CN104592739B - A kind of ignition coil framework PPO alloy material and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of ignition coil framework PPO alloy material and preparation method thereof, it is made up of the raw material of following weight portion: polyphenylene oxide PPO 20 50 parts, polystyrene 20 40 parts, toughener 26 parts, 10 30 parts of glass fibre, epoxy curing agent 1 10 parts, maleic anhydride 0.5 3 parts, tertiary amine-type epoxy resin curing accelerator 0.5 2 parts, 0.2 1.5 parts of antioxidant.By the PPO alloy material of the present invention, there is excellent epoxy bond and excellent dimensional stability and ageing-resistant performance, can be applicable to the coil rack in engine igniting coil.The PPO alloy material preparation technology of the present invention is simple, easy to operate, is more suitable for industrialization large-scale production.

Description

A kind of ignition coil framework PPO alloy material and preparation method thereof

Technical field

The invention belongs to polymeric material field, specifically, be a kind of ignition coil framework PPO alloy Material and preparation method thereof.

Background technology

Engine igniting coil is that the group of engine igniting system wants part, and its effect is by automobile electricity The low-voltage of bottle is promoted to cause the high voltage of the 20kv to 40kv of spark-discharge.Therefore to it is anti- Only high voltage down-firing coil is electrically shocked and wears, and the dielectric strength of increasing ignition coil component generally uses embedding Each for ignition coil parts are carried out insulation-encapsulated by the method for epoxy resin.If but used by ignition coil parts Material can not form good bonding with epoxy resin, then worst between material and epoxy resin bonding point, Minimum insulating point will be become, material breakdown or short circuit will be caused under high voltages, make ignition coil lose Effect.Further, in the automobile ignition coil course of work, due to constant ignition, coil heating, temperature is the highest can Reaching more than 100 DEG C, after quitting work, temperature can be reduced to again air themperature, winter cold district, temperature meeting The most subzero 20 DEG C even 30 DEG C, even lower.Ignition coil uses under the environment that colds and heat succeed each other, due to point Fire coil parts there are differences at linear expansion coefficient with epoxy resin embedding adhesive, when alternating hot and cold when, Thermal stress will be produced between epoxy resin and ignition coil parts, cause ignition coil to ftracture, cause igniting Coil failure.If there being good caking property between material and epoxy resin, then can effectively resist due to cold Thermal shock produces the thermal stress between material and epoxy resin, thus improves the service life of ignition coil.Base In above-mentioned reason, it is desirable to have good caking property between ignition coil framework material and epoxy resin.

Polyphenylene oxide (chemical name poly-2,6-dimethyl-Isosorbide-5-Nitrae-phenylate are called for short PPO) is the heat of a kind of excellent performance Plastic engineering plastics, have higher mechanical property and heat resistance, good stability of the dimension, and hydroscopicity is low, are situated between Electric constant and dielectric loss are not affected by temperature, humidity and frequency, and its dielectric strength is engineering In plastics best, be the engineering plastics of a kind of excellent electrical property, be particularly well-suited to make for ignition coil Inside is subjected to the ignition coil framework of extra-high pressure.In prior art, pass through official the most in the course of the polymerization process Energy dough improves the compatibility of PPO and epoxy resin, and does epoxy resin modification with PPO, as specially Profit CN102516532A, discloses the preparation method of a kind of amination polyphenyl ether, and it is will at polymerization stage PPO amination improves the compatibility of PPO and epoxy resin, but it prepares loaded down with trivial details, operation complexity, simultaneously This patent does not provides any proof PPO material and the caking property of epoxy resin and the experiment number of ageing-resistant performance thereof According to.Patent CN201210246089.0 discloses a kind of low dielectric high heat-resistant epoxy resin composition and preparation thereof Method, it is by using polyphenylene oxide grafted maleic anhydride and reactive diluent to reduce the viscosity of system to solve Polyphenylene oxide and epoxy resin compatibility problem, thus improve dielectric and the mechanical property of system, equally this patent Also PPO material and the bonding of epoxy resin and ageing-resistant performance it are not directed to.Therefore, research and development one has well The engine igniting coil skeleton PPO of epoxy bond, excellent dimensionally stable and ageing-resistant performance Alloy material is the most necessary.

Summary of the invention

It is an object of the invention to for deficiency of the prior art, it is provided that a kind of ignition coil framework PPO closes Gold copper-base alloy.

Another purpose of the present invention is to provide the preparation side of a kind of ignition coil framework PPO alloy material Method.

For achieving the above object, the present invention adopts the technical scheme that:

A kind of ignition coil framework PPO alloy material, it is made up of the raw material of following weight portion: polyphenylene oxide PPO 20-50 part, polystyrene 20-40 part, toughener 2-6 part, glass fibre 10-30 part, asphalt mixtures modified by epoxy resin Fat curing agent 1-10 part, maleic anhydride 0.5-3 part, tertiary amine-type epoxy resin curing accelerator 0.5-2 part, Antioxidant 0.2-1.5 part.

Described polyphenylene oxide PPO inherent viscosity in 25 DEG C of chloroforms is 0.2-0.6dl/g.

Described polystyrene is General Purpose Polystyrenre GPPS or impact resistant polystyrene HIPS.

Described toughener be SBS, styrene-ethylene-butadiene- One or more of styrene block copolymer, styrene ethylene-propylene-styrene type block copolymer.

Described glass fibre is alkali-free roving glass fiber or chopped glass fiber.

Described epoxy curing agent is aromatic anhydride type epoxy curing agent.

Described aromatic anhydride type epoxy curing agent is phthalic anhydride, trimellitic anhydride, all PMDA or Benzophenone carboxylic acid dianhydride.

Described tertiary amine-type epoxy resin curing accelerator is triethanolamine, dimethylaniline, DMP-30 and first One or more in base THPA.

Described antioxidant is that described antioxidant is: antioxidant 24-44 (four (2,4-di-tert-butylphenol)-4,4'- Xenyl diphosphites CAS:119345-01-6), irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphorous acid Ester CAS:31570-04-4), antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] seasons Doutrate CAS:6683-19-8), carbon free radical scavenger HP136 (xylyl dibutyl benzofuran Ketone CAS:181314-48-7) by weight the compound for 1:0.5:0.5:0.3.

For realizing above-mentioned second purpose, the present invention adopts the technical scheme that:

The preparation method of a kind of ignition coil framework PPO alloy material, comprises the following steps:

(1) get the raw materials ready according to the component described in any of the above and parts by weight；

(2) polyphenylene oxide and maleic anhydride are put into high-speed mixer and mixing 2-5 minute, after by double screw extruder First paragraph cylinder adds, blending extrusion, granulation；

(3) step (2) is prepared product, polystyrene, toughener, epoxy curing agent, tertiary amine High-speed mixer and mixing 3-8 minute put into by type epoxy resin curing accelerator, antioxidant；

(4) being added by twin-screw extrusion owner's spout by each raw material of step (3), glass fibre is by double Screw extruder middle and lower reaches add；The rotating speed of described double screw extruder is 180-600 rev/min, and temperature is 235-275℃。

The present invention pretreatment by reactive processing, carries out reactive extrursion by PPO with maleic anhydride, promotes PPO itself and epoxy resin have the content of the maleic anhydride functional groups of respond.

In this alloy material production phase, introduce the anhydrides solidification that can participate in epoxy resin cure reaction Agent, improves the content that can react anhydride functional group in material further.

In this alloy material production phase, add the accelerator that epoxy resin cure can be promoted to react, such Accelerator can promote the open loop of maleic anhydride functional groups, promotes the activity of maleic anhydride functional groups.

The PPO alloy material of the present invention has more response type acid anhydrides official compared with tradition PPO alloy material Can roll into a ball, it is possible to occur chemistry to make with epoxy resin in the Curing Process of Epoxy of ignition coil encapsulated phase With, so that forming good interfacial adhesion between material and epoxy resin.

The present invention has the ignition coil framework PPO alloy material of good adhesion with epoxy resin, tool There are superior epoxy bond and excellent dimensional stability and ageing-resistant performance, can be applicable to engine Coil rack in ignition coil.

Advantage is:

1, the present invention is pre-processed by reactive processing, and with maleic anhydride, PPO is carried out reactive extrursion, promotes PPO itself and epoxy resin have the content of the maleic anhydride functional groups of respond；In process of production, Add acid anhydride type curing agent, promote reactive anhydride-functional mass contg in material further；Addition can promote Enter the accelerator of epoxy resin cure reaction, promote the open loop of maleic anhydride functional groups, promote maleic anhydride official The activity that can roll into a ball.The PPO alloy material of the present invention has more response type anhydride functional group, is solidifying With epoxy resin generation chemical action in journey so that form excellent interfacial adhesion between material and epoxy resin.

2, the antioxidant of the present invention is that antioxidant 24-44, irgasfos 168, antioxidant 1010 and carbon are freely caught Catch agent HP136 to compound in specific proportions, between each component, there is synergy so that the material tool of the present invention There is the ageing resistace of excellence, meet the ageing resistace requirement of engine periphery material.

3, the PPO alloy material preparation technology of the present invention is simple, easy to operate, is more suitable for industrialization extensive Produce.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in this area Technical staff be further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, To those skilled in the art, without departing from the inventive concept of the premise, it is also possible to if making Dry deformation and improvement.These broadly fall into protection scope of the present invention.

Embodiment 1-6

(1) get the raw materials ready according to the component in table 1 and content；

(2) polyphenylene oxide and maleic anhydride are put into high-speed mixer and mixing 2-5 minute, after by double screw extruder First paragraph cylinder adds, blending extrusion, granulation；

(3) step (2) is prepared product, polystyrene, toughener, epoxy curing agent, tertiary amine High-speed mixer and mixing 3-8 minute put into by type epoxy resin curing accelerator, antioxidant；

(4) being added by twin-screw extrusion owner's spout by each raw material of step (3), glass fibre is by double Screw extruder middle and lower reaches add；The rotating speed of described double screw extruder is 180 revs/min, and temperature is 235 DEG C.

It should be understood that

In embodiment 1, screw rod rotating speed is 180 revs/min, and temperature is 235 DEG C；In embodiment 2, spiral Bar rotating speed is 500 revs/min, and temperature is 245 DEG C；In embodiment 3, screw rod rotating speed is 600 revs/min, temperature Degree is 255 DEG C；In embodiment 4, screw rod rotating speed is 400 revs/min, and temperature is 275 DEG C；In embodiment 5, Screw rod rotating speed is 300 revs/min, and temperature is 255 DEG C；In embodiment 6, screw rod rotating speed is 400 revs/min, Temperature is 265 DEG C

In embodiment 1-6, polyphenylene oxide PPO used inherent viscosity in 25 DEG C of chloroforms is 0.2-0.6dl/g, choosing The LXR045 produced with Ruicheng branch company of blue star Chinese workers new material limited company.

In embodiment 1-3, polystyrene used is impact resistant polystyrene HIPS, Shanghai match section petrochemical industry Produce HIPS 622P；In embodiment 4-6, polystyrene (PS) used is General Purpose Polystyrenre GPPS.

In embodiment 1-2, toughener used is SBS, is purchased from Ke Teng company of U.S. G1651；In embodiment 3-4, toughener used is styrene-ethylene-butylene-styrene Block copolymer；In embodiment 5-6, toughener used is styrene ethylene-propylene-styrene Thing.

In embodiment 1-3, glass fibre used is alkali-free roving glass fiber, and megalith group produces 988A；Implement In example 4-6, glass fibre used is chopped glass fiber.

In embodiment 1-6, maleic anhydride molecule formula used is C₄H₂O₃, dawn chemical plant, Nanjing produce.

In embodiment 1-3, epoxy curing agent used is phthalic anhydride, Shanghai Jiaohua Co., Ltd (CAS:85-44-9)；Epoxy curing agent used by embodiment 4 is trimellitic anhydride；Embodiment 5 Epoxy curing agent used is pyromellitic acid anhydride；Epoxy curing agent used by embodiment 6 is Benzophenone carboxylic acid dianhydride.

In embodiment 1-3, tertiary amine-type epoxy resin curing accelerator used is mountain peak, Changzhou Chemical Co., Ltd. The DMP-30 (CAS:90-72-2) produced；Tertiary amine-type epoxy resin curing accelerator used by embodiment 4 For triethanolamine；Tertiary amine-type epoxy resin curing accelerator used by embodiment 5 is dimethylaniline；Implement Tertiary amine-type epoxy resin curing accelerator used by example 6 is methyl tetrahydro phthalic anhydride.

In embodiment 1-6, antioxidant used is antioxidant 24-44 (four (2,4-di-tert-butylphenols)-4,4'-biphenyl Base diphosphites CAS:119345-01-6), irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphite ester CAS:31570-04-4), antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi Alcohol ester CAS:6683-19-8), carbon free radical scavenger HP136 (xylyl dibutyl benzofuranone CAS:181314-48-7) by weight the compound for 1:0.5:0.5:0.3.

Table 1

Comparative example 1

(1) raw material is weighed by following percentage by weight: polyphenylene oxide (PPO): 41.8%；HIPS 622P:30%； SEBS G1651:7%；Antioxidant: 1.2%.Put into high mixer to mix 6 minutes；

(2) each raw material of step (1) is added by twin-screw extrusion owner's feeding, 20% glass fibre 988A Being added by double screw extruder middle and lower reaches, the rotating speed of double screw extruder is 350 revs/min, and temperature is 255 DEG C.

Comparative example 2

(1) weigh PPO LXR04537.5%, maleic anhydride 2% by following percentage by weight, put into height Mixed machine mixes 5 minutes, after added by double screw extruder first paragraph cylinder, blending extrusion, granulation；

(2) raw material is weighed by following percentage by weight: the extrudate through step (1): 39.5%；HIPS 622P: 30%；SEBS G1651:6%；Phthalic anhydride: 3%；DMP-30:1.5%；Put into high mixer to mix Close 7 minutes；

(3) each raw material of step (2) is added by twin-screw extrusion owner's feeding, 20% glass fibre 988A Being added by double screw extruder middle and lower reaches, the rotating speed of double screw extruder is 450 revs/min, and temperature is 265 DEG C.

It should be understood that

In comparative example 1, comparative example 2, polyphenylene oxide PPO used inherent viscosity in 25 DEG C of chloroforms is 0.2-0.6dl/g, selects the LXR045 that Ruicheng branch company of blue star Chinese workers new material limited company produces.

In comparative example 1, antioxidant used is antioxidant 24-44 (four (2,4-di-tert-butylphenols)-4,4'-biphenyl Base diphosphites CAS:119345-01-6), irgasfos 168 (three [2.4-di-tert-butyl-phenyl] phosphite ester CAS:31570-04-4), antioxidant 1010 (four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi Alcohol ester CAS:6683-19-8), carbon free radical scavenger HP136 (xylyl dibutyl benzofuranone CAS:181314-48-7) by weight the compound for 1:0.5:0.5:0.3.

Comparative example 3

(1) weigh raw material: polyphenylene oxide PPO 38.7%, polystyrene 20% by following percentage by weight, increase Tough dose 6%, glass fibre 20%, epoxy curing agent 10%, maleic anhydride 3%, tertiary amine-type asphalt mixtures modified by epoxy resin Fat curing accelerator 2%, antioxidant 0.3%；Put into high mixer mixing 3-8 minute；

(2) by each raw material of step (2) by twin-screw extrusion owner's spout add, 20% glass fibre by Double screw extruder middle and lower reaches add, and the rotating speed of double screw extruder is 180 revs/min, and temperature is 235 DEG C.

Polyphenylene oxide PPO inherent viscosity in 25 DEG C of chloroforms used is 0.2-0.6dl/g, selects blue star Chinese workers' green wood The LXR045 that Ruicheng branch company of material limited company produces；Polystyrene used is resistance to impact polyphenyl second Alkene HIPS, Shanghai match section petrochemical iy produced HIPS 622P；Toughener used is s-B-S Triblock copolymer, purchased from Ke Teng company of U.S. G1651；Glass fibre used is alkali-free roving glass fiber, huge Stone group produces 988A；Epoxy curing agent used is phthalic anhydride, Shanghai Jiaohua Co., Ltd (CAS:85-44-9)；Tertiary amine-type epoxy resin curing accelerator used is mountain peak, Changzhou Chemical Co., Ltd. The DMP-30 (CAS:90-72-2) produced；Antioxidant used is antioxidant 24-44, irgasfos 168, Antioxidant 1010 and carbon free agent for capturing HP136 are by weight the compound for 1:0.5:0.5:0.3.

Comparative example 4

(1) weigh raw material: polyphenylene oxide PPO 38.7%, polystyrene 20% by following percentage by weight, increase Tough dose 6%, glass fibre 20%, epoxy curing agent 10%, maleic anhydride 3%, tertiary amine-type asphalt mixtures modified by epoxy resin Fat curing accelerator 2%, antioxidant 0.3%；

(2) polyphenylene oxide and maleic anhydride are put into high-speed mixer and mixing 2-5 minute, after by double screw extruder First paragraph cylinder adds, blending extrusion, granulation；

(3) step (2) is prepared product, polystyrene, toughener, epoxy curing agent, tertiary amine High-speed mixer and mixing 3-8 minute put into by type epoxy resin curing accelerator, antioxidant；

(4) being added by twin-screw extrusion owner's spout by each raw material of step (3), glass fibre is by double Screw extruder middle and lower reaches add；The rotating speed of described double screw extruder is 180 revs/min, and temperature is 235 DEG C.

Polyphenylene oxide PPO inherent viscosity in 25 DEG C of chloroforms used is 0.2-0.6dl/g, selects blue star Chinese workers' green wood The LXR045 that Ruicheng branch company of material limited company produces；Polystyrene used is resistance to impact polyphenyl second Alkene HIPS, Shanghai match section petrochemical iy produced HIPS 622P；Toughener used is s-B-S Triblock copolymer, purchased from Ke Teng company of U.S. G1651；Glass fibre used is alkali-free roving glass fiber, huge Stone group produces 988A；Epoxy curing agent used is phthalic anhydride, Shanghai Jiaohua Co., Ltd (CAS:85-44-9)；Tertiary amine-type epoxy resin curing accelerator used is mountain peak, Changzhou Chemical Co., Ltd. The DMP-30 (CAS:90-72-2) produced；Antioxidant used is antioxidant 24-44.

Material properties test: after above-mentioned material is dried 4 hours in 90 DEG C in convection oven, note with plastics Molding machine is molded into standard batten；By the batten of injection formed in the relative humidity of 50%, 23 DEG C of placements at least Performance test is carried out after 24 hours.Method of testing is as follows:

Hot strength: by ISO 527 method, draw speed 5mm/min；

Bending strength: by ISO 178 method, test speed 2mm/min；

Impact strength: by ISO 179 method, notch shock, simply supported beam；

Heat distortion temperature (HDT): by ISO 75 method, 1.82MPa loads；

Epoxy bond is evaluated: according to ISO 4587 method, epoxy resin uses KYOCERA 1695, at 90 DEG C It is warming up to 130 DEG C of resolidifications 3 hours after solidifying 1.5 hours, and placement was tested after 24 hours at 23 DEG C.

Accelerated ageing performance evaluation:

Tensile bars and notch shock batten are placed in 120 DEG C of convection oven, test performance after 1000 hours. F presses ISO 527 method, draw speed 5mm/min, the hot strength of test material；By ISO 179 method, Simply supported beam, the notch impact strength of test material.

The product preparing embodiment 1-6 and comparative example 1-4 carries out performance test comparison, and result is as shown in table 2.

Table 2

As shown in Table 2, commonly strengthen PPO alloy material with comparative example 1 compared with, pass through the present invention The tensile shear strength of the PPO alloy material with good epoxy bond of preparation significantly improves, should The tensile shear strength of alloy material promotes by about one time, therefore PPO alloy material prepared by the present invention effectively changes It is apt to the caking property of PPO alloy and epoxy resin.Compared with comparative example 2, the antioxidant system of present invention application Having excellent thermo oxidative aging performance, in comparative example 2, the performance of aging rear material is decreased obviously, the lower range of decrease Degree even more than 30%, and the fall adding this antioxidant system is respectively less than 25%, the most only 20%.

The ignition coil framework of present invention PPO alloy material, has superior epoxy bond and excellent Good dimensional stability and ageing-resistant performance, can be applicable to the coil rack in engine igniting coil.

The above is only the preferred embodiment of the present invention, it is noted that common for the art Technical staff, on the premise of without departing from the inventive method, it is also possible to makes some improvement and supplements, these Improve and supplement and also should be regarded as protection scope of the present invention.

Claims (10)

1. an ignition coil framework PPO alloy material, it is characterised in that it is by following weight portion Raw material forms: polyphenylene oxide PPO 20-50 part, polystyrene 20-40 part, toughener 2-6 part, glass fibers Dimension 10-30 part, epoxy curing agent 1-10 part, maleic anhydride 0.5-3 part, tertiary amine-type epoxy resin is solid Change accelerator 0.5-2 part, antioxidant 0.2-1.5 part.

PPO alloy material the most according to claim 1, it is characterised in that described polyphenylene oxide PPO In 25 DEG C of chloroforms, inherent viscosity is 0.2-0.6dl/g.

PPO alloy material the most according to claim 1, it is characterised in that described polystyrene is General Purpose Polystyrenre GPPS or impact resistant polystyrene HIPS.

PPO alloy material the most according to claim 1, it is characterised in that described toughener is benzene Ethylene-butadiene-styrene triblock copolymer, styrene-ethylene-butylene-styrene block copolymer, benzene second One or more of alkene-ethylene-propylene, Styrene type block copolymer.

PPO alloy material the most according to claim 1, it is characterised in that described glass fibre is Alkali-free roving glass fiber or chopped glass fiber.

PPO alloy material the most according to claim 1, it is characterised in that described epoxy resin is solid Agent is aromatic anhydride type epoxy curing agent.

PPO alloy material the most according to claim 6, it is characterised in that described aromatic anhydride Type epoxy curing agent is phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride or benzophenone Tetracarboxylic dianhydride.

PPO alloy material the most according to claim 1, it is characterised in that described tertiary amine-type epoxy Solidified resin promoter is the one in triethanolamine, dimethylaniline, DMP-30 and methyl tetrahydro phthalic anhydride Or it is multiple.

PPO alloy material the most according to claim 1, it is characterised in that described antioxidant is anti- Oxygen agent 24-44, irgasfos 168, antioxidant 1010 and carbon free radical scavenger HP136 are by weight The compound of 1:0.5:0.5:0.3.

10. the ignition coil framework preparation method of PPO alloy material, it is characterised in that include following Step:

(1) get the raw materials ready according to the arbitrary described component of claim 1-9 and parts by weight；

(2) polyphenylene oxide and maleic anhydride are put into high-speed mixer and mixing 2-5 minute, after by double screw extruder First paragraph cylinder adds, blending extrusion, granulation；

(3) step (2) is prepared product, polystyrene, toughener, epoxy curing agent, tertiary amine High-speed mixer and mixing 3-8 minute put into by type epoxy resin curing accelerator, antioxidant；

(4) being added by twin-screw extrusion owner's spout by each raw material of step (3), glass fibre is by double Screw extruder middle and lower reaches add；The rotating speed of described double screw extruder is 180-600 rev/min, and temperature is 235-275℃。