CN105038200A - Multiple-composite-toughened nylon-6 composite material, composite toughening agent and preparation method thereof - Google Patents
Multiple-composite-toughened nylon-6 composite material, composite toughening agent and preparation method thereof Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a multiple-composite-toughened nylon-6 composite material which includes following components, by mass, 100 parts of nylon 6, 5-50 parts of a composite toughening agent, 0.05-1 part of an anti-oxidant and 1-10 parts of an inorganic powder material. The invention also discloses a preparation method of the multiple-composite-toughened nylon-6 composite material. The preparation method includes the steps of pre-treatment of raw materials, preparation of the toughening agent, weighing, mixing and extrusion to prepare the multiple-composite-toughened nylon-6 composite material. The invention also discloses a composite toughening agent and a preparation method thereof. In the invention, waste tire poser is pre-treated, so that not only is shock resistance of nylon 6 is improved, but also a problem that adverse influence on the processing rheological property of the nylon 6 due to addition of the toughening agent can be avoided. The preparation method of the toughened nylon is not changed in technical route in the prior art, is simple in operation, is strong in adaptability and is easy to carry out industrially.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of multiple elements design toughner, the invention still further relates to a kind of multiple elements design toughened Nylon 6 matrix material, the invention still further relates to a kind of preparation method of multiple elements design toughner, the invention still further relates to a kind of preparation method of multiple elements design toughened Nylon 6 matrix material.
Background technology
Polyamide 6 (PA6) is commonly called as nylon 6, is the engineering plastics that a kind of conventional output is large, has that intensity is high, wear resistance is good, have the advantage such as oil resistant, resist chemical concurrently simultaneously.Compared with other engineering plastics, nylon 6 is easier to shaping, consumes energy low in the course of processing.Have a wide range of applications in household electrical appliance, automotive industry, high-abrasive material industry (carrying roller used in as bearing, gear, pulley, belt conveyor system) etc.But containing a large amount of polar amide keys in nylon 6 molecular structure, make it have larger water absorbability, cause the dimensional stabilizing of moulded products bad; In addition, its low temperature and dry state notch impact toughness poor, limit its application field.
At present, the tradition and the most popular method that improve nylon 6 toughness add rubber or elastomerics and nylon 6 to carry out blending and modifying.By rubber or elastomerics are dispersed in nylon-6 matrix body, when it is subject to foreign impacts effect, be dispersed in the rubber in system or elastomeric absorbent energy, formed in material modified system or produce Voiding effect and surrender, crazing and shear zone is caused again by the transmission at interface, the energy that further consumption is a large amount of, thus the shock resistance (i.e. toughness) improving nylon 6.In the process, rubber or the elastomerics dispersion size in system, homogeneity and be the key issue that impact property improves with the interface binding power of nylon-6 matrix body.
Authorization Notice No. is CN102964822B patent of invention, disclose a kind of toughened with silicon rubber modify nylon resins and preparation method thereof, take polysiloxane as toughner, employing amido silicon oil is compatilizer, melt blending is carried out after mixing with nylon, and then add containing hydrogen silicone oil and make linking agent and platinum complex catalyst makes the disperse phase organosilicon in nylon matrix carry out dynamic vulcanization, thus it is toughness reinforcing to realize nylon.To be increase-volume synchronously carry out with toughness reinforcing for the maximum feature of the method, and toughening effect is better.But prepared material cost is too high, limit its popularization commercially.Authorization Notice No. is respectively CN102115591B, CN101880459B, CN101235197B, CN101191013B, CN102051043B, CN102391431B patent of invention, disclose and adopt elastomerics [mainly ethylene-octene (POE), ethylene-propylene diene copolymer (EPDM)], compatilizer etc. with nylon blending to improve toughness and the cold tolerance of nylon, all have good toughening effect.But in above-mentioned technical scheme disclosed in these, the properties-correcting agent adopted is all pure elastomerics, and these material prices are higher, cause the material sexual valence prepared lower.In addition, owing to effectively not improving the mobility of toughner, its dispersing property in modifying process and modified nylon composite materials mobility not good, not only will affect subsequent material forming process to produce, and the performance of properties-correcting agent is not also not fully exerted, therefore, there is certain limitation.
Summary of the invention
In order to overcome the deficiency that prior art exists, the present invention aims to provide a kind of multiple elements design toughened Nylon 6 matrix material.This multiple elements design modified nylon 6 composites combines the good mechanical performance of nylon 6, oil resistant, corrosion-resistant; the toughness of waste rubber powder and low cost; and the feature such as the toughness of thermoplastic elastomer POE excellence; produce the advantages such as the dimensional stability with good toughness, resistance to deterioration, oil resistant erosion resistance and excellence, have concurrently simultaneously energy-saving and cost-reducing, reduce costs and the demand of large-scale production.
Another object of the present invention is to provide a kind of preparation method of multiple elements design toughened Nylon 6 matrix material.
Another object of the present invention is to provide a kind of composite toughing agent and preparation method thereof.
First technical scheme of the present invention is, a kind of multiple elements design toughened Nylon 6 matrix material, comprises following component according to mass parts: nylon 6 is 100 parts; Composite toughing agent 5 parts ~ 50 parts; 0.05 part ~ 1 part, oxidation inhibitor; Inorganic powder material 1 part ~ 10 parts.
In technique scheme, further, this multiple elements design toughened Nylon 6 matrix material, comprises following component according to mass parts: nylon 6 is 100 parts; Composite toughing agent 10 parts ~ 30 parts; 0.05 part ~ 0.08 part, oxidation inhibitor; Inorganic powder material 5 parts ~ 8 parts.
Composite toughing agent comprises following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts; Wherein, modified elastomer terpolymer EP rubber comprises following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts; Modified waste-tyre rubber-powder comprises following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts.
The particle diameter of waste rubber powder is 40 order ~ 100 orders, and oxidation inhibitor is antioxidant 1010.
Second technical scheme of the present invention is, a kind of preparation method of multiple elements design toughened Nylon 6 matrix material, specifically implements according to following steps:
Step 1, raw materials pretreatment: by nylon 6, waste-tyre rubber-powder, inorganic powder filler etc. after surface treatment 50 DEG C ~ 100 DEG C dry 1 ~ 24 hour respectively;
Step 2, prepare composite toughing agent, be specially;
Step 2.1, prepare modified elastomer terpolymer EP rubber;
Step 2.2, surface modification is carried out to waste-tyre rubber-powder;
Step 2.3, prepare composite toughing agent;
Step 3, weighing, weigh following component according to mass parts: NYLON610 0 part, composite toughing agent 5 parts ~ 50 parts, inorganic powder material 1 part ~ 10 parts, 0.05 part ~ 1 part, oxidation inhibitor;
Step 4, mixing, join load weighted nylon 6, composite toughing agent, inorganic powder material and oxidation inhibitor in high-speed mixer and mix 3-10min, mix;
Step 5, extruding, join in the hopper of twin screw extruder by the above-mentioned material mixed, carry out extruding pelletization, and cooling is dried, obtained multiple elements design toughened Nylon 6 matrix material.
In technique scheme,
Prepare composite toughing agent in step 2, be specially:
Step 2.1, prepare modified elastomer terpolymer EP rubber, be specially:
Step 2.1.1, weigh following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts;
Step 2.1.2, by load weighted modified monomer maleic anhydride, initiator dicumyl peroxide acetone solution evenly after, be sprayed onto in EPDM, then it is mixed in high-speed mixer with load weighted polypropylene, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM of MAH grafting, i.e. EPDM-MAH; Wherein, extrusion temperature is: 170 ~ 205 DEG C; Extruder screw rotating speed is: 60 ~ 120r/min;
Step 2.2, surface modification is carried out to waste-tyre rubber-powder, be specially;
Step 2.2.1, weigh following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts;
Step 2.2.2, load weighted solubilizing agent is sprayed onto unlatching be equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 3-5 days, put it in high-speed mixer, open mixing machine, coupling agent is sprayed wherein, after mixing, obtain modified waste-tyre rubber-powder; Wherein, coupling agent is silane series, and solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil;
Step 2.3, prepare composite toughing agent, be specially:
Step 2.3.1, weighing: weigh following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts;
Step 2.3.2, load weighted modified elastomer terpolymer EP rubber and modified waste-tyre rubber-powder put into high-speed mixer mixing, prepare composite toughing agent.
Forcing machine condition setting in step 6: first paragraph is respectively 190 DEG C-210 DEG C, 200 DEG C-220 DEG C, 200 DEG C-220 DEG C, 200 DEG C-220 DEG C, 200 DEG C-225 DEG C, 200 DEG C-225 DEG C, 200 DEG C-220 DEG C to the 7th section of temperature, and head temperature is 228 DEG C.
3rd technical scheme of the present invention is, a kind of preparation method of composite toughing agent specifically implements according to following steps:
Steps A, prepare modified elastomer terpolymer EP rubber, be specially:
Step a1, weigh following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts;
Step a2, by load weighted modified monomer maleic anhydride, initiator dicumyl peroxide acetone solution evenly after, be sprayed onto in EPDM, then it is mixed in high-speed mixer with load weighted polypropylene, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM of MAH grafting, i.e. EPDM-MAH; Wherein, extrusion temperature is: 170 ~ 205 DEG C; Extruder screw rotating speed is: 60 ~ 120r/min;
Step B, surface modification is carried out to waste-tyre rubber-powder, be specially;
Step b1, weigh following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts;
Step b2, load weighted solubilizing agent is sprayed onto unlatching be equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 3-5 days, put it in high-speed mixer, open mixing machine, coupling agent is sprayed wherein, after mixing, obtain modified waste-tyre rubber-powder; Wherein, coupling agent is silane series, and solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil;
Step C, prepare composite toughing agent, be specially:
Step c1, weighing: weigh following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts;
Step c2, load weighted modified elastomer terpolymer EP rubber and modified waste-tyre rubber-powder put into high-speed mixer mixing, prepare composite toughing agent.
4th technical scheme of the present invention is that a kind of composite toughing agent, comprises following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts; Wherein, modified elastomer terpolymer EP rubber comprises following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts; Modified waste-tyre rubber-powder comprises following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts.
In technique scheme, coupling agent is silane series; Solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil, and the particle diameter of waste rubber powder is 40 order ~ 100 orders, and oxidation inhibitor is antioxidant 1010.
The invention has the beneficial effects as follows: the present invention is by carrying out pre-treatment to junked tire powder, then using its together with elastomerics as composite toughing agent, for toughened Nylon 6, preparing in toughened Nylon 6, composite toughing agent can be scattered in nylon-6 matrix body preferably, not only increase the shock resistance of nylon 6, and significantly reduce because the interpolation of toughner is to nylon 6 material processing rheological property adverse effect.Secondly, owing to have employed rubber powder made by junked tire for plasticized modifier, not only cheap, reduce the production cost of material, there is good economic benefit, and its pollution to environment can also be reduced.In addition, the preparation method of tenacity increased nylon of the present invention, does not change current technology technological line, simple to operate, and suitability is strong, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is process flow sheet prepared by a kind of composite toughing agent;
Fig. 2 is process flow sheet prepared by a kind of multiple elements design toughened Nylon 6 matrix material.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
The invention provides a kind of multiple elements design toughened Nylon 6 matrix material, comprise following component according to mass parts: nylon 6 is 100 parts; Composite toughing agent 5 parts ~ 50 parts; 0.05 part ~ 1 part, oxidation inhibitor; Inorganic powder material 1 part ~ 10 parts.
Further, following component is comprised according to mass parts: nylon 6 is 100 parts; Composite toughing agent 10 parts ~ 30 parts; 0.05 part ~ 0.08 part, oxidation inhibitor; Inorganic powder material 5 parts ~ 8 parts.
Composite toughing agent comprises following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts; Wherein, modified elastomer terpolymer EP rubber comprises following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts; Modified waste-tyre rubber-powder comprises following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts.
The present invention also provides a kind of preparation method of multiple elements design toughened Nylon 6 matrix material, specifically implements according to following steps:
Step 1, raw materials pretreatment: by nylon 6, waste-tyre rubber-powder, inorganic powder filler etc. after surface treatment 50 DEG C ~ 100 DEG C dry 1 ~ 24 hour respectively;
Step 2, prepare composite toughing agent, be specially:
Step 2.1, prepare modified elastomer terpolymer EP rubber, be specially:
Step 2.1.1, weigh following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts;
Step 2.1.2, by load weighted modified monomer maleic anhydride, initiator dicumyl peroxide acetone solution evenly after, be sprayed onto in EPDM, then it is mixed in high-speed mixer with load weighted polypropylene, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM of MAH grafting, i.e. EPDM-MAH; Wherein, extrusion temperature is: 170 ~ 205 DEG C; Extruder screw rotating speed is: 60 ~ 120r/min; The consumption of DCP is 0.02 ~ 0.15% of EPDM consumption; The consumption of MAH is 0.5 ~ 1.5% of EPDM consumption.Because EPDM has crosslinked tendency strongly under the effect of DCP, in grafting process, the viscosity of system increases rapidly, cause percentage of grafting on the low side, for this reason, adopt the PP adding 5 ~ 10% of its weight in EPDM, by the degraded of PP under DCP effect cushion system viscosity in grafting process increase sharply cause to graft reaction disadvantageous effect, to obtaining the percentage of grafting of wishing.The transformation period of DCP at 170 DEG C of temperature be the sublimation temperature of 1min, MAH at about 200 DEG C, therefore, the top temperature extruded should control near 200 DEG C, can not be too high, otherwise percentage of grafting (or graft effect) not only can be caused not good, also can because of its pollution caused environment that distils.Require that the percentage of grafting of MAH is 0.6 ~ 1% in the present invention.
Step 2.2, surface modification is carried out to waste-tyre rubber-powder, be specially;
Step 2.2.1, weigh following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts;
Step 2.2.2, load weighted solubilizing agent is sprayed onto unlatching be equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 3-5 days, put it in high-speed mixer, open mixing machine, coupling agent is sprayed wherein, after mixing, obtain modified waste-tyre rubber-powder; Wherein, coupling agent is silane series, and solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil;
Step 2.3, prepare composite toughing agent, be specially:
Step 2.3.1, weighing: weigh following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts;
Step 2.3.2, load weighted modified elastomer terpolymer EP rubber and modified waste-tyre rubber-powder put into high-speed mixer mixing, prepare composite toughing agent.
Step 3, weighing, weigh following component according to mass parts: NYLON610 0 part, composite toughing agent 5 parts ~ 50 parts, inorganic powder material 1 part ~ 10 parts, 0.05 part ~ 1 part, oxidation inhibitor;
Step 4, mixing, join load weighted nylon 6, composite toughing agent, inorganic powder material and oxidation inhibitor in high-speed mixer and mix 3-10min, mix;
Step 5, extruding, the above-mentioned material mixed is joined in the hopper of twin screw extruder, carry out extruding pelletization, cooling, dry, obtain multiple elements design toughened Nylon 6 matrix material, first paragraph is respectively 190 DEG C-210 DEG C, 200 DEG C-220 DEG C, 200 DEG C-220 DEG C, 200 DEG C-220 DEG C, 200 DEG C-225 DEG C, 200 DEG C-225 DEG C, 200 DEG C-220 DEG C to the 7th section of temperature, and head temperature is 228 DEG C.
The matrix of modified elastomer selects terpolymer EP rubber (EPDM).EPDM has lower second-order transition temperature, is Polymer Toughening the most frequently used at present.Because base nylon 6 belongs to the stronger superpolymer of polarity, EPDM belongs to non-polar polymer, and when it is for toughened matrix polymer nylon 6, both exist the problem of poor compatibility, therefore, must carry out surface modification treatment to elastomerics.
Modified monomer selects maleic anhydride (MAH).This monomer is mainly used in modifying the surface of EPDM, obtain the EPDM (EPDM-MAH) of maleic anhydride graft, make its surface with the carboxylic group containing polarity, on the one hand the polarity of EPDM is increased, on the other hand, the carboxylic group on its surface with the amino generation chemical reaction on nylon 6 molecular chain, can solve the problem of the poor compatibility of toughner and base nylon 6.
Dicumyl peroxide (DCP) selected by initiator.For reacting elastomeric finishing monomer radical initiation grafting.
Using rubber powder of waste tire, be obtained through pulverizing by automobile-used junked tire, market can have been bought, and its particle diameter is 40 ~ 200 orders.Because these rubber powders are from tire for vehicles, be the product that rubber part is cross-linked, and the rubber after being cross-linked normally is difficult to dissolve, and therefore, by swelling method, just will can make its recuperation section elasticity.In addition, the common rubber for tire for vehicles belongs to non-polar polymer usually, with base nylon 6 poor compatibility, therefore, must carry out surface modification treatment to using rubber powder of waste tire.
The mixture of one or more in naphthenic oil, Stockholm tar, hydrocarbon oil selected by solubilizing agent.Solubilizing agent is mainly used for carrying out pre-treatment to using rubber powder of waste tire, makes it swelling, recuperation section elasticity.
Inorganic powder filler, select in anhydrite powder, talcum powder one or both.Anhydrite powder and talcum powder all have fibrous texture structure, play certain enhancing or strengthening action in this composite system; In addition, adding of filler, not only reduce the cost of material system, also can solve the technical bottleneck that the product dimensional stability that causes because of contraction problem is not good.
Silane series KH-550 selected by coupling agent, it is amino due to its small molecules chain containing, there is structural similarity with base nylon 6, be conducive to the raising of substance to be processed consistency in this material prescription system, also improve the dispersiveness of treated material in base nylon 6 simultaneously.In system of the present invention, KH-550 is mainly used for the using rubber powder of waste tire after to solubilising and inorganic powder filler carries out surface treatment.
It is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester that oxidation inhibitor is selected, and commodity are called antioxidant 1010.Oxidation inhibitor is mainly used in slowing down the catabiosis of matrix material in the course of processing, improves the stability of material.
Nylon 6 raw material of the present invention is mass-produced commodity in the market, and the specification rank of use is sticky in being, directly can buy and obtain.Owing to carrying out using rubber powder of waste tire using solubilizing agent in pre-treatment treating processes, it not only serves the swelling effect to rubber powder, also can play the effect of softening agent, therefore, does not need to add softening agent in addition.
Embodiment 1
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=5 after process: 5, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) following component is weighed according to mass parts: modified monomer maleic anhydride (MAH) 1.5 parts, initiator dicumyl peroxide (DCP) 0.11 part, matrix terpolymer EP rubber (EPDM) 100 parts, polypropylene (PP) 7.5 parts; By load weighted monomer (MAH), initiator (DCP) with acetone solution evenly after, be sprayed onto in the EPDM of grafting, then it is mixed 3 minutes with appropriate PP in high speed blender, after acetone volatilization, mixture (length-to-diameter ratio 40:1, screw diameter is 75) in twin screw extruder melt extrudes.The engine speed of twin screw extruder is 200 revs/min, rate of feeding is 150 kgs/hr, the temperature of each warm area of forcing machine is followed successively by 168 DEG C, 175 DEG C, 185 DEG C, 188 DEG C, 195 DEG C, 200 DEG C, 200 DEG C, head temperature is 205 DEG C, cool after extruding pelletization, drying, obtains the EPDM (EPDM-MAH) of MAH grafting.
2) according to a certain percentage, what appropriate solubilizing agent is sprayed onto unlatching is equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 4 days, put it in high-speed mixer, open mixing machine, KH-550 is sprayed wherein, after mixing, obtains modified waste-tyre rubber-powder.Wherein, the consumption of solubilizing agent is 4% of waste-tyre rubber-powder weight; The usage quantity of KH-550 is 5 ‰ of using rubber powder of waste tire weight.
3) by dried nylon 6, anhydrite powder, pretreated waste rubber powder, EPDM-MAH, antioxidant 1010 mixes 5 minutes in high speed blender, the material mixed is joined twin screw extruder (length-to-diameter ratio 40:1, screw diameter is 75) middle melt pelletization, the engine speed of twin screw extruder is 250 revs/min, rate of feeding is 250 kgs/hr, the temperature of each warm area of forcing machine is followed successively by 200 DEG C, 200 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 200 DEG C, 215 DEG C, head temperature is 225 DEG C, cool after extruding pelletization, dry, obtain multiple elements design toughened Nylon 6 matrix material, its physical property is as shown in table 1.
Embodiment 2
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=5 after process: 5, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) following component is weighed according to mass parts: modified monomer maleic anhydride 0.5 part, initiator dicumyl peroxide 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts; By a certain percentage by monomer (MAH), initiator (DCP) with acetone solution evenly after, be sprayed onto in the EPDM of grafting, then it is mixed in high-speed mixer with appropriate PP, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM (EPDM-MAH) of MAH grafting.Extrusion temperature is: 170 DEG C; Extruder screw rotating speed is: 120r/min.
2) according to a certain percentage, what appropriate solubilizing agent is sprayed onto unlatching is equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 4 days, put it in high-speed mixer, open mixing machine, KH-550 is sprayed wherein, after mixing, obtains modified waste-tyre rubber-powder.Wherein, the consumption of solubilizing agent is 6% of waste-tyre rubber-powder weight; The usage quantity of KH-550 is 8 ‰ of using rubber powder of waste tire weight.
3) nylon 6 slice, anhydrite powder dry 8h in the loft drier of 100 DEG C, by nylon 6, anhydrite powder, pretreated waste rubber powder, EPDM-MAH, antioxidant 1010 mixes 5 minutes in high speed blender, mixed material is joined twin screw extruder (length-to-diameter ratio 40:1, screw diameter is 75) middle melt pelletization, the engine speed of twin screw extruder is 280 revs/min, rate of feeding is 250 kgs/hr, the temperature of each warm area of forcing machine is followed successively by 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 215 DEG C, head temperature is 225 DEG C, cool after extruding pelletization, dry, obtain multiple elements design toughened Nylon 6 matrix material, its physical property is as shown in table 1.
Embodiment 3
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=6 after process: 4, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) following component is weighed according to mass parts: modified monomer maleic anhydride 2.5 parts, initiator dicumyl peroxide 0.02, matrix terpolymer EP rubber 100 parts, polypropylene 10 parts; By load weighted modified monomer maleic anhydride, initiator dicumyl peroxide acetone solution evenly after, be sprayed onto in EPDM, then it is mixed in high-speed mixer with load weighted polypropylene, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM of MAH grafting, i.e. EPDM-MAH; Wherein, extrusion temperature is: 205 DEG C; Extruder screw rotating speed is: 60r/min;
2) prepare modified waste tire rubber powder, the consumption that this step removes solubilizing agent is 7% of waste-tyre rubber-powder weight; The usage quantity of KH-550 be using rubber powder of waste tire weight 8 ‰ outside, other conditions because of identical with embodiment 1, therefore omitted and are not stated.
3) nylon 6 slice, anhydrite powder dry 8h in the loft drier of 100 DEG C, by nylon 6, anhydrite powder, pretreated waste rubber powder, EPDM-MAH, antioxidant 1010 mixes 5 minutes in high speed blender, mixed material is joined twin screw extruder (length-to-diameter ratio 40:1, screw diameter is 75) middle melt pelletization, the engine speed of twin screw extruder is 280 revs/min, rate of feeding is 250 kgs/hr, the temperature of each warm area of forcing machine is followed successively by 205 DEG C, 210 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, head temperature is 228 DEG C, cool after extruding pelletization, dry, obtain multiple elements design toughened Nylon 6 matrix material, its physical property is as shown in table 1.
Embodiment 4
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=6 after process: 4, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) this step implementation condition is because of identical with embodiment 1, therefore omits and do not state.
2) this step removes the consumption of solubilizing agent is 7% of waste-tyre rubber-powder weight; The usage quantity of KH-550 be using rubber powder of waste tire weight 8 ‰ outside, other conditions because of identical with embodiment 1, therefore omitted and are not stated.
3) nylon 6 slice, anhydrite powder dry 8h in the loft drier of 100 DEG C, by nylon 6, anhydrite powder, pretreated waste rubber powder, EPDM-MAH, antioxidant 1010 mixes 5 minutes in high speed blender, mixed material is joined twin screw extruder (length-to-diameter ratio 40:1, screw diameter is 75) middle melt pelletization, the engine speed of twin screw extruder is 300 revs/min, rate of feeding is 280 kgs/hr, the temperature of each warm area of forcing machine is followed successively by 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 220 DEG C, 225 DEG C, 220 DEG C, head temperature is 230 DEG C, cool after extruding pelletization, dry, obtain multiple elements design toughened Nylon 6 matrix material, its physical property is as shown in table 1.
Embodiment 5
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=6 after process: 4, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) this step implementation condition is because of identical with embodiment 1, therefore omits and do not state.
2) this step removes the consumption of solubilizing agent is 6% of waste-tyre rubber-powder weight; The usage quantity of KH-550 be using rubber powder of waste tire weight 8 ‰ outside, other conditions because of identical with embodiment 1, therefore omitted and are not stated.
3) nylon 6 slice, anhydrite powder dry 8h in the loft drier of 100 DEG C, by nylon 6, anhydrite powder, pretreated waste rubber powder, EPDM-MAH, antioxidant 1010 mixes 5 minutes in high speed blender, mixed material is joined twin screw extruder (length-to-diameter ratio 40:1, screw diameter is 75) middle melt pelletization, the engine speed of twin screw extruder is 300 revs/min, rate of feeding is 280 kgs/hr, the temperature of each warm area of forcing machine is followed successively by 210 DEG C, 215 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 225 DEG C, 220 DEG C, head temperature is 230 DEG C, cool after extruding pelletization, dry, obtain nylon 6 composite material, its physical property is as shown in table 1.
Embodiment 6
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=8 after process: 2, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) with embodiment 1.
2) according to a certain percentage, what appropriate solubilizing agent is sprayed onto unlatching is equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 4 days, put it in high-speed mixer, open mixing machine, KH-550 is sprayed wherein, after mixing, obtains modified waste-tyre rubber-powder.Wherein, the consumption of solubilizing agent is 10% of waste-tyre rubber-powder weight; The usage quantity of KH-550 is 1 ‰ of using rubber powder of waste tire weight.
3) its extrusion condition is 190 DEG C, 220 DEG C, 200 DEG C, 220 DEG C, 200 DEG C, 225 DEG C, 200 DEG C, and head temperature is 228 DEG C, and all the other steps are with embodiment 1.
Embodiment 7
(1) weight part of each component of composite toughening nylon 6 composite material is as follows:
Wherein: composite toughing agent is EPDM-MAH by weight: the percentage of grafting of waste-tyre rubber-powder=7.5 after process: 2.5, EPDM-MAH is 0.8%, and solubilizing agent is technical grade Stockholm tar; The order number of waste rubber powder is 100 orders.
(2) preparation method is as follows:
1) with embodiment 1.
2) according to a certain percentage, what appropriate solubilizing agent is sprayed onto unlatching is equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 4 days, put it in high-speed mixer, open mixing machine, KH-550 is sprayed wherein, after mixing, obtains modified waste-tyre rubber-powder.Wherein, the consumption of solubilizing agent is 0.5% of waste-tyre rubber-powder weight; The usage quantity of KH-550 is 5% of using rubber powder of waste tire weight.
3) its extrusion condition is 210 DEG C, 200 DEG C, 220 DEG C, 200 DEG C, 225 DEG C, 200 DEG C, 220 DEG C, and head temperature is 228 DEG C, and all the other steps are with embodiment 1.
The performance test results of the multiple elements design toughened Nylon 6 matrix material that table 1 is embodiment 1 ~ 5 compares
| Performance | Testing method | Unit | Nylon 6 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Izod notched impact strength | GB/T1843-2008 | KJ/m 2 | 6.4 | 12.7 | 15.9 | 18.9 | 21.4 | 29.8 |
| Elongation at break | GB/T1040.5-2008 | ％ | 22.4 | 39.8 | 45.9 | 54.8 | 61.8 | 65.9 |
| Tensile strength | GB/T1040.5-2008 | MPa | 77.3 | 89.4 | 80.4 | 81.2 | 87.9 | 85.4 |
| Flexural strength | GB/T9341-2008 | MPa | 90.5 | 109.6 | 101.7 | 104.3 | 110.4 | 107.5 |
Claims (10)
1. a multiple elements design toughened Nylon 6 matrix material, is characterized in that, comprises following component according to mass parts: nylon 6 is 100 parts; Composite toughing agent 5 parts ~ 50 parts; 0.05 part ~ 1 part, oxidation inhibitor; Inorganic powder material 1 part ~ 10 parts.
2. multiple elements design toughened Nylon 6 matrix material according to claim 1, is characterized in that, further, comprises following component according to mass parts: nylon 6 is 100 parts; Composite toughing agent 10 parts ~ 30 parts; 0.05 part ~ 0.08 part, oxidation inhibitor; Inorganic powder material 5 parts ~ 8 parts.
3. multiple elements design toughened Nylon 6 matrix material according to claim 1 and 2, it is characterized in that, described composite toughing agent comprises following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts; Wherein, modified elastomer terpolymer EP rubber comprises following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts; Modified waste-tyre rubber-powder comprises following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts.
4. multiple elements design toughened Nylon 6 matrix material according to claim 3, is characterized in that, the particle diameter of described waste rubber powder is 40 order ~ 100 orders, and described oxidation inhibitor is antioxidant 1010.
5. a preparation method for multiple elements design toughened Nylon 6 matrix material, is characterized in that, specifically implements according to following steps:
Step 1, raw materials pretreatment: by nylon 6, waste-tyre rubber-powder, inorganic powder filler etc. after surface treatment 50 DEG C ~ 100 DEG C dry 1 ~ 24 hour respectively;
Step 2, prepare composite toughing agent, be specially:
Step 2.1, prepare modified elastomer terpolymer EP rubber;
Step 2.2, surface modification is carried out to waste-tyre rubber-powder;
Step 2.3, prepare composite toughing agent;
Step 3, weighing, weigh following component according to mass parts: NYLON610 0 part, composite toughing agent 5 parts ~ 50 parts, inorganic powder material 1 part ~ 10 parts, 0.05 part ~ 1 part, oxidation inhibitor;
Step 4, mixing, join load weighted nylon 6, composite toughing agent, inorganic powder material and oxidation inhibitor in high-speed mixer and mix 3-10min, mix;
Step 5, extruding, join in the hopper of twin screw extruder by the above-mentioned material mixed, carry out extruding pelletization, and cooling is dried, obtained multiple elements design toughened Nylon 6 matrix material.
6. the preparation method of multiple elements design toughened Nylon 6 matrix material according to claim 5, is characterized in that, prepare composite toughing agent, be specially in described step 2:
Step 2.1, prepare modified elastomer terpolymer EP rubber, be specially:
Step 2.1.1, weigh following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts;
Step 2.1.2, by load weighted modified monomer maleic anhydride, initiator dicumyl peroxide acetone solution evenly after, be sprayed onto in EPDM, then it is mixed in high-speed mixer with load weighted polypropylene, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM of MAH grafting, i.e. EPDM-MAH; Wherein, extrusion temperature is: 170 ~ 205 DEG C; Extruder screw rotating speed is: 60 ~ 120r/min;
Step 2.2, surface modification is carried out to waste-tyre rubber-powder, be specially;
Step 2.2.1, weigh following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts;
Step 2.2.2, load weighted solubilizing agent is sprayed onto unlatching be equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 3-5 days, put it in high-speed mixer, open mixing machine, coupling agent is sprayed wherein, after mixing, obtain modified waste-tyre rubber-powder; Wherein, coupling agent is silane series, and solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil;
Step 2.3, prepare composite toughing agent, be specially:
Step 2.3.1, weighing: weigh following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts;
Step 2.3.2, load weighted modified elastomer terpolymer EP rubber and modified waste-tyre rubber-powder put into high-speed mixer mixing, prepare composite toughing agent.
7. the preparation method of multiple elements design toughened Nylon 6 matrix material according to claim 5, it is characterized in that, forcing machine condition setting in described step 6: first paragraph is respectively 190 DEG C-210 DEG C, 200 DEG C-220 DEG C, 200 DEG C-220 DEG C, 200 DEG C-220 DEG C, 200 DEG C-225 DEG C, 200 DEG C-225 DEG C, 200 DEG C-220 DEG C to the 7th section of temperature, and head temperature is 228 DEG C.
8. a preparation method for composite toughing agent, is characterized in that, specifically implements according to following steps:
Steps A, prepare modified elastomer terpolymer EP rubber, be specially:
Step a1, weigh following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts;
Step a2, by load weighted modified monomer maleic anhydride, initiator dicumyl peroxide acetone solution evenly after, be sprayed onto in EPDM, then it is mixed in high-speed mixer with load weighted polypropylene, after acetone volatilization, mixture is extruded in twin screw extruder, granulation, drying, obtain the EPDM of MAH grafting, i.e. EPDM-MAH; Wherein, extrusion temperature is: 170 ~ 205 DEG C; Extruder screw rotating speed is: 60 ~ 120r/min;
Step B, surface modification is carried out to waste-tyre rubber-powder, is specially:
Step b1, weigh following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts;
Step b2, load weighted solubilizing agent is sprayed onto unlatching be equipped with in the mixing machine of waste-tyre rubber-powder, after mixing, poured out, place after 3-5 days, put it in high-speed mixer, open mixing machine, coupling agent is sprayed wherein, after mixing, obtain modified waste-tyre rubber-powder; Wherein, coupling agent is silane series, and solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil;
Step C, prepare composite toughing agent, be specially:
Step c1, weighing: weigh following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts;
Step c2, load weighted modified elastomer terpolymer EP rubber and modified waste-tyre rubber-powder put into high-speed mixer mixing, prepare composite toughing agent.
9. a composite toughing agent, is characterized in that, comprises following component according to mass parts: modified elastomer terpolymer EP rubber 60 parts-80 parts; Modified waste-tyre rubber-powder 20 parts-40 parts; Wherein, modified elastomer terpolymer EP rubber comprises following component according to mass parts: modified monomer maleic anhydride 0.5 ~ 2.5 part, initiator dicumyl peroxide 0.02 ~ 0.2 part, matrix terpolymer EP rubber 100 parts, polypropylene 5 parts-10 parts; Modified waste-tyre rubber-powder comprises following component according to mass parts: waste-tyre rubber-powder 100 parts, solubilizing agent 0.5 part-10 parts, coupling agent 0.1 part-5 parts.
10. composite toughing agent according to claim 9, is characterized in that, described coupling agent is silane series; Described solubilizing agent is one or more in naphthenic oil, Stockholm tar, hydrocarbon oil, and the particle diameter of described waste rubber powder is 40 order ~ 100 orders, and described oxidation inhibitor is antioxidant 1010.
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