CN105504796B - Regenerate the anion in situ preparation method of ABS plastic in-situ flexible MC nylon 6 composite materials - Google Patents
Regenerate the anion in situ preparation method of ABS plastic in-situ flexible MC nylon 6 composite materials Download PDFInfo
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- CN105504796B CN105504796B CN201511027912.9A CN201511027912A CN105504796B CN 105504796 B CN105504796 B CN 105504796B CN 201511027912 A CN201511027912 A CN 201511027912A CN 105504796 B CN105504796 B CN 105504796B
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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
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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
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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
Abstract
The invention discloses a kind of anion in situ preparation method for regenerating ABS plastic in-situ flexible MC nylon 6 composite materials.Its raw material includes caprolactam, regeneration ABS plastic, catalyst, activator etc., caprolactam monomer is heated first and melted, vacuum dehydration, catalyst is added, regeneration ABS is added and is stirred until homogeneous scattered, continuation vacuum dehydration, add activator, it is cast to after being well mixed rapidly in the mould of preheating, cooling and demolding, produces regeneration ABS plastic in-situ flexible MC nylon 6 composite materials.The composite prepared with the present invention, its tensile strength, impact flexibility have obtained significantly improving.
Description
Technical field
The present invention relates to using the anionic polymerization side in situ for preparing the composite of regeneration ABS plastic toughened MC nylon 6
Method, belong to materials science field.
Background technology
MC Nylon 6 (MC nylon 6) is one kind in nylon material, during World War II by the Du Pont in the U.S.
The I.G companies of company (Dupont) and Germany succeed in developing jointly.Have that polymerization temperature is low, technique is simple compared with other nylon
Single, crystallinity height, molecular weight is big, mechanical property is excellent higher than common nylon, abrasion performance, self-lubricating, damping and silencing, grease resistance etc.
Point, largely the metals such as steel, copper, aluminium are replaced to make bearing, axle sleeve, bearing shell, gear, worm gear, loom shuttle, spiral in the industry
The parts such as oar and various sealing rings.With further expanding for MC nylon applications, more and more higher is proposed to its performance
Requirement.ABS plastic is one of five big synthetic plastics, its impact resistance, heat resistance, lower temperature resistance, chemical proofing and electricity
Gas function admirable, also have the characteristics that easy processing, product size are stable, lustrous surface is good, easy application, coloring can be with
Carry out the secondary operation such as surface metallization, plating, welding, hot pressing and bonding, be widely used in machinery, automobile, electronic apparatus,
The industrial circles such as instrument and meter, weaving and building, it is a kind of extremely wide thermoplastic engineering plastic of purposes.ABS plastic is by propylene
The terpolymer of nitrile, butadiene and styrene composition.In the production process of ABS plastic, unavoidable leftover pieces etc. can not
The product that uses and cause to waste.Final products as ABS plastic simultaneously, such as computer shell, television cabin, meter housing, car face
The products such as plate, ornament materials, eventually abandoned by people and be unable to secondary use, cause the waste of resource.Therefore we look for
To a kind of method for being capable of effective secondary use ABS plastic product.It is that one kind effectively carries using ABS plastic toughened MC nylon 6
The method of its high mechanical property, but ABS plastic generally requires surface treatment, can just make the combination jail between plastics and matrix
Gu so as to improve the mechanical property of composite.Therefore, in ABS plastic toughened system, how easily, effectively improve
Combination between plastics and matrix is the key of ABS plastic toughening composition.
The content of the invention
It is an object of the invention to provide a kind of anion for regenerating ABS plastic in-situ flexible MC nylon 6 composite materials is former
Position preparation method, by the composite prepared by this method, the combination between ABS plastic and MC nylon 6 is in polymerization process
What situ was formed, there is the characteristics of need not being surface-treated.The prepared compound premium properties not only with MC nylon 6,
And stretch intensity, tensile modulus of elasticity, notch impact strength with the mechanical performance more more excellent than MC nylon 6, particularly position and have
It is greatly improved.
To achieve these goals, the present invention adopts the following technical scheme that：
The cloudy from in-situ polymerization of ABS plastic in-situ flexible MC nylon 6 composite materials is regenerated, it is real through the following steps
It is existing：
The first step, caprolactam monomer is heated to 100-120 DEG C in reaction vessel, melts caprolactam, vacuum
Dehydration, vacuum 10-1-10-3Pa；
Second step, reaction vessel is heated to 150-170 DEG C, catalyst is added, continues to vacuumize, wherein catalyst and oneself
The weight ratio of lactam monomers is 0.1-2：100, vacuum 10-1-10-3Pa；
3rd step, reaction vessel is heated to 160-180 DEG C, according to the weight of regeneration ABS plastic and caprolactam monomer
Than for 0-10：100 ratio adds regeneration ABS plastic, magnetic agitation, regeneration ABS plastic is uniformly dispersed in caprolactam,
Dispersed regeneration ABS plastic/caprolactam melt is made；
4th step, it is 0-1.0 according to the weight of activator and caprolactam monomer ratio：100 ratio adds activator, fast
It is cast to after speed is well mixed in the mould for being preheated to 160-180 DEG C, is cooled down after being incubated 30-60min, produce regeneration ABS plastic
In-situ flexible MC nylon 6 composite materials.
Above-mentioned regeneration ABS plastic is using factory's leftover pieces or the dead meal of ABS plastic.
Above-mentioned catalyst is using metallic sodium, metallic potassium, magnesium metal, lithium metal, sodium hydroxide, sodium carbonate, sodium hydride and each
One kind in class organo-metallic compound.
Above-mentioned activator uses one kind in various isocyanates, vinylcaprolactam, carbonic ester and carboxylate.
It is the effective ways for improving its intensity using ABS plastic toughened MC nylon, the present invention utilizes the nitrile for regenerating ABS plastic
Base, there occurs certain Basic fluxing raction, in situ generated such as acid amides, amidine etc. and polyamide in the alkaline environment of caprolactam
In the same or analogous group of segment, have good compatibility with matrix MC nylon 6, finally cause ABS plastic and matrix Buddhist nun
It is firmly combined between dragon.Using fiber intensity in itself and good interface cohesion between matrix, MC nylon is improved
Mechanical property, be expected to extend the application of MC nylon 6, and the combination between ABS plastic and MC nylon 6 is in polymerization process
What situ was formed, there is the characteristics of need not being surface-treated.The tensile strength of the composite prepared by this law is 65-
85Mp, modulus of elasticity 380-620Mpa, elongation at break 150%-200%, notch impact strength 25-35KJ/m2。
Embodiment
Example below is the further explanation to the present invention, and be not intended to limit the present invention scope.
The present invention regenerates the cloudy from in-situ polymerization of ABS plastic in-situ flexible MC nylon 6 composite materials, passes through following step
It is rapid to realize：
The first step, caprolactam monomer is heated to 100-120 DEG C in reaction vessel, melts caprolactam, vacuum
Dehydration, vacuum 10-1-10-3Pa；
Second step, reaction vessel is heated to 150-170 DEG C, catalyst is added, continues to vacuumize, wherein catalyst and oneself
The weight ratio of lactam monomers is 0.1-2：100, vacuum 10-1-10-3Pa；
3rd step, reaction vessel is heated to 160-180 DEG C, according to the weight of regeneration ABS plastic and caprolactam monomer
Than for 0-10：100 ratio adds regeneration ABS plastic, magnetic agitation, regeneration ABS plastic is uniformly dispersed in caprolactam,
Dispersed regeneration ABS plastic/caprolactam melt is made；
4th step, it is 0-1.0 according to the weight of activator and caprolactam monomer ratio：100 ratio adds activator, fast
It is cast to after speed is well mixed in the mould for being preheated to 160-180 DEG C, is cooled down after being incubated 30-60min, produce regeneration ABS plastic
In-situ flexible MC nylon 6 composite materials.
Wherein, regenerate ABS plastic can use one kind in the dead meal of various factory's leftover pieces and various ABS plastic or
It is a variety of.The dead meal of ABS plastic can use discarded computer shell, television cabin, meter housing, car panel, ornament materials etc..
Wherein, catalyst is using metallic sodium, metallic potassium, magnesium metal, lithium metal, sodium hydroxide, sodium carbonate, sodium hydride and each
One kind in class organo-metallic compound.
Wherein, activator uses one kind in various isocyanates, vinylcaprolactam, carbonic ester and carboxylate.
Embodiment 1：
The anion in situ preparation method of present invention regeneration ABS plastic in-situ flexible MC nylon 6 composite materials, by following
Step is realized：
The first step, the caprolactam monomer of 100 parts by weight is placed in reaction vessel and is heated to 110 DEG C, makes caprolactam
Molten monomer obtains caprolactam melt, vacuum dehydration 30min, vacuum 10-1-10-3Pa。
Second step, the valve of reaction vessel is opened, release vacuum, reaction vessel is heated to 160 DEG C, added toward reaction vessel
Enter the sodium hydroxide of 0.4 parts by weight, vacuum dehydration 30min, vacuum 10-1-10-3Pa。
3rd step, the valve of reaction vessel is opened, release vacuum, reaction vessel is heated to 160 DEG C, added toward reaction vessel
Enter the regeneration ABS plastic of 1 parts by weight, magnetic agitation 30 minutes, regeneration ABS plastic is uniformly dispersed in caprolactam melt,
And certain Basic fluxing raction occurs, dispersed regeneration ABS plastic/caprolactam melt is made.
4th step, the valve of reaction vessel is opened, release vacuum, 2, the 4- toluene of 0.5 parts by weight is added toward reaction vessel
Diisocyanate, after being mixed rapidly, the material being mixed is poured into and is preheated in 180 DEG C of mould, natural cooling after being incubated 1 hour
Produce regeneration ABS plastic in-situ flexible MC nylon 6 composite materials.
It is equal through electron microscope observation, regeneration ABS plastic by composite impact section made from the present embodiment method
Even is dispersed in MC nylon-6 matrix bodies, and impact fracture surface becomes coarse, and into cloud sheet shape, matrix is substantially surrendered and caused
Plastic deformation, but it is empty caused by Presence of an interface unsticking, illustrate the feature of flexible fracture, therefore break for the toughness of half fragility half
Split.Its performance is as follows：Tensile strength 85Mpa, modulus of elasticity 610MPa, notch impact strength 27KJ/m2, elongation at break
155%.
Embodiment 2：
The first step, the caprolactam monomer of 100 parts by weight is placed in reaction vessel and is heated to 110 DEG C, makes caprolactam
Molten monomer obtains caprolactam melt, vacuum dehydration 30min, vacuum 10-1-10-3Pa。
Second step, the valve of reaction vessel is opened, release vacuum, reaction vessel is heated to 160 DEG C, adds 0.5 weight
The sodium hydride of part, vacuum dehydration 30min, vacuum 10-1-10-3Pa。
3rd step, the valve of reaction vessel is opened, release vacuum, reaction vessel is heated to 170 DEG C, added toward reaction vessel
Enter the regeneration ABS plastic of 5 parts by weight, magnetic agitation 30 minutes, regeneration ABS plastic is uniformly dispersed in caprolactam melt,
And certain Basic fluxing raction occurs, dispersed regeneration ABS plastic/caprolactam melt is made.
4th step, opens the valve of reaction vessel, releases vacuum, toward reaction vessel add 0.6 parts by weight acetyl group oneself
Lactams, after being mixed rapidly, the material being mixed is poured into and is preheated in 180 DEG C of mould, natural cooling produces after being incubated 1 hour
Regenerate ABS plastic in-situ flexible MC nylon 6 composite materials.
It is as follows by composite property made from the present embodiment method：Tensile strength 68Mpa, modulus of elasticity 588MPa,
Notch impact strength 30KJ/m2, elongation at break 170%.
Embodiment 3：
The first step, the caprolactam monomer of 100 parts by weight is placed in reaction vessel and is heated to 110 DEG C, makes caprolactam
Molten monomer obtains caprolactam melt, vacuum dehydration 30min, vacuum 10-1-10-3Pa。
Second step, valve is opened, releases vacuum, reaction vessel is heated to 160 DEG C, adds the sodium methoxide of 0.6 parts by weight,
Vacuum dehydration 30min, vacuum 10-1-10-3Pa。
3rd step, the valve of reaction vessel is opened, release vacuum, reaction vessel is heated to 180 DEG C, added toward reaction vessel
Enter the regeneration ABS plastic of 10 parts by weight, magnetic agitation 30 minutes, regeneration ABS plastic is uniformly dispersed in caprolactam melt,
And certain Basic fluxing raction occurs, dispersed regeneration ABS plastic/caprolactam melt is made.
4th step, opens the valve of reaction vessel, releases vacuum, toward reaction vessel add 0.7 parts by weight acetyl group oneself
Lactams, after being mixed rapidly, the material being mixed is poured into and is preheated in 180 DEG C of mould, natural cooling produces after being incubated 1 hour
Regenerate ABS plastic in-situ flexible MC nylon 6 composite materials.
It is as follows by composite property made from the present embodiment method：Tensile strength 55Mpa, modulus of elasticity 560MPa,
Notch impact strength 28KJ/m2, elongation at break 166%.
Embodiment 4：
The first step, the caprolactam monomer of 100 parts by weight is placed in reaction vessel and is heated to 110 DEG C, makes caprolactam
Molten monomer obtains caprolactam melt, vacuum dehydration 30min, vacuum 10-1-10-3Pa。
Second step, valve is opened, releases vacuum, reaction vessel is heated to 160 DEG C, adds the metallic sodium of 0.3 parts by weight,
Vacuum dehydration 30min, vacuum 10-1-10-3Pa。
3rd step, the valve of reaction vessel is opened, release vacuum, reaction vessel is heated to 180 DEG C, added toward reaction vessel
Enter the regeneration ABS plastic of 10 parts by weight, magnetic agitation 30 minutes, regeneration ABS plastic is uniformly dispersed in caprolactam melt,
And certain Basic fluxing raction occurs, dispersed regeneration ABS plastic/caprolactam melt is made.
4th step, the valve of reaction vessel is opened, release vacuum, 2, the 4- toluene of 0.4 parts by weight is added toward reaction vessel
Diisocyanate, after being mixed rapidly, the material being mixed is poured into and is preheated in 180 DEG C of mould, natural cooling after being incubated 1 hour
Produce regeneration ABS plastic in-situ flexible MC nylon 6 composite materials.
It is as follows by composite property made from the present embodiment method：Tensile strength 58Mpa, modulus of elasticity 586MPa,
Notch impact strength 33KJ/m2, elongation at break 195%.
Claims (4)
1. regenerate the anionic in-situ polymerization method of ABS plastic in-situ flexible MC nylon 6 composite materials, it is characterised in that pass through
The following steps are realized：
The first step, caprolactam monomer is heated to 100-120 DEG C in reaction vessel, melts caprolactam, vacuum dehydration,
Vacuum is 10-1-10-3Pa；
Second step, reaction vessel is heated to 150-170 DEG C, catalyst is added, continues to vacuumize, wherein catalyst and acyl in oneself
The weight ratio of amine monomers is 0.1-2：100, vacuum 10-1-10-3Pa；
3rd step, reaction vessel is heated to 160-180 DEG C, the weight ratio according to regeneration ABS plastic and caprolactam monomer is
1-5：100 ratio adds regeneration ABS plastic, magnetic agitation, regeneration ABS plastic is uniformly dispersed in caprolactam, is made
Dispersed regeneration ABS plastic/caprolactam melt；
4th step, it is 0-1.0 according to the weight of activator and caprolactam monomer ratio：100 ratio adds activator, rapid mixed
It is cast in the mould for being preheated to 160-180 DEG C after closing uniformly, is cooled down after being incubated 30-60min, it is in situ produces regeneration ABS plastic
The composite of toughened MC nylon 6.
2. the anionic in-situ polymerization side of regeneration ABS plastic in-situ flexible MC nylon 6 composite materials according to claim 1
Method, it is characterised in that：Above-mentioned regeneration ABS plastic is using factory's leftover pieces or the dead meal of ABS plastic.
3. the anionic in-situ polymerization side of regeneration ABS plastic in-situ flexible MC nylon 6 composite materials according to claim 1
Method, it is characterised in that：Above-mentioned catalyst is using metallic sodium, metallic potassium, magnesium metal, lithium metal, sodium hydroxide, sodium carbonate, hydrogenation
One kind in sodium and all kinds of organo-metallic compounds.
4. the anionic in-situ polymerization side of regeneration ABS plastic in-situ flexible MC nylon 6 composite materials according to claim 1
Method, it is characterised in that：Above-mentioned activator uses one in various isocyanates, vinylcaprolactam, carbonic ester and carboxylate
Kind.
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