CN101735449A - Preparation method of reinforced nylon 6 material - Google Patents
Preparation method of reinforced nylon 6 material Download PDFInfo
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- CN101735449A CN101735449A CN200810234387A CN200810234387A CN101735449A CN 101735449 A CN101735449 A CN 101735449A CN 200810234387 A CN200810234387 A CN 200810234387A CN 200810234387 A CN200810234387 A CN 200810234387A CN 101735449 A CN101735449 A CN 101735449A
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Abstract
The invention belongs to the technical field of polymer composite materials and relates to a preparation method of a reinforced nylon 6 material. The method comprises the following steps: adding 100 parts of caprolactam monomer and 0.1-15 parts of catalyst into a reaction kettle to react, entering a twin screw reaction extruder, adding 0.15-20 parts of auxiliary agent, adding glass fiber in the rear half section of the twin screw reaction extruder to carry out reaction and extrusion, thus reinforcing and modifying, and simultaneously, vacuumizing and removing unreacted caprolactam monomer, thus obtaining the glass fiber reinforced nylon 6 material. The material has higher tensile strength, flexural strength, flexural modulus, notch impact strength and heat distortion temperature, and as the material is good-performance engineering plastics, the material can be widely applied to the fields of electronics, mechanics, automobiles, textile, architecture and the like.
Description
Technical field: the invention belongs to technical field of polymer composite materials, relate to a kind of preparation method of reinforced nylon 6 material.
Background technology: because the glass fibre superior performance, the fifties has begun the Application and Development of glass fiber reinforced nylon 6 material, macrofiber (rove) adding technique that toray company introduces Fiberfill company begins to produce the glass fiber reinforced nylon 6 material, and is used widely.The specific tenacity of glass fibre and Young's modulus are bigger 10～20 times than nylon 6, and linear expansivity is 1/20 of a nylon 6, and water-intake rate approaches zero, have heat-resisting and the good characteristic of drug-resistant.Glass fibre cooperates with nylon 6, the intensity height, might replace metal to use, general long glass fibres and the short glass fiber of using carries out enhancing modified to nylon 6, because long glass fibres Reinforced Nylon 6 increases in performances such as intensity, modulus, shock-resistance, creep resistant, thermotolerances, so 6 application of long glass fibres Reinforced Nylon are wider.
Because the range of application of glass fiber reinforced nylon 6 constantly enlarges, its processing technology also attains full development, many new modification technologies have appearred, reaction is extruded processing technology and is occurred under such environment, it is used for the technological processs such as increase-volume of polymerization, polymer modification, polymer blends with screw extrusion press as flow reactor, and in the superiority that demonstrates it aspect economy and the efficient two.
Aspect reactive extrusion technology, U.S. Pat 5298594 is exactly to utilize reaction to extrude processing technology to react and extrude nylon 6 catalyst researches, mainly comprise catalyzer such as isocyanates, carbonates, in twin screw extruder, react and extrude, and to obtain relative viscosity be 3.5 nylon 6.Narrated a kind of preparation method of polyamide nano-composite among the Chinese patent CN1354201A, it adopts reactive extrusion technology step in twin screw extruder to obtain polyamide nano-composite, wherein relate to the pre-treating technology condition of reaction raw materials, the use of catalyzer, and twin screw extruder expressing technique condition etc.
Aspect glass fiber reinforced nylon 6, narrated the method for making of macrofiber enhanced polyamide composite material among the China CN1022189C, it is that macrofiber is carried out dip-coating with the prepolymer or the oligopolymer of polymeric amide, again with it heating so that before pulling out, carry out polyreaction, so that polymer chain increases, carry out moulding by pulling out then.On each end of prepolymer or oligomer molecules chain, have one and easily carry out reactive activity functional group, a molecule and another molecule of prepolymer or oligopolymer are reacted.
What above-mentioned pertinent literature was reported is to utilize reactive extrusion technology, in twin screw extruder, directly prepares high visocity nylon 6 and nano-nylon 6 composite process and process by caprolactam monomer; What other patent documentation was reported then is to add glass fibre and other material by polymeric amide, preparation composition or matrix material are extruded in blend in twin screw extruder, some method or mixture exist the degraded of polymkeric substance when carrying out secondary processing etc., cause the degradation of polymer matrix material, thereby influence the over-all properties of glass fiber reinforced nylon 6 material.
Summary of the invention: the present invention seeks to propose a kind of new Reinforced Nylon 6 preparation methods that glass fibre is used for.Thereby obtain the glass fiber reinforced nylon 6 material.The gained material has good performance.
Because the present invention begins the glass fiber reinforced nylon 6 material that a step obtains from caprolactam monomer, reduced the defectives such as degradation of nylon 6 when secondary processing in the general technology method, therefore with common nylon 6 glass fibre reinforced modified material compared, be significantly improved aspect intensity, modulus and the thermal characteristics, as the engineering plastics of excellent property, on industries such as machinery, electrical equipment, automobile, weaving and building, be widely used.
Method provided by the invention promptly adopts double screw rod extruder as polyreaction and enhancing modified equipment, after comprising the steps: 100 parts of caprolactam monomers and 0.1～15 part of adding reactor of catalyzer reacted, enter double screw rod extruder, be metered into 0.15～20 part of auxiliary agent, and add glass fibre in the double screw rod extruder second half section and react and extrude enhancing modified, vacuumize simultaneously and remove the intact caprolactam monomer of unreacted, thereby obtain the glass fiber reinforced nylon 6 material.
The method of the invention provides is about to hexanolactam and catalyzer reacts in reactor, and processing condition are: reaction pressure scope-0.1～0.2Mpa, and 90～170 ℃ of temperature of reaction, the reaction times is 1～5hr.In reactor, ring-opening reaction takes place in hexanolactam in the presence of catalyzer, form active material, thereafter the sufficient reacting active material is metered into twin screw extruder, is metered into auxiliary agent and treated long glass fibres simultaneously, active material in double screw rod extruder with the auxiliary agent rapid reaction, constantly carry out transfer reaction, and form mortise with the long glass fibres surface.Because polyreaction and enhancing modified time are short, polymericular weight is high and easy to control, thereby makes high performance glass fiber reinforced nylon 6 material.
The present invention adopts the length-to-diameter ratio (25～60) of double screw rod extruder: 1, be divided into 9～15 sections, and temperature range is 150～320 ℃, rotating speed is at 50～500 rev/mins, cylindrical shell is a bimetallic material, and leaves a plurality of exhausts and charging opening, and the left-hand thread combination block is wherein arranged in the threaded block.Reaction is extruded the enhancing modified processing condition and is: each section of double screw rod extruder temperature range is 200～280 ℃, and it is 1～20min that the enhancing modified time is extruded in reaction.
Raw materials used caprolactam monomer, catalyzer, auxiliary agent and the glass fibre etc. of mainly comprising of the present invention are industrial raw material; Used catalyzer mainly is in water, alcohols, the bases one or more, and wherein using in the bases is a kind of among NaOH, the KOH; The auxiliary agent that is adopted mainly is in isocyanates, ester class, the acyl caprolactam one or more.In the isocyanates used mainly be among HDI, TDI, the MDI one or more.Ester class such as diphenyl carbonate, dimethyl terephthalate (DMT) etc.Amides such as N-ethanoyl hexanolactam, amino hexanolactam; Used glass fibre mainly is a long glass fibres, handles through coupling agent, tensio-active agent, bases, and its diameter is at 5～20 microns, and glass fibre massfraction in the glass fiber reinforced nylon 6 material is 5%～45%, the preferred KH-550 of used coupling agent.
Glass fiber reinforced nylon 6 material involved in the present invention is to adopt the reaction extrusion molding to make, compare with common nylon 6 glass fibre reinforcements, have higher draw tensile strength, flexural strength, modulus in flexure and notched Izod impact strength, the heat-drawn wire height, because this material is the engineering plastics of excellent property, therefore be widely used in fields such as electronics, machinery, automobile, weaving, building.
Embodiment: the present invention is described in detail below in conjunction with embodiment.
Embodiment 1: with caprolactam monomer 1000g, catalyzer 15g adds in the reactor, vacuum condition is fully reaction dehydration down, the reaction dewatering time is 3hr, the reaction dehydration temperaturre is 140 ℃, good material is squeezed into double screw rod extruder with volume pump will to react dehydration then, be metered into auxiliary agent 30g simultaneously, adding long glass fibres in the double screw rod extruder second half section reacts for 10 strands and extrudes enhancing modified, vacuumize simultaneously and remove the intact caprolactam monomer of unreacted, each of double screw rod extruder section temperature is at 200～250 ℃, extrudate is through cooling, dry up, pelletizing, drying is 15% glass fiber reinforced nylon 6 material thereby obtain the glass fibre massfraction.
Embodiment 2: with example 1, only elongated glass fibre is 20 strands and reacts and extrude enhancing modified that obtaining the glass fibre massfraction is 30% glass fiber reinforced nylon 6 material.
Example 2 samples of the present invention are compared with simple glass fiber reinforced nylon 6 materials and common nylon 6, and every performance is significantly better than the performance of common nylon 6 glass fibre reinforcements and common nylon 6, and heat-drawn wire also increases.
Claims (1)
1. the preparation method of a reinforced nylon 6 material, obtain the glass fiber reinforced nylon 6 material by caprolactam monomer one step, after its feature comprises the steps: 100 parts of caprolactam monomers and 0.1～15 part of adding reactor of catalyzer reacted, enter in the double screw rod extruder, and be metered into 0.15～20 part of auxiliary agent, thereafter react at double screw rod extruder second half section adding glass fibre and extrude enhancing modified, vacuumize simultaneously and remove the intact caprolactam monomer of unreacted, thereby obtain the glass fiber reinforced nylon 6 material; The processing condition that hexanolactam and catalyzer react at reactor are reaction pressure scope-0.1～0.2Mpa, 90～170 ℃ of temperature of reaction, and the reaction times is 1～5hr; Double screw rod extruder length-to-diameter ratio (25～60): 1, be divided into 9～15 sections, temperature range is 150～320 ℃, rotating speed is at 50～500 rev/mins; Catalyzer is one or more in water, alcohols, the bases; Auxiliary agent is one or more in isocyanates, ester class, the acyl caprolactam; Glass fibre is to handle through coupling agent, tensio-active agent, bases, and glass fibre is a long glass fibres, and its diameter is at 5～20 microns, and glass fibre massfraction in the glass fiber reinforced nylon 6 material is 5%～45%; Reaction is extruded the enhancing modified processing condition and is: each section of double screw rod extruder temperature range is 200～280 ℃, and it is 1～20min that the enhancing modified time is extruded in reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810234387A CN101735449A (en) | 2008-11-18 | 2008-11-18 | Preparation method of reinforced nylon 6 material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810234387A CN101735449A (en) | 2008-11-18 | 2008-11-18 | Preparation method of reinforced nylon 6 material |
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| CN101735449A true CN101735449A (en) | 2010-06-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087515A (en) * | 2013-01-18 | 2013-05-08 | 江门市奇德工程塑料科技有限公司 | High-content glass fiber reinforced nylon 6 composite material and preparation method thereof |
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2008
- 2008-11-18 CN CN200810234387A patent/CN101735449A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087515A (en) * | 2013-01-18 | 2013-05-08 | 江门市奇德工程塑料科技有限公司 | High-content glass fiber reinforced nylon 6 composite material and preparation method thereof |
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Open date: 20100616 |