CN107974032A

CN107974032A - A kind of fire retardation PC/ABS compounds and preparation method and application

Info

Publication number: CN107974032A
Application number: CN201711092822.7A
Authority: CN
Inventors: 肖华明; 汪炉林; 陈国雄; 宋晓辉; 孙超正; 宋晓东
Original assignee: Tianjin Kingfa Advanced Materials Co Ltd
Current assignee: Tianjin Kingfa Advanced Materials Co Ltd
Priority date: 2017-11-08
Filing date: 2017-11-08
Publication date: 2018-05-01

Abstract

The present invention provides a kind of fire retardation PC/ABS compounds and preparation method and application, count in parts by weight, including following component：10 50 parts of PC resin；30 80 parts of ABS resin；2 10 parts of compatilizer；8 15 parts of bromide fire retardant；15 parts of fire retarding synergist；1 10 parts of cohesion modifiers；Bond modified 0.1 0.5 parts of synergist；0.1 3 parts of auxiliary agent.Fire retardation PC of the present invention/ABS compound excellent in mechanical performance, flame retardant rating reach 1.5 3.0mm V 0 of UL94@.

Description

A kind of fire retardation PC/ABS compounds and preparation method and application

Technical field

The invention belongs to polymeric material field, more particularly, to a kind of fire retardation PC/ABS compounds and preparation method thereof with Using.

Background technology

PC/ABS alloys are by certain ratio by PC (makrolon) and ABS (acrylonitrile-butadiene-styrene copolymer) A kind of alloy material of example synthesis.Makrolon (PC) has impact strength height, creep resistant, good stability of the dimension, heat-resisting, saturating Bright, the advantages that dielectric properties are excellent, but at the same time there is also processing fluidity it is poor, stress cracking easily occurs, to notch sensitive, resistance to The shortcomings of mill property is poor；Acrylonitrile/butadiene/styrene copolymer (ABS) has preferable chemical proofing and processing and forming Property, but its heat-resisting and weatherability difference is relatively poor.PC/ABS alloys obtained by both blending and modifyings can be complementary in performance, no Only the heat resistance of blend alloy, impact strength and tensile strength are better than ABS, and its melt viscosity is lower than PC, processing performance Good, product internal stress and impact strength all substantially reduce the sensitiveness of products thickness, in electric, automobile and many height New technical field is widely used.

PC/ABS alloy materials in gluing field using more and more extensive, such as lead-acid accumulator field.Lead-acid battery electrode Mainly it is made of lead and its oxide, electrolyte is a kind of storage battery of sulfuric acid solution.Sent out from Frenchman Pulan spy in 1859 Bright lead-acid accumulator, has been subjected to the development course of nearly 150 years, lead-acid accumulator in terms of theoretical research, in product category and Kind, product electric property etc. are obtained for significant progress, whether in traffic, communication, electric power, military or navigating Sea, each economic field of aviation, lead-acid accumulator all play indispensable important function.In recent years, with urbanization Accelerate and the expansion of city scope, the magnitude of traffic flow increase severely.Although the vehicles such as automobile are quickly grown, it is subject to use price phase Influence to factors such as expensive and rises of the oil price, make electric bicycle with its is spry and light, conveniently, the advantage such as cheap, at home City's field depth is welcome by consumers in general.Lead-acid accumulator because it is cost-effective, power characteristic is good, self discharge is small, cheap, closely Get back over year in electric bicycle application；

PC/ABS alloy materials are applied to gluing field, it is necessary to which it possesses high adhesion strength and stability；Such as plumbic acid Battery field PC/ABS alloy materials, it is desirable to its initial stage adhesion strength Wei≤76.2Kgf/1.27cm²；And at present on the market PC/ABS alloy materials, its adhesion strength is mostly 50-70Kgf/1.27cm²；It can not meet the requirement of battery field.

The content of the invention

In view of this, the present invention is directed to propose a kind of fire retardation PC/ABS compounds and preparation method and application, to solve The above problem.

To reach above-mentioned purpose, the technical proposal of the invention is realized in this way：

A kind of fire retardation PC/ABS compounds, is counted in parts by weight, including following component：

Further, the PC resin is bisphenol A polycarbonate, its molecular weight is 10000-40000.

Further, the ABS resin for acrylonitrile, butadiene, the terpolymer of styrene, wherein, acrylonitrile Weight percent content is 15-32%, and the weight percent content of butadiene is 10-55%, and the percentage by weight of styrene contains Measure as 30-70%.

Further, the compatilizer is the graft of maleic anhydride, and the grafting rate of the graft is 0.3-1.2%, Melt index of the graft under 190 DEG C, 2.16kg loads is 50-120g/10min.Maleic anhydride grafting compatilizer leads to Cross and introduce highly polar reactive group, make material that there is high polarity and reactivity, the compatibility of composite material can be greatly improved.

Further, the bromide fire retardant is brominated triazine, i.e., three (three-bromophenyl) cyanurates.

Further, the fire retarding synergist is antimony oxide, colloidal antimony pentoxide, antimony trichloride, Antimony pentachloride In one or more of mixtures.

Further, the cohesion modifiers are ethylene-methyl acrylate-glyceryl methacrylate ternary polymerization Thing, its melt mass flow rate under 190 DEG C, 2.16kg loads are 5-10g/10min., can after adding cohesion modifiers To form hydrogen bond between resin and adhesive, the formation of a large amount of hydrogen bonds can be with the Van der Waals between reinforced resin and adhesive Power, so as to improve the adhesion strength of compound.

Further, the modified synergist of bonding be high boiling small-molecule substance, specially turpentine oil, coal tar, Mixture more than one or both of furfuryl alcohol, castor oil, epoxidized soybean oil.After adding high boiling small-molecule substance, this The addition of a little small-molecule substances can increase the locomitivity of strand, improve flexibility, so that glue-line is not crisp, further carry The adhesion strength of high compound；

Auxiliary agent includes such as heat stabilizer, light stabilizer, processing aid, pigment in the composition of the present invention.Can be according to not Above-mentioned additive is used alone in structure, technical requirements with product etc., or is used in combination.

Heat stabilizer can improve heat aging property of the material during processing and use, usually may be selected from phenols, Phosphorous acid esters, thio esters one or both of compound more than mixture.

Light stabilizer can improve the light aging resisting property of material in use, can be hindered amine light stabilizer or Ultra-violet absorber.

Processing aid is low molecule esters stearic acid, metallic soap (such as Cast, Znst), stearic acid complex ester or amide-type More than one or both of (such as erucyl amide).

The preparation method of fire retardation PC of the present invention/ABS compounds, includes the following steps：

(1) PC resin, ABS resin, compatilizer, bromide fire retardant, fire retarding synergist, cohesion modifiers, bonding are modified Synergist, auxiliary agent are sufficiently mixed 10-60 minutes in high-speed mixer obtains mixture；

(2) said mixture is transported in double screw extruder by feed device, each section of extruder temperature of extruder Control is between 180~230 DEG C, and the draw ratio of double screw extruder is 25~40, and screw speed is 200-800 revs/min, Under the shearing of screw rod, mixing and conveying, material is able to fully fusing, compound, then by extruding pelletization, be dried to obtain fire retardation PC/ ABS compounds；

(3) fire retardation PC/ABS compounds are added in injection molding machine and are processed into required batten, the injecting condition is：Barrel 190-240 DEG C of temperature, 60~70 DEG C of mold temperature, injection pressure 6-10MPa.

Above-mentioned fire retardation PC/ABS compounds can be widely applied in the glue such as storage battery envelope technique.

Relative to the prior art, fire retardation PC of the present invention/ABS compounds have the advantage that：

1) fire retardation PC of the present invention/ABS compounds, excellent in mechanical performance, its flame retardant rating reach UL94@1.5- 3.0mm V-0；

2) fire retardation PC of the present invention/ABS compounds have excellent adhesion strength, and stability is high；

3) fire retardation PC of the present invention/ABS compound preparation methods are simple and practicable, handling ease, are very suitable for glue envelope Field (such as storage battery) promotes and applies.

Embodiment

In addition to being defined, technical term used has universal with those skilled in the art of the invention in following embodiments The identical meanings of understanding.Test reagent used, is routine biochemistry reagent unless otherwise specified in following embodiments；It is described Experimental method, is conventional method unless otherwise specified.

Now the raw material used in embodiment and comparative example are done as described below, but be not limited to these materials：

PC resin is selected from the PC L-1225L of Japanese Supreme Being people；

ABS resin selects the ABS AG10NP-AK of platform；

Compatilizer is selected from the KT-1 of Sheyang Ketong Plastic Co., Ltd.；

Bromide fire retardant selects the SR-245 of Japanese first drugmaker；

Fire retarding synergist selects the antimony oxide producer of Anhua Hua Yuti industry Co., Ltd；

Cohesion modifiers select A Kema AX-8900；

Bonding modified synergist selects Longkou city dragon to reach epoxidized soybean oil；

Auxiliary agent is pigment, the pigment that weight ratio is 1 part is added in embodiment 1-3 and comparative example 1-3, because of the pigment pair The physical property of composition is not put into table without influence.

Have in the embodiment of the present invention in the instrument and equipment for preparing and testing used in fire retardation PC/ABS compounds：

The flame-retardant modified double screw extruder used of thermoplastic is given birth to by Nanjing Rhea high polymer Equipment Limited The SHJ-30 of production.

The injection molding machine that thermoplastic test bars use is the B-920 produced by Zhejiang Hai Tian injection molding machines Co., Ltd Type.

The instrument of test melt flow rate (MFR) is that the ZR21452 of Mei Site industrial systems (China) Co., Ltd production melts Body flow rate instrument.

The impact experiment machine of test impact strength is the T92 types of Tinius Olsenis companies of U.S. production.

The universal testing machine of test tensile strength is the H10K-S of Hounsfield companies production.

The UL-94 Vertical combustion instruments that test flame retardant rating uses are U.S. ATLAS HVUL-2.

With reference to embodiment, the present invention will be described in detail.

Embodiment 1

By 30 parts of PC resins, 53.9 parts of ABS resins, 2 parts of compatilizers, 10 parts of bromide fire retardants, 3 parts of fire retarding synergists, 1 part Cohesion modifiers, the modified synergist of 0.1 part of bonding, are sufficiently mixed 10-60 minutes by proportioning in high-speed mixer；By above-mentioned mixing Thing is transported in double screw extruder (wherein, the processing of double screw extruder melting extrusion by the feed device of delicate metering Condition is as follows：One 190 DEG C of area's temperature, two 210 DEG C of area's temperature, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five area's temperature 240 DEG C, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight 240 DEG C of area's temperature, nine 240 DEG C of area's temperature, ten 250 DEG C of area's temperature, head 260 DEG C of temperature；Screw speed is 200-800 revs/min, draw ratio 40：1), under the shearing of screw rod, mixing and conveying, thing Material be able to fully fusing, it is compound, then by extruding pelletization, be dried to obtain fire retardation PC/ABS compounds；Fire retardation PC/ABS is compound Thing, which is added in injection molding machine, is processed into required batten, and the injecting condition is：190-260 DEG C of barrel temperature, mold temperature 60 ~70 DEG C, injection pressure 6-10MPa.

Embodiment 2

By 30 parts of PC resins, 49.8 parts of ABS resins, 2 parts of compatilizers, 10 parts of bromide fire retardants, 3 parts of fire retarding synergists, 5 parts Cohesion modifiers, the modified synergist of 0.2 part of bonding, are sufficiently mixed 10-60 minutes by proportioning in high-speed mixer；By above-mentioned mixing Thing is transported in double screw extruder (wherein, the processing of double screw extruder melting extrusion by the feed device of delicate metering Condition is as follows：One 190 DEG C of area's temperature, two 210 DEG C of area's temperature, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five area's temperature 240 DEG C, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight 240 DEG C of area's temperature, nine 240 DEG C of area's temperature, ten 250 DEG C of area's temperature, head 260 DEG C of temperature；Screw speed is 200-800 revs/min, draw ratio 40：1), under the shearing of screw rod, mixing and conveying, thing Material be able to fully fusing, it is compound, then by extruding pelletization, be dried to obtain fire retardation PC/ABS compounds；Fire retardation PC/ABS is compound Thing, which is added in injection molding machine, is processed into required batten, and the injecting condition is：190-260 DEG C of barrel temperature, mold temperature 60 ~70 DEG C, injection pressure 6-10MPa.

Embodiment 3

By 30 parts of PC resins, 44.5 parts of ABS resins, 2 parts of compatilizers, 10 parts of bromide fire retardants, 3 parts of fire retarding synergists, 10 Part cohesion modifiers, the modified synergist of 0.5 part of bonding, are sufficiently mixed 10-60 minutes by proportioning in high-speed mixer；Will be above-mentioned mixed Compound by delicate metering feed device be transported in double screw extruder (wherein, double screw extruder melting extrusion plus Work condition is as follows：One 190 DEG C of area's temperature, two 210 DEG C of area's temperature, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five area's temperature 240 DEG C, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, eight 240 DEG C of area's temperature, nine 240 DEG C of area's temperature, ten 250 DEG C of area's temperature, 260 DEG C of head temperature；Screw speed is 200-800 revs/min, draw ratio 40：1), in the shearing, mixing and conveying of screw rod Under, material be able to fully fusing, it is compound, then by extruding pelletization, be dried to obtain fire retardation PC/ABS compounds；By fire retardation PC/ABS Compound, which is added in injection molding machine, is processed into required batten, and the injecting condition is：190-260 DEG C of barrel temperature, mold temperature For 60~70 DEG C, injection pressure 6-10MPa.

Comparative example 1

30 parts of PC resins, 54 parts of ABS resins, 2 parts of compatilizers, 10 parts of bromide fire retardants, 3 parts of fire retarding synergists, 1 part are glued Modifying agent is tied, is sufficiently mixed 10-60 minutes in high-speed mixer by proportioning；Said mixture is filled by the feeding of delicate metering Put and be transported in double screw extruder that (wherein, the processing conditions of double screw extruder melting extrusion is as follows：One 190 DEG C of area's temperature, Two 210 DEG C of area's temperature, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five 240 DEG C of area's temperature, six 240 DEG C of area's temperature, seven area's temperature 240 DEG C of degree, eight 240 DEG C of area's temperature, nine 240 DEG C of area's temperature, ten 250 DEG C of area's temperature, 260 DEG C of head temperature；Screw speed is 200-800 revs/min, draw ratio 40：1), the shearing of screw rod, mixing and conveying under, material be able to fully fusing, it is compound, Pass through extruding pelletization again, be dried to obtain fire retardation PC/ABS compounds；Fire retardation PC/ABS compounds are added in injection molding machine and processed Into required batten, the injecting condition is：190-260 DEG C of barrel temperature, mold temperature are 60~70 DEG C, injection pressure 6- 10MPa。

Comparative example 2

By 30 parts of PC resins, 54.8 parts of ABS resins, 2 parts of compatilizers, 10 parts of bromide fire retardants, 3 parts of fire retarding synergists, 0.2 Part bonds modified synergist, is sufficiently mixed 10-60 minutes in high-speed mixer by proportioning；Said mixture is passed through into delicate metering Feed device be transported in double screw extruder that (wherein, the processing conditions of double screw extruder melting extrusion is as follows：One area's temperature 190 DEG C of degree, two 210 DEG C of area's temperature, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five 240 DEG C of area's temperature, six area's temperature 240 DEG C, seven 240 DEG C of area's temperature, eight 240 DEG C of area's temperature, nine 240 DEG C of area's temperature, ten 250 DEG C of area's temperature, 260 DEG C of head temperature；Screw rod Rotating speed is 200-800 revs/min, draw ratio 40：1), under the shearing of screw rod, mixing and conveying, material is able to fully molten Change, it is compound, then by extruding pelletization, be dried to obtain fire retardation PC/ABS compounds；Fire retardation PC/ABS compounds are added to injection Required batten is processed into machine, the injecting condition is：190-260 DEG C of barrel temperature, mold temperature are 60~70 DEG C, injection pressure Power is 6-10MPa.

Comparative example 3

By 30 parts of PC resins, 55 parts of ABS resins, 2 parts of compatilizers, 10 parts of bromide fire retardants, 3 parts of fire retarding synergists, by with Than being sufficiently mixed 10-60 minutes in high-speed mixer；Said mixture is transported to double spiral shells by the feed device of delicate metering (wherein, the processing conditions of double screw extruder melting extrusion is as follows in bar extruder：One 190 DEG C of area's temperature, two area's temperature 210 DEG C, three 230 DEG C of area's temperature, four 240 DEG C of area's temperature, five 240 DEG C of area's temperature, six 240 DEG C of area's temperature, seven 240 DEG C of area's temperature, 8th area 240 DEG C of temperature, nine 240 DEG C of area's temperature, ten 250 DEG C of area's temperature, 260 DEG C of head temperature；Screw speed is 200-800 revs/min, Draw ratio is 40：1), the shearing of screw rod, mixing and conveying under, material be able to fully fusing, it is compound, then by extruding pelletization, It is dried to obtain fire retardation PC/ABS compounds；Fire retardation PC/ABS compounds are added in injection molding machine and are processed into required batten, it is described Injecting condition is：190-260 DEG C of barrel temperature, mold temperature are 60~70 DEG C, injection pressure 6-10MPa.

The batten that embodiment 1-3 and comparative example 1-3 are obtained tests its correlated performance using iso standard, wherein, adhesive strength Test method be：

1st, first resin sheet (i.e. batten, similarly hereinafter) is cut from centre；

2nd, away from making marks at disconnected 10mm, and with 50% ethanol surface；

3rd, solid is dipped using cotton swab, two drop solids is added dropwise in the label range of wherein a piece of resin sheet, are added dropwise Quality be 0.06-0.08g；

4th, two panels resin sheet is superimposed according to mark and alignd, the mark of two panels resin sheet is bonded together, two The top pressure of piece resin sheet is improved quality as the special pressing plate of 500g, while ensures that resin sheet is horizontal and not in gap shell tool Misplace, the solid of spilling is removed；

5th, resin streak is put into drying equipment dry, it is ensured that to ensure to drying equipment is put into from configuration solid Completed in 10min, drying temperature is 60 DEG C, time 2h；

6th, adhesive strength is tested：The dried resin sheet that step 5 is obtained is set under the draw speed of 5mm/min The adhesive strength of fat piece.

The specific proportioning and the performance test results of embodiment 1-3 and comparative example 1-3 see the table below：

1 embodiment of table matches somebody with somebody when performance test data with the specific of each component in comparative example

From the embodiment and comparative example of table 1 as can be seen that addition cohesion modifiers and bond synergist after, embodiment with The mechanical property of comparative example is essentially the same, and mechanical property and anti-flammability are retainable very well, but adhesion strength differs greatly；It is real Example 1 is applied compared with comparative example 1, with the addition of 0.1 part of cohesive synergist, adhesion strength is from 79.0Kgf/1.27cm²Bring up to 83.4Kgf/1.27cm²；Embodiment 2 with the addition of 5 parts of cohesion modifiers compared with comparative example 2, and adhesion strength is from 71.8Kgf/ 1.27cm²Bring up to 94.1Kgf/1.27cm²；Embodiment 3 with the addition of 10 parts of cohesion modifiers and 0.5 part compared with comparative example 3 Synergist is bonded, adhesion strength is from 66.7Kgf/1.27cm²Bring up to 108.5Kgf/1.27cm²。

As can also be seen from Table 1, cohesion modifiers are not added and bond synergist, and the adhesion strength of compound only has 66.7Kgf/1.27cm², compared from comparative example 1, comparative example 2 with comparative example 3, it can be seen that addition cohesion modifiers or bonding Synergist can improve the adhesion strength of compound, but add cohesion modifiers at the same time and bond synergist, can cause The adhesion strength of compound increases substantially.

Fire retardation PC of the present invention/ABS compounds have excellent comprehensive performance, and while adhesion strength is improved, its is fire-retardant Performance, mechanical property are held essentially constant, and can be applied to glue closure material field (such as storage battery).

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention With within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention god.

Claims

A kind of 1. fire retardation PC/ABS compounds, it is characterised in that：Count in parts by weight, including following component：
2. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The PC resin is the poly- carbon of bisphenol A-type Acid esters, its molecular weight are 10000-40000.
3. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The ABS resin is acrylonitrile, fourth two The terpolymer of alkene, styrene, wherein, the weight percent content of acrylonitrile is 15-32%, the percentage by weight of butadiene Content is 10-55%, and the weight percent content of styrene is 30-70%.
4. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The compatilizer connects for maleic anhydride Branch thing, the grafting rate of the graft is 0.3-1.2%, and melt index of the graft under 190 DEG C, 2.16kg loads is 50-120g/10min。
5. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The bromide fire retardant is bromo three Piperazine.
6. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The fire retarding synergist is three oxidations two Mixture more than one or both of antimony, colloidal antimony pentoxide, antimony trichloride, Antimony pentachloride.
7. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The cohesion modifiers are ethene-the third E pioic acid methyl ester-glycidyl methacrylate terpolymer, its melt mass flow under 190 DEG C, 2.16kg loads Speed is 5-10g/10min.
8. fire retardation PC according to claim 1/ABS compounds, it is characterised in that：The modified synergist of bonding is turpentine Mixture more than one or both of oil, coal tar, furfuryl alcohol, castor oil, epoxidized soybean oil.
A kind of 9. preparation method of fire retardation PC/ABS compounds, it is characterised in that：The preparation method includes the following steps：

(1) by PC resin, ABS resin, compatilizer, bromide fire retardant, fire retarding synergist, cohesion modifiers, the modified synergistic of bonding Agent, auxiliary agent are sufficiently mixed 10-60 minutes in high-speed mixer obtains mixture；

(2) mixture that step (1) obtains is transported in double screw extruder by feed device, the screw extruder it is each Section extruder temperature control is between 180~230 DEG C, and the draw ratio of double screw extruder is 25~40, screw speed 200-800 Rev/min, mixture fully melts, it is compound after again by extruding pelletization, be dried to obtain fire retardation PC/ABS compounds；

(3) fire retardation PC/ABS compounds are added in injection molding machine and are processed into required batten, the injecting condition is：Barrel temperature 190-240 DEG C, 60~70 DEG C of mold temperature, injection pressure 6-10MPa.
A kind of 10. any fire retardation PC/application of the ABS compounds in battery rubber closure material in claim 1-9.