CN106700525B - A kind of HI high impact halogen-free flameproof POK/PA alloy material - Google Patents
A kind of HI high impact halogen-free flameproof POK/PA alloy material 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
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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
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Abstract
The present invention relates to polymeric material field, specifically a kind of HI high impact halogen-free flameproof POK/PA alloy material is made of following component by following parts by weight: 200-400 parts of polyketone POK；400-700 parts of nylon PA6；Compatible impact modifying agent 10-100 parts；50-150 parts of halogen-free flame retardants；5-15 parts of auxiliary agent.HI high impact halogen-free flameproof POK/PA alloy material of the invention has good high impact property, and 23 DEG C can achieve 250J/M；- 30 DEG C can achieve 150J/M, and halogen-free flameproof can achieve V-0；The barasion coefficient of material is better than simple flame-proof PA 6, reaches 6.9mm3/kg/km；The heat distortion temperature of material is higher than simple flame-proof PA 6, reaches 190 DEG C.
Description
Technical field
The present invention relates to polymeric material fields, specifically, being a kind of HI high impact halogen-free flameproof POK/PA alloy material.
Background technique
Polyamide (PA6) has thermoplasticity, lightweight, excellent mechanical performance, chemicals-resistant and a characteristics such as durability is good, and one
As for the products such as auto parts and components, mechanical part, electric equipment products, engineering accessory.The disadvantage is that water absorption rate is high, dry and tide
Strength difference is larger under wet environment, and notch shock is not high, and wearability is general, and shrinking percentage is larger etc..
Polyketone (POK) is the novel green polymer material synthesized by carbon monoxide, alkene (ethylene, propylene), molecule master
Chain passes through the highly crystalline engineering plastics for forming close crystalline structure, excellent chemical resistance, shock resistance, frictional property by hydrocarbon
Energy and high barrier, compared with nylon, shock resistance is eager to excel 3 times, is also significantly improved to the stability of chemical substance, surface
Hardness is also better than POM, can be used for the components of automobile, electronics, industry material.But the simple POK range of work is narrow, to molding
Tooling and technique are more demanding, so that using being greatly limited the experiment has found that the alloy surface wearability of POK and PA6
It is significantly improved than PA6, the intensity ratio PA6 of wet environment is obvious high, and the more simple POK of processing temperature, which has, obviously to be widened.Consideration is got home
Electricity and electronic apparatus have flame-retardancy requirements, but POK/PA alloy improvement anti-flammability is rarely reported at present, and halogen-free flameproof is even more not have.
Nitrogenated flame retardant have Halogen, low toxicity, stability is good, flame retarding efficiency is high, the advantages such as environmentally friendly, 20th century 90
It has been developed rapidly since age.Currently, being mainly melamine and its derivative using more nitrogenated flame retardant
(MCA).The product of the fire-retardant burning of MCA will not be CO, NH with controversial halide and phosphorus system product, main component3
Equal substances.MCA has excellent high temperature resistant processing performance, and 300 DEG C or less are heated highly stable, and 350 DEG C start to distil, but regardless of
Solution.It can just be decomposed at 440-450 DEG C of temperature and generate melamine and cyanuric acid, play the work for absorbing heat and cooling heat source
With.And the melamine that has gasified provides inert gas source, can dilution oxygen and the fuel gas that is generated because high polymer decomposes it is dense
Degree, to reach fire-retardant purpose.MCA non-volatile component at 300 DEG C, and solubility is low in water.When this fire retardant burns
Nitrogen oxides is discharged, there is no highly acid substance is generated after hydrogen halides and phosphorus flame retardant burning, so because of its environmental protection
Characteristic and be widely used in PA6.
Number of patent application 98121442.8 " polyketone flame retardant composition " uses merely trimeric-cyanamide cyanurate fire-retardant
POK, anti-flammability can only achieve V-2, and be not directed to the assessment of fire proofing mechanical performance.
A kind of HI high impact halogen-free flameproof POK/PA alloy material how is developed, continuous explore and study is worth.Currently, not yet
See the relevant report of PA/POK alloy fire proofing, halogen-free flameproof is even more not have.
Summary of the invention
The purpose of the present invention is to provide a kind of HI high impact halogen-free flameproof POK/PA alloy material, can be applicable to it is fire-retardant and
The outdoor industry accessories of the plug for industrial use of wear-resisting requirement, geared parts and cold district low temperature requirements.
The first aspect of the present invention provides a kind of HI high impact halogen-free flameproof POK/PA alloy material, by following component by such as
Lower parts by weight composition:
Wherein, the polyketone POK is the copolymer of carbon monoxide and alkene, number-average molecular weight 10000-100000；Institute
Stating nylon PA 6 is the nylon 6 by caprolactam open loop polycondensation, number-average molecular weight 16000-33000；The compatible impact changes
Property agent be core-shell structure the epoxy-modified polymer of silicon-acrylate-, using silicon rubber-acrylate composite rubber as core, poly- first
Base glycidyl acrylate (GMA) is the graft copolymer of the core-shell structure of shell.
Further, the alkene is ethylene, propylene or the mixture of both.
Further, the polyketone POK is the copolymer of carbon monoxide, ethylene, propylene, number-average molecular weight 60000-
90000。
Further, the number-average molecular weight of the nylon PA6 is 20000-30000.Further, the halogen-free flame retardants
For melamine cyanurate.
Further, the auxiliary agent includes the following components of percentage meter by weight: antioxidant 20-30%, antiultraviolet add
Add agent 30-35%, processing aid 30-35% and toner 8-10%.
Further, the antioxidant is selected from phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen
The mixing of one or both of agent 1098, hindered phenol antioxygen 1076；Preferably, the antioxidant is irgasfos 168 and resists
The mixing of oxygen agent 1098.
Further, the antiultraviolet additive is the light stabilizer of weight ratio 1:1 and the compounding of ultraviolet absorbing agent
Object；Preferably, the light stabilizer be light stablize 770 or light stablize one of 622；The ultraviolet absorbing agent be UV234,
In UV-328 or UV-320；It is furthermore preferred that the antiultraviolet additive is the compound that light stablizes 770 and UV-234.
Further, the processing aid is selected from polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate, long-chain
The mixing of one or more of fatty acid polyfunctional group ester.Preferably, the processing aid is polyethylene wax.
Further, the toner is mainly made of pigment and spread powder.
The second aspect of the present invention provides the preparation method of above-mentioned HI high impact halogen-free flameproof POK/PA alloy material, including
Following steps:
Raw material is weighed by the component ratio, all raw materials are 3-5 minutes dry-mixed at room temperature in super mixer,
Then squeezed out at 220~240 DEG C through double screw extruder, be cooling, be granulated, gained pellet after 100 DEG C 4 hours dry
Be molded at 240~260 DEG C standard sample item to get.
The compatible impact modifying agent that the present invention uses, the GMA epoxy polymer in structure improve the compatible of PA6 and POK
Property, while silicon rubber-acrylate composite rubber improves the room temperature and low-temperature flexibility of material, silicon rubber therein grinds reduction
Consumption coefficient also has certain synergistic effect.
The invention has the advantages that:
1, with good high impact property, (23 DEG C can achieve 250J/M to material；- 30 DEG C can achieve 150J/M), and
Halogen-free flameproof can achieve V-0.
2, the barasion coefficient of material is better than simple flame-proof PA 6, reaches 6.9mm3/kg/km。
3, the heat distortion temperature of material is higher than simple flame-proof PA 6, reaches 190 DEG C.
Specific embodiment
It elaborates below with reference to embodiment to specific embodiment provided by the invention.
In the following examples, each raw material uses following compositions:
1, it polyketone POK: is provided by Hyosung group of South Korea, model M630A；
2, it nylon PA 6: using the PA6 by caprolactam open loop polycondensation, is provided by Honeywell Inc., model
H8202NLB；
3, compatible impact modifying agent: being provided by Mitsubishi Li Yang company, and model S2200 is (with silicon rubber-acrylate
Compounded rubber is core, and poly (glycidyl methacrylate) is the graft copolymer of the core-shell structure of shell)；
4, melamine cyanurate based flame retardant: being provided by Hangzhou JLS Flame Retardants Chemical Co., Ltd., model
JLS-MC810；
5, it irgasfos 168, antioxidant 1098: is manufactured by BASF AG；
6, light stablizes 770, ultraviolet absorbing agent UV234: being manufactured by BASF AG；
7, process flow promortor: polyethylene wax, oxidized polyethylene wax are manufactured by BASF AG, pentaerythritol stearate by
The manufacture of Long Sha company of the U.S., long chain fatty acids polyfunctional group ester are manufactured by German Kening Co., Ltd.
Embodiment 1
By following component in parts by weight:
Above-mentioned raw materials component is mixed 3-5 minutes in a high speed mixer, is then squeezed at 220~240 DEG C through twin-screw
Machine squeezes out, is cooling, being granulated out, and gained pellet is molded into standard sample item after 100 DEG C 4 hours dry at 240~260 DEG C, i.e.,
?.
Embodiment 2-6
Raw material is weighed by the parts by weight in table 1, the preparation method is the same as that of Example 1.
The component and proportion of 1 embodiment 1-6 of table
The evaluation of implementation result
The sample that above-described embodiment 1 is obtained to embodiment 6, according to American Society Testing and Materials (ASTM) standard testing
Mechanical property, optical property, according to UL94 standard testing flame retardant property, according to the abrasion system of GB 3960-83 Standards for Testing Materials
Number, test result is as follows shown in table 2:
The test result of 2 embodiment 1-6 of table
| Performance parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Density (g/cm3) | 1.18 | 1.27 | 1.22 | 1.20 | 1.18 | 1.17 |
| Melt flow rate (MFR) (g/10min) | 20 | 9 | 18 | 15 | 13 | 13 |
| Elongation at break (%) | 17% | 220% | 65% | 79% | 102% | 125% |
| Tensile strength (MPa) is dry | 75 | 70 | 72 | 68 | 65 | 62 |
| Tensile strength (MPa) is wet | 50 | 62 | 58 | 61 | 59 | 56 |
| Bending modulus (MPa) is dry | 3000 | 2200 | 2850 | 2700 | 2550 | 2400 |
| Bending modulus (MPa) is wet | 1700 | 2050 | 1950 | 2200 | 2250 | 2200 |
| 23 DEG C of lzod notch impact strength (J/m) | 52 | 145 | 73 | 150 | 250 | 300 |
| - 30 DEG C of lzod notch impact strength (J/m) | 35 | 89 | 38 | 96 | 150 | 180 |
| Heat distortion temperature (DEG C) 0.45MPa | 180 | 210 | 196 | 193 | 190 | 188 |
| Anti-flammability | V-0 | V-2 | V-0 | V-0 | V-0 | V-2 |
| Barasion coefficient (mm3/kg/km) | 12 | 0.6 | 7.8 | 7.3 | 6.9 | 6.8 |
The test performance of table 2 the result shows that:
(1) it analyzes to obtain from Examples 1 to 3, MCA is used in pure polyketone material, and flame retardant effect is poor, but in PA/POK
Flame retardant rating can be made to reach V-0 grades in alloy.Also, the addition of POK reduces PA6 to the sensibility of moisture, reduces PA6
Barasion coefficient, improve the heat distortion temperature of PA6.
(2) it is obtained from the analysis of embodiment 4~6, the addition of compatible impact modifying agent S2200, the GMA epoxide polymerization in structure
Object improves the compatibility of PA6 and POK, at the same silicon rubber-acrylate composite rubber improve material room temperature and low temperature it is tough
Property, and as additive amount increases, toughness obviously increases, and barasion coefficient reduces.But reach 10% or more in additive amount, anti-flammability is bright
Aobvious decline has been unable to satisfy V-0 requirement.Therefore the optimum addition of compatible impact modifying agent S2200 is in the 8% (conjunction of embodiment 5
Golden material comprehensive performance is optimal).
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (6)
1. a kind of HI high impact halogen-free flameproof POK/PA alloy material is made of following component by following parts by weight:
Wherein, the polyketone POK be carbon monoxide and alkene copolymer, alkene be ethylene, propylene or the mixture of both,
Polyketone POK number-average molecular weight is 10000-100000；The nylon PA 6 is the nylon 6 by caprolactam open loop polycondensation, and number is equal
Molecular weight is 16000-33000；The compatible impact modifying agent is the epoxy-modified polymer of silicon-acrylate-of core-shell structure,
Using silicon rubber-acrylate composite rubber as core, poly (glycidyl methacrylate) is the graft copolymerization of the core-shell structure of shell
Object；The halogen-free flame retardants is melamine cyanurate.
2. a kind of HI high impact halogen-free flameproof POK/PA alloy material according to claim 1, it is characterised in that: the polyketone
POK is the copolymer of carbon monoxide, ethylene, propylene, number-average molecular weight 60000-90000.
3. a kind of HI high impact halogen-free flameproof POK/PA alloy material according to claim 1, it is characterised in that: the nylon
The number-average molecular weight of PA 6 is 20000-30000.
4. a kind of HI high impact halogen-free flameproof POK/PA alloy material according to claim 1, it is characterised in that: the auxiliary agent
Following components including percentage meter by weight: antioxidant 20-30%, antiultraviolet additive 30-35%, processing aid 30-
35% and toner 8-10%.
5. a kind of HI high impact halogen-free flameproof POK/PA alloy material according to claim 4, it is characterised in that: the antioxygen
Agent is in phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen 1098, hindered phenol antioxygen 1076
One or two kinds of mixing；The antiultraviolet additive is the light stabilizer of weight ratio 1:1 and answering for ultraviolet absorbing agent
With object；It is multifunctional that the processing aid is selected from polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate, long chain fatty acids
The mixing of one or more of group's ester.
6. a kind of preparation method of HI high impact halogen-free flameproof POK/PA alloy material according to claim 1-5,
The following steps are included:
Raw material is weighed by the component ratio, all raw materials are 3-5 minutes dry-mixed at room temperature in super mixer, then
Squeezed out at 220~240 DEG C through double screw extruder, be cooling, be granulated, gained pellet after 100 DEG C 4 hours dry 240~
Be molded at 260 DEG C standard sample item to get.
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| CN107189420B (en) * | 2017-06-14 | 2019-09-27 | 上海长伟锦磁工程塑料有限公司 | A kind of low warpage POK-PA alloy material of high wear-resistance anti-static |
| CN107189402A (en) * | 2017-07-07 | 2017-09-22 | 东莞市卡帝德塑化科技有限公司 | Modified engineered plastic material and preparation method for manufacturing lithium cell core shell |
| CN109608878B (en) * | 2018-12-13 | 2021-06-04 | 上海长伟锦磁工程塑料有限公司 | Damp-heat-aging-resistant halogen-free flame-retardant reinforced PA/POK alloy material |
| CN113480807A (en) * | 2021-05-27 | 2021-10-08 | 广州辰东新材料有限公司 | Polyamide, polyketone and polyolefin alloy material and preparation method thereof |
| CN114656744B (en) * | 2022-05-20 | 2022-07-29 | 广东乔艺塑胶有限公司 | Low-odor PP/AS/POK ternary composite resin, cosmetic packaging material and preparation method thereof |
| WO2024041953A1 (en) | 2022-08-23 | 2024-02-29 | Basf Se | Flame retardant polyamide composition and article produced from the composition |
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| WO1999055782A1 (en) * | 1998-04-29 | 1999-11-04 | Bp Chemicals Limited | Polymer blends from polyketone and polyamide |
| CN101023137A (en) * | 2004-09-21 | 2007-08-22 | Ems化学股份公司 | Use of stabilized thermoplastic polyamide molding compounds as a coating for optical waveguides |
| CN102746639A (en) * | 2011-04-19 | 2012-10-24 | 现代自动车株式会社 | Composition of polyketone with high impact strength |
| CN105885398A (en) * | 2016-01-25 | 2016-08-24 | 南京德尔隆工程塑料有限公司 | Hydrolysis-resistant polyamide composite and preparation method thereof |
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2016
- 2016-12-27 CN CN201611224517.4A patent/CN106700525B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999055782A1 (en) * | 1998-04-29 | 1999-11-04 | Bp Chemicals Limited | Polymer blends from polyketone and polyamide |
| CN101023137A (en) * | 2004-09-21 | 2007-08-22 | Ems化学股份公司 | Use of stabilized thermoplastic polyamide molding compounds as a coating for optical waveguides |
| CN102746639A (en) * | 2011-04-19 | 2012-10-24 | 现代自动车株式会社 | Composition of polyketone with high impact strength |
| CN105885398A (en) * | 2016-01-25 | 2016-08-24 | 南京德尔隆工程塑料有限公司 | Hydrolysis-resistant polyamide composite and preparation method thereof |
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