CN102516732A - Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof - Google Patents

Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof Download PDF

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Publication number
CN102516732A
CN102516732A CN2011103947264A CN201110394726A CN102516732A CN 102516732 A CN102516732 A CN 102516732A CN 2011103947264 A CN2011103947264 A CN 2011103947264A CN 201110394726 A CN201110394726 A CN 201110394726A CN 102516732 A CN102516732 A CN 102516732A
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China
Prior art keywords
abs
parts
alloy
polycarbonate resin
resin
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CN2011103947264A
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Chinese (zh)
Inventor
雷春堂
周刚
潘晓勇
王炼
陈伟
纪敏
聂军
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Sichuan Changhong Electric Co Ltd
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Sichuan Changhong Electric Co Ltd
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Priority to CN2011103947264A priority Critical patent/CN102516732A/en
Publication of CN102516732A publication Critical patent/CN102516732A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

Abstract

The invention relates to the technical field of polymer engineering plastics, in particular to polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and a preparation method thereof, and provides high-impact-strength halogen-free flame retardant PC resin/ABS alloy. The PC resin/ABS alloy is prepared from the following raw materials in part by weight: 20 to 50 parts of ABS resin, 30 to 60 parts of PC resin, 2 to 20 parts of halogen-free flame retardant, 1 to 15 parts of compatilizer, and 3 to 30 parts of toughening agent. The ratio of ABS to PC in the alloy material can be adjusted reasonably, the added halogen-free flame retardant ensures that the flame retardant property of the alloy material can reach the American UL94V-0-grade requirement, does not contain halogen, does not release a large amount of dense smoke or corrosive toxic gas when combusted, and has the advantages of high safety and environment-friendliness and the like. The added compatilizer and toughening agent can obviously improve the mechanical property and impact strength of the alloy material, and ensures that the ABS/PC alloy material has high toughness at low temperature of -40 DEG C.

Description

Polycarbonate resin/ABS Alloy And Preparation Method
Technical field
The present invention relates to macromolecule engineering plastics technology field, particularly polycarbonate resin/ABS Alloy And Preparation Method.
Background technology
Acrylonitrile-butadiene-styrene resin (ABS) is a kind of novel universal thermoplastic engineering plastic of the exploitation forties in 20th century, and it is a kind of terpolymer that is formed by vinylbenzene, the monomer-grafted copolymerization of acrylonitrile and butadiene.It has good electrical property, chemical resistant properties, shock-resistance, tinctorial property and dimensional stability, is easy to machine-shaping, but its thermotolerance and weathering resistance are poor.Polycarbonate (PC) resin transparent degree is good, and thermotolerance is high, good light stability, and dimensional stability is good, good toughness, but it is responsive to breach, and the product internal stress is big, and melt viscosity is high, and is mobile poor, difficult forming.
ABS and PC resin are that the blend of main raw material is a kind of important engineering polyblend, and this material has certain shock resistance, good thermotolerance and good workability.Said composition is widely used in aspects such as mobile phone, computer casing, electrical connector, automobile component, electrical and electronic component.Because electric equipment products and office appliance sheating material have the heat-proof combustion-resistant requirement; And in the early stage ABS/PC alloy add halogen compounds require to reach its flame retardant properties (as the patent No. be the ZL200610036820.1 name be called employing bromide fire retardant and Sb system fire retardant modification PC/ABS alloy are disclosed in " modification PC/ABS alloy "); But the fire retardant material of halogen contained compound can discharge a large amount of dense smoke and corrosive gases when burning; Be prone to produce secondary disaster, can cause certain pollution to environment during burning.Along with the corresponding promulgation of Europe RoHS and REACH instruction, the application of halogen fire-retardant agent is limited; In addition, the ABS/PC product of halogen containing flame-retardant also exists the consistency of some defectives: ABS and PC relatively poor, causes material mechanical performance not good enough; The resistance to impact shock of ABS/PC alloy material is relatively poor, and particularly its resistance to impact shock sharply reduces when low-temperature condition.
Summary of the invention
The present invention is directed to above-mentioned defective, a kind of polycarbonate resin/ABS alloy with high impact strength, halogen-free flameproof is provided, this polycarbonate resin/ABS alloy materials is counted by weight:
20~50 parts of ABS resins;
30~60 parts of PC resins;
2~20 parts of halogen-free flame retardantss;
1~15 part of compatilizer;
3~30 parts of toughner.
Preferably, this polycarbonate resin/ABS alloy materials is counted by weight:
25~45 parts of ABS resins;
35~50 parts of PC resins;
4~15 parts of halogen-free flame retardantss;
2~12 parts of compatilizers;
4~20 parts of toughner.
Preferably, the content of vinyl cyanide is 10~26% in the said ABS resin.
Preferably, said ABS resin Vicat softening point is greater than 105 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.2~3.0g/10min.
Preferably, said PC resin heat-drawn wire is: 105~160 ℃.
Preferably, said halogen-free flame retardants is phosphonium flame retardant or contains at least a in the nitrogen combustion inhibitor; Wherein phosphonium flame retardant is at least a in phosplate, biphosphonate, the red phosphorus coating; Contain nitrogen combustion inhibitor and be at least a in trimeric cyanamide, three isocyanide esters, the Dyhard RU 100.
Preferred, said halogen-free flame retardants is the composite flame-retardant agent agent, by phosphonium flame retardant with contain nitrogen combustion inhibitor and form, phosphonium flame retardant and the weight proportion that contains nitrogen combustion inhibitor are 1~3: 1, more preferably 2: 1.
Preferably, said compatilizer is the phenylethylene graft copolymer, and wherein cinnamic weight percent content is 5~50%.
Said toughner is methyl acrylate-butadiene-styrene terpolymer, and wherein the weight percent content of methyl acrylate is 5~45%, and butadiene content is 10~40%, and styrene content is 15~60%.
The present invention also provides the preparation method of above-mentioned polycarbonate resin/ABS alloy, is specially: promptly make carrying out mechanical blending in its temperature more than fusing point, below the heat decomposition temperature behind each raw material blending.
Preferably, adopt forcing machine to carry out blend during mechanical blending, Heating temperature is 200~265 ℃, and the head extrusion temperature is 225~235 ℃.
Preferred, Heating temperature is 210~255 ℃, and the head extrusion temperature is 230 ℃.
During blend, main-machine screw rotating speed 450~550r/min, reinforced rotating speed 45~55r/min; The blend time is 1~6 minute.
The blend time is preferably 2 minutes.
Preferably, among the preparation method of polycarbonate resin/ABS alloy, need dry before ABS resin, PC resin, compatilizer and toughner mix in the raw material.
Wherein, ABS resin, compatilizer and toughner drying temperature are 70~90 ℃, 3~6 hours time of drying.80 ℃ of preferred drying temperatures.
PC resin drying temperature is 100~135 ℃, 3~6 hours time of drying.125 ℃ of preferred drying temperatures.
Beneficial effect of the present invention:
The present invention has reasonably regulated the ratio of ABS and PC in the alloy material; The halogen-free flame retardants that adds can make the flame retardant properties of polycarbonate resin/ABS alloy material reach the requirement of U.S. UL94V-0 level; And it is not halogen-containing; Product the time can not discharge a large amount of dense smokes and corrosive poisonous gas in burning, has advantages such as safety, the feature of environmental protection are good; Meet the environmental requirement of various countries, the world today (particularly European Union).And the compatilizer and the toughner that add can significantly improve the mechanical property and the resistance to impact shock of alloy material, make the ABS/PC alloy material under-40 ℃ low temperature, still have toughness preferably.
Embodiment
The invention provides a kind of polycarbonate resin/ABS alloy with high impact strength, halogen-free flameproof, this polycarbonate resin/ABS alloy materials is counted by weight:
20~50 parts of ABS resins;
30~60 parts of PC resins;
2~20 parts of halogen-free flame retardantss;
1~15 part of compatilizer;
3~30 parts of toughner.
Preferably, this polycarbonate resin/ABS alloy materials is counted by weight:
25~45 parts of ABS resins;
35~50 parts of PC resins;
4~15 parts of halogen-free flame retardantss;
2~12 parts of compatilizers;
4~20 parts of toughner.
Also can add usual auxiliaries in polycarbonate resin of the present invention/ABS alloy, for example: inhibitor, photostabilizer, lubricant, processing aid or color master-batch.
Said inhibitor is a hindered phenol antioxidant.
Preferably, said oxidation inhibitor comprises main anti-oxidant and auxilliary inhibitor, and the weight ratio of main anti-oxidant and auxilliary inhibitor is 1: 1~4: 1, more preferably 3: 1.
Preferred, main anti-oxidant is that model is 1010 hindered phenol antioxidant, and auxilliary inhibitor is that model is 168 hindered phenol antioxidant.
Said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester, two (1,2; 2,6,6-pentamethyl--4-piperidines) sebate, 1-methyl-8-(1,2,2; 6,6-pentamethyl--4-piperidines) sebate, 2,2,6, at least a in the 6-tetramethyl piperidine nitrogen oxygen free radical.
Preferably, said photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester.
Said lubricant is Triple Pressed Stearic Acid, butyl stearate, oleylamide, ethylene bis stearamide, native paraffin, whiteruss, at least a in microcrystalline wax, polyethylene wax, the low-molecular-weight polypropylene.
Preferably, said lubricant is an ethylene bis stearamide.
Said color master-batch is mineral dye, pigment dyestuff, dyestuff.
Preferably, said color master-batch is a pigment dyestuff.
Said processing aid is thermo-stabilizer, static inhibitor, releasing agent, filler, fortifying fibre or Antidrip agent.
Optimized technical scheme is that polycarbonate resin/ABS alloy raw material is counted by weight when adding auxiliary agent:
20~50 parts of ABS resins;
30~60 parts of PC resins;
2~20 parts of halogen-free flame retardantss;
1~15 part of compatilizer;
3~30 parts of toughner;
0.2~0.4 part of inhibitor;
0.05~0.2 part of photostabilizer;
0.05~0.5 part of lubricant;
0.01~0.2 part of processing aid;
1~5 part of color master-batch.
Preferably, polycarbonate resin/ABS alloy materials is counted by weight:
25~45 parts of ABS resins;
35~50 parts of PC resins;
4~15 parts of halogen-free flame retardantss;
2~12 parts of compatilizers;
4~20 parts of toughner;
0.2~0.3 part of inhibitor;
0.05~0.1 part of photostabilizer;
0.05~0.4 part of lubricant;
0.01~0.15 part of processing aid;
2~4 parts of color master-batchs.
The adding of inhibitor, photostabilizer, lubricant and processing aid can improve the resistance of oxidation and the ultraviolet radiation resisting ability of ABS/PC alloy material, increases the work-ing life of ABS/PC alloy material.
Through embodiment the present invention is specifically described below; It is important to point out that embodiment only is used for further specifying of the present invention; Can not be interpreted as the restriction to protection domain of the present invention, these those skilled in the art can make some nonessential improvement and adjustment according to the present invention.
The preparation and the performance of embodiment 1 polycarbonate resin/ABS alloy
Take by weighing various raw materials according to table 1 composition of raw materials; Wherein (weight percent content of methyl acrylate is 22% to ABS resin; Vicat softening point is greater than 105 ℃, and under the condition of 200 ℃/5Kg, its melting index is at 1.5g/10min), compatilizer (phenylethylene graft copolymer; Wherein cinnamic weight percent content is 35%) and toughner (methyl acrylate-butadiene-styrene terpolymer; Wherein the weight percent content of methyl acrylate is 25%, and butadiene content is 15%, and styrene content is 60%); Respectively under 80 ℃ of conditions dry 3 hours before use; PC resin under 125 ℃ of conditions dry 3 hours before use adds the high-speed mixer high speed with various raw materials (comprising auxiliary material) and mixed low speed discharging again 2 minutes.Material behind the mixing obtains polycarbonate resin/ABS alloy through fusing and pelleting, and product property detects data and sees table 2.The melt pelletization condition is: main-machine screw rotating speed 500r/min, and reinforced rotating speed 50r/min, the Heating temperature section: 1 section/210 ℃, 2 sections/220 ℃; 3 sections/230 ℃, 4 sections/240 ℃, 5 sections/250 ℃, 6 sections/255 ℃; 7 sections/245 ℃, 8 sections/235 ℃, 9 sections/220 ℃, head temperature: 230 ℃.
The preparation and the performance of embodiment 2-5 polycarbonate resin/ABS alloy
The preparation method of embodiment 2~5 is identical with embodiment 1, and concrete proportioning raw materials is seen table 1; The product of embodiment 2~5 is tested according to GB, and the product performance data are as shown in table 2.
The preparation and the performance of Comparative Examples 1 polycarbonate resin/ABS alloy
The preparation method of Comparative Examples 1 is identical with embodiment 1, and concrete proportioning raw materials is seen table 1; The products obtained therefrom performance data is as shown in table 2.
Table 1 polycarbonate resin/ABS alloy materials and proportioning unit: kilogram
Component Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative Examples 1
ABS 31.36 35.2 40.16 20 50 34.56
PC 50.2 42.36 32.4 60 30 51.5
Halogen-free flame retardants 6 10 15 7.56 7.56 1.5
Compatilizer 5 5 5 5 5 5
Toughner 4 4 4 4 4 4
Inhibitor 0.2 0.2 0.2 0.2 0.2 0.2
Photostabilizer 0.08 0.08 0.08 0.08 0.08 0.08
Lubricant 0.06 0.06 0.06 0.06 0.06 0.06
Processing aid 0.1 0.1 0.1 0.1 0.1 0.1
Color master-batch 3 3 3 3 3 3
In the table 1; Inhibitor is antioxidant 1010 (four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester) and the compound of inhibitor 168 (tricresyl phosphite (24-di-tert-butyl-phenyl) ester), antioxidant 1010: oxidation inhibitor 168=3: 1 by weight; Fire retardant is a phosphonium flame retardant and the compound that contains nitrogen combustion inhibitor, phosphonium flame retardant with contain nitrogen combustion inhibitor by weight counting 2: 1; Photostabilizer is that sebacic acid is two 2,2,6,6-tetramethyl piperidine alcohol ester; Lubricant is an ethylene bis stearamide; Color master-batch is a pigment dyestuff.
The performance of table 2 polycarbonate resin/ABS alloy
Among the present invention, tensile strength is tested according to GB GB/T1040.2-2006; Flexural strength, modulus in flexure are tested according to GB GB/T9341-2000; The socle girder notched Izod impact strength is tested according to GB GB/T1843-2008; Heat-drawn wire is tested according to GB GB/T1634.2-2004; Melt flow rate(MFR) is tested according to GB GB/T3682-2000; According to the described vertical flame test standard of the UL standard of U.S. UL-94 (94V-0), use 1/16 inch thick test bars evaluation of flame retardancy.
From table 2, can find out; Ratio and composition through each component in the reasonable control prescription; Add the polycarbonate resin/ABS alloy that can obtain a kind of low cigarette, Halogen, H.T. under the situation of a certain amount of halogen-free flame retardants, compatilizer and toughner; Thereby realized the preparation of the ABS/PC resin combination of low cigarette, Halogen, H.T. with lower cost through the method for blending and modifying, this method is simple to operate, and required starting material are easy to get.But; Comparative Examples 1 is because the add-on of halogen-free flame retardants has exceeded scope of the present invention, and add-on is too little, though good mechanical performance and melt flow rate(MFR) are arranged; But the flame retardant properties of products obtained therefrom can not reach V0 or V1 rank, can not be applied to actual production.

Claims (10)

1. polycarbonate resin/ABS alloy, raw material is counted by weight:
20~50 parts of ABS resins;
30~60 parts of PC resins;
2~20 parts of halogen-free flame retardantss;
1~15 part of compatilizer;
3~30 parts of toughner.
2. polycarbonate resin according to claim 1/ABS alloy is characterized in that raw material is counted by weight:
25~45 parts of ABS resins;
35~50 parts of PC resins;
4~15 parts of halogen-free flame retardantss;
2~12 parts of compatilizers;
4~20 parts of toughner.
3. polycarbonate resin according to claim 1 and 2/ABS alloy is characterized in that, said halogen-free flame retardants is phosphonium flame retardant or contains at least a in the nitrogen combustion inhibitor; Wherein phosphonium flame retardant is at least a in phosplate, biphosphonate, the red phosphorus coating; Contain nitrogen combustion inhibitor and be at least a in trimeric cyanamide, three isocyanide esters, the Dyhard RU 100.
4. polycarbonate resin according to claim 3/ABS alloy is characterized in that, said halogen-free flame retardants for by phosphonium flame retardant with contain nitrogen combustion inhibitor and form composite flame-retardant agent, wherein phosphonium flame retardant and the weight proportion that contains nitrogen combustion inhibitor are 1~3: 1.
5. according to each described polycarbonate resin/ABS alloy of claim 1~4, it is characterized in that the content of vinyl cyanide is 10~26% in the said ABS resin.
6. according to each described polycarbonate resin/ABS alloy of claim 1~4, it is characterized in that said PC resin heat-drawn wire is 105~160 ℃.
7. according to each described polycarbonate resin/ABS alloy of claim 1~4, it is characterized in that said compatilizer is the phenylethylene graft copolymer, wherein cinnamic weight percent content is 5~50%.
8. according to each described polycarbonate resin/ABS alloy of claim 1~4; It is characterized in that; Said toughner is methyl acrylate-butadiene-styrene terpolymer; Wherein the weight percentage of methyl acrylate is 5~45%, and the weight percentage of divinyl is 10~40%, and cinnamic weight percentage is 15~60%.
9. the preparation method of each described polycarbonate resin/ABS alloy of claim 1-8 is specially: promptly make carrying out mechanical blending in its temperature more than fusing point, below the heat decomposition temperature behind each raw material blending.
10. the preparation method of the described polycarbonate resin of claim 9/ABS alloy is characterized in that, adopts forcing machine to carry out blend during mechanical blending, and Heating temperature is 200~265 ℃, and the head extrusion temperature is 225~235 ℃.
CN2011103947264A 2011-12-02 2011-12-02 Polycarbonate (PC) resin/acrylonitrile-butadiene-styrene (ABS) alloy and preparation method thereof Pending CN102516732A (en)

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Cited By (7)

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CN104371258A (en) * 2014-07-09 2015-02-25 南通帝诚华信实业有限公司 Modified material for impact-resistant fog lamp frame
CN104592731A (en) * 2015-01-27 2015-05-06 奉化市兴杨塑业有限公司 Silicon-based flame-retardant PC/ABS alloy
CN104877329A (en) * 2015-05-27 2015-09-02 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
CN104974461A (en) * 2015-06-30 2015-10-14 深圳光华伟业股份有限公司 ABS alloy material, and preparation method thereof
CN104987688A (en) * 2015-06-08 2015-10-21 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
CN104987691A (en) * 2015-06-09 2015-10-21 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
CN108504062A (en) * 2017-02-28 2018-09-07 汉达精密电子(昆山)有限公司 Halogen-free flame retardant PC/ABS composite material and products thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371258A (en) * 2014-07-09 2015-02-25 南通帝诚华信实业有限公司 Modified material for impact-resistant fog lamp frame
CN104592731A (en) * 2015-01-27 2015-05-06 奉化市兴杨塑业有限公司 Silicon-based flame-retardant PC/ABS alloy
CN104877329A (en) * 2015-05-27 2015-09-02 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
CN104987688A (en) * 2015-06-08 2015-10-21 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
CN104987688B (en) * 2015-06-08 2017-03-08 金发科技股份有限公司 A kind of polycarbonate compositions and preparation method thereof
CN104987691A (en) * 2015-06-09 2015-10-21 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
WO2016197907A1 (en) * 2015-06-09 2016-12-15 金发科技股份有限公司 Polycarbonate composition and preparation method therefor
CN104974461A (en) * 2015-06-30 2015-10-14 深圳光华伟业股份有限公司 ABS alloy material, and preparation method thereof
CN108504062A (en) * 2017-02-28 2018-09-07 汉达精密电子(昆山)有限公司 Halogen-free flame retardant PC/ABS composite material and products thereof

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