CN1057543C - Coal-base polymer interpenetration network alloy and its preparation technology - Google Patents
Coal-base polymer interpenetration network alloy and its preparation technology Download PDFInfo
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- CN1057543C CN1057543C CN94104380A CN94104380A CN1057543C CN 1057543 C CN1057543 C CN 1057543C CN 94104380 A CN94104380 A CN 94104380A CN 94104380 A CN94104380 A CN 94104380A CN 1057543 C CN1057543 C CN 1057543C
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a coal-base polymer interpenetration network alloy and a preparation process thereof, wherein the content of a first polymer, namely coal is from 65 to 80%(weight); the content of a second polymer is from 35 to 20%(weight); the second polymer is polyphenyl alkene, polyethylene, an ABS resin and nitrile rubber, or one of corresponding monomers of the polyphenyl alkene, the polyethylene, the ABS resin and the nitrile rubber, or multiple equal-proportion combined objects of the corresponding monomers; the first polymer and the second polymer are swollen and dissolved by a solvent, carried out with polymerization crosslinking reaction at a temperature of 80 to 90 DEG C under existence of an initiator, and carried out with the processes of sedimentation, suction filtration, vacuum drying, mixing and granulation. The alloy has the characteristics of heat resistance, antistatic performance and electromagnetic shielding, can be processed into flexible tubes, instrument outer casings, packing boxes, plates, etc., has wide sources and low price of raw materials of the present invention, and has development prospects.
Description
The invention belongs to other macromolecular compound fields, particularly relate to a kind of coal-base polymer interpenetration network alloy.
In the background technology of the present invention, the U.S.4 of the application U.S. in October, 1978,122,050 mix coal after nitration treatment with Resins, epoxy, but make the foamable polymer matrix material through thermal treatment again.And for example Britain is filled in polyethylene, polypropylene, polyvinyl chloride, Resins, epoxy etc. in any one with the coal fine powder, makes coal-based plastics.France increases the adhesion component of coal with containing the low price coal of soluble constituent or add compounds such as polyvalent alcohol, aldehyde in coal, makes the coal plasticizing then under 623-723 ° of K, and compression moulding makes thermoset sheet material etc.In sum, at present make coal-based plastics as raw material and have many deficiencies, need that on the one hand coal is done complicated redox and handle, the product that simple on the other hand mechanically mixing and hot pressing form with coal, its mechanical property and mechanical property are not ideal enough, are difficult to realize commercialization.
The objective of the invention is to utilize coal to have the feature of macromolecular network structure Heat stability is good, with coal as polymer network I, introduce another kind or two or more polymkeric substance therein as network II, be prepared into coal-base polymer interpenetration network alloy through crosslinking reaction, this interpenetration network alloy has good mechanical and mechanical property, easily be processed into various section bars, make to become to have widely to be worth higher commodity.
In order to realize purpose of the present invention, technical scheme of the present invention is achieved in that uses the coal that contains 65-80% weight as the I network polymer, and at least a or two above synthetic or natural polymer of 35-20% weight is as the II network polymer.I network polymer and II network polymer are by solvent-swollen or after dissolving, in the presence of initiator, carry out the polymerization crosslinking reaction in temperature 80-90 ℃, the II network polymer includes polypropylene, polystyrene, ABS resin (acrylonitrile-butadiene-styrene resin), paracril, styrene-butadiene rubber(SBR), polyamine fat, polymeric amide, natural rubber, when using above-mentioned two or more different polymkeric substance, its volume proportion is the equal proportion combination, but total amount is no more than the weight of 35-20%.Its solvent is tetrahydrofuran (THF), naphthane, sherwood oil etc., the concentration 20-50% weight of solution, initiator has naphthalene one sodium, stearic acid, benzoyl peroxide, its volume is the heavy 1-2% weight of coal, as precipitation agent, its precipitation agent equates or 30% volume with the volume of solvent with methyl alcohol or ethanol or water.
The step of preparation process of preparation coal-base polymer interpenetration network alloy is as follows successively:
A, first network polymer are heat-treated in inert gas filled pyrolysis oven or carbide furnace through 100-650 ℃ temperature;
B, carry out the promptly broken granularity≤1mm of three grades of fragmentations, the granularity of fine crushing≤75 μ m, the granularity of super fine crushing＜10 μ m through heat treated coal;
C, the coal of three grades of fragmentations is put into container with solvent-swollen dissolving, the concentration of coal is 20-50%wt;
D, coal add the naphthalene-sodium of the heavy 1-2% of coal and the benzoyl peroxide of 1-2% simultaneously in swelling process, and stir 0.5-1 hour;
E, the II network polymer of 35-20% weight, use with the swelling coal facies with solvent-swollen up to dissolving, the concentration of polymkeric substance is 2-5%;
F, lysed II network polymer is joined in the I network polymer, stir simultaneously, and in 80-90 ℃ temperature, carry out polymerization crosslinking and reacted 0.5-1.5 hour, the precipitation agent that adds again after reaction finishes with solvent volume equivalent or 30% precipitates, and its precipitation agent is methyl alcohol or ethanol or water;
The throw out that g, suction filtration obtain temperature be 70-90 ℃ through vacuum-drying, under 100-200 ℃ of temperature, carried out mixing 9-15 minute then, promptly get the alloy first product.
H, alloy first product make the alloy masterbatch through granulation;
I, with plastics or rubber tooling and technology the alloy masterbatch is dissolved and to squeeze out difform standardized product, when needing surface treatment, can spray different color.
Coal used in the present invention can not heat-treated yet, and depends mainly on the self property of coal, can not heat-treat for the low-rank coal of brown coal and functional group content height, pore structure prosperity and directly carry out three grades of fragmentations.
The present invention compared with prior art, be that it is interspersed mutually together the network of two or more polymkeric substance by chemical reaction, formation is than the monomer network macromolecular structure of crypto set more, matter is crisp when having overcome coal and using as material, unmanageable shortcoming, the exploitation of this alloy not only have actual value for coal utilization develops to the advanced material direction.The characteristics that also have heat-resisting, anti-solvent, antistatic and electromagnetic shielding, can partly replace the high synthesis technique complex engineering of price plastics, it can be processed into Flexible pipes, instrument shell, tr, sheet material etc., the surface can spray various colors, and its mechanics and electrical property are:
Pressure resistance 〉=10
5N/cm
2, bending strength 〉=10
3N/cm
2
Shock strength 60N.cm/cm
2, resistivity 〉=10
3-10
12Ω .cm.
The material source of this alloy is extensive, and is cheap, is to utilize the counter good approach of going back timber, steel of coal.
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Get the I polymkeric substance coal of 70-80% weight, heat-treat in inert gas filled pyrolysis oven or carbide furnace with 100-650 ℃ temperature, heat treated coal is carried out three grades be crushed to particle diameter＜10 μ m, be added to the solution that is made into 20-50% weight in the I polymkeric substance coal with tetrahydrofuran solvent, coal is carried out swelling, also to add the stearic acid of the heavy 1-2% of coal and the initiator that the heavy 1-2% benzoyl peroxide of coal is made compound linking agent simultaneously, and stirred 0.5-1 hour, get the II polymkeric substance paracril of 30-20% weight again, wherein acrylonitrile content 40%, be made into the 2-5% nitrile rubber solution with solvents tetrahydrofurane again, make the dissolving of paracril swelling, after this lysed nitrile rubber solution is joined in the I polymkeric substance, make its temperature of reaction rise to 80-85 ℃, reaction times is 0.5-1 hour, and stir simultaneously, after the polymerization crosslinking reaction finishes, the precipitation agent that adds again with tetrahydrofuran solvent volume equivalent or 30% precipitates, precipitation agent is a methyl alcohol, and sedimentary mixed solution separates through suction filtration, fractionation process reclaims solvent and precipitation agent respectively.To precipitate good coal-base polymer interpenetration network alloy first product simultaneously after 70-90 ℃ of vacuum-drying, carry out carrying out again in mixing 10 minutes granulation at 130-160 ℃, just make coal-base polymer interpenetration network alloy masterbatch product, its alloy masterbatch can be processed into instrument, the meter case of tubing, plate or different shape again by vulcanizing press or injection molding machine of plastic, spray into various colors simultaneously on the surface.
Embodiment 2
Get the ultra-fine I polymkeric substance coal of 70-80% weight, the liquid that is made into 20-50% weight with naphthane adds and to carry out the swelling dissolving in the coal, goes back the Vinylstyrene of 2-5% of coal weight and the vinylbenzene of 2-5% simultaneously; The benzoyl peroxide that adds the heavy 1-2% of coal again, and stirred 1-1.5 hour, get the II polymer poly vinylbenzene of 30-20%, with naphthane solution dissolved polystyrene, polystyrene concentration is 2-5%, this solution is added in the I polymkeric substance with 80-90 ℃ thermotonus 1 hour, and precipitation agent is a methyl alcohol, and other steps are with embodiment 1.
Claims (5)
1, a kind of coal-base polymer interpenetration network alloy, it is characterized in that containing the coal of 65-80% weight ratio as the I network polymer, synthetic or the natural polymer of one or more of 35-20% weight ratio is as the II network polymer, the II network polymer includes: polystyrene, polypropylene, acrylonitrile-butadiene-styrene resin, paracril; styrene-butadiene rubber(SBR); polyamine fat; polymeric amide; natural rubber; I; the II polymkeric substance dissolves by solvent-swollen; its solvent has tetrahydrofuran (THF); naphthane; sherwood oil; the liquid after swelling dissolving carries out the polymerization crosslinking reaction in 80-90 ℃ in the presence of initiator; the reaction times is 0.5-1.5 hour; its initiator includes naphthalene-sodium; stearic acid; benzoyl peroxide; above-mentioned mixing solutions is through precipitating suction filtration; vacuum-drying; carried out mixing 9-15 minute at 100-200 ℃, granulation coal-base polymer interpenetration network alloy.
2, coal-base polymer interpenetration network alloy according to claim 1, it is characterized in that the II network polymer can be that one or more add in the I network polymer simultaneously, when using two or more different polymkeric substance, the shared part by weight of each polymkeric substance makes up with equal proportion, but total amount is no more than the weight of 35-20%.
3, a kind of preparation technology who makes the described coal-base polymer interpenetration network alloy of claim 1 comprises precipitation, suction filtration, vacuum-drying, granulation common process, it is characterized in that also comprising following steps successively:
A, first network polymer are heat-treated in inert gas filled pyrolysis oven or carbide furnace through 100-650 ℃ temperature;
B, carry out the promptly broken granularity≤1mm of three grades of fragmentations, the granularity of fine crushing≤75 μ m, the granularity of super fine crushing＜10 μ m through heat treated coal;
C, the coal of three grades of fragmentations is put into container with solvent-swollen dissolving, the concentration of coal is 20-50%wt;
D, coal add initiator and the linking agent of the heavy 1-2% of coal simultaneously in swelling process, and stir 0.5-1 hour;
E, the II network polymer of 35-20 is placed in the container, use with the swelling coal facies with solvent-swollen up to dissolving, the concentration of polymkeric substance is 2-5%;
F, lysed II network polymer is joined in the I network polymer, stir simultaneously, and in 80-90 ℃ temperature, carry out polymerization crosslinking and reacted 0.5-1.5 hour, the precipitation agent that adds again after reaction finishes with solvent volume equivalent or 30% precipitates, and its precipitation agent is methyl alcohol or ethanol or water;
The throw out that g, suction filtration obtain temperature be 70-90 ℃ through vacuum-drying, under 100-200 ℃ of temperature, carried out mixing 9-15 minute then, promptly get the alloy first product.
4, the preparation technology of coal-base polymer interpenetration network alloy according to claim 3, it is characterized in that precipitation agent that suction filtration goes out and solvent liquid can by separate, fractionation process reclaims precipitation agent and solvent respectively.
5, the preparation technology of coal-base polymer interpenetration network alloy according to claim 3 is characterized in that melting temperature is 130-160 ℃ of mixing 9-15 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104380A CN1057543C (en) | 1994-04-27 | 1994-04-27 | Coal-base polymer interpenetration network alloy and its preparation technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94104380A CN1057543C (en) | 1994-04-27 | 1994-04-27 | Coal-base polymer interpenetration network alloy and its preparation technology |
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| Publication Number | Publication Date |
|---|---|
| CN1110689A CN1110689A (en) | 1995-10-25 |
| CN1057543C true CN1057543C (en) | 2000-10-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94104380A Expired - Fee Related CN1057543C (en) | 1994-04-27 | 1994-04-27 | Coal-base polymer interpenetration network alloy and its preparation technology |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591457B (en) * | 2009-04-24 | 2012-05-23 | 中国核动力研究设计院 | Rubber-base flexible shielding material and preparation method thereof |
| CN112812489A (en) * | 2021-02-04 | 2021-05-18 | 浙江科普特新材料有限公司 | Modified plastic based on interpenetrating network structure and preparation method thereof |
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1994
- 1994-04-27 CN CN94104380A patent/CN1057543C/en not_active Expired - Fee Related
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