claim 6, it is characterized by the polymerization degree that is made by polyvalent alcohol, diprotic acid, unsaturated acid condensation dehydration is the oligopolymer of 1-2, i.e. oligomer ester.
8. according to the aggretion type liquid plasticizer of claim 6, it is characterized by viscosity-average molecular weight (M
vThe liquid ethylene propylene rubber of)＜8000.
9. according to the aggretion type liquid plasticizer of claim 6, it is characterized by number-average molecular weight (M
nThe liquid 1 of)＜5000, the 2-polybutadiene.
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| CN103613861A (en) * | 2013-11-19 | 2014-03-05 | 南京金三力橡塑有限公司 | Coating rubber roller for high-grade automobile plate production line and manufacturing method thereof |
| CN106243528A (en) * | 2016-09-07 | 2016-12-21 | 东莞市长锦成电器有限公司 | The formula of a kind of rubber roll rubber and production technology thereof |
| CN107337824A (en) * | 2017-06-05 | 2017-11-10 | 薛念念 | A kind of anti-static and abrasion-resistant damages rubber roll elastomeric material |
| CN108250592A (en) * | 2018-01-25 | 2018-07-06 | 南京金三力橡塑有限公司 | A kind of preparation method of actinobacillus wheel and its cover material and the cover material |
| CN108250592B (en) * | 2018-01-25 | 2020-08-07 | 南京金三力橡塑有限公司 | Paying-off wheel, rubber coating material thereof and preparation method of rubber coating material |
| CN111961289A (en) * | 2020-08-27 | 2020-11-20 | 东莞市利群榕兴高分子科技有限公司 | High-hardness EPDM rubber composition and preparation method thereof |
| CN113583355A (en) * | 2021-07-30 | 2021-11-02 | 浙江元通线缆制造有限公司 | Rubber material for one-to-two vulcanization production line and preparation method thereof |
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| CN101792559B (en) | 2012-05-30 |
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