CN110172242A - Resistance to thermal level blow molding enhances modified polyamide composite material - Google Patents

Resistance to thermal level blow molding enhances modified polyamide composite material Download PDF

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Publication number
CN110172242A
CN110172242A CN201910491391.4A CN201910491391A CN110172242A CN 110172242 A CN110172242 A CN 110172242A CN 201910491391 A CN201910491391 A CN 201910491391A CN 110172242 A CN110172242 A CN 110172242A
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resistance
blow molding
composite material
modified polyamide
thermal level
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CN110172242B (en
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秦增增
韩辉
马英哲
姚利
陈晓杭
何瑞平
郭鹏杰
裴迅
孙雪楠
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Tianjin Changlu Haijing Group Co Ltd
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Tianjin Changlu Haijing Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

The invention discloses a kind of resistance to thermal level blow moldings to enhance modified polyamide composite material, and polyamide compoiste material is made of polyamide substrate, filler, impact modifying agent, lubricant and thermostabilization auxiliary agent packet.The present invention provides a kind of resistance to thermal level blow molding enhancing modified polyamide composite material, can tri-dimensional blow moulding form various pipelines, processing performance is excellent, and high heat resistance densification shell imparts the excellent long-term high heat resistance ageing properties of material, has the stronger market competitiveness.This product is obviously improved material heatproof air aging performance by addition thermal conducting agent, heat stabilizer, dense protective layer and free radical scavenger, while meeting 3D blow molding to the processing request of material.

Description

Resistance to thermal level blow molding enhances modified polyamide composite material
Technical field
The invention belongs to modified nylon material fields, and in particular to a kind of resistance to thermal level blow molding enhancing modified polyamide is multiple Condensation material.
Background technique
With the development of Hyundai Motor technology, automotive light weight technology develops into extremely urgent new issue, to reach energy conservation Complete vehicle weight is lowered in emission reduction, increasing using the dosage of functor made of plastics in the car.With automotive light weight technology Development, Polyamide Engineering Plastic have the characteristics such as lightweight, durable because its is easy to process, are widely used in automobile engine Periphery and power drive system.
Polyamide Engineering Plastic enhances the modified raw material through frequently as engine periphery heat-resistant part and uses, engine week Side heat-resistant part is exposed to the high oil pollution environment of high temperature for a long time, frequent occurrence thermo-oxidative ageing degradation problem, and shortening components makes Use the service life.How to overcome and solve polyamide in the high temperature environment long period exposure performance do not deteriorate, extend plastic structural part make Become the task of top priority with the service life.
Currently, high-performance common nylon construct blow-molded, only several transnational company produce, such as German BASF, U.S. Du Nation, French Rhodia, domestic rare manufacturing enterprise.CN 102702733 and CN 101921476 disclose the system of blow-molding nylon Preparation Method, but heat resistance is not introduced deeply.
Summary of the invention
The present invention is proposed to overcome disadvantage existing in the prior art, and the purpose is to provide a kind of resistance to thermal level to blow It is moulded into type enhancing modified polyamide composite material.
The technical scheme is that
A kind of resistance to thermal level blow molding enhancing modified polyamide composite material, the component and each component of the polyamide compoiste material Mass percentage it is as follows:
Polyamide substrate 55% ~ 60%；
Filler 10% ~ 30%；
Impact modifying agent 5% ~ 15%；
Lubricant 0.2% ~ 1%；
Thermostabilization auxiliary agent packet 3% ~ 8%.
The polyamide substrate be relative viscosity >=3.3(96% concentrated sulfuric acid, 1g/dl) PA6, PA66, PA 6/66 be copolymerized Object or its any mixture；
The filler is the appointing in alkali-free glass fibre, glass microballoon, wollastonite, kaolin, montmorillonite or barium sulfate that be chopped It anticipates one or more mixtures, the mixture of be preferably chopped alkali-free glass fibre, glass microballoon or both.
The impact modifying agent is maleic anhydride grafting, maleic anhydride grafting, ethylene butyl acrylate copolymer or ethylene The mixture of any one or more in acrylic copolymer, preferably ethylene butyl acrylate copolymer.
The lubricant be silicone powder, ethylene bis stearamide, montanate, montanic acid calcium ethylene acrylic acid co polymer or The mixture of any one or more in calcium stearate, preferably montanic acid calcium.
The thermostabilization auxiliary agent packet includes thermal conducting agent, heat stabilizer, free radical scavenger and high heat resistance densification Shell Materials, Mass fraction of the thermal conducting agent in polyamide compoiste material is 0.5% ~ 3%；The heat stabilizer is in polyamide compoiste material In mass fraction be 0.3% ~ 0.7%；Mass fraction of the free radical scavenger in polyamide compoiste material is 0.9% ~ 3 %；Mass fraction of the high heat resistance densification Shell Materials in polyamide compoiste material is 0.5% ~ 5%.
The thermal conducting agent is the mixture of any one or more in iron powder, graphene or carbon nanotube, preferably carbon Nanotube.
The heat stabilizer is mantoquita heat stabilizer.
The free radical scavenger is N, (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of N '-two and height The mixture of active MgO.
The high heat resistance densification Shell Materials are any in fluorine silicone rubber, polytetrafluoroethylene (PTFE) or aromatic series high-barrier nylon One or more mixtures, preferably fluorine silicone rubber.
The beneficial effects of the present invention are:
The present invention provides a kind of resistance to thermal level blow molding enhancing modified polyamide composite material, can the various pipes of tri-dimensional blow moulding molding Road, processing performance is excellent, and high heat resistance densification shell imparts the excellent long-term high heat resistance ageing properties of material, has stronger city Field competitiveness.This product makes the heat-resisting oxygen of material by addition thermal conducting agent, heat stabilizer, dense protective layer and free radical scavenger Ageing properties are obviously improved, while meeting 3D blow molding to the processing request of material.
Specific embodiment
The present invention resistance to thermal level blow molding enhancing modified polyamide composite material is carried out specifically below with reference to embodiment It is bright:
A kind of resistance to thermal level blow molding enhancing modified polyamide composite material, the mass percentage including component and each component is such as Under:
Polyamide substrate 55% ~ 60%；
Filler 10% ~ 30%；
Impact modifying agent 5% ~ 15%；
Lubricant 0.2% ~ 1%.
Thermostabilization auxiliary agent packet 3% ~ 8%.
Wherein, the polyamide substrate be relative viscosity >=3.3(96% concentrated sulfuric acid, 1g/dl) PA6, PA66, PA 6/ The mixture of any one or more in 66 copolymers；Filler is selected from be chopped alkali-free glass fibre, glass microballoon, silicon ash Stone, kaolin, montmorillonite, the mixture of any one or more in barium sulfate, be preferably chopped alkali-free glass fibre, glass are micro- The mixture of pearl or both；Impact modifying agent is selected from maleic anhydride grafting POE, maleic anhydride is grafted EPDM, ethylene acrylic fourth The mixture of any one or more in ester copolymer EBA, ethylene acrylic acid co polymer EAA, optimal ethylene butyl acrylate Copolymer EBA.Lubricant is selected from silicone powder, ethylene bis stearamide, montanate, montanic acid calcium ethylene acrylic acid co polymer A- The mixture of any one or more in C540A, calcium stearate, preferably montanic acid calcium.
Thermostabilization auxiliary agent packet mainly includes following substance:
Thermal conducting agent 0.5% ~ 3%；
Heat stabilizer 0.3% ~ 0.7%；
0.9% ~ 3 % of free radical scavenger；
High heat resistance densification Shell Materials 0.5% ~ 5%.
The thermal conducting agent iron powder, graphene, the mixture of any one or more in carbon nanotube, preferably carbon nanometer Pipe.
The heat stabilizer is mantoquita heat stabilizer, can be cuprous iodide: potassium iodide=1:4 (mass ratio) or iodine Change potassium: potassium bromide: cuprous iodide=8:1:1 (mass ratio), also or the mixture of other commercially available mantoquita heat stabilizers.
The free radical scavenger is the N, (letter of N '-two (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide Claim SEED) and high activity MgO mixture.SEED has the ability for capturing free radical at high temperature, controls material aging and property It can deteriorate, MgO and SEED is public can to play certain synergy, improve SEED and capture free ability.
The high heat resistance densification Shell Materials can the plastic surface after blow molding formed one layer of fine and close protective film with Material property is prevented further to deteriorate, this high heat resistance dense material is fluorine silicone rubber, polytetrafluoroethylene (PTFE), aromatic series high-barrier Buddhist nun Imperial (MXD6) or any combination thereof object, preferably fluorine silicone rubber.
The resistance to thermal level blow molding enhancing modified polyamide composite material the preparation method comprises the following steps: will gather in certain proportion Amide matrix, filler, impact modifying agent, lubricant and other auxiliary agents be added in double screw extruder melt, squeeze out, be granulated, It is drying to obtain.The temperature of the melting is 240 DEG C ~ 295 DEG C when preparation.
Embodiment 1
Weigh 66.7 parts of polyamide 6s (relative viscosity 3.8-4.0), 17 parts of glass fibres, 8 parts of impact modifying agent EBA, 0.3 part of profit Lubrication prescription montanic acid calcium, 2 parts of thermal conducting agents (carbon nanotube master batch), 0.5 part of mantoquita heat stabilizer, 1.5 parts of free radical scavengers and 2 parts Fluorine silicone rubber.
By the above-mentioned group in addition to glass fibre be placed in high-speed mixer and mixing it is uniform after, from main spout be added twin-screw In extruder (extrusion temperature is at 240-295 DEG C), glass is added in extruder from side spout and carries out extruding pelletization, gained particle Standard batten is molded into for performance test after drying 4 hours in 110 DEG C of convection oven.
Embodiment 2 ~ 4
According to the method for embodiment 1, the different component formula in table 1 is respectively adopted, obtains the different product of embodiment 2 ~ 4.
The properties of product comparison of embodiment 1 ~ 4 is shown in Table 2
The product form of 1 embodiment 1 ~ 4 of table
The comparison of 2 embodiment of table, 1 ~ 4 properties of product
The present invention provides it is a kind of can tri-dimensional blow moulding form the polyamide compoiste materials of various pipelines, have processing performance it is excellent, High heat resistance densification shell imparts the excellent long-term high heat resistance ageing properties of material, has the stronger market competitiveness.This product The advantages of be to make material heat oxygen aging resistance by addition thermal conducting agent, heat stabilizer, dense protective layer and free radical scavenger Performance is obviously improved, while meeting 3D blow molding to the processing request of material.

Claims (10)

1. a kind of resistance to thermal level blow molding enhances modified polyamide composite material, it is characterised in that: the polyamide compoiste material Component and each component mass percentage it is as follows:
Polyamide substrate 55% ~ 60%；
Filler 10% ~ 30%；
Impact modifying agent 5% ~ 15%；
Lubricant 0.2% ~ 1%；
Thermostabilization auxiliary agent packet 3% ~ 8%.
2. resistance to thermal level blow molding according to claim 1 enhances modified polyamide composite material, it is characterised in that: described Polyamide substrate is relative viscosity >=3.3(96% concentrated sulfuric acid, 1g/dl) 6/66 copolymer of PA6, PA66, PA or it is any mixed Close object.
3. resistance to thermal level blow molding according to claim 1 enhances modified polyamide composite material, it is characterised in that: described Filler be chopped alkali-free glass fibre, glass microballoon, wollastonite, kaolin, montmorillonite or barium sulfate in any one or A variety of mixtures, the mixture of be preferably chopped alkali-free glass fibre, glass microballoon or both.
4. resistance to thermal level blow molding according to claim 1 enhances modified polyamide composite material, it is characterised in that: described Impact modifying agent is maleic anhydride grafting, maleic anhydride grafting, ethylene butyl acrylate copolymer or ethylene acrylic acid co polymer In the mixture of any one or more, preferably ethylene butyl acrylate copolymer.
5. resistance to thermal level blow molding according to claim 1 enhances modified polyamide composite material, it is characterised in that: described Lubricant is in silicone powder, ethylene bis stearamide, montanate, montanic acid calcium ethylene acrylic acid co polymer or calcium stearate The mixture of any one or more, preferably montanic acid calcium.
6. resistance to thermal level blow molding according to claim 1 enhances modified polyamide composite material, it is characterised in that: described Thermostabilization auxiliary agent packet includes that thermal conducting agent, heat stabilizer, free radical scavenger and high heat resistance densification Shell Materials, the thermal conducting agent exist Mass fraction in polyamide compoiste material is 0.5% ~ 3%；Mass fraction of the heat stabilizer in polyamide compoiste material It is 0.3% ~ 0.7%；Mass fraction of the free radical scavenger in polyamide compoiste material is 0.9% ~ 3 %；The high heat resistance Mass fraction of the fine and close Shell Materials in polyamide compoiste material is 0.5% ~ 5%.
7. resistance to thermal level blow molding according to claim 6 enhances modified polyamide composite material, it is characterised in that: described Thermal conducting agent is the mixture of any one or more in iron powder, graphene or carbon nanotube, preferably carbon nanotube.
8. resistance to thermal level blow molding according to claim 6 enhances modified polyamide composite material, it is characterised in that: described Heat stabilizer is mantoquita heat stabilizer.
9. resistance to thermal level blow molding according to claim 6 enhances modified polyamide composite material, it is characterised in that: described Free radical scavenger is N, and (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of N '-two and high activity MgO's is mixed Close object.
10. resistance to thermal level blow molding according to claim 6 enhances modified polyamide composite material, it is characterised in that: institute Stating high heat resistance densification Shell Materials is any one or more in fluorine silicone rubber, polytetrafluoroethylene (PTFE) or aromatic series high-barrier nylon Mixture, preferably fluorine silicone rubber.
CN201910491391.4A 2019-06-06 2019-06-06 Heat-resistant blow molding reinforced modified polyamide composite material Active CN110172242B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574829A (en) * 2020-04-24 2020-08-25 金发科技股份有限公司 Polyamide composite material and preparation method thereof
CN111961257A (en) * 2020-09-03 2020-11-20 华东理工大学 Composite copper salt antioxidant system and application thereof in nylon material
CN116554697A (en) * 2023-06-08 2023-08-08 安徽中纤新材料有限公司 Processing technology for preparing high-toughness composite material by glass fiber composite PA single 6

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111574829A (en) * 2020-04-24 2020-08-25 金发科技股份有限公司 Polyamide composite material and preparation method thereof
CN111574829B (en) * 2020-04-24 2022-07-26 金发科技股份有限公司 Polyamide composite material and preparation method thereof
JP2023522263A (en) * 2020-04-24 2023-05-29 金発科技股▲ふん▼有限公司 Polyamide composite material and its manufacturing method
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CN111961257A (en) * 2020-09-03 2020-11-20 华东理工大学 Composite copper salt antioxidant system and application thereof in nylon material
CN116554697A (en) * 2023-06-08 2023-08-08 安徽中纤新材料有限公司 Processing technology for preparing high-toughness composite material by glass fiber composite PA single 6
CN116554697B (en) * 2023-06-08 2024-04-23 安徽中纤新材料有限公司 Processing technology for preparing high-toughness composite material by glass fiber composite PA single 6

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