CN105368032A - Preparation method of toughened modified polycarbonate - Google Patents
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Abstract
The invention discloses a preparation method of toughened modified polycarbonate and belongs to the technical field of polymer materials. The preparation method comprises the following steps: Step 1, preparing modified PET; Step 2, preparing modified rigid nano-filler; and Step 3, putting 110-150 parts by weight of polycarbonate, modified PET, the modified rigid nano-filler, 6-15 parts by weight of chlorinated polyethylene, 5-12 parts by weight of a styrene/methyl methacrylate copolymer and 6-15 parts by weight of polybutyl acrylate into a twin-screw extruder, carrying out melt blending and molding. According to the modified polycarbonate, polycarbonate is modified through the modified PET and the modified rigid nano-filler. Thus, defects and insufficiencies of polycarbonate in aspects of toughness and shock resistance are effectively overcome, and the whole mechanical property of polycarbonate used as a scuttlebutt material is enhanced.
Description
Technical field
The invention discloses a kind of preparation method of Toughening Modification of Polycarbonate, belong to high polymer material technical field.
Background technology
Polycarbonate (being called for short PC), the features such as polycarbonate has water white transparency, heat-resisting, shock resistance, fire-retardant, all have good mechanical property in common use temperature.At present, three large Application Areass of PC engineering plastics are glazing, automotive industry and electronics, electrical equipment industry, secondly also have office equipment, medical treatment and health care, film, leisure and the protective equipments etc. such as industrial machinery part, CD, packaging, computer.
Wherein, PC prepares scuttlebutt, i.e. bottle blowing grade polycarbonate, is the another important application of polycarbonate.PC bucket is transparent, lightweight, impact-resistance is good, and resistance to certain high temperature and etchant solution washing, use as recoverable container.From 1999 so far, China puts into effect the quality standard of multi-section Regular application bucket, therein defining the use material of scuttlebutt, i.e. PC bucket.
PET, i.e. polyethylene terephthalate are high polymers, by ethylene glycol terephthalate generation dehydration condensation.PET is oyster white or polymkeric substance that is light yellow, highly crystalline, surface smoothing is glossy, in wide temperature range, have excellent physical and mechanical properties, life-time service temperature can reach 120 DEG C, and electrical insulating property is excellent, even under high-temperature high-frequency, its electrical property is still better, shortcoming but corona resistance is poor, creep resistance, resistance to fatigue, rub resistance, dimensional stability are all fine.
PET equally also Zeng Zuowei scuttlebutt uses, afterwards because PET bucket easily produces objectionable impurities when high temperature, react with in weakly acidic pure water, cause the reason of aqueous metamorphism or shortened shelf life, country cancels the material of PET as scuttlebutt gradually, now commercially, the most widely used is PC bucket, i.e. polycarbonate scuttlebutt.Although PC bucket has many advantages, it shows poor in shock strength and toughness properties, brings inconvenience to its use.And output is lower at home due to polycarbonate, relies on import in a large number, cause improving constantly of cost, limit the use of PC on the contrary.
In addition, along with the development of superpolymer field technology, PET, by modification, can reach the quality standard of scuttlebutt, and PET cost is lower.
CN104710749A discloses the patent documentation of one " the high impact modified PC/PET alloy of high strength ", its component by mass percent proportioning is: PC45% ~ 60%, PET15% ~ 30%, toughner 5% ~ 15%, alkali free glass fibre 5% ~ 10%, nano imvite 2% ~ 6%, compatilizer 2% ~ 5%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%, this alloy material is mainly used in the fields such as household electrical appliances, automobile, component of machine.Restrained by this technical scheme, by PET modification PC, to make PC, there is high strength and high-impact becomes a reality, but first, this scheme is not also suitable for scuttlebutt field, and because the content of PC is too low, other component concentrations are higher, certainly will affect the performance of PC itself, be secondly be unfavorable for prolonged and repeated use; 3rd, resistance to elevated temperatures is poor, uses, can produce toxin for a long time as scuttlebutt, the health of harm people health.
Summary of the invention
The object of the invention is to solve defect in toughness and shock resistance of scuttlebutt polycarbonate and deficiency, mainly by modified PET and modified rigid Nano filling, modification is carried out to polycarbonate and prepare modified polycarbonate.
Technical scheme: a kind of preparation method of Toughening Modification of Polycarbonate, comprises the steps:
The preparation of the 1st step, modified PET: by weight, get polyethylene terephthalate 10 ~ 15 parts, polybutylene terephthalate 2 ~ 5 parts, terephthalic acid 1.5 ~ 2.5 parts, 0.2 ~ 0.6 part, glass fibre, polyimide fiber 0.2 ~ 0.8 part, dioctyl phthalate (DOP) 0.5 ~ 1.2 part and ethylene-vinyl acetate copolymer 0.5 ~ 1.5 part and put into rheometer, after 220 ~ 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: by weight, get alumina powder jointed 2 ~ 5 parts, nano imvite 1.5 ~ 3.5 parts, beta-silicon nitride powder 0.5 ~ 1.0 part and white carbon black 1.5 ~ 2.5 parts put into mould, be placed in High Temperature Furnaces Heating Apparatus and carry out High Temperature High Pressure calcining, calcination time 2 ~ 5h, broken after cooling, put into nano-level grinder and be ground to median size 10 ~ 100nm, obtain modified rigid Nano filling;
3rd step, by weight, get polycarbonate 110 ~ 150 parts, modified PET, modified rigid Nano filling, chlorinatedpolyethylene 6 ~ 15 parts, styrene/methacrylic acid methyl terpolymer 5 ~ 12 parts and butyl polyacrylate 6 ~ 15 parts, put into twin screw extruder, melt blending aftershaping.
In described 1st step, ethylene-vinyl acetate copolymer is one or more in model EVA460, EVA550, EVA310 and EVA40W.
In described 2nd step, the temperature of High Temperature High Pressure calcining is 1380 ~ 1500 DEG C.
In described 2nd step, the pressure of High Temperature High Pressure calcining is 350 ~ 650MPa.
In described 2nd step, the median size of modified rigid Nano filling is 10 ~ 30nm.
beneficial effect
Modified polycarbonate provided by the invention carries out modification by PET and Nano filling to polycarbonate to obtain.For the performance of REINFORCED PET, first carry out modification to PET, modified PET has more preferably toughness; Modified nanoparticle and superpolymer compound, because nanoparticle surface is long-pending larger, there is certain toughness reinforcing performance in the base, also the toughness of polycarbonate matrix can be improved, therefore, with modified PET and modified rigid Nano filling, modification is carried out to PC, effectively overcome the defect of polycarbonate in toughness and shock resistance and deficiency, improve the mechanical property of polycarbonate as scuttlebutt material monolithic.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Polyethylene terephthalate (PET) model that the present invention adopts is RE5264PET, and Dupont is produced.
Polybutylene terephthalate (PBT) model that the present invention adopts is EC44G-30, and toray company produces.
The rheometer model that the present invention adopts is RM-200C mixing type torque rheometer, and Harbin Ha Pu electrical technology company limited produces.
The nano-level grinder model that the present invention adopts is MEANS/MSG-KM, and dynamo-electric production is executed in Shanghai inscription.
The styrene/methacrylic acid methyl terpolymer model that the present invention adopts is PM-600, the strange U.S. production in Taiwan.
The twin screw extruder model that the present invention adopts is SAT-95, and Nanjing Yue Sheng extrusion equipment company limited produces.
Embodiment 1
A preparation method for Toughening Modification of Polycarbonate, comprises the steps:
The preparation of the 1st step, modified PET: get polyethylene terephthalate 1Kg, polybutylene terephthalate 0.2Kg, terephthalic acid 0.15Kg, glass fibre 0.02Kg, polyimide fiber 0.02Kg, dioctyl phthalate (DOP) 0.05Kg and ethylene-vinyl acetate copolymer EVA4600.05Kg and put into rheometer, after 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: get alumina powder jointed 0.3Kg, nano imvite 0.25Kg, beta-silicon nitride powder 0.08Kg and white carbon black 0.21Kg and put into mould, be placed in High Temperature Furnaces Heating Apparatus to calcine, temperature 1450 DEG C, pressure 550MPa, calcination time 3h, broken after cooling, put into nano-level grinder and be ground to median size 100nm, obtain modified rigid Nano filling;
3rd step, get polycarbonate 12Kg part, modified rigid Nano filling, chlorinatedpolyethylene 1.2Kg, styrene/methacrylic acid methyl terpolymer 0.8Kg and butyl polyacrylate 1.1Kg that modified PET that the 1st step obtains, the 2nd step obtain, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Embodiment 2
A preparation method for Toughening Modification of Polycarbonate, comprises the steps:
The preparation of the 1st step, modified PET: get polyethylene terephthalate 1.5Kg, polybutylene terephthalate 0.5Kg, terephthalic acid 0.25Kg, glass fibre 0.06Kg, polyimide fiber 0.08Kg, dioctyl phthalate (DOP) 0.12Kg and ethylene-vinyl acetate copolymer EVA4600.15Kg and put into rheometer, after 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: get alumina powder jointed 0.3Kg, nano imvite 0.25Kg, beta-silicon nitride powder 0.08Kg and white carbon black 0.21Kg and put into mould, be placed in High Temperature Furnaces Heating Apparatus to calcine, temperature 1450 DEG C, pressure 550MPa, calcination time 3h, broken after cooling, put into nano-level grinder and be ground to median size 50nm, obtain modified rigid Nano filling;
3rd step, get polycarbonate 12Kg part, modified rigid Nano filling, chlorinatedpolyethylene 1.2Kg, styrene/methacrylic acid methyl terpolymer 0.8Kg and butyl polyacrylate 1.1Kg that modified PET that the 1st step obtains, the 2nd step obtain, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Embodiment 3
A preparation method for Toughening Modification of Polycarbonate, comprises the steps:
The preparation of the 1st step, modified PET: get polyethylene terephthalate 1.3Kg, polybutylene terephthalate 0.4Kg, terephthalic acid 0.22Kg, glass fibre 0.05Kg, polyimide fiber 0.06Kg, dioctyl phthalate (DOP) 0.09Kg and ethylene-vinyl acetate copolymer EVA3100.12Kg and put into rheometer, after 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: get alumina powder jointed 0.4Kg, nano imvite 0.28Kg, beta-silicon nitride powder 0.08Kg and white carbon black 0.22Kg and put into mould, be placed in High Temperature Furnaces Heating Apparatus to calcine, temperature 1450 DEG C, pressure 550MPa, calcination time 3h, broken after cooling, put into nano-level grinder and be ground to median size 30nm, obtain modified rigid Nano filling;
3rd step, get polycarbonate 11Kg, modified rigid Nano filling, chlorinatedpolyethylene 0.6Kg, styrene/methacrylic acid methyl terpolymer 0.5Kg and butyl polyacrylate 0.6Kg that modified PET that the 1st step obtains, the 2nd step obtain, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Embodiment 4
The preparation of the 1st step, modified PET: get polyethylene terephthalate 1.3Kg, polybutylene terephthalate 0.4Kg, terephthalic acid 0.22Kg, glass fibre 0.05Kg, polyimide fiber 0.06Kg, dioctyl phthalate (DOP) 0.09Kg and ethylene-vinyl acetate copolymer EVA3100.12Kg and put into rheometer, after 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: get alumina powder jointed 0.4Kg, nano imvite 0.28Kg, beta-silicon nitride powder 0.08Kg and white carbon black 0.22Kg and put into mould, be placed in High Temperature Furnaces Heating Apparatus to calcine, temperature 1450 DEG C, pressure 550MPa, calcination time 3h, broken after cooling, put into nano-level grinder and be ground to median size 30nm, obtain modified rigid Nano filling;
3rd step, get polycarbonate 15Kg, modified rigid Nano filling, chlorinatedpolyethylene 1.5Kg, styrene/methacrylic acid methyl terpolymer 1.2Kg and butyl polyacrylate 1.5Kg that modified PET that the 1st step obtains, the 2nd step obtain, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Embodiment 5
A preparation method for Toughening Modification of Polycarbonate, comprises the steps:
The preparation of the 1st step, modified PET: get polyethylene terephthalate 1.2Kg, polybutylene terephthalate 0.4Kg, terephthalic acid 0.22Kg, glass fibre 0.05Kg, polyimide fiber 0.06Kg, dioctyl phthalate (DOP) 0.09Kg and ethylene-vinyl acetate copolymer EVA3100.12Kg and put into rheometer, after 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: get alumina powder jointed 0.4Kg, nano imvite 0.3Kg, beta-silicon nitride powder 0.08Kg and white carbon black 0.2Kg and put into mould, be placed in High Temperature Furnaces Heating Apparatus to calcine, temperature 1450 DEG C, pressure 550MPa, calcination time 3h, broken after cooling, put into nano-level grinder and be ground to median size 30nm, obtain modified rigid Nano filling;
3rd step, get polycarbonate 13Kg part, modified rigid Nano filling, chlorinatedpolyethylene 1.2Kg, styrene/methacrylic acid methyl terpolymer 0.8Kg and butyl polyacrylate 1.2Kg that modified PET that the 1st step obtains, the 2nd step obtain, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Reference examples 1
Be with the difference of embodiment 5: the PET not adding modification.
The preparation of the 1st step, modified rigid Nano filling: get alumina powder jointed 0.4Kg, nano imvite 0.3Kg, beta-silicon nitride powder 0.08Kg and white carbon black 0.2Kg and put into mould, be placed in High Temperature Furnaces Heating Apparatus to calcine, temperature 1450 DEG C, pressure 550MPa, calcination time 3h, broken after cooling, put into nano-level grinder and be ground to median size 30nm, obtain modified rigid Nano filling;
2nd step, get polycarbonate 13Kg part, modified rigid Nano filling, chlorinatedpolyethylene 1.2Kg, styrene/methacrylic acid methyl terpolymer 0.8Kg and butyl polyacrylate 1.2Kg that the 1st step obtains, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Reference examples 2
Be with the difference of embodiment 5: do not add modified rigid Nano filling.
The preparation of the 1st step, modified PET: get polyethylene terephthalate 1.2Kg, polybutylene terephthalate 0.4Kg, terephthalic acid 0.22Kg, glass fibre 0.05Kg, polyimide fiber 0.06Kg, dioctyl phthalate (DOP) 0.09Kg and ethylene-vinyl acetate copolymer EVA3100.12Kg and put into rheometer, after 230 DEG C of melt blendings, cooling, obtains modified PET;
2nd step, get polycarbonate 13Kg part, modified PET, chlorinatedpolyethylene 1.2Kg, styrene/methacrylic acid methyl terpolymer 0.8Kg and butyl polyacrylate 1.2Kg that the 1st step obtains, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
Reference examples 3
Be with the difference of embodiment 5: PET is unmodified directly adds the 3rd step, does not add modified rigid Nano filling.
2nd step, get polycarbonate 13Kg part, styrene/methacrylic acid methyl terpolymer 0.8Kg and butyl polyacrylate 1.2Kg, put into twin screw extruder, extrusion moulding after melt blending, the thick PC plate of preparation 1mm;
In whole moulding process: forcing machine Heating temperature is 280 DEG C, head temperature 270 DEG C, machine head port mould temperature 270 DEG C, molding cycle time 30s, post-processing temperature 130 DEG C, time 30min, finally cools, traction, cutting.
PC bucket above-described embodiment and reference examples prepared, carries out performance test:
First, detect the fundamental property index of each PC sheet material, result is as shown in table 1:
Table 1 embodiment 1 ~ 5 and reference examples 1 ~ 3PC plate fundamental property data
As seen from the above table, embodiment 1 ~ 5 and the performance gap of reference examples 1 ~ 3 on flame retardant properties, water-intake rate and molding shrinkage little, and in heat-drawn wire, improved by the PC plate thermal transition temperature after modified PET and the process of modified rigid Nano filling, use range is wider.
Carry out mechanical test according to ASTMD associated test standards to the PC sheet material that embodiment 1 ~ 5 and reference examples 1 ~ 3 obtain, result is as shown in table 2:
Table 2 embodiment 1 ~ 5 and reference examples 1 ~ 3PC plate data of mechanical
Tensile strength/MPa | Elongation at break/% | Flexural strength/MPa | Bending elastic modulus/GPa | Notched Izod impact strength (KJ/m 2) | Brinell hardness | |
Embodiment 1 | 92 | 145 | 137 | 5.3 | 98 | 182 |
Embodiment 2 | 93 | 143 | 134 | 5.5 | 102 | 183 |
Embodiment 3 | 95 | 142 | 135 | 5.3 | 99 | 179 |
Embodiment 4 | 93 | 144 | 137 | 5.4 | 102 | 183 |
Embodiment 5 | 96 | 146 | 138 | 5.8 | 105 | 187 |
Reference examples 1 | 81 | 135 | 127 | 4.5 | 88 | 165 |
Reference examples 2 | 82 | 136 | 125 | 4.7 | 92 | 161 |
Reference examples 3 | 72 | 131 | 106 | 4.2 | 71 | 153 |
As seen from the above table, the PC plate of embodiment 1 ~ 5, after modified PET and modified rigid Nano filling carry out modification to polycarbonate, the mechanical property of PC slab integral gets a promotion, and wherein, elongation at break, perfect elasticity modulus, notched Izod impact strength obtain significant lifting, show, polycarbonate, after modification, enhances its toughness properties, solves the technical problem of the poor toughness that PC exists in prior art.
Claims (5)
1. a preparation method for Toughening Modification of Polycarbonate, is characterized in that, comprises the steps:
The preparation of the 1st step, modified PET: by weight, get polyethylene terephthalate 10 ~ 15 parts, polybutylene terephthalate 2 ~ 5 parts, terephthalic acid 1.5 ~ 2.5 parts, 0.2 ~ 0.6 part, glass fibre, polyimide fiber 0.2 ~ 0.8 part, dioctyl phthalate (DOP) 0.5 ~ 1.2 part and ethylene-vinyl acetate copolymer 0.5 ~ 1.5 part and put into rheometer, after 220 ~ 230 DEG C of melt blendings, cooling, obtains modified PET;
The preparation of the 2nd step, modified rigid Nano filling: by weight, get alumina powder jointed 2 ~ 5 parts, nano imvite 1.5 ~ 3.5 parts, beta-silicon nitride powder 0.5 ~ 1.0 part and white carbon black 1.5 ~ 2.5 parts put into mould, be placed in High Temperature Furnaces Heating Apparatus and carry out High Temperature High Pressure calcining, calcination time 2 ~ 5h, broken after cooling, put into nano-level grinder and be ground to median size 10 ~ 100nm, obtain modified rigid Nano filling;
3rd step, by weight, get polycarbonate 110 ~ 150 parts, modified PET, modified rigid Nano filling, chlorinatedpolyethylene 6 ~ 15 parts, styrene/methacrylic acid methyl terpolymer 5 ~ 12 parts and butyl polyacrylate 6 ~ 15 parts, put into twin screw extruder, melt blending aftershaping.
2. the preparation method of Toughening Modification of Polycarbonate according to claim 1, is characterized in that: in described 1st step, ethylene-vinyl acetate copolymer is one or more in model EVA460, EVA550, EVA310 and EVA40W.
3. the preparation method of Toughening Modification of Polycarbonate according to claim 1, is characterized in that: in described 2nd step, and the temperature of High Temperature High Pressure calcining is 1380 ~ 1500 DEG C.
4. the preparation method of Toughening Modification of Polycarbonate according to claim 1, is characterized in that: in described 2nd step, and the pressure of High Temperature High Pressure calcining is 350 ~ 650MPa.
5. the preparation method of Toughening Modification of Polycarbonate according to claim 1, is characterized in that: in described 2nd step, and the median size of modified rigid Nano filling is 10 ~ 30nm.
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Cited By (5)
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CN105670431A (en) * | 2016-03-09 | 2016-06-15 | 刘平 | Preparation method of weather-resistant anticorrosive paint for municipal sewage pipelines |
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CN109836795A (en) * | 2019-02-01 | 2019-06-04 | 华政炎 | One kind is from capacity increasing modifying PET/PC alloy and preparation method thereof |
CN111087769A (en) * | 2019-12-30 | 2020-05-01 | 张成美 | Polyester engineering plastic and preparation method thereof |
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