CN101525486A - Halogen-free glass fiber reinforced nylon resin and preparing method thereof - Google Patents
Halogen-free glass fiber reinforced nylon resin and preparing method thereof Download PDFInfo
- Publication number
- CN101525486A CN101525486A CN200910134863A CN200910134863A CN101525486A CN 101525486 A CN101525486 A CN 101525486A CN 200910134863 A CN200910134863 A CN 200910134863A CN 200910134863 A CN200910134863 A CN 200910134863A CN 101525486 A CN101525486 A CN 101525486A
- Authority
- CN
- China
- Prior art keywords
- nylon
- halogen
- glass fiber
- fiber reinforced
- free glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
-
- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a halogen-free glass fiber reinforced nylon resin and a preparing method thereof. The material comprises the following raw materials with the weight percentage: 38-55 percent of nylon 66 or nylon 6, 17-30 percent of halogen-free intumescent nylon flame retardant of phosphorus-nitrogen structure, 4-8 percent of toughening agent, 25-35 percent of glass fiber and 0.5-1.5 percent of other promoters.
Description
Technical field
The present invention relates to a kind of halogen-free glass fiber reinforced nylon resin and preparation method thereof.
Background technology
Nylon resin is the engineering plastics of developing the earliest, and it has tough and tensile, wear-resisting, anti-solvent, oil resistant, melt viscosity is low, raw material is easy to obtain, recyclable and cost performance advantages of higher.The nylon plastic poor fire that does not add fire retardant makes it be restricted in many Application Areass, and the adding of fire retardant has enlarged the range of application of nylon plastic.Its fire retardant commonly used mainly is a halogen sb system fire retardant, wherein again based on bromide fire retardant, the bromine antimony based flame retardant that adds has improved the flame retardant resistance of material to a certain extent, but the electrical property of material is subjected to very big influence, decline to a great extent as phase ratio creepage tracking index, influenced the application of material at electronic enterprises.In addition, along with the raising of environmental requirement, the implementation of ROHS of European Union and WEEE instruction, a lot of industries have proposed the requirement of halogen-free environmental one after another in order better to observe this instruction to the material that uses.Halogen-free environmental Reinforced Nylon for market mainly adopts red phosphorus fire-retardant, but limited because of its color, can not satisfy service requirements aspect a lot; And be difficult to because market value is too high promote for the halogen-free environmental Reinforced Nylon that can satisfy the color matching requirement.Therefore, exploitation can be satisfied the color matching requirement, can have the low halogen-free glass fiber enhanced nylon of superperformance and cost to become developing direction again.
At present, the technology of preparation halogen-free glass fiber reinforced nylon resin adopts the most widely that flame-retardant system is the fire-retardant body of red phosphorus class, P-N type expandable flame retardant system.
The preparation method of preparation glass fibre reingorced no-halogen flame-retardant nylon dragon 66 has introduced in Northeast Forestry University in the CN1944534 patent, it is fire-retardant to adopt halogen-free flame retardants M-MPP to carry out, and has solved that present glass fibre reingorced no-halogen flame-retardant nylon dragon 66 consistencies are relatively poor, mechanical property is low, flame retardant properties is poor, the problem of resistance toheat difference.Chen Wurong, Zhong Lisong etc. have delivered " researchs of halogen-free flame-retardant reinforced nylon plastics " article in " insulating material " 2007 the 3rd phases, employing encapsulated red phosphorus master batch, trimeric cyanamide urate (MC) have been studied, the tests in Reinforced Nylon 66 such as (M200) of trimeric cyanamide phosphoric acid ester, conclusion is to be fire retardant with the encapsulated red phosphorus, and add suitable toughner, make the halogen-free reinforced nylon plastics with excellent flame retardancy and high-impact performance, these plastics also have good resistance toheat and electric property.Zhang Wei, other group plum etc. have been delivered " research of high CTI value, halogen-free flame-retardant glass fiber enhanced nylon 66 and application " article in " engineering plastics application " the 8th phase in 2006, employing red phosphorus master batch, melamine cyanurate (MCA), TDE, brominated epoxy resin have been studied to glass enhancing PA66 Effect on Performance, it is relatively good in guaranteeing over-all propertieies such as flame retardant properties, electrical property, mechanical property that conclusion is the red phosphorus master batch, and institute's material of doing is approaching or reached the performance of the A3X2G5 of BASF simultaneously.At the Clariant fire retardant 1312 that is used for fiber glass reinforced halogen-free flame retardant nylon on the market now, above the fiber glass reinforced halogen-free flame retardant nylon that is used in various color matchings of energy comparative maturity, but cost is too high, is difficult at home promote the use of.
Summary of the invention
The objective of the invention is at above-mentioned technology status, a kind of new halogen-free glass fiber reinforced nylon resin is provided, can satisfy requirement at aspects such as color matching, electrical property and low costs.
Another object of the present invention provides the preparation method of above-mentioned halogen-free glass fiber reinforced nylon resin.
Technical scheme of the present invention is as follows: a kind of halogen-free glass fiber reinforced nylon resin, and by comprising that weight percent is that 38 ~ 55% nylon 66 (PA66) or nylon 6 (PA6), the halogen-free expansible nylon fire retardant (HJ-1) of 17 ~ 30% phosphorus N structures, 4 ~ 8% toughner (HJ-2), 25 ~ 35% glass (GF), other auxiliary agent of 0.5 ~ 1.5% are formed.
Above-mentioned nylon 66 (PA66) or nylon 6 (PA6) component size and distribution different, the viscosity difference is bigger, viscosity scope having between 2.2 ~ 4.5 considered and the composite factor of intensity, flowability and cost mainly adopted the nylon of viscosity scope between 2.4 ~ 3.0.Nylon 66 or nylon 6 are easy to suction, before use will be in 90 ~ 110 ℃ drying hopper dry 3 ~ 4 hours.Ratio in whole weight is formed is 38 ~ 55% for PA66 or PA6.
The halogen-free expansible nylon fire retardant (HJ-1) of above-mentioned phosphorus N structure is the expansion type flame retardant of special phosphorus N structure, is white powder, can guarantee that like this doing discharging can join shades of colour; Decomposition temperature 〉=350 ℃, what be fit to the glass fiber enhanced nylon high temperature process requires CTI value 〉=500V, good electric property, the suitable high occasion of electric requirement.For the ratio of HJ-1 in whole weight is formed is 17 ~ 30%.
Above-mentioned toughner (HJ-2) is maleic anhydride grafted vinyl elastomerics, and percentage of grafting is 1.2%, has guaranteed the raising of toughness and consistency in whole system.For the ratio of HJ-2 in whole weight is formed is 4 ~ 8%.
Other auxiliary agent of above-mentioned 0.5 ~ 1.5% mainly is 0.3 ~ 0.8% lubricant, 0.2 ~ 0.5% coupling agent, about 0.4% oxidation inhibitor and thermo-stabilizer.
The phosphorus-nitrogen type expanding fire retardant that is adopted, its fire retardant cost be Clariant fire retardant 1312 1/3rd less than, by with the adjustment of toughner and other auxiliary agent, prepare the halogen-free glass fiber reinforced nylon resin that can be used in various color matching conditions, satisfy its requirement at aspects such as color matching, electrical property and low costs.
Preparation method of the present invention is: nylon 66 (PA66) or nylon 6 (PA6) in 90 ~ 110 ℃ drying hopper dry 3 ~ 5 hours, mix in the high-speed stirring bucket preparing material on request, from the batch mixing mouth, join temperature be set at 220 ℃ ~ 280 ℃, length-to-diameter ratio (L/D) be 32: 1 ~ 40:1, screw combinations by in the twin screw extruder of process stipulation, vacuumize granulation and make halogen-free glass fiber reinforced nylon resin.
The product appearance that makes by twin screw extruder is good, and over-all properties is than more excellent, and is respond well.
Embodiment one
The halogen-free glass fiber reinforced nylon 6 resin
Table one embodiment 1 ~ 4
HJ-1: the expansion type flame retardant of special phosphorus N structure
HJ-2: toughner
GF: glass
Nylon in 90～110 ℃ drying hopper dry 3～4 hours, after nylon 6 (PA6), the halogen-free expansible nylon fire retardant (HJ-1) of phosphorus N structure, toughner (HJ-2), the various auxiliary agent of formula ratio mixed in the high-speed stirring bucket on request, from the batch mixing mouth, join temperature and be set at 220～270 ℃, length-to-diameter ratio (L/D) be 32: 1～40: 1, screw combinations by in the twin screw extruder of process stipulation, vacuumize granulation and make the halogen-free glass fiber reinforced nylon 6 resin.The sampling material is injection molded into the standard batten after dry 3～4 hours in 90～110 ℃, carry out performance test, and performance sees Table two.
The The performance test results of table two embodiment 1～4
Embodiment two
The halogen-free glass fiber enhanced nylon 66 resin
Table three embodiment 5 ~ 8
HJ-1: the expansion type flame retardant of special phosphorus N structure
HJ-2: toughner
GF: glass
Nylon 66 in 90～110 ℃ drying hopper dry 3～4 hours, after nylon 6 (PA6), the halogen-free expansible nylon fire retardant (HJ-1) of phosphorus N structure, toughner (HJ-2), the various auxiliary agent of formula ratio mixed in the high-speed stirring bucket on request, from the batch mixing mouth, join temperature and be set at 230～280 ℃, length-to-diameter ratio (L/D) be 32: 1～40: 1, screw combinations by in the twin screw extruder of process stipulation, vacuumize granulation and make the halogen-free glass fiber enhanced nylon 66 resin.The sampling material is injection molded into the standard batten after dry 3～4 hours in 90～110 ℃, carry out performance test, and performance sees Table four.
The The performance test results of table four embodiment 5 ~ 8
Claims (3)
1, a kind of halogen-free glass fiber reinforced nylon resin, it is characterized in that: by comprising that weight percent is 38～55% nylon 66 or nylon 6, the halogen-free expansible nylon fire retardant of 17～30% phosphorus N structures, 4～8% toughner, 25～35% glass, 0.5～1.5% lubricant, coupling agent, oxidation inhibitor, thermo-stabilizer are formed.
2, require described halogen-free glass fiber reinforced nylon resin according to right 1, it is characterized in that: the viscosity of described nylon 66 or nylon 6 is between 2.4～3.0.
3, require the preparation method of described halogen-free glass fiber reinforced nylon resin according to right 1, it is characterized in that: nylon 66 or nylon 6 in 90～110 ℃ drying hopper dry 3～5 hours, mix in the high-speed stirring bucket preparing material on request, from the batch mixing mouth, join temperature be set at 220 ℃～280 ℃, length-to-diameter ratio be 32: 1～40: 1, screw combinations by in the twin screw extruder of process stipulation, vacuumize granulation and make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910134863A CN101525486A (en) | 2008-04-03 | 2009-04-03 | Halogen-free glass fiber reinforced nylon resin and preparing method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810027207 | 2008-04-03 | ||
| CN200810027207.2 | 2008-04-03 | ||
| CN200910134863A CN101525486A (en) | 2008-04-03 | 2009-04-03 | Halogen-free glass fiber reinforced nylon resin and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101525486A true CN101525486A (en) | 2009-09-09 |
Family
ID=41093562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910134863A Pending CN101525486A (en) | 2008-04-03 | 2009-04-03 | Halogen-free glass fiber reinforced nylon resin and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101525486A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337029A (en) * | 2011-08-11 | 2012-02-01 | 古道尔工程塑胶（深圳）有限公司 | Halogen-free flame-retardant nylon 66 composite material and preparation method thereof |
| CN102382467A (en) * | 2011-11-25 | 2012-03-21 | 深圳市科聚新材料有限公司 | High-temperature and heat-ageing resistant PA66 material and preparation method thereof |
| CN103013098A (en) * | 2012-11-26 | 2013-04-03 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant continuous long glass fiber reinforced polyamide 6 composite material and preparation method thereof |
| CN103044912A (en) * | 2012-11-28 | 2013-04-17 | 江苏金发科技新材料有限公司 | Halogen-free flame retardant continuous long glass fiber reinforced polyamide 66 composite material and preparation method thereof |
| CN103965623A (en) * | 2014-05-20 | 2014-08-06 | 古道尔工程塑胶（深圳）有限公司 | High-dimensional-stability reinforced flame-retardant cold-resistant composite material and preparation method thereof |
| CN104479350A (en) * | 2014-12-29 | 2015-04-01 | 江西固康新材料有限公司 | Halogen-free flame-retarded polycaprolactam compound with low smoke and extremely low odor |
| CN110922518A (en) * | 2019-11-30 | 2020-03-27 | 华东理工大学 | Water-resistant intumescent flame retardant and preparation method and application thereof |
| CN114702817A (en) * | 2022-03-17 | 2022-07-05 | 广东华聚科技有限公司 | High-strength flame-retardant nylon and preparation process thereof |
| CN115678272A (en) * | 2022-11-15 | 2023-02-03 | 芜湖聚发新材料有限公司 | Halogen-free flame-retardant PA66 material and preparation method thereof |
-
2009
- 2009-04-03 CN CN200910134863A patent/CN101525486A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337029A (en) * | 2011-08-11 | 2012-02-01 | 古道尔工程塑胶（深圳）有限公司 | Halogen-free flame-retardant nylon 66 composite material and preparation method thereof |
| CN102382467A (en) * | 2011-11-25 | 2012-03-21 | 深圳市科聚新材料有限公司 | High-temperature and heat-ageing resistant PA66 material and preparation method thereof |
| CN103013098B (en) * | 2012-11-26 | 2016-05-18 | 江苏金发科技新材料有限公司 | Continuous roving glass fiber reinforced polyamide 6 composites of halogen-free flameproof and preparation method thereof |
| CN103013098A (en) * | 2012-11-26 | 2013-04-03 | 江苏金发科技新材料有限公司 | Halogen-free flame-retardant continuous long glass fiber reinforced polyamide 6 composite material and preparation method thereof |
| CN103044912A (en) * | 2012-11-28 | 2013-04-17 | 江苏金发科技新材料有限公司 | Halogen-free flame retardant continuous long glass fiber reinforced polyamide 66 composite material and preparation method thereof |
| CN103044912B (en) * | 2012-11-28 | 2016-09-21 | 江苏金发科技新材料有限公司 | Halogen-free flameproof continuous long glass fiber reinforced polyamide 66 composite material and preparation method thereof |
| CN103965623A (en) * | 2014-05-20 | 2014-08-06 | 古道尔工程塑胶（深圳）有限公司 | High-dimensional-stability reinforced flame-retardant cold-resistant composite material and preparation method thereof |
| CN104479350A (en) * | 2014-12-29 | 2015-04-01 | 江西固康新材料有限公司 | Halogen-free flame-retarded polycaprolactam compound with low smoke and extremely low odor |
| CN110922518A (en) * | 2019-11-30 | 2020-03-27 | 华东理工大学 | Water-resistant intumescent flame retardant and preparation method and application thereof |
| CN110922518B (en) * | 2019-11-30 | 2021-04-23 | 华东理工大学 | Water-resistant intumescent flame retardant and preparation method and application thereof |
| CN114702817A (en) * | 2022-03-17 | 2022-07-05 | 广东华聚科技有限公司 | High-strength flame-retardant nylon and preparation process thereof |
| CN114702817B (en) * | 2022-03-17 | 2022-12-02 | 广东华聚科技有限公司 | High-strength flame-retardant nylon and preparation process thereof |
| CN115678272A (en) * | 2022-11-15 | 2023-02-03 | 芜湖聚发新材料有限公司 | Halogen-free flame-retardant PA66 material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525486A (en) | Halogen-free glass fiber reinforced nylon resin and preparing method thereof | |
| CN101875761B (en) | Flame-retardant strengthening polythylene terephthalate (PET) material and preparation method thereof | |
| CN101798460B (en) | Composite flame retardant glass fibre reinforced nylon 66 insulating strip and preparation method thereof | |
| CN100590146C (en) | Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material | |
| CN102337029B (en) | Halogen-free flame-retardant nylon 66 composite material and preparation method thereof | |
| CN101747616A (en) | Modified polyphenyl ether material and preparation method thereof | |
| CN102311577B (en) | Glass fiber reinforced flame-retarded polypropylene composite and preparation method thereof | |
| CN102108181B (en) | Thermoplastic alloy and preparation method thereof | |
| CN104194161A (en) | Precipitation resistant, toughening and flame-retardant polypropylene composite material and preparation method thereof | |
| CN102115579A (en) | High-toughness high-glowing-filament-ignition-temperature flame-retardant reinforced PBT (polybutylene terephthalate) material and preparation method thereof | |
| CN105273388A (en) | High-heat-resistance halogen-free flame-retardant polyphenyl ether composite material and preparation method thereof | |
| CN103951959A (en) | Intumescent flame-retardant reinforced PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof | |
| CN110157174A (en) | A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement | |
| CN101717568A (en) | Polycarbonate/nylon 6 alloy material and preparation method thereof | |
| CN106854359A (en) | Inexpensive high heat-resistant halogen-free flame-retardant reinforced plastic PA66 composition and preparation method thereof | |
| CN103709659A (en) | Glass fiber reinforced PBT/PET alloy material | |
| CN102993555A (en) | High impact halogen-free flame retardant PP/PPO (Propene Polymer/Poly Phenylene Oxide) alloy material and preparation method and application thereof | |
| CN102040810A (en) | Polybutylece terephthalate (PBT) engineering plastics as well as preparation method and application thereof | |
| CN102424716A (en) | High-glow wire ignition temperature flame-retardant reinforced polybutylece terephthalate (PBT) material and preparation method thereof | |
| CN103205017A (en) | Halogen-free fire retardant and preparation method of halogen-free fire-retardant PBT (polybutylece terephthalate) composite material | |
| CN106398128B (en) | Halogen-free flameproof long glass fiber reinforced TPEE composite material and preparation method | |
| CN108530887A (en) | A kind of high heat-resisting, high intensity semiaromatic polyamide composition/polyester alloy material and its preparation method and application | |
| CN101921472A (en) | High impact-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof | |
| CN103073855A (en) | Polyester composition, preparation method and applications thereof | |
| CN103709663A (en) | Modified PET/PBT alloy material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090909 |