KR960016587B1 - Method for recycling polyester bumper backbeam material for an automobile - Google Patents

Abstract

The polyester bumper is recycled by the steps of introducing the mixture of waste polyester bumper and polyfunctional epoxy resin through a first hole into a extruder; introducing the mixture of waste polyester bumper and n-butyl triphenyl phosphonium bromide catalyst through a second hole into the extruder; and reacting the mixtures in the extruder. The weight percent ratio of waste bumper, epoxy resin and catalyst is 100 : 01-5.0 : 0.01-0.5.

Description

Recycling method of polyester-based bumper-back beam material

The present invention relates to a method for regenerating scrap, defective molding bumper and waste bumper used for a long time, which occurs when blow molding a bumper using a polyester-based polymer alloy (Alloy) resin.

More specifically, poly (Butylene Terephalate) [Poly (Butylene Terephalate)], core-shell (impound reinforcing), a polyester-based material consisting of polycarbonate occurs during the blow molding of the bumper-back beam for automobiles The present invention relates to an extrusion process for effective regeneration of scrap, poor mold bumper and long-used waste bumper.

In general, the thermoplastic hollow molding generates a lot of scrap and some molding defects due to its processing characteristics, and also generates a large number of waste bumpers during the replacement of a car or repair.

However, since thermoplastic resin blow molding receives excessive heat history while performing blow molding, some of the resin is also decomposed in a considerable amount, and the blow molding ability is remarkably inferior.

Therefore, if the scrap, molding defective product and long-term use bumper is properly pretreated and blow molded for regeneration, a problem arises in that the parison is sagging, making it difficult to reuse it as a raw material.

In addition, due to environmental problems, it is very difficult and expensive to dispose of itself, and thus there is a growing interest in developing an effective polyester-based bumper scrap molding defect and recycling technology for long-term used waste bumpers.

Therefore, the present invention effectively recycles polyester bumper scraps, mold defects and waste bumpers used for a long time through an effective chain extension reaction for polyester bumper scraps, mold defects and waste bumpers used for a long time. The present invention relates to the research and development of an extrusion process for the process.

There are few examples of techniques that have solved these problems in the past, and in the case of scrap regeneration, a burnout method of blow molding by adding a small amount (less than 20% by weight) of scrap to a new material (new material) during blow molding is used. In the process.

However, this exhausting method has a disadvantage in that it is impossible to regenerate polyester bumper scraps, mold defects, and waste bumpers used for a long time according to the blow molding ability of new materials to be used.

Therefore, in order to improve the above problems and develop a more effective regeneration method, EOCN, which is a polyfunctional epoxy resin, is used as a chain extender for polyester bumper scraps, molding defects and long-used waste bumpers that require regeneration. -104S (manufactured by Nippon Kayaku Co., Ltd.), and the processing conditions when the chain extension reaction in a twin-screw extruder using n-butyl triphenyl phosphonium bromide as Lewis While changing, the hollow molding was found to be different, it was completed, the features of the present invention will be described in more detail as follows.

That is, the polyester-based bumper powder and the polyfunctional epoxy resin to be recycled are pre-mixed into the first inlet of the twin-screw compressor shown in FIG. 1, and the second (L / D = 10 or less, L / D = extruder Length / diameter ratio) or the method of separating and inputting in advance mixing and injecting the polyester-based bumper powder and n-butyl triphenyl phosphonium bromide to be recycled into the third inlet (L / D = 20 or less) is a feature of the present invention. That's the part.

In addition, a feature of the present invention is that the material can be recycled regardless of the state of the product (polyester-based bumper scrap, defective molding and long-term waste bumper, etc.) that needs to be recycled.

In other words, the present invention is a twin-screw shown in Figure 1 a composition consisting of 100 parts by weight of the polyester bumper to be regenerated, 0.1-5.0 parts by weight of polyfunctional epoxy resin, 0.01-0.5 parts by weight of n-butyl triphenyl phosphonium bromide as a catalyst When the chain extension reaction is performed in the extruder, the polyester bumper / polyfunctional epoxy to be recycled is premixed and introduced into the first inlet, and the polyester bumper / n-butyl triphenyl phosphonium bromide to be recycled is mixed in advance. Chain extender for regeneration of polyester bumper scrap molding defects and long-term use of bumper scraps to be recycled using the separate injection method into the (L / D = 10 or less) or the third (L / D = 20 or less) inlet. It is all about the reaction process. The twin-screw extruder used in the present invention is manufactured by Leistriz, and its size is 34 mm in diameter, L / D = 35, screw speed 0-399min ^-1 , and 10 barrels. And a twin-screw extruder, in particular having at least two inlets.

Polyester bumper when necessary the reproduction used in the present invention (Note) reokti Lu Fox ^R (Lupox) molding scraps of TE-5020, characteristics of the base molding defect and with long-term virgin resin in a closed bumper Fox TE-5020 is: same.

Melt strength, which is a measure of blow molding performance, is 22-40CN (centi Newton, linear velocity 40cm / s) at a resin temperature of 240 ° C and 3mm strand, and the melt viscosity is 14 at low shear rate of 1red / sec. It is a polyester bumper with a viscosity characteristic of melt index of 1-6g / 10min when preheated at -200,000 poise, 250 ℃, 5kgf for 6 minutes, and the multistrength is 21CN at a linear speed of 40cm / s. In the case of the following, since the ratio of the defective blow molding of the polyester-based bumper is increased, the polyester-based bumper having the following viscosity characteristics is more advantageous.

In other words, the melt strength is 22-30CN (linear speed 40cm / s) at 240 ℃ and 3mm strand, and the melt melt viscosity is 14-160,000 poise, 250 ℃, 5kgf 6 minutes preheating at 1 rad / sec. It is a polyester-based automobile bumper having a viscosity characteristic of 2-6g / 10min.

The chain extender used by this invention is EOCN-104S (made by Nippon Kayaku Co., Ltd.) which is a polyfunctional epoxy, The structural formula is the same as General formula (1).

In addition, the amount used is 0.1-5.0 parts by weight, more preferably 1.5-3.0 parts by weight.

Where X is hydrogen or methyl

Y: hydrogen, bromine or hydroxyl groups

n: integer of 3-7

The catalyst used in the present invention is an alkyl triphenyl phosphonium halide such as alkenyl triphenyl phosphonium halide, alkenyl triphenyl phosphonium halide, or tetraphenyl phosphonium borate. n-butyl triphenyl phosphonium bromide is used in amounts of 0.01-0.5, more preferably 0.1-0.2.

Another feature of the present invention is a 10-90% range according to the blow molding capacity of the polyester-based bumper (scrap, long-term waste bumper used for defective molding products) that needs to be regenerated using a separate dosing method. There is also a feature that can be mixed in a weight ratio of to reproduce the polyester bumper that needs to be regenerated.

The regeneration reaction (chain extension reaction) in the present invention was carried out in a lystrisch twin-screw extruder, wherein the processing conditions are as follows.

That is, the processing temperature ranged from 220 ° C.-260 ° C., the screw rotation speed was about 100 rpm, and the raw material input speed was 12 kg / g.

In addition, the evaluation of the hollow moldability improvement of the polyester-based automobile bumper scrap, defective molding and long-term waste bumper used in the present invention was evaluated using a melt strand using a Haake single extruder / Rheotens. In addition, the melt index was measured and evaluated, and the conditions were as follows.

Melt strength

Haake single extruder: 220-240 ℃

-Rheotens: 3mm strand, linear velocity 40cm / s CN (in centinewtons)

Melt Index

-250 ℃, 5kgf, 6 minutes preheat

-g / 10min

Hereinafter, the present invention will be described in detail with reference to the following Comparative Examples and Examples.

(Comparative Example 1)

1.5 parts by weight of chain extender, epox EOCN-104S (Japanese chemical), 100 parts by weight of polyester bumper (bumper scrap molding defective product used for a long time), catalyst, n-butyl triphenyl phosphonium 0.15 parts by weight of bromide was mixed at room temperature in a Henshell mixer for 5 minutes at RPM 200, and then the first inlet of a lystrisch twin-screw extruder with a temperature of 250 ° C. for all the barrels (10 barrels) shown in Figure 1 At the same time, the chain extension reaction of the polyester-based bumper, which requires regeneration, was carried out.

At this time, the melt strength of the regenerated polyester bumper was 21 CN at a linear speed of 40 cm / s, and the melt index was 6.4 g / 10 min at 250 ° C. and 5 kgf.

(Example 1)

66.7 parts of polyester bumper which needs to be regenerated, 1.5 parts by weight of epoxy extender EOCN-104S (manufactured by Nippon Kayaku), a chain extender, was mixed in a Henschel mixer at room temperature in the same manner as in Comparative Example 1 and the lystrisch pair shown in Fig. Into the first inlet of the screw extruder, 0.15 parts by weight of n-butyl triphenyl phosphonium bromide as a catalyst was added to 33.3 parts by weight of the polyester bumper which needs to be regenerated, and mixed in a Henschel mixer as well. The chain extension reaction was carried out by feeding into the second feed port of the bobbin twin-screw extruder. (The feed rates of the first feed port and the second feed port were adjusted so that the composition of Example 1 was the same as that of Comparative Example 1.)

At this time, the melt strength of the regenerated polyester bumper was 41.5CN at a linear speed of 40cm / s, and the melt index was 1.8g / 10min at 250 ° C and 5kgf.

(Example 2)

All conditions were the same as Example 1, and the composition which was just added to the second inlet was added to the third inlet. At this time, the melt strength of the regenerated polyester bumper was 61CN at a linear speed of 40cm / s, and the melt index was 0.7g / 10min at 250 ° C and 5kgf.

(Example 3)

All conditions are the same as those of Example 1, and only the barrel temperature of the RiceleyC twin-screw extruder is H ₁ : 250 ° C. → 220 ° C., H _2, H ₃ : 250 ° C. → 230 ° C., H ₄ , H ₅ : 250 ° C. → Chain extension reaction of the polyester bumper which changed to 240 degreeC and regeneration is needed was performed.

At this time, the melt strength of the regenerated polyester bumper was 32.7CN at a linear speed of 40cm / s, and the melt index was 2.9g / 10min at 250 ° C and 5kgf.

(Example 4)

20 parts by weight of the regenerated polyester bumper (hereinafter referred to as "A component") obtained in Example 2 was mixed with 80 parts by weight of a polyester bumper (hereinafter referred to as "B component") which needs to be regenerated in a Henschel mixer to measure the blow molding ability. .

In this case, the blow molding ability of the mixture was 25.1CN at a linear velocity of 40cm / s, and a melt index of 5.6g / 10min at 250 ° C and 5kgf.

Example 5

All the conditions as in Example 4 were the same and only 50/60 weight ratios of component A and component B were mixed.

At this time, the melt strength of the mixture was 37CN at a linear speed of 40cm / s, and the melt index was 2.3g / 10min at 250 ° C and 5kgf.

Example 6

All the conditions as in Example 4 were the same and only the weight ratio of components A and B was mixed at 80/20.

At this time, the melt strength of the mixture was 46CN at a linear velocity of 40cm / s, and the melt index was 1.5g / 10min at 250 ° C and 5kgf.

Claims (6)

At least three polyfunctional epoxy resins (oxirane groups) per 100 parts by weight of a polyester-based bumper (bumper scrap, defective molding and a used waste bumper) which require regeneration. 0.1-5.0 parts by weight, Lewis acid catalyst 0.01-0.5 parts by weight pairs-Pre-mixed polyester bumper and polyfunctional epoxy resin to be recycled into the first inlet of the screw extruder, and the second or third inlet A method for regenerating a bumper for a polyester automobile, characterized in that the reaction is carried out by mixing the polyester bumper and the Lewis acid catalyst, which are required to be recycled, in advance. The polyester bumper according to claim 1, wherein the polyester bumper that needs to be regenerated has a melt strength of 240 ° C. or less and 21 CN at 3 mm strand, a melt viscosity of 130,000 poise or less at 1 rad / sec, a low shear rate, and 250 ° C. and 5 kgf. And jumbo properties having a melt index of 7 g / 10 min or more when preheated for 6 minutes. The regeneration method according to claim 1, wherein the polyfunctional epoxy resin is a compound represented by the following general formula (1). Where X is hydrogen or methyl Y: hydrogen, bromine or hydroxyl groups n: integer between 3-7 According to claim 1, wherein the Lewis acid catalyst is characterized in that the alkyl triphenyl phosphonium halide (Alkyl triphenyl phosphonium halide), alkenyl triphenyl phosphonium halide (Alkenyl triphenyl phosphonium halide), Tetraphenyl phosphonium borate How to play. 2. The method of claim 1, wherein the twin-screw extruder has two or more inlets, wherein the second inlet is within L / D = 10 and the third inlet is within L / D = 20. A polyester-based automobile comprising a polyester bumper recycled by the method of claim 1 in a polyester bumper (bumper scrap, defective molding and long-used waste bumper) that needs to be recycled in a 10 to 90 weight ratio. How to Play Bumper