CN100558804C - A kind of hardwood plate of producing with reclaimed rubber and preparation method thereof - Google Patents
A kind of hardwood plate of producing with reclaimed rubber and preparation method thereof Download PDFInfo
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- CN100558804C CN100558804C CNB200710156122XA CN200710156122A CN100558804C CN 100558804 C CN100558804 C CN 100558804C CN B200710156122X A CNB200710156122X A CN B200710156122XA CN 200710156122 A CN200710156122 A CN 200710156122A CN 100558804 C CN100558804 C CN 100558804C
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Abstract
The invention discloses a kind of hardwood plate of producing with reclaimed rubber and preparation method thereof.The preparation method of hardwood plate: at first waste rubber goods is made reclaimed rubber through desulfurization, then will be mixing evenly by 0.1~5 part of 100 parts of reclaimed rubber, 10~20 parts of vulcanizing agents, 0.3~5 part of vulcanization accelerator, 0.1~10 part in activator, 1~80 part of weighting agent, 0.1~1.5 part in anti-aging agent, softening agent in weight part with kneader, send into vulcanizing press compression molding, sulfuration again, 140~180 ℃ of curing temperatures, pressure 20~40MPa, 20~60 minutes time, make needed vulcanite sheet material.Hardwood plate of the present invention has very high MOR and modulus, makes it can be used as structured material, and to substitute traditional hard wood, hardwood plate also has excellent ageing-resistant performance, long service life.
Description
Technical field
The invention belongs to a kind of preparation method who produces hardwood plate, that be specifically related to is a kind of preparation method who produces hardwood plate with reclaimed rubber.
Background technology
The natural timber inadequate resource has become a worldwide problem, and China is the country that timber resources is extremely poor especially, therefore, seeks new wood substitutes, creates " second forest ", has become the problem that presses for solution.
On the other hand,, annual produce a large amount of rubber and plastic wastes, just can produce about 5,000,000 every day as the waste rubber tire whole world only along with the widespread use of product of rubber and plastic.The waste ' s reclamation deficiency has not only caused huge waste, and has caused the overcut of forest, causes a series of society and ecological problem thus.
Under above-mentioned background, the exploitation of wood plastic composite and suitability for industrialized production have been subjected to extensive attention in recent years.The exploitation wood plastic composite helps alleviating the pressure that is becoming tight timber day, helps conserving forests and the comprehensive utilization of plastic refuse.But wood plastic composite exists poor flexibility, problem such as not anti-skidding, and has series of advantages with the vulcanite sheet material of reclaimed rubber production, some performance even be better than timber, as the distortion that do not absorb water, do not ftracture, do not damage by worms, corrosion-resistant, antistatic etc.In addition, hardwood plate is difficult for creep strain, shock-resistant and wet and slippery property is good.
Goods such as waste and used rubber tyre reclaim comprehensive utilization and mainly obtain reclaimed rubber and rubber powder.Rubber powder is a kind of material of being made up of multiple materials such as rubber, carbon black, tenderizer and vulcanization accelerators that contains crosslinking structure, and therefore, rubber powder can only use as weighting agent, to reduce the consumption of rubber.In addition, vulcanized rubber powder is inertia, and is relatively poor with the consistency of material of main part, causes material property to descend easily if directly or too much fill.Adopt reclaimed rubber then not have above problem substantially as the raw material of hard plate material.
General rubber product has excellent elasticity, but poor rigidity, needs certain rigid as the sheet material of structured material, and this just requires rubber to have higher cross-linking density.Increase sulfur consumption and help to improve the cross-linking density of rubber, but when adopting common rubber, increase with sulfur consumption and can produce sulfur blooming, influence the dispersing uniformity of sulphur in sizing material, make the quality reduction of cross-linked rubber as raw material.The present invention adopt waste and used rubber tyre etc. for the reclaimed rubber of raw material production as raw material because its molecular weight is lower, can increase the solvability of sulphur, make sulphur better dispersed in sizing material, thereby improve the performance of hardwood plate.
Because the cross-linking density of vulcanite sheet material is higher, the saturation ratio of polymer molecular chain is increased, thereby improved the ageing-resistant performance of vulcanite goods, prolonged the work-ing life of goods.
In addition, can add glasscloth, to improve the intensity of the hardwood plate that adopts reclaimed rubber production as strongthener.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have high MOR and high-modulus with reclaimed rubber production, and the preparation method of the hardwood plate of excellent in resistance aging resistance.
The hardwood plate of producing with reclaimed rubber: raw material in weight part by 100 parts of reclaimed rubbers, 10~20 parts of vulcanizing agents, 0.3~5 part of vulcanization accelerator, 0.1~10 part in activator, 1~80 part of weighting agent, 0.1~1.5 part in anti-aging agent, 0.1~5 part in softening agent.
Described vulcanizing agent is a sulphur, and vulcanization accelerator is a kind of of 2-benzothiazolyl mercaptan, dibenzothiazyl disulfide, vulkacit D or tetramethyl-thiuram disulfide or their mixture.Activator is magnesium oxide, zinc oxide or stearic a kind of or their mixture.Weighting agent is a kind of of white carbon black, silica powder, diatomite, magnesiumcarbonate, talcum powder, pure aluminium silicate, lime carbonate, barium sulfate, mica powder, potter's clay or carbon black or their mixture.Anti-aging agent is N-phenyl-2-naphthylamines, 2,2 '-methylene-bis (4-methyl-6-special phenol), N, N '-diphenyl-para-phenylene diamine or 2,2,4-front three-1, polymeric a kind of or their mixture of 2-dihyaroquinoline.Softening agent is a kind of of stearic acid, oleic acid, Stockholm tar or paraffin or their mixture.
The preparation method of hardwood plate: at first make reclaimed rubber through desulfurization with waste rubber product, then will be mixing evenly by 0.1~5 part of 100 parts of reclaimed rubber, 10~20 parts of vulcanizing agents, 0.3~5 part of vulcanization accelerator, 0.1~10 part in activator, 1~80 part of weighting agent, 0.1~1.5 part in anti-aging agent, softening agent in weight part with kneader, send into vulcanizing press compression molding, sulfuration again, 140~180 ℃ of curing temperatures, pressure 20~40MPa, 20~60 minutes time, make needed vulcanite sheet material.
Hardwood plate of the present invention is that the reclaimed rubber that adopts waste rubber goods to obtain through desulfurization is made, have very high MOR and modulus, make it can be used as structured material, to substitute traditional hard wood, hardwood plate also has excellent ageing-resistant performance, long service life.
The hardwood plate applied range, as being used as the substitute of timber under various conditions, wherein be specially adapted to substitute outdoor garden landscape decoration timber, as as outdoor floor, fence, handrail, flower case, rubbish container, wayside pavilion, log cabin, balcony, stair, balcony etc., goods have under the condition of exposing to the sun and rain that the creep strain of being difficult for, shock-resistant and wet and slippery property are good, the distortion that do not absorb water, do not ftracture, do not damage by worms, series of advantages such as corrosion-resistant.In addition, the raw material sources of this hardwood plate are in waste rubber goods, and product cost is low, and improved the utilization ratio of waste rubber goods.
Embodiment
The influence that the present invention mainly is subjected to vulcanizing agent and promotor kind and consumption, weighting agent kind and consumption etc. with the intensity and the modulus of the vulcanite sheet material of reclaimed rubber production, and can change its intensity and modulus by regulating above-mentioned factor.
Vulcanizing agent sulphur can make polymkeric substance change netted macromole into by long chain molecule, because the large usage quantity of sulphur in the vulcanite goods, in order to obtain high-quality cross-linked rubber, the uniform distribution of sulphur in sizing material is extremely important.Adopt reclaimed rubber as basic glue, can increase the solvability of sulphur, make the dispersiveness of sulphur in sizing material better, thereby improve the performance of hardwood plate.
Vulcanization accelerator can promote the sulfuration of rubber, reduces the needed temperature of sulfuration, shortens curing time, and improves the physical and mechanical properties of cross-linked rubber.A kind of in 2-benzothiazolyl mercaptan, dibenzothiazyl disulfide, vulkacit D and the tetramethyl-thiuram disulfide or their mixture can be used as the vulcanization accelerator of reclaimed rubber.
In order to quicken to bring into play the activity and the promoter action of promotor, also can add metal oxide (as magnesium oxide, zinc oxide), organic acid (as stearic acid) as activator.
Reclaimed rubber has contained reinforcing filler usually, for the volume that increases sizing material saving reclaimed rubber, thereby reduce cost or improve processing performance, can add inert filler.Can be used as a kind of in the white carbon black of having of weighting agent, silica powder, diatomite, magnesiumcarbonate, talcum powder, pure aluminium silicate, lime carbonate, barium sulfate, mica powder, potter's clay or the carbon black or their mixture.
Though the cross-linking density of vulcanite sheet material is higher, the saturation ratio of polymer molecular chain is increased, ageing-resistant performance improves, but polymkeric substance is subject to the oxygenizement of oxygen and ozone, light and heat can both the promotes oxidn effect, makes molecular rupture, branching or further crosslinked, thereby makes the rubber hardening of being clamminess, physical and mechanical properties degenerates, so that lose use value.For improving the ageing-resistant performance of rubber plate, need to add anti-aging agent, can be as anti-aging agent be N-phenyl-2-naphthylamines, 2,2 '-methylene-bis (the special phenol of 4-methyl-6-), N, N '-diphenyl-para-phenylene diamine (antioxidant H), 2,2,4-trimethylammonium-1, a kind of in the 2-dihyaroquinoline polymer or their mixture.
In order to make reclaimed rubber softening, increase plasticity-and be convenient to processing, reduce power consumption, and the autohension and the viscosity of promoting sizing material, can add softening agent.A kind of in stearic acid, oleic acid, Stockholm tar, the paraffin or their mixture can be used as softening agent.
Different rubber plate specifications are varied with requiring, and the thin plate that is as thin as 0.3~2.0mm is arranged, and the middle plate of 3~10mm also has thick slab to 10~60mm; Width can reach 100~1500mm.What the offset plate surface had is smooth smooth, and what have has a groove decorative pattern.
Vulcanite preparation of plates method is with kneader that each component is mixing evenly, and through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration again, 140~180 ℃ of curing temperatures, pressure 20~40MPa, 20~60 minutes time.
Embodiment 1
In the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 12 parts in sulphur, 0.6 part of dibenzothiazyl disulfide, 0.6 part of tetramethyl-thiuram disulfide, 1 part in potter's clay, 2 parts in zinc oxide, 0.5 part of stearic acid, N with following material, N '-0.5 part of diphenyl-para-phenylene diamine, 0.8 part in paraffin, after each component mixes, through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration again, 160 ℃ of curing temperatures, pressure 25MPa, 35 minutes time.
The hardwood plate that makes has following physicals: MOR is 62.7MPa; Quiet modulus in elasticity in bending is 7150MPa.
Embodiment 2
In the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 0.8 part in 16 parts in sulphur, 1.2 parts of dibenzothiazyl disulfides, 20 parts in potter's clay, 2 parts in magnesium oxide, stearic acid, 2 with following material, 0.8 part of 2 '-methylene-bis (the special phenol of 4-methyl-6-), 1.5 parts of oleic acid, after each component mixes, through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration again, 160 ℃ of curing temperatures, pressure 30MPa, 30 minutes time.
The hardwood plate that makes has following physicals: MOR is 77.5MPa; Quiet modulus in elasticity in bending is 11550MPa.
Embodiment 3
In the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 1.2 parts in 12 parts in sulphur, 0.6 part of dibenzothiazyl disulfide, 0.8 part of vulkacit D, 40 parts in barium sulfate, 3 parts in zinc oxide, stearic acid, 2 with following material, 2,4-trimethylammonium-1,0.5 part of 2-dihyaroquinoline polymer, 2.0 parts of Stockholm tars, after each component mixes, again through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration, 160 ℃ of curing temperatures, pressure 35MPa, 35 minutes time.
The hardwood plate that makes has following physicals: MOR is 43.7MPa; Quiet modulus in elasticity in bending is 3560MPa.
Embodiment 4
In the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 12 parts in sulphur, 1.8 parts of tetramethyl-thiuram disulfides, 70 parts in lime carbonate, 5 parts in magnesium oxide, 1.8 parts of stearic acid, N-phenyl-0.3 part of 2-naphthylamines, 4.0 parts of oleic acid with following material, after each component mixes, again through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration, 150 ℃ of curing temperatures, pressure 40MPa, 40 minutes time.
The hardwood plate that makes has following physicals: MOR is 33.4MPa; Quiet modulus in elasticity in bending is 5960MPa.
Embodiment 5
In the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 12 parts in sulphur, 0.8 part of tetramethyl-thiuram disulfide, 0.8 part of vulkacit D with following material, 1.8 parts in 50 parts in magnesiumcarbonate, 4 parts in zinc oxide, stearic acid, 2,0.7 part of 2 '-methylene-bis (the special phenol of 4-methyl-6-), 1.0 parts in paraffin, after each component mixes, again through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration, 150 ℃ of curing temperatures, pressure 40MPa, 40 minutes time.
The hardwood plate that makes has following physicals: MOR is 39.7MPa; Quiet modulus in elasticity in bending is 4660MPa.
Claims (3)
1. the preparation method of a hard plate material of producing with reclaimed rubber, it is characterized in that: in the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 12 parts in sulphur with following material, 0.6 part of dibenzothiazyl disulfide, 0.6 part of tetramethyl-thiuram disulfide, 1 part in potter's clay, 2 parts in zinc oxide, 0.5 part of stearic acid, N, 0.5 part of N '-diphenyl-para-phenylene diamine, 0.8 part in paraffin, after each component mixes, again through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into the vulcanizing press compression molding, sulfuration, 160 ℃ of curing temperatures, pressure 25MPa, 35 minutes time.
2. the preparation method of a hard plate material of producing with reclaimed rubber, it is characterized in that: in the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 12 parts in sulphur with following material, 0.6 part of dibenzothiazyl disulfide, 0.8 part of vulkacit D, 40 parts in barium sulfate, 3 parts in zinc oxide, 1.2 parts of stearic acid, 2,2,4-trimethylammonium-1,0.5 part of 2-dihyaroquinoline polymer, 2.0 parts of Stockholm tars, after each component mixes, again through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into the vulcanizing press compression molding, sulfuration, 160 ℃ of curing temperatures, pressure 35MPa, 35 minutes time.
3. the preparation method of a hard plate material of producing with reclaimed rubber, it is characterized in that: in the reclaimed rubber of 100 weight parts, in in kneader, mixing under the room temperature: 12 parts in sulphur, 1.8 parts of tetramethyl-thiuram disulfides, 70 parts in lime carbonate, 5 parts in magnesium oxide, 1.8 parts of stearic acid, N-phenyl-0.3 part of 2-naphthylamines, 4.0 parts of oleic acid with following material, after each component mixes, again through the mixing rubber unvulcanizate that obtains of rubber mixing machine, rubber unvulcanizate is sent into vulcanizing press compression molding, sulfuration, 150 ℃ of curing temperatures, pressure 40MPa, 40 minutes time.
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