CN105733253A - Halogen-free flame-retardant high-temperature-resistant nylon composite - Google Patents

Abstract

The invention discloses a non-halogen flame-retardant high-temperature nylon composite material, which is prepared from a formula comprising the following components: polyamide, polyphenylene ether, polytetrafluoroethylene, a flame retardant, and an additive; the flame retardant is The mixture of melamine cyanurate or melamine cyanurate and polybismaleimide; the additive is stabilizer, adhesion promoter, antioxidant, antistatic agent, plasticizer, blowing agent or One or a combination of dispersants. In the present invention, by using polyphenylene ether, polybismaleimide and melamine cyanurate as synergists, when the thickness of the obtained flame-retardant and high-temperature-resistant nylon is between 1.5 and 3.2 mm, the flame-retardant performance can reach UL94 V ?0 level, suitable for high temperature fields such as electronic devices or aerospace, as well as home appliances, construction, consumer, electronics, medical, industrial, packaging, textile, transportation, also includes metal replacement of wire and cable, electrical transformer joints and accessories, fuses Seats, brackets, etc.

Description

A non-halogen flame retardant high temperature nylon composite material

technical field

The invention belongs to the technical field of polymer material synthesis. More specifically, it relates to a non-halogen flame-retardant high-temperature nylon composite material.

Background technique

Nylon (PA) is polyamide fiber, which is a general term for thermoplastic resins containing repeated amide groups - [NHCO] - in the main molecular chain. Nylon is the first synthetic fiber to appear in the world. Due to its good mechanical properties, drug resistance and ease of processing, nylon is widely used in various industries such as textiles, medical treatment, and national defense.

With the miniaturization of electronic devices and the rapid development of high frequency, the development of miniaturization, densification and high-density assembly technology of electronic components has been promoted. The temperature resistance requirements for materials are also continuously increasing. Especially when the surface mount process is used, various electrical components are heated in the infrared heating device at the same time, so higher requirements are put forward for the heat resistance and dimensional stability of the material. Various high-temperature resistant nylons such as semi-aromatic high-temperature nylons that have appeared in recent years have been greatly used.

The melting point of high-temperature nylon should be greater than 295°C or at least 50°C higher than that of traditional nylon. At the same time, it should be able to maintain stability at 220°C. However, during use, this type of nylon is often not flame retardant. Therefore, flame retardants, dripping agents and mineral fillers are often used as functional additives to modify nylon. When the commonly used halogenated flame retardants are burned or degraded, they will produce hydrogen halide gas and dense smoke, which are not conducive to the environment and human health. Therefore, the industry is gradually turning to the research of halogen-free flame retardants. However, materials currently using halogen-free flame retardants tend to have greater difficulties in processing, and their mechanical and mechanical properties are reduced.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the defects and deficiencies of the existing high-temperature nylon, and provide a non-halogen flame-retardant high-temperature nylon composite material, which not only has high-temperature resistance, but also has a flame-retardant performance that can reach UL94 V-0 level, and can Suitable for high temperature fields such as electronic devices or aerospace.

The purpose of the present invention is to provide a non-halogen flame retardant high temperature nylon composite material.

Another object of the present invention is to provide a method for preparing the above-mentioned non-halogen flame-retardant high-temperature nylon composite material.

The above object of the present invention is achieved through the following technical solutions:

A non-halogen flame-retardant high-temperature nylon composite material prepared from a formula containing the following components: polyamide, polyphenylene ether, polytetrafluoroethylene, flame retardant, additive; the flame retardant is melamine cyanuric acid Esters, or the flame retardant is a mixture of melamine cyanurate and polybismaleimide; the additives are stabilizers, adhesion promoters, antioxidants, antistatic agents, plasticizers, hair One or a combination of foaming agents or dispersing agents.

Wherein, the molecular formula of the melamine cyanurate is C ₆ H ₉ N ₉ O ₃ , which is commercially available.

Preferably, the polyamide is selected from semiaromatic polyamides, blends of semiaromatic polyamides and aliphatic polyamides, mixtures of semiaromatic polyamides and aliphatic polyamides.

More preferably, the polyamide is high-temperature nylon, that is, polydecanediamide terephthalamide (PA10T for short), which is commercially available.

Preferably, the polyphenylene ether (PPE) has a molecular weight of 2000-20000 g/mol, and is a thermoplastic, linear, Amorphous polyether. PPE is commercially available.

More preferably, the preparation method of the polyphenylene ether (PPE) is: mixing polyphenylene ether, bisphenol A and dicumyl peroxide in a 16 mm twin-screw extruder, and the mass fraction of the three is 98.29% respectively , 0.62% and 1.09%; the mixture is respectively extruded at 320°C, 310°C, and 300°C in zone one, zone two and zone three to nine; the mold temperature is 300°C, and particles are formed at a speed of 250 rpm.

Preferably, the polybismaleimide is, but not limited to, N,N-1,3 phenylene bismaleimide or 1,4-bis(maleimide)butane .

Polybismaleimide can be used to mix with polyphenylene ether while reducing the amount of polyphenylene ether.

Preferably, the polytetrafluoroethylene has a particle size ranging from 5 μm to 25 μm. Although polytetrafluoroethylene contains halogen, because of its extremely small amount, it can still be considered that the present invention is a halogen-free flame-retardant high-temperature nylon.

PTFE is often easily elongated into fibers during the injection molding process and thus acts as an anti-dripping agent. The fibers contract when exposed to the flame thereby retarding the dripping of the matrix.

In addition, preferably, when the flame retardant is melamine cyanurate, the mass percentages of melamine cyanurate and polyphenylene ether are 10% to 25% and 5% to 20% respectively, and the total of the two Amount of at least 30%;

When the flame retardant is a mixture of melamine cyanurate and polybismaleimide, the mass percentage of melamine cyanurate is 20% to 25%, and polyphenylene ether and polybismaleimide The mass percentages of amines are 5%-15% and 5%-10%, respectively.

More preferably, when the flame retardant is melamine cyanurate, the mass percentages of the components of the non-halogen flame-retardant high-temperature nylon composite material are: 60% to 69.8% of polyamide, 5% of polyphenylene ether %～20%, polytetrafluoroethylene 0.1%～1%, flame retardant 10%～25%, additive 0.1%～0.5%, of which the total amount of flame retardant and polyphenylene ether is at least 30%;

When the flame retardant is a mixture of melamine cyanurate and polybismaleimide, the mass percentages of each component of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 60% to 69.8% %, polyphenylene ether 5%~15%, polytetrafluoroethylene 0.1%~1%, flame retardant 25%~30%, additive 0.1%~0.5%; the mass of melamine cyanurate in the flame retardant The percentage content is 20%-25%, and the mass percentage content of polybismaleimide is 5%-10%.

In addition, the above-mentioned additives in the present invention can be used but not limited to one or a combination of stabilizers, adhesion promoters, antioxidants, antistatic agents, plasticizers, foaming agents, and dispersants.

Specifically preferably, the additive is an antioxidant, an antistatic agent or a plasticizer.

More preferably, the antioxidant is phosphite PEP 36A, phosphite PEP 8T or phosphite DPDP.

More preferably, the antistatic agent is Entira AS SD 100, CYASTAT SN or Basionics LQ 01.

More preferably, the plasticizer is JZ-218, JZ-506 or N-butylbenzenesulfonamide (N-BBSA).

In addition, the preparation method of the above-mentioned non-halogen flame-retardant high-temperature nylon composite material includes the following steps: the raw materials of the formula are mixed in an internal mixer with a rotation speed of 50 rpm, and the temperature is not lower than 300°C, and then placed in a mold Molding in medium, to obtain products with stable chemical properties and good mechanical properties.

Preferably, the preparation method includes the following steps: mix the raw materials of the recipe amount in an internal mixer with a rotation speed of 50 rpm, set the temperature at 310° C., take it out after 3 hours, dry it, and then place it in a mold at 300 ° C. Preheat in a flat vulcanizing machine at ℃ for 10 minutes, hold the pressure at 10Mpa for 15 minutes, cold press, cut samples, and test.

The non-halogen flame-retardant high-temperature nylon composite material of the present invention can be molded into various plastic products by extrusion molding, calendering or other means. When tested under the condition that the thickness is not greater than 3.18mm, its vertical combustion level is UL94 V-0, which can Used in home appliances, construction, consumer, electronics, medical, industrial, packaging, textile, transportation, and wire and cable, metal replacement for electrical transformer connectors and accessories, fuse holders, brackets, etc.

The present invention has the following beneficial effects:

In the present invention, by using polyphenylene ether or a compound of polyphenylene ether and bismaleimide, and melamine cyanurate as a synergist, the obtained flame-retardant and high-temperature-resistant nylon has a thickness of 1.5 to 3.2 mm (preferably 1.59 mm) ~3.18mm), the flame retardant performance can reach UL94 V-0 level, which can be applied to high temperature fields such as electronic devices or aerospace, as well as home appliances, construction, consumer, electronics, medical, industrial, packaging, textile, transportation, Also includes wire and cable, metal replacement for electrical transformer connectors and accessories, fuse holders, brackets, and more.

detailed description

The present invention will be further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

The raw material sources used in the following examples are:

PA10T: Degussa Vestamid HT Plus M3000;

Polytetrafluoroethylene (PTFE): American DuPont TEFLON 6C;

Melamine cyanurate: Sichuan Fine Chemicals;

Polyphenylene ether: China National Bluestar LXR 40 PPE;

N,N-1,3-phenylene bismaleimide: Mitsui Chemicals.

Example 1 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. The flame retardant is melamine cyanurate, and the mass percentages of each component are: polyamide 60%~69.8%, polyphenylene ether 5%~20%, polytetrafluoroethylene 0.1%~1%, The flame retardant is 20%-25%, and the additive is 0.1%-0.5%. The total amount of melamine cyanurate and polyphenylene ether in the flame retardant should be at least 30%.

Wherein, the additive is one or a combination of stabilizers, adhesion promoters, antioxidants, antistatic agents, plasticizers, foaming agents or dispersants.

2. The preparation method includes the following steps: the raw materials of the formula are mixed in an internal mixer with a rotational speed of 50 rpm, the temperature is set at 310°C, taken out after 3 hours, dried, and then placed in a mold, placed on a flat plate at 300°C Preheat in the vulcanizing machine for 10 minutes, hold the pressure at 10Mpa for 15 minutes, cold press, cut samples, and test.

3. After testing, the flame retardant performance of the flame retardant and high temperature resistant nylon with a thickness between 1.59 mm and 3.18 mm obtained by the above formula and preparation method can reach UL94 V-0 level.

Example 2 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. The flame retardant is a mixture of melamine cyanurate and polybismaleimide. The mass percentages of each component are: polyamide 60%~69.8%, polyphenylene ether 5%~15%, 0.1% to 1% of polytetrafluoroethylene, 25% to 30% of flame retardant, 0.1% to 0.5% of additives; the mass percentage of melamine cyanurate in the flame retardant is 20% to 25%, poly The mass percent content of bismaleimide is 5%-10%.

Wherein, the additive is one or a combination of stabilizers, adhesion promoters, antioxidants, antistatic agents, plasticizers, foaming agents or dispersants.

2. The preparation method includes the following steps: the raw materials of the formula are mixed in an internal mixer with a rotational speed of 50 rpm, the temperature is set at 310°C, taken out after 3 hours, dried, and then placed in a mold, placed on a flat plate at 300°C Preheat in the vulcanizing machine for 10 minutes, hold the pressure at 10Mpa for 15 minutes, cold press, cut samples, and test.

3. After testing, the flame retardant performance of the flame retardant and high temperature resistant nylon with a thickness between 1.59 mm and 3.18 mm obtained by the above formula and preparation method can reach UL94 V-0 level.

Example 3 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. Preparation of low molecular weight polyphenylene ether

Polyphenylene ether, bisphenol A and dicumyl peroxide were mixed in a 16mm twin-screw extruder, and the mass fractions of the three were 98.29%, 0.62% and 1.09%, respectively. The mixture is extruded at 320°C, 310°C, 300°C in Zone 1, Zone 2 and Zones 3 to 9, respectively. The mold temperature was 300°C and pellets were formed at 250 rpm to obtain low molecular weight polyphenylene ether (LMW PPE).

The molecular weight is tested by GPC, using chloroform as a solvent and polystyrene as a reference. Based on GPC UV calculation, the weight average molecular weight of the low molecular weight polyphenylene ether is 58219 g/mol, and the number average molecular weight is 10231 g/mol.

2. Preparation of non-halogen flame retardant high temperature nylon composite materials

According to the ratio of LMW PPE obtained in Example 1: polydecanediamide terephthalamide (PA10T): melamine cyanurate: antioxidant: polytetrafluoroethylene = 150:644:200:1:5 Finally, mix in a mixer with a rotating speed of 50 rpm, set the temperature at 310°C, take it out after 3 hours, dry it, then place it in a mold, preheat it in a flat vulcanizer at 300°C for 10min, and keep it at 10Mpa. After pressing for 15 minutes, cold pressing, sample cutting and testing.

Wherein, the antioxidant is phosphite PEP 36A.

3. After testing, the flame retardancy of the obtained 1.59mm sample is UL94 V-0 level.

Example 4 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. Combine commercially available PPE with a number average molecular weight of 30,000g/mol with PXD10, N,N-1,3 phenylene bismaleimide, melamine cyanurate, antioxidant, and polytetrafluoroethylene at 50: 694:50:200:1:5 After pre-polymerization, put it into a 16mm twin-screw extruder, mix it in an internal mixer with a rotation speed of 50 rpm, set the temperature at 310°C, take it out after 3 hours, dry it, and then It is placed in a mold, preheated in a flat vulcanizing machine at 300°C for 10 minutes, kept at 10Mpa for 15 minutes, cold pressed, sample cut, and tested. The flame retardancy of the 3.18mm sample is UL94 V-0 level.

Wherein, the antioxidant is phosphite PEP 36A.

3. After testing, the flame retardancy of the obtained 1.59mm sample is UL94 V-0 level.

Example 5 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. When the flame retardant is melamine cyanurate, the mass percentages of the components of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 60%, polyphenylene ether 19.4%, polytetrafluoroethylene 0.1%, flame retardant 20%, additive 0.5%.

Wherein, the additives are stabilizer phosphite PEP 8T 0.28% and JZ-218 0.22%.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2mm sample was UL94 V-0 level.

Example 6 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. When the flame retardant is melamine cyanurate, the mass percentages of the components of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 64.4%, polyphenylene ether 10%, polytetrafluoroethylene 0.1%, flame retardant 25%, additive 0.5%.

Wherein, the additives are stabilizer 0.3%, CYASTAT SN 0.1%, N-butylbenzenesulfonamide (N-BBSA) 0.1%

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2.5mm sample was UL94 V-0 level.

Example 7 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. When the flame retardant is melamine cyanurate, the mass percentages of the components of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 69.8%, polyphenylene ether 9%, polytetrafluoroethylene 0.1%, flame retardant 21%, stabilizer 0.1%.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2.5mm sample was UL94 V-0 level.

Example 8 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. When the flame retardant is melamine cyanurate, the mass percentages of the components of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 66.3%, polyphenylene ether 10%, polytetrafluoroethylene 0.5%, flame retardant 23%, additive 0.2%.

Wherein, the additives are stabilizer 0.1%, Basionics LQ 01 0.1%.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2.3mm sample was UL94 V-0 level.

Example 9 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. The flame retardant is a mixture of melamine cyanurate and polybismaleimide. The mass percentages of each component of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 63.5%, polyamide 10% phenylene ether, 1% polytetrafluoroethylene, 20% melamine cyanurate, 5% polybismaleimide, 0.5% additive.

Wherein, the additives are stabilizer 0.4%, phosphite DPDP 0.1%.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2mm sample was UL94 V-0 level.

Example 10 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. The flame retardant is a mixture of melamine cyanurate and polybismaleimide. The mass percentages of each component of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 69.8%, polyamide 5% phenylene ether, 0.1% polytetrafluoroethylene, 20% melamine cyanurate, 5% polybismaleimide, 0.1% stabilizer.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2.2mm sample was UL94 V-0 level.

Example 11 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. The flame retardant is a mixture of melamine cyanurate and polybismaleimide. The mass percentages of each component of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 61.5%, polyamide 7% phenylene ether, 1% polytetrafluoroethylene, 20% melamine cyanurate, 10% polybismaleimide, 0.5% additive.

Wherein, the additives are stabilizer 0.35%, phosphite PEP 36A 0.05%, Entira AS SD 1000.1%.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2.25mm sample was UL94 V-0 level.

Example 12 Preparation of Non-Halogen Flame Retardant High Temperature Nylon Composite Material

1. The flame retardant is a mixture of melamine cyanurate and polybismaleimide. The mass percentages of each component of the non-halogen flame-retardant high-temperature nylon composite material are: polyamide 62%, polyamide 10% phenylene ether, 0.7% polytetrafluoroethylene, 19% melamine cyanurate, 8% polybismaleimide, 0.3% additive.

Wherein, the additives are stabilizer 0.2%, CYASTAT SN 0.1%.

2. The non-halogen flame-retardant high-temperature nylon composite material was prepared by the above-mentioned method of the present invention. After testing, the flame-retardant ability of the obtained 2.5mm sample was UL94 V-0 level.

Apparently, the above-mentioned embodiments are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, on the basis of the above descriptions and ideas, other changes or changes in different forms can also be made, and it is not necessary and impossible to exhaustively enumerate all implementation modes here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

1. a non-halogen fire-retardant high-temperature nylon composite, it is characterised in that be prepared from by the formula comprising following components: poly- Amide, polyphenylene oxide, politef, fire retardant, additive；Described fire retardant is melamine cyanurate, or described fire-retardant Agent is the mixture of melamine cyanurate and polybismaleimide；Described additive be stabilizer, adhesion promoter, The combination of one or more in antioxidant, antistatic additive, plasticizer, foaming agent or dispersant.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that described polyamide is optionally from half Aromatic polyamide, semiaromatic polyamide composition and the blend of fatty polyamide, semiaromatic polyamide composition and aliphatic polyamides The mixture of amine.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that described polyamide is high temperature Buddhist nun Dragon, the most poly-terephthalate decamethylene diamine.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that the molecular weight of described polyphenylene oxide Being 2000～20000g/mol, be by 2,6-xylenol oxidative condensation in the presence of copper-amine complex catalyst is made.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that described polybismaleimide For double (maleimide) butane of N, N-1,3 phenylene BMI or 1,4-.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that the grain of described politef Degree scope is 5 μm～25 μm.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that when fire retardant is tripolycyanamide During cyanurate, the weight/mass percentage composition of melamine cyanurate and polyphenylene oxide is respectively 10%～25% and 5%～20%, and The total amount of the two is at least 30%；

When the mixture that fire retardant is melamine cyanurate and polybismaleimide, the matter of melamine cyanurate Amount percentage composition be 20%～25%, and the weight/mass percentage composition of polyphenylene oxide and polybismaleimide be respectively 5%～15% with 5%~10%。

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that when fire retardant is tripolycyanamide During cyanurate, the weight/mass percentage composition of each component of described non-halogen fire-retardant high-temperature nylon composite is respectively as follows: polyamide 6 0% ～69.8%, polyphenylene oxide 5%～20%, politef 0.1%～1%, fire retardant 10%～25%, additive 0.1%～0.5%, wherein The total amount of fire retardant and polyphenylene oxide is at least 30%；

When the mixture that fire retardant is melamine cyanurate and polybismaleimide, described non-halogen fire-retardant high-temperature nylon The weight/mass percentage composition of each component of composite is respectively as follows: polyamide 6 0%～69.8%, polyphenylene oxide 5%～15%, polytetrafluoroethyl-ne Alkene 0.1%～1%, fire retardant 25%～30%, additive 0.1%～0.5%；The quality of melamine cyanurate in described fire retardant Percentage composition is 20%～25%, and the weight/mass percentage composition of polybismaleimide is 5%～10%.

Non-halogen fire-retardant high-temperature nylon composite the most according to claim 1, it is characterised in that described additive is antioxygen Agent, antistatic additive or plasticizer.

10. according to the arbitrary described non-halogen fire-retardant high-temperature nylon composite of claim 1～9, it is characterised in that its preparation method Comprise the steps: that the raw material of formula ratio mixes in the banbury that rotating speed is 50 turns every point, temperature be set and be not less than 300 DEG C, Then die for molding it is placed on.