CN105504796A - Anionic in-situ preparation method of renewable ABS plastic in-situ toughening MC nylon 6 composite material - Google Patents
Anionic in-situ preparation method of renewable ABS plastic in-situ toughening MC nylon 6 composite material Download PDFInfo
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- CN105504796A CN105504796A CN201511027912.9A CN201511027912A CN105504796A CN 105504796 A CN105504796 A CN 105504796A CN 201511027912 A CN201511027912 A CN 201511027912A CN 105504796 A CN105504796 A CN 105504796A
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- abs plastic
- nylon
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- composite material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
- C08G69/18—Anionic polymerisation
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses an anionic in-situ preparation method of a renewable ABS plastic in-situ toughening MC nylon 6 composite material. Raw materials comprise caprolactam, renewable ABS plastics, a catalyst and an activator. The preparation method comprises the following steps: first heating and melting caprolactam monomers, vacuum dehydrating, adding the catalyst, adding the renewable ABS, stirring, uniformly dispersing, continuously vacuum dehydrating, adding the activator, rapidly uniformly mixing, pouring into a preheated mold, cooling, and demolding to obtain the renewable ABS plastic in-situ toughening MC nylon 6 composite material. The tensile strength and the impact flexibility of the composite material prepared by adopting the method are greatly improved.
Description
Technical field
The present invention relates to the method adopting anionic polymerization original position to prepare regeneration ABS plastic toughened MC nylon 6 matrix material, belong to materials science field.
Background technology
MC Nylon 6 (MC nylon 6) is the one in nylon material, is jointly succeeded in developing during World War II by the E.I.Du Pont Company (Dupont) of the U.S. and the I.G company of Germany.Have compared with other nylon that polymerization temperature is low, technique is simple, degree of crystallinity is high, molecular weight is large, mechanical property higher than advantages such as common nylon, abrasion performance, self-lubricating, damping and silencing, grease resistances, the metals such as replacement steel, copper, aluminium a large amount of in the industry makes the component such as bearing, axle sleeve, bearing shell, gear, worm gear, loom shuttle, water screw and various sealing-rings.Along with further expanding of MC nylon range of application, more and more higher requirement is proposed to its performance.ABS plastic is one of five large synthetic plasticss, its shock resistance, thermotolerance, lower temperature resistance, chemical proofing and excellent electrical properties, also there is the features such as easy processing, product size is stable, surface luster property is good, easy application, painted, surface metallization, plating, welding, hot pressing and the secondary processing such as bonding can also be carried out, being widely used in the industrial circles such as machinery, automobile, electronic apparatus, instrument, weaving and building, is the thermoplastic engineering plastic that a kind of purposes is extremely wide.ABS plastic is by vinyl cyanide, the terpolymer of divinyl and vinylbenzene composition.In the production process of ABS plastic, keep away product that unavoidable scrap stock etc. cannot use and cause waste.Simultaneously as the finished product of ABS plastic, as computer shell, television cabin, meter housing, car panel, the products such as finishing material, finally can to abandon by people and can not second stage employ, cause the waste of resource.Therefore we find a kind of can the method for effective second stage employ ABS plastic product.Utilize ABS plastic toughened MC nylon 6 to be methods of effective its mechanical property of raising a kind of, but ABS plastic generally needs surface treatment, the combination between plastics and matrix just can be made firm, thus improve the mechanical property of matrix material.Therefore, in ABS plastic toughened system, how easily, effectively the combination improved between plastics and matrix be the key of ABS plastic toughening composition.
Summary of the invention
The object of the present invention is to provide a kind of anion in situ preparation method regenerating ABS plastic in-situ flexible MC nylon 6 composite material, by the matrix material prepared by the method, combination between ABS plastic and MC nylon 6 is that original position is formed in the course of the polymerization process, has and does not need surface-treated feature.Prepared compound not only has the premium properties of MC nylon 6, and has that the mechanical property, particularly position more outstanding than MC nylon 6 stretch intensity, modulus in tension, notched Izod impact strength are greatly improved.
To achieve these goals, the present invention adopts following technical scheme:
The moon of regeneration ABS plastic in-situ flexible MC nylon 6 composite material, from in-situ polymerization, realizes through the following steps:
The first step, is heated to 100-120 DEG C by caprolactam monomer in reaction vessel, makes hexanolactam melting, vacuum hydro-extraction, and vacuum tightness is 10
-1-10
-3pa;
Second step, is heated to 150-170 DEG C by reaction vessel, adds catalyzer, continues to vacuumize, and wherein the weight ratio of catalyzer and caprolactam monomer is 0.1-2:100, and vacuum tightness is 10
-1-10
-3pa;
3rd step, reaction vessel is heated to 160-180 DEG C, the ratio being 0-10:100 according to the weight ratio regenerating ABS plastic and caprolactam monomer adds regeneration ABS plastic, magnetic agitation, regeneration ABS plastic is uniformly dispersed in hexanolactam, obtained homodisperse regeneration ABS plastic/hexanolactam melt;
4th step, the ratio being 0-1.0:100 according to the weight ratio of activator and caprolactam monomer adds activator, be cast in the mould being preheated to 160-180 DEG C after mixing rapidly, cool after insulation 30-60min, ABS plastic in-situ flexible MC nylon 6 composite material must be regenerated.
Above-mentioned regeneration ABS plastic adopts the dead meal of factory's scrap stock or ABS plastic.
Above-mentioned catalyzer adopts the one in sodium Metal 99.5, potassium metal, MAGNESIUM METAL, metallic lithium, sodium hydroxide, sodium carbonate, sodium hydride and all kinds of organometallic compound.
Above-mentioned activator adopts the one in various isocyanic ester, vinylcaprolactam, carbonic ether and carboxylicesters.
ABS plastic toughened MC nylon is adopted to be the effective ways improving its intensity, the present invention utilizes the itrile group of regeneration ABS plastic to there occurs certain Basic fluxing raction in the alkaline environment of hexanolactam, in-situ preparation such as acid amides, the group same or analogous with the segment in polymeric amide such as amidine, have good consistency with matrix MC nylon 6, finally make between ABS plastic and base nylon in conjunction with firm.Utilize the intensity of fiber itself and and matrix between good interface cohesion, improve the mechanical property of MC nylon, be expected to the range of application expanding MC nylon 6, and the combination between ABS plastic and MC nylon 6 is that original position is formed in the course of the polymerization process, has and does not need surface-treated feature.The tensile strength of the matrix material prepared by this law is 65-85Mp, and Young's modulus is 380-620Mpa, elongation at break 150%-200%, and notched Izod impact strength is 25-35KJ/m
2.
Embodiment
Embodiment further illustrates of the present invention below, and the unrestricted scope of the invention.
The present invention regenerates the moon of ABS plastic in-situ flexible MC nylon 6 composite material from in-situ polymerization, realizes through the following steps:
The first step, is heated to 100-120 DEG C by caprolactam monomer in reaction vessel, makes hexanolactam melting, vacuum hydro-extraction, and vacuum tightness is 10
-1-10
-3pa;
Second step, is heated to 150-170 DEG C by reaction vessel, adds catalyzer, continues to vacuumize, and wherein the weight ratio of catalyzer and caprolactam monomer is 0.1-2:100, and vacuum tightness is 10
-1-10
-3pa;
3rd step, reaction vessel is heated to 160-180 DEG C, the ratio being 0-10:100 according to the weight ratio regenerating ABS plastic and caprolactam monomer adds regeneration ABS plastic, magnetic agitation, regeneration ABS plastic is uniformly dispersed in hexanolactam, obtained homodisperse regeneration ABS plastic/hexanolactam melt;
4th step, the ratio being 0-1.0:100 according to the weight ratio of activator and caprolactam monomer adds activator, be cast in the mould being preheated to 160-180 DEG C after mixing rapidly, cool after insulation 30-60min, ABS plastic in-situ flexible MC nylon 6 composite material must be regenerated.
Wherein, regeneration ABS plastic can adopt one or more in the dead meal of various factories scrap stock and various ABS plastic.The dead meal of ABS plastic can adopt discarded computer shell, television cabin, meter housing, car panel, finishing material etc.
Wherein, catalyzer adopts the one in sodium Metal 99.5, potassium metal, MAGNESIUM METAL, metallic lithium, sodium hydroxide, sodium carbonate, sodium hydride and all kinds of organometallic compound.
Wherein, activator adopts the one in various isocyanic ester, vinylcaprolactam, carbonic ether and carboxylicesters.
Embodiment 1:
The present invention regenerates the anion in situ preparation method of ABS plastic in-situ flexible MC nylon 6 composite material, realizes through the following steps:
The first step, is placed in reaction vessel by the caprolactam monomer of 100 weight parts and is heated to 110 DEG C, makes caprolactam monomer melting obtain hexanolactam melt, vacuum hydro-extraction 30min, and vacuum is 10
-1-10
-3pa.
Second step, opens the valve of reaction vessel, removes vacuum, reaction vessel is heated to 160 DEG C, and add the sodium hydroxide of 0.4 weight part toward reaction vessel, vacuum hydro-extraction 30min, vacuum is 10
-1-10
-3pa.
3rd step, open the valve of reaction vessel, remove vacuum, reaction vessel is heated to 160 DEG C, add the regeneration ABS plastic of 1 weight part toward reaction vessel, magnetic agitation 30 minutes, makes regeneration ABS plastic be uniformly dispersed in hexanolactam melt, and there is certain Basic fluxing raction, obtained homodisperse regeneration ABS plastic/hexanolactam melt.
4th step, open the valve of reaction vessel, remove vacuum, 2 of 0.5 weight part is added toward reaction vessel, 4-tolylene diisocyanate, after being mixed rapidly, the material be mixed is poured in the mould being preheated to 180 DEG C, be incubated naturally cooling after 1 hour and namely obtain regeneration ABS plastic in-situ flexible MC nylon 6 composite material.
The composite impact section obtained by the present embodiment method is through electron microscope observation, regeneration ABS plastic is dispersed in MC nylon-6 matrix body uniformly, impact fracture surface becomes coarse, become cloud sheet shape, the viscous deformation that matrix obviously there occurs surrender and produces, the cavity of Presence of an interface unsticking generation again, the feature that flexible ruptures is described, is therefore half fragility half ductile rupture.Its performance is as follows: tensile strength 85Mpa, Young's modulus 610MPa, notched Izod impact strength 27KJ/m
2, elongation at break 155%.
Embodiment 2:
The first step, is placed in reaction vessel by the caprolactam monomer of 100 weight parts and is heated to 110 DEG C, makes caprolactam monomer melting obtain hexanolactam melt, vacuum hydro-extraction 30min, and vacuum is 10
-1-10
-3pa.
Second step, opens the valve of reaction vessel, and remove vacuum, reaction vessel is heated to 160 DEG C, adds the sodium hydride of 0.5 weight part, vacuum hydro-extraction 30min, vacuum is 10
-1-10
-3pa.
3rd step, open the valve of reaction vessel, remove vacuum, reaction vessel is heated to 170 DEG C, add the regeneration ABS plastic of 5 weight parts toward reaction vessel, magnetic agitation 30 minutes, makes regeneration ABS plastic be uniformly dispersed in hexanolactam melt, and there is certain Basic fluxing raction, obtained homodisperse regeneration ABS plastic/hexanolactam melt.
4th step; open the valve of reaction vessel; remove vacuum; the vinylcaprolactam of 0.6 weight part is added toward reaction vessel; after being mixed rapidly; the material be mixed is poured in the mould being preheated to 180 DEG C, be incubated naturally cooling after 1 hour and namely obtain regeneration ABS plastic in-situ flexible MC nylon 6 composite material.
The composite property obtained by the present embodiment method is as follows: tensile strength 68Mpa, Young's modulus 588MPa, notched Izod impact strength 30KJ/m
2, elongation at break 170%.
Embodiment 3:
The first step, is placed in reaction vessel by the caprolactam monomer of 100 weight parts and is heated to 110 DEG C, makes caprolactam monomer melting obtain hexanolactam melt, vacuum hydro-extraction 30min, and vacuum is 10
-1-10
-3pa.
Second step, opens valve, and remove vacuum, reaction vessel is heated to 160 DEG C, adds the sodium methylate of 0.6 weight part, vacuum hydro-extraction 30min, vacuum is 10
-1-10
-3pa.
3rd step, open the valve of reaction vessel, remove vacuum, reaction vessel is heated to 180 DEG C, add the regeneration ABS plastic of 10 weight parts toward reaction vessel, magnetic agitation 30 minutes, makes regeneration ABS plastic be uniformly dispersed in hexanolactam melt, and there is certain Basic fluxing raction, obtained homodisperse regeneration ABS plastic/hexanolactam melt.
4th step; open the valve of reaction vessel; remove vacuum; the vinylcaprolactam of 0.7 weight part is added toward reaction vessel; after being mixed rapidly; the material be mixed is poured in the mould being preheated to 180 DEG C, be incubated naturally cooling after 1 hour and namely obtain regeneration ABS plastic in-situ flexible MC nylon 6 composite material.
The composite property obtained by the present embodiment method is as follows: tensile strength 55Mpa, Young's modulus 560MPa, notched Izod impact strength 28KJ/m
2, elongation at break 166%.
Embodiment 4:
The first step, is placed in reaction vessel by the caprolactam monomer of 100 weight parts and is heated to 110 DEG C, makes caprolactam monomer melting obtain hexanolactam melt, vacuum hydro-extraction 30min, and vacuum is 10
-1-10
-3pa.
Second step, opens valve, and remove vacuum, reaction vessel is heated to 160 DEG C, adds the sodium Metal 99.5 of 0.3 weight part, vacuum hydro-extraction 30min, vacuum is 10
-1-10
-3pa.
3rd step, open the valve of reaction vessel, remove vacuum, reaction vessel is heated to 180 DEG C, add the regeneration ABS plastic of 10 weight parts toward reaction vessel, magnetic agitation 30 minutes, makes regeneration ABS plastic be uniformly dispersed in hexanolactam melt, and there is certain Basic fluxing raction, obtained homodisperse regeneration ABS plastic/hexanolactam melt.
4th step, open the valve of reaction vessel, remove vacuum, 2 of 0.4 weight part is added toward reaction vessel, 4-tolylene diisocyanate, after being mixed rapidly, the material be mixed is poured in the mould being preheated to 180 DEG C, be incubated naturally cooling after 1 hour and namely obtain regeneration ABS plastic in-situ flexible MC nylon 6 composite material.
The composite property obtained by the present embodiment method is as follows: tensile strength 58Mpa, Young's modulus 586MPa, notched Izod impact strength 33KJ/m
2, elongation at break 195%.
Claims (4)
1. the moon regenerating ABS plastic in-situ flexible MC nylon 6 composite material, from in-situ polymerization, is characterized in that, realizes through the following steps:
The first step, is heated to 100-120 DEG C by caprolactam monomer in reaction vessel, makes hexanolactam melting, vacuum hydro-extraction, and vacuum tightness is 10
-1-10
-3pa;
Second step, is heated to 150-170 DEG C by reaction vessel, adds catalyzer, continues to vacuumize, and wherein the weight ratio of catalyzer and caprolactam monomer is 0.1-2:100, and vacuum tightness is 10
-1-10
-3pa;
3rd step, reaction vessel is heated to 160-180 DEG C, the ratio being 0-10:100 according to the weight ratio regenerating ABS plastic and caprolactam monomer adds regeneration ABS plastic, magnetic agitation, regeneration ABS plastic is uniformly dispersed in hexanolactam, obtained homodisperse regeneration ABS plastic/hexanolactam melt;
4th step, the ratio being 0-1.0:100 according to the weight ratio of activator and caprolactam monomer adds activator, be cast in the mould being preheated to 160-180 DEG C after mixing rapidly, cool after insulation 30-60min, ABS plastic in-situ flexible MC nylon 6 composite material must be regenerated.
2. the moon of regeneration ABS plastic in-situ flexible MC nylon 6 composite material according to claim 1 is from in-situ polymerization, it is characterized in that: above-mentioned regeneration ABS plastic adopts the dead meal of factory's scrap stock or ABS plastic.
3. the moon of regeneration ABS plastic in-situ flexible MC nylon 6 composite material according to claim 1 is from in-situ polymerization, it is characterized in that: above-mentioned catalyzer adopts the one in sodium Metal 99.5, potassium metal, MAGNESIUM METAL, metallic lithium, sodium hydroxide, sodium carbonate, sodium hydride and all kinds of organometallic compound.
4. the moon of regeneration ABS plastic in-situ flexible MC nylon 6 composite material according to claim 1 is from in-situ polymerization, it is characterized in that: above-mentioned activator adopts the one in various isocyanic ester, vinylcaprolactam, carbonic ether and carboxylicesters.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511027912.9A CN105504796B (en) | 2015-12-31 | 2015-12-31 | Regenerate the anion in situ preparation method of ABS plastic in-situ flexible MC nylon 6 composite materials |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511027912.9A CN105504796B (en) | 2015-12-31 | 2015-12-31 | Regenerate the anion in situ preparation method of ABS plastic in-situ flexible MC nylon 6 composite materials |
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| CN105504796A true CN105504796A (en) | 2016-04-20 |
| CN105504796B CN105504796B (en) | 2018-01-16 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243346A (en) * | 2016-08-19 | 2016-12-21 | 邢台中车环保科技有限公司 | Fiber reinforcement MC nylon composite materials and forming method thereof |
| CN115637043A (en) * | 2022-10-28 | 2023-01-24 | 江苏宏盛尼龙有限公司 | High-strength super-wear-resistant MC nylon composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4443889A1 (en) * | 1994-12-09 | 1996-06-13 | Bayer Ag | Compatibilising of polyamide 6 in recyclate of ABS-polycarbonate blend and opt. ABS |
| CN102391642A (en) * | 2011-08-31 | 2012-03-28 | 李刚 | Preparation method of modified monomer cast (MC) nylon 6 blending material |
-
2015
- 2015-12-31 CN CN201511027912.9A patent/CN105504796B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4443889A1 (en) * | 1994-12-09 | 1996-06-13 | Bayer Ag | Compatibilising of polyamide 6 in recyclate of ABS-polycarbonate blend and opt. ABS |
| CN102391642A (en) * | 2011-08-31 | 2012-03-28 | 李刚 | Preparation method of modified monomer cast (MC) nylon 6 blending material |
Non-Patent Citations (1)
| Title |
|---|
| 李枭 等: "浇铸尼龙6/ABS聚合物合金的研究", 《塑料工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243346A (en) * | 2016-08-19 | 2016-12-21 | 邢台中车环保科技有限公司 | Fiber reinforcement MC nylon composite materials and forming method thereof |
| CN115637043A (en) * | 2022-10-28 | 2023-01-24 | 江苏宏盛尼龙有限公司 | High-strength super-wear-resistant MC nylon composite material and preparation method thereof |
| CN115637043B (en) * | 2022-10-28 | 2023-10-27 | 江苏宏盛尼龙有限公司 | High-strength super-wear-resistant MC nylon composite material and preparation method thereof |
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