CN103192569A - Ultra-high molecular weight polyethylene composite board - Google Patents
Ultra-high molecular weight polyethylene composite board Download PDFInfo
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- CN103192569A CN103192569A CN2013101377161A CN201310137716A CN103192569A CN 103192569 A CN103192569 A CN 103192569A CN 2013101377161 A CN2013101377161 A CN 2013101377161A CN 201310137716 A CN201310137716 A CN 201310137716A CN 103192569 A CN103192569 A CN 103192569A
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Abstract
The invention relates to an ultra-high molecular weight polyethylene composite board which comprises a UHMWPE (Ultra-high Molecular Weight Polyethylene) layer, a rubber layer and an adhesive layer, wherein the adhesive layer is positioned between the UHMWPE layer and the rubber layer. The production method of the ultra-high molecular weight polyethylene composite board comprises the following steps of: a, mixing a UHMWPE raw material and a processing auxiliary agent, and processing into a sheet material by adopting an extrusion or compression moulding forming method; b, carrying out surface treatment on the adhered part of the UHMWPE sheet material and rubber, and coating an adhesive on a surface which is subjected to the surface treatment; and c, compositing the UHMWPE sheet material in the step b and a rubber mixed sheet, sulphurizing, and sizing.
Description
Technical field
The present invention relates to a kind of ultra-high molecular weight polyethylene composite board, especially fender with shock-resistant ultra-high molecular weight polyethylene composite board.
Background technology
Ultra-high molecular weight polyethylene is one of most widely used thermoplastic engineering plastic, its English name is Ultra high molecular weight polyethylene, be called for short UHMWPE, its strand is extremely long, and arranges in the same direction, has typical linear structure, its strand twines very easily mutually, length of run surpasses one kilometer, and viscosity average molecular weigh is usually between 200 ten thousand to 800 ten thousand, and is even higher.The high molecular weight of UHMWPE has been given its special performance, its anti-wear performance and stress crack resistance performance are superior, and wearability is charcoal steel and stainless 3 ~ 7 times, and coefficient of friction is little, confficient of static friction is 0.07, self lubricity is good, does not absorb water, non-caked material acid and alkali resistance, salt corrosion, resistive connection dirt, aging, low temperature resistant, health is nontoxic, and is in light weight, and comprehensive mechanical performance is good.And UHMWPE has high impact strength and viscoelastic damping performance, is the highest in the present thermoplastic, and it can replace steel, copper or aluminium for the manufacture of wearing piece under some occasions.UHMWPE resistance to low temperature excellence still has high impulse strength in the time of-40 ℃, even can use down at-269 ℃.As a kind of engineering thermoplasties with premium properties, it can be widely used in numerous areas such as national defence, building, traffic, weaving.
So far, fender peculiar to vessel is installed to dock wall, and when boats and ships are moored to the harbour of harbour, river course, repairing dock etc., fender peculiar to vessel is avoided collision, vibrations and wearing and tearing etc. for the protection of dock wall and boats and ships.Mostly the fender that uses is the rubber material at present; yet; coefficient of friction height between the iron and steel of the outer surface of rubber and main composition ship (usually greater than 0.4); and ship moves along the shear direction of rubber; because friction, scraping, cutting etc. cause rubber to wear and tear fast; the hull surface protective finish damages, and causes hull to descend service life.Rubber surface resistive connection dirt ability, a lot of marine organisms accumulated growths in the above also can cause fender to use and go wrong, and need cleaning in time to change.UHMWPE has the deficiency that characteristics such as high abrasion resistance, coefficient of friction be little just in time can remedy rubber fender and hull serious wear, and corrosion-resistant in the use, resistive connection is dirty, do not wear out etc. reduces maintenance cost, and high impact strength and viscoelastic damping performance can improve the performance that fender is accepted vibration again greatly.
States such as Japan have begun one's study and have used the little synthetic resin material of coefficient of friction as the material of fender and hull contact-making surface.For example, Japan Patent JP-A-2000-309914 discloses a kind of fender peculiar to vessel, wherein has the synthetic resin layer littler than the coefficient of friction of rubber and is arranged at the end face that contacts with boats and ships.In addition, JP-A-H11-93141 discloses a kind of fender peculiar to vessel, this fender comprises the fender main body of rubber material and covers the superficial layer of the vibrations receiving plane of fender main body that wherein superficial layer is made by the polymer blend of crystalline polyolefin resin and high unsaturation diene rubber.On the other hand, known a kind of fender peculiar to vessel wherein scribbles animi resin for the vibration receiving plane that receives vibration when ship berths and directly contacts with ship with the rubber section that prevents fender, and the coefficient of friction between this animi resin and the iron is lower than the coefficient of friction between rubber and the iron.This shows that the structure of following fender is that the vibration receiving surface adopts the little resin material of coefficient of friction, and UHMWPE has These characteristics, is that a kind of very desirable fender vibration receives material.
Yet UHMWPE seldom is applied to rubber fender really at present, Japan Bridgestone Corp. adopts UHMWPE as the surface vibration receiving layer in Chinese patents 201210027367.3, fix with machine riveting method and rubber, this is because the surface characteristic of UHMWPE makes very difficult directly compound with other materials.The fixing mode of machine riveting is generally adopted in the use occasion of above-mentioned fender peculiar to vessel, ultra-high molecular weight polyethylene (UHMWPE), has certain defective, and the UHMWPE surface needs punching to handle on the one hand, has reduced the vibration receiving area; On the other hand, use certain hour after, the riveted joint position generally can produce loosening, anchoring strength reduces between UHMWPE and the rubber, causes that obstacle appears in the energy transmission between vibration receiving layer and rubber.。
Summary of the invention
The present invention is difficult for and the bonding shortcoming of other materials because of surface inertness in order to overcome UHMWPE, and by UHMWPE is carried out surface treatment, application of adhesive again with rubber combined integrated vulcanizing moulding, prepares fender ultra-high molecular weight polyethylene composite board.Described composite board comprises, UHMWPE layer 1, and rubber layer 3 and the adhesive phase 2 between UHMWPE layer 1 and rubber layer 3 can also comprise reserving to be implanted in installing and fixing parts 4 in the rubber layer.Described composite board can be coated on and be used for the ship fender on the hull, also can be fixed in port and pier and be used for Anti-bumping protection.
In order to make above-mentioned composite board, the present invention proposes to produce the method for composite board, may further comprise the steps:
A. UHMWPE raw material and processing aid are mixed, employing is extruded or compression-moulding methods is processed into sheet material, carries out secondary operations according to the fender size then;
B. UHMWPE sheet material is needed and rubber carries out bonding surface and handles the surface-coated adhesive after the processing, dry processing then;
C. UHMWPE sheet material and rubber mixed sheet after will handling are compound, put into vulcanizer sulfuration typing then, are assembled into fender product through at last.
Preferably, described high molecular weight polyethylene board material is not less than 2000000 with the viscosity average molecular weigh of raw material, and more preferably viscosity average molecular weigh is between 2500000 ~ 9000000.
Preferably, the proportioning of described ultra-high molecular weight polyethylene and processing aid is:
Ultra-high molecular weight polyethylene 100 mass parts
Antioxidant 0.05 ~ 2 mass parts
UV resistant agent 0.05 ~ 1 mass parts
Nano modifier 1 ~ 20 mass parts
The effect of processing aid is processing stability, weatherability, hardness and the wearability that increases sheet material.This technology need not other any thinner and flow ability modifying agents;
Described antioxidant comprises one or more the composite uses in antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant 2246, the phosphite ester kind antioxidant.
Described UV resistant agent comprises one or more the composite uses among UV-531, UV-327, the UV-326.
Described nano modifier comprises nano imvite, nano silicon or nanometer muscovite.
Preferably, adopt nearly fusing point extruding technology in the extruding process thereof of above-mentioned steps a, the extruder processing temperature is 140 ~ 220 ℃, and sheet material is extruded thickness and is not more than 10mm.
In the compression-moulding methods of above-mentioned steps a, make UHMWPE 180 ~ 240 ℃ of fusions, moulding press is pressurized to 100 ~ 300MPa moulding, and sheet metal thickness is greater than 10mm.
Preferably, the described high molecular weight polyethylene board material surface treatment method of above-mentioned steps b comprises sand paper or roller polishing, surperficial flame inject process, plasma treatment, Corona discharge Treatment, radiation initiation surface grafting processing or chromic acid oxidation processes; More preferably plasma treatment.
Preferably, described method of plasma processing adopts air atmosphere and oxygen atmosphere, more preferably adopts oxygen atmosphere;
Preferably, the described adhesive of above-mentioned steps b comprises epobond epoxyn, polyurethane binder or commercial rubber and the single coating adhesive of metallic framework bonding, these single coating adhesives comprise the Cilbond-24 of Britain west nation chemical industry, the T7325 of Guangzhou Henkel chemical industry etc., the adhesive coating thickness is greater than 0.5mm.
Preferably, the prescription of the described rubber mixed sheet of above-mentioned steps c comprises: rubber 100 mass parts, carbon black 30 ~ 60 mass parts, zinc oxide 2 ~ 6 mass parts, promoter 1 ~ 2 mass parts, sulphur 2 ~ 4 mass parts, age resistor 1 ~ 2 mass parts, antioxidant 1 ~ 2 mass parts, plasticizer 5 ~ 10 mass parts.
Described rubber comprises one or more the composite uses in natural rubber (NR), butadiene-styrene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), ethylene propylene diene rubber (EPDM), the butyl rubber (IIR).
Described carbon black comprises one or more the composite uses among N754, N330, the N660.
Described promoter comprises one or more the composite uses in promoter PX, promoter ZDC, captax, diphenylguanidine, TM monex TD, promoter 808, the accelerant CZ.
Described plasticizer is phthalate, pine tar or four line oil, because environmental requirement reduces and uses phthalic ester plasticizer as far as possible.
Described age resistor comprises one or more the composite uses in age resistor 4020, antioxidant 4010NA, the anti-aging agent RD;
Preferably, the described sulfuration typing of above-mentioned steps c, 110 ~ 140 ℃ of curing temperatures, cure time is decided on prescription and rubber layer thickness, generally is no more than 1 hour.
Description of drawings
The structure chart of Fig. 1 ultra-high molecular weight polyethylene composite board of the present invention
The sectional structure chart of Fig. 2 ultra-high molecular weight polyethylene composite board of the present invention fender optimal way 1
The three-dimensional structure diagram of Fig. 3 ultra-high molecular weight polyethylene composite board of the present invention fender optimal way 2
The sectional structure chart of Fig. 4 ultra-high molecular weight polyethylene composite board of the present invention fender optimal way 3.
The specific embodiment
Below in conjunction with accompanying drawing, the present invention is described in more detail.
Embodiment 1:
UHMWPE layer formula: UHMWPE viscosity average molecular weigh 2500000 ~ 3500000,100 mass parts; Antioxidant 1010,1.0 mass parts; Antioxidant CA, 0.3 mass parts; UV-326,0.5 mass parts; UV-531,0.2 mass parts; Nano imvite, 6 mass parts.Processing temperature: extrude 140 ℃ in a district, extrude 165 ℃ in two districts, extrude 185 ℃ in three districts, 220 ℃ in mould one district, 220 ℃ in mould two districts, 195 ℃ in mould three districts.UHMWPE layer thickness 10mm, width 600mm.
The UHMWPE laminar surface is with 400 ~ 600 order sand paperings, and air purge is then with ethanol or acetone wiping, handle through plasma apparatus, adopt oxygen atmosphere, handle the back adhesive coating, adhesive adopts the Cilbond-24 of Britain west nation chemical industry, dry 30min.
Rubber mixed slice prescription: NR, 100 mass parts; Carbon black N754,25 mass parts; Carbon black N330,20 mass parts; Carbon black N660,15 mass parts; Zinc oxide, 5 mass parts; Sulphur, 2.5 mass parts; Captax, 0.75 mass parts; Diphenylguanidine, 0.75 mass parts; TM monex TD, 0.3 mass parts; Antioxidant 4010NA, 1 mass parts; Antioxidant 1010,1 mass parts; Pine tar, 3 mass parts; Four line oil, 6 mass parts; Dispersant T-78,2 mass parts.
As shown in Figure 1, UHMWPE layer 1 applies Cilbond-24 adhesive 2 through Surface Treatment with Plasma, dry processing then, and final adhesive layer 2 and rubber mixed sheet 3 are compound.Rubber mixed sheet thickness 40mm, the metal nuts 4 that inline processed is crossed is put into mould, vulcanizes 120 ℃ of curing temperatures, cure time 40min then at vulcanizing press.
Assemble according to shown in Figure 2, ultra-high molecular weight polyethylene composite board 1-4 after the moulding, wherein UHMWPE layer 1 towards outside, as the vibration dash receiver contact with hull, rubber face is installed on metallic plate 5 and the metallic support 6, and metallic support is fixed on the port and pier 7 then.
Embodiment 2:
UHMWPE layer formula: UHMWPE viscosity average molecular weigh 2500000 ~ 3500000,100 mass parts; Antioxidant 1010,1.0 mass parts; Antioxidant CA, 0.3 mass parts; UV-326,0.5 mass parts; UV-531,0.2 mass parts; Nano silicon, 10 mass parts.Raw material mixes the back and adds mould, 180 ℃ of processing temperatures, pressure 300MPa.UHMWPE layer thickness 15mm.The UHMWPE layer surface treatment method is with embodiment 1.
Rubber mixed slice prescription: NR, 70 mass parts; BR, 30 mass parts; Carbon black N330,35 mass parts; Carbon black N660,15 mass parts; Zinc oxide, 5 mass parts; Sulphur, 2.2 mass parts; Captax, 1.4 mass parts; Diphenylguanidine, 0.6 mass parts; TM monex TD, 0.3 mass parts; Antioxidant 4010NA, 1 mass parts; Antioxidant 1010,1 mass parts; Pine tar, 3 mass parts; Four line oil, 3 mass parts; Dispersant quality T-78,2 parts.Dish-type sheet rubber prescription is identical with it.
Rubber bag tank mixed sheet prescription: NR, 30 mass parts; Butyl rubber, 70 mass parts; Carbon black N754,35 mass parts; Carbon black N660,20 mass parts; Zinc oxide, 5 mass parts; Sulphur, 2.5 mass parts; Captax, 1.4 mass parts; Diphenylguanidine, 0.6 mass parts; TM monex TD, 0.3 mass parts; Antioxidant 4010NA, 0.7 mass parts; Anti-aging agent RD, 0.3 mass parts; Antioxidant 1010,1.5 mass parts; Pine tar, 3 mass parts; Four line oil, 3 mass parts; Dispersant T-78,2 mass parts.
As shown in Figure 3, UHMWPE layer 1 applies Cilbond-24 adhesive 2 through Surface Treatment with Plasma, then dry the processing, final adhesive layer 2 and rubber mixed sheet 3 are compound, rubber mixed sheet thickness 20mm, being connected with a diameter with rubber face is 500mm, height 600mm, the rubber bag tank 8 of wall thickness 20mm, rubber bag tank 8 opposite sides are connected with a dish-type sheet rubber 9, and sheet rubber 9 is connected with port and pier, a kind ofly like this protect that string is referred to as drum type or π type air bag protects string.Above-mentioned composite is put into mould, vulcanize at vulcanizing press, 110 ℃ of curing temperatures, cure time 50min.Rubber bag tank 8 is inflatable.
Embodiment 3:
The processing of UHMWPE layer and surface treatment method are with embodiment 1.As shown in Figure 4,1 is the UHMWPE layer, and 2 is adhesive layer, and 3 is rubber layer.Rubber layer 3 elastomeric compound prescriptions are with embodiment 1 film for rubber prescription, and the mixed sheet prescription of internal layer rubber is with embodiment 2 rubber bag tank films prescription in the rubber layer 3, and 4 metal nuts of crossing for inline processed are riveted with hull if desired, can embed.
According to rubber part structure shown in Figure 4 extrusion molding, rubber layer internal diameter 400mm, wall thickness 30mm, the UHMWPE layer of the surperficial bonding adhesive coating of the rubber layer die head that enters another heating vulcanizes 140 ℃ of curing temperatures, cure time 25min then.
According to the hull waterline length, measure certain-length High molecular weight polyethylene composite board fender and be coated on the hull, rubber layer 3 is bonding with hull then, and by the heating butt joint, because rubber has elasticity and can rely on elastic force to be coated on the hull preferably.
Claims (16)
1. a ultra-high molecular weight polyethylene composite board comprises, UHMWPE layer, rubber layer and the adhesive phase between UHMWPE layer and rubber layer.
2. according to the described ultra-high molecular weight polyethylene composite board of claim 1, it is characterized in that also comprising that reservation is implanted in the parts that install and fix in the rubber layer.
3. according to the described ultra-high molecular weight polyethylene composite board of claim 1, it is characterized in that the viscosity average molecular weigh of described ultra-high molecular weight polyethylene is not less than 2000000.
4. according to claim 1 or 3 described ultra-high molecular weight polyethylene composite boards, it is characterized in that the viscosity average molecular weigh of described ultra-high molecular weight polyethylene is between 2500000 ~ 9000000.
5. according to the production method of any described ultra-high molecular weight polyethylene composite board of claim 1-4, may further comprise the steps:
A. UHMWPE raw material and processing aid are mixed, employing is extruded or compression-moulding methods is processed into sheet material;
B. UHMWPE sheet material and rubber are carried out bonding position and carry out surface treatment, the surface-coated adhesive after the processing;
C. UHMWPE sheet material and the rubber mixed sheet of step b is compound, the sulfuration typing.
6. according to the production method of the described ultra-high molecular weight polyethylene composite board of claim 5, it is characterized in that the proportioning of described ultra-high molecular weight polyethylene and processing aid is:
Ultra-high molecular weight polyethylene 100 mass parts
Antioxidant 0.05 ~ 2 mass parts
UV resistant agent 0.05 ~ 1 mass parts
Nano modifier 1 ~ 20 mass parts;
Described antioxidant comprises one or more the composite uses in antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant 2246, the phosphite ester kind antioxidant;
Described UV resistant agent comprises one or more composite uses of UV-531, UV-327, UV-326;
Described nano modifier comprises a kind of in nano imvite, nano silicon, the nanometer muscovite.
7. according to the production method of the described ultra-high molecular weight polyethylene composite board of claim 5, it is characterized in that adopting nearly fusing point extruding technology in the extruding process thereof of step a, the extruder processing temperature is 140 ~ 220 ℃, sheet material is extruded thickness and is not more than 10mm;
In the compression-moulding methods of step a, make UHMWPE 180 ~ 240 ℃ of fusions, moulding press is pressurized to 100 ~ 300MPa moulding, and sheet metal thickness is greater than 10mm.
8. according to the described ultra-high molecular weight polyethylene composite board of claim 5 production method, it is characterized in that the described high molecular weight polyethylene board material surface treatment method of above-mentioned steps b comprises sand paper or roller polishing, surperficial flame inject process, plasma treatment, Corona discharge Treatment, radiation initiation surface grafting processing or chromic acid oxidation processes.
9. according to claim 5 or 8 described ultra-high molecular weight polyethylene composite board production methods, it is characterized in that the described high molecular weight polyethylene board material surface treatment method of above-mentioned steps b is plasma processing method.
10. according to the described high molecular weight polyethylene board material production method of claim 9, it is characterized in that described plasma processing method adopts air atmosphere and oxygen atmosphere.
11. according to the described ultra-high molecular weight polyethylene composite board of claim 10 production method, it is characterized in that plasma treatment adopts oxygen atmosphere.
12. according to the described ultra-high molecular weight polyethylene composite board of claim 5 production method, it is characterized in that the described adhesive of step b comprises that epobond epoxyn, polyurethane binder or commercial rubber and metallic framework bonding uses single coating adhesive, the adhesive coating thickness is greater than 0.5mm; Described single coating adhesive comprises the Cilbond-24 of Britain west nation chemical industry, the T7325 of Guangzhou Henkel chemical industry.
13. according to the described ultra-high molecular weight polyethylene composite board of claim 5 production method, the prescription that it is characterized in that the described rubber mixed sheet of step c comprises: rubber 100 mass parts, carbon black 30 ~ 60 mass parts, zinc oxide 2 ~ 6 mass parts, promoter 1 ~ 2 mass parts, sulphur 2 ~ 4 mass parts, age resistor 1 ~ 2 mass parts, antioxidant 1 ~ 2 mass parts, plasticizer 5 ~ 10 mass parts;
Described rubber comprises one or more the composite uses in natural rubber (NR), butadiene-styrene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), ethylene propylene diene rubber (EPDM), the butyl rubber (IIR);
Described carbon black comprises one or more the composite uses among N754, N330, the N660;
Described promoter comprises one or more the composite uses in promoter PX, promoter ZDC, captax, diphenylguanidine, TM monex TD, promoter 808, the accelerant CZ;
Described plasticizer is phthalate, pine tar or four line oil;
Described age resistor comprises one or more the composite uses in age resistor 4020, antioxidant 4010NA, the anti-aging agent RD.
14. according to the described ultra-high molecular weight polyethylene composite board of claim 13 production method, it is characterized in that described plasticizer is pine tar or four line oil.
15. according to the described ultra-high molecular weight polyethylene composite board of claim 5 production method, it is characterized in that the described sulfuration typing of step c, 110 ~ 140 ℃ of curing temperatures, cure time is no more than 1 hour.
16. according to the described ultra-high molecular weight polyethylene composite board of claim 1, it is characterized in that described composite board is coated on the hull and be used for the ship fender or be fixed in port and pier being used for Anti-bumping protection.
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| CN104961963A (en) * | 2015-07-13 | 2015-10-07 | 山东鲍尔浦实业有限公司 | High-weatherability ultra-high molecular weight polyethylene board material and application thereof |
| CN105256767A (en) * | 2015-10-15 | 2016-01-20 | 河南省超贝工程设备有限公司 | Ship board protection plate structure for wharf |
| CN110497624A (en) * | 2019-07-30 | 2019-11-26 | 华南理工大学 | A method of ultra-high molecular weight polyethylene is processed using discharge plasma sintering |
| CN110982133A (en) * | 2019-12-27 | 2020-04-10 | 苏州力达精密配件有限公司 | High-friction-coefficient rubber material and preparation method thereof |
| CN113863065A (en) * | 2021-09-24 | 2021-12-31 | 洛阳双瑞橡塑科技有限公司 | Low-resistance base plate and production method thereof |
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Application publication date: 20130710 |