CN106366646A - High-performance ultraviolet-resistant nylon 6 composite and preparation method thereof - Google Patents

High-performance ultraviolet-resistant nylon 6 composite and preparation method thereof Download PDF

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Publication number
CN106366646A
CN106366646A CN201610787276.8A CN201610787276A CN106366646A CN 106366646 A CN106366646 A CN 106366646A CN 201610787276 A CN201610787276 A CN 201610787276A CN 106366646 A CN106366646 A CN 106366646A
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China
Prior art keywords
composite
performance
nylon
resistant nylon
ultraviolet resistant
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Pending
Application number
CN201610787276.8A
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Chinese (zh)
Inventor
王晶
张天荣
王俊
朱春龙
陆佳琦
张珂
范寅青
彭庆益
夏新宇
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POLYSTAR ENGINEERING PLASTICS (SHANGHAI) Co Ltd
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POLYSTAR ENGINEERING PLASTICS (SHANGHAI) Co Ltd
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Priority to CN201610787276.8A priority Critical patent/CN106366646A/en
Publication of CN106366646A publication Critical patent/CN106366646A/en
Pending legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high-performance ultraviolet-resistant nylon 6 composite. The composite is prepared from, by weight, 55-70 parts of nylon resin, 25-35 parts of glass fiber, 1-6 parts of silver-loaded TiO2, 1-5 parts of light stabilizer, 0.1-1 part of antioxidant and 0.2-0.6 part of lubricating agent. The raw materials adopted in the technical route are high in blending compatibility, strong in performance complementarity and excellent in processing property, and a PA6/GF/Ag-TiO2 alloy product excellent in comprehensive performance can be obtained through blending, screw extruding and injection molding.

Description

A kind of high-performance, ultraviolet resistant nylon 6 composite and preparation method thereof
Technical field
The present invention provides a kind of high-performance, ultraviolet resistant nylon 6 composite and preparation method thereof.Composite is increased by glass Strong nylon 6 composite material and Ag-carried nanometer titanium dioxide (tio2) composition；Described glass fiber reinforced nylon 6 composite particles are by Buddhist nun Dragon 6, glass fibre, silver-carrying nano tio2, light stabilizer, lubricant, antioxidant constitute.It is old that this material has stronger uvioresistant Change characteristic, there is high intensity and the high tenacity of glass fiber reinforced nylon 6 composite simultaneously.The Buddhist nun being obtained using technique scheme The product that imperial 6 composites are made, has high-performance, the advantages of uvioresistant, surface gloss are high, can be applicable to manufacture sunshade Plate, the inner and outer decorative parts of automobile such as grid.
Background technology
Glass fiber reinforced nylon 6 composite becomes a kind of widely used composite with its excellent mechanical performance.For Realize fiberglass reinforced class material for open air, the steady agent of all kinds of light is used for such composite system, very widely used today All in alkalescence, there is antagonism with the faintly acid of fiberglass reinforced system in this to the steady agent of hindered amines light, cause the anti-purple of material Outer ageing properties are poor, secondly with nanometer tio2Then need to add higher amount as uvioresistant stabilizer and can be only achieved preferable effect Really, therefore, how to realize the excellent mechanical performance of glass fiber enhanced nylon composite and realize anti-ultraviolet ageing simultaneously becoming one The problem needing to solve.
Content of the invention
It is an object of the invention to provide a kind of prepare the silver-carrying nano tio with anti-ultraviolet function2Nylon 6 composite wood The method of material.Make only need to add in this way less amount of silver-carrying nano tio2Just can have while anti-ultraviolet function also Higher mechanical performance can be kept.
Nanometer tio2There is good ultraviolet shielded effect.But, due to nanometer tio2Energy gap wider (3.2ev), only The ultraviolet excitation of 387.5nm can be less than or equal to by wavelength, therefore the ratio using sunlight is low.Multiple for improving nanometer further The photocatalytic activity of condensation material, need to be to nanometer tio2Composite carries out further modification.Metal ion mixing has method Simply, effect is good, be more beneficial for the advantages of improve light-catalyzed reaction speed.Silver ion can expand its photoresponse scope, suppression Electronics is compound with hole.
For achieving the above object, the technical scheme is that
Configuration ag2co3Mass fraction is the ag of 1wt%2co3/tio2Mixture, after being sufficiently mixed, is placed in constant-temperature tubular stove Under air atmosphere, constant temperature 1 hour at 300 DEG C, furnace cooling obtains silver-carrying nano tio2.
This project is intended adopting pa6, glass fibre, silver-carrying nano tio2, light stabilizer, lubricant, antioxidant and its correlation Auxiliary agent is preparing high-performance uvioresistant engineering plastic alloy.Above material is blended, is extruded by double screw extruder Pelletize, obtains high-performance uvioresistant plastic alloy material (pa6/gf/ag-tio2) particle.
A kind of high-performance, ultraviolet resistant nylon 6 composite, are made up of the component comprising following parts by weight:
Nylon resin 55-70 part
Glass fibre 25-35 part
Carry silver-colored tio21-6 part
Light stabilizer 1-5 part
Antioxidant 0.1-1 part
Lubricant 0.2-1.6 part.
Described glass fibre is the alkali-free glass fiber through coupling agent modified process.
Light stabilizer is n, n '-two formyl-n, n '-two (2,2,6,6- tetramethyl -4- piperidines)-hexamethylene diamine (uvinul 4050h), one of double -2,2,6,6- tetramethyl piperidine alcohol esters (tinuvin 770) of decanedioic acid or one kind with On.
Antioxidant is cuprous halide, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, n, n'- pair-(3- (3,5- di-t-butyl -4- Hydroxy phenyl) propiono) one of hexamethylene diamine (antioxidant 1098) or more than one.
Described lubricant is selected from ethylene bis stearamide, tetramethylolmethane stearate, polysiloxanes, white beeswax oil or brown coal One of wax or more than one.
A kind of high-performance, the preparation method of ultraviolet resistant nylon 6 composite, comprise the following steps:
(1) weigh each component raw material: nylon resin 55-65 part, glass fibre 25-35 part by said ratio, carry silver tio21-6 part, light stabilizer 1-5 part, antioxidant 0.1-1 part, lubricant 0.2-1.6 part, mix homogeneously in high-speed mixer；
(2) material of mix homogeneously is carried out in double screw extruder extruding pelletization；
Nylon resin in described step (1) is dry nylon resin, forced air drying at 90-110 DEG C before mixing 2-6 hour.
In described step (2), the temperature of double screw extruder is 160-280 DEG C.
The present invention has the advantages that with respect to prior art
Raw material employed in this technology route, blending compatibility is good, and performance complement is strong, and processing technology is excellent, can By blending, Screw Extrusion, injection mo(u)lding, to obtain the superior pa6/gf/ag-tio of combination property2Alloy product.
1st, the present invention utilizes nylon resin, adds glass fibre, carries silver-colored tio2, light stabilizer, antioxidant, lubricant is obtained Uvioresistant is tough nylon engineering plastic resin, can be made into inner and outer decorative parts of automobile through injection.
2nd, the gadget that material of the present invention produces has that density is little, lightweight, intensity is high, toughness is high, uvioresistant is excellent, light The advantages of Ze Dugao.
3rd, utilize material of the present invention convenient for production it is easy to molding, with low cost.
Brief description
Fig. 1 is the chart of embodiment each properties of product test result.
Specific embodiment
Describe the present invention with reference to each embodiment in detail.
Embodiment 1
Weigh 66 parts of pa6 forced air drying 3 hours at 100 DEG C, weigh 30 parts of glass fibre, carry silver-colored tio22.7 parts, light steady Determine agent tinuvin7700.3 part, 0.3 part of cuprous halide, 0.7 part of polysiloxanes, mix 5 minutes in high-speed mixer；
By the material of mix homogeneously in double screw extruder extruding pelletization.
Extruder temperature is set to: 190 DEG C of area, 220 DEG C of area, 230 DEG C of area, 235 DEG C of area, 230 DEG C of area, 230 DEG C of area, 235 DEG C of head, after material extrusion, water cooled, pelletizing, pellet forced air drying 3 hours at 100 DEG C.Gained is combined Material property is shown in Table 1.
Embodiment 2
Weigh 67 parts of pa6 forced air drying 3 hours at 100 DEG C, weigh 30 parts of glass fibre, carry silver-colored tio22 parts, light stable 0.3 part of agent uvinul4050h, 10980.3 parts of antioxidant, 0.4 part of ethylene bis stearamide, mix 5 points in high-speed mixer Clock；
By the material of mix homogeneously in double screw extruder extruding pelletization.
Extruder temperature is set to: 190 DEG C of area, 220 DEG C of area, 230 DEG C of area, 235 DEG C of area, 230 DEG C of area, 230 DEG C of area, 235 DEG C of head, after material extrusion, water cooled, pelletizing, pellet forced air drying 3 hours at 100 DEG C.Gained is combined Material property is shown in accompanying drawing table 1.
Embodiment 3
Weigh 66 parts of pa6 forced air drying 3 hours at 100 DEG C, weigh 30 parts of glass fibre, carry silver-colored tio22.7 parts, light steady Determine 0.4 part of agent uvinul4050h, 0.3 part of antioxidant 1076,0.7 part of lignite wax, mix 5 minutes in high-speed mixer；
By the material of mix homogeneously in double screw extruder extruding pelletization.
Extruder temperature is set to: 190 DEG C of area, 220 DEG C of area, 230 DEG C of area, 235 DEG C of area, 230 DEG C of area, 230 DEG C of area, 235 DEG C of head, after material extrusion, water cooled, pelletizing, pellet forced air drying 3 hours at 100 DEG C.Gained is combined Material property accompanying drawing table 1.
Comparative example in table is the silver-carrying nano tio in embodiment 12Replace with common nanometer tio2.Although the present invention with Preferred embodiment discloses as above, and so it is not limited to the present invention, and any those skilled in the art, without departing from the present invention's In spirit and scope, when making a little modification and perfect, therefore protection scope of the present invention is when being defined with claims Be defined.

Claims (8)

1. a kind of high-performance, ultraviolet resistant nylon 6 composite, is made up of the component comprising following parts by weight:
Nylon resin 55-70 part
Glass fibre 25-35 part
Carry silver-colored tio21-6 part
Light stabilizer 1-5 part
Antioxidant 0.1-1 part
Lubricant 0.2-1.6 part.
2. as claimed in claim 1 a kind of high-performance, ultraviolet resistant nylon 6 composite it is characterised in that: described glass fibers Dimension is the alkali-free glass fiber through coupling agent modified process.
3. as claimed in claim 1 a kind of high-performance, ultraviolet resistant nylon 6 composite it is characterised in that: light stabilizer be n, N '-two formyl-n, n '-two (2,2,6,6- tetramethyl -4- piperidines)-hexamethylene diamine (uvinul 4050h), the last of the ten Heavenly stems two One of double -2,2,6,6- tetramethyl piperidine alcohol ester (tinuvin 770) of acid or more than one.
4. as claimed in claim 1 a kind of high-performance, ultraviolet resistant nylon 6 composite it is characterised in that: antioxidant be halogenation Cuprous, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester (antioxidant 1010), β-(3,5- bis- tertiary fourths Base -4- hydroxy phenyl) propanoic acid positive octadecanol ester, n, n'- be double-(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) oneself One of diamidogen (antioxidant 1098) or more than one.
5. as claimed in claim 1 a kind of high-performance, ultraviolet resistant nylon 6 composite it is characterised in that: described lubricant Selected from ethylene bis stearamide, tetramethylolmethane stearate, polysiloxanes, white beeswax oil or one of lignite wax or one kind with On.
6. a kind of high-performance, the preparation method of ultraviolet resistant nylon 6 composite, comprises the following steps:
(1) weigh each component raw material: nylon resin 55-65 part, glass fibre 25-35 part by said ratio, carry silver-colored tio21-6 part, Light stabilizer 1-5 part, antioxidant 0.1-1 part, lubricant 0.2-1.6 part, mix homogeneously in high-speed mixer；
(2) material of mix homogeneously is carried out in double screw extruder extruding pelletization；
7. a kind of high-performance, the preparation method of ultraviolet resistant nylon 6 composite as claimed in claim 6, described step (1) In nylon resin be dry nylon resin, before mixing at 90-110 DEG C forced air drying 2-6 hour.
8. a kind of high-performance, the preparation method of ultraviolet resistant nylon 6 composite as claimed in claim 6, described step (2) The temperature of middle double screw extruder is 160-280 DEG C.
CN201610787276.8A 2016-08-31 2016-08-31 High-performance ultraviolet-resistant nylon 6 composite and preparation method thereof Pending CN106366646A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251525A (en) * 2018-07-31 2019-01-22 西安工程大学 It is a kind of for making the preparation method of the composite material of antibiotic property air-conditioning trim panel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423664A (en) * 2007-10-29 2009-05-06 比亚迪股份有限公司 Reinforced nylon composition and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101423664A (en) * 2007-10-29 2009-05-06 比亚迪股份有限公司 Reinforced nylon composition and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张榕: "抗紫外兼具抗菌聚酰胺 6 纤维的开发", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251525A (en) * 2018-07-31 2019-01-22 西安工程大学 It is a kind of for making the preparation method of the composite material of antibiotic property air-conditioning trim panel

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Application publication date: 20170201