CN101857716A - Polycarbonate/polyethylene terephthalate resin composition and preparation method - Google Patents
Polycarbonate/polyethylene terephthalate resin composition and preparation method Download PDFInfo
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Abstract
The invention relates to a polycarbonate/polyethylene terephthalate resin composition and a preparation method, the composition comprises the following components by weight percent (wt%): 60-75% of waste polycarbonate resin (PC), 20-30% of waste polyethylene terephthalate (PET), 4-15% of impact modifier, 0.5-1.5% of chain extender and 0.1-1.5% of processing aids, the chain extender is used for carrying out chain extension and granulation on the waste PC and the waste PET, then the PC and the PET after the chain extension, the impact modifier and the processing aids are pre-mixed in a high-speed mixer and then melted and extruded through a twin-screw extruder, and cooling and granulation are finally carried out for obtaining a product. The preparation process is reasonable, the chain extension is carried out on the waste PC material and the waste PET material, and then the alloying technology is further used for modification, thereby having excellent performances and simultaneously having short production cycle and low cost; furthermore, the whole process is more environment-friendly and has better economic benefits and social benefits.
Description
Technical field
The present invention relates to a kind of macromolecule resin composition and preparation method, especially relate to a kind of polycarbonate/pet resin composition and preparation method.
Background technology
PET (polyethylene terephthalate) resin is widely used for producing PET bottle, PET film etc.Along with the human living standard improves, use these PET bottles, PET film in a large number and after use, go out of use, thereby cause serious environmental to pollute.From the energy-saving and environmental protection angle, developed countries such as America and Europe recycle for the PET resin and have carried out many research and development, also begin this respect research and development domestic recent years.The recoverying and utilizing method of PET is a lot, and 1) by methods such as alcoholysis, hydrolysis, acidolysis the pet waste resin is cracked into low molecular compound, as polymer raw, spinning or uses such as production hot melt adhesive, coating and unsaturated polyester resin.2) directly use adding in the virgin material after the direct pulverizing of pet waste resin.3) the pet waste resin is pulverized, strengthened by simple chain extension then and carry out modification and prepare some low value-added products, describe as CN1887958A and uses recovery PET to prepare the PET fireproof reinforced composite material by chain extension, fire-retardant, enhancing modified as matrix.4) thus purify to use by selective dissolution, describe as US436078 waste material resins such as PET bottle carried out the selective dissolution Separation and Recovery by solvent, mixes the raising molecular weight again with virgin material and uses as raw material.
PC (polycarbonate) resin is widely used for producing PC scuttlebutt, PC sunlight board, PC CD etc., is easy to cause serious environmental to pollute too after discarding.From the energy-saving and environmental protection angle, developed countries such as America and Europe recycle for the PC resin equally and have carried out many research and development, also begin this respect research and development domestic recent years.The recoverying and utilizing method of PC is also a lot: 1) by methods such as alcoholysis, hydrolysis, acidolysis PC waste material resin is cracked into low molecular compound or monomer, as uses such as polymer raws, describes a kind of with aromatic copolycarbonate cracked method as WO03/035592.2) directly use adding in the virgin material after the direct pulverizing of PC waste material resin.3) PC waste material resin is pulverized, carried out modification by simple chain extension enhancing then and prepare some low value-added products.4) thus purify to use by selective dissolution, describe to purify obtaining reclaiming PC, directly use by selective dissolution as CN1233625A.
From more top schemes as can be seen, 1) can make material more pure by cracked methods such as alcoholysis, hydrolysis, acidolysis, but exist cost to have high input, a large amount of dischargings of solvent the like waste that produce in cracking process still can serious environment pollution, and economic benefit is not high; 2) use by directly pulverizing, relatively environmental protection, but material property can not well be guaranteed, and influences the later stage use, can only be used for low-end product, and economic benefit is not good; 3) exist product performance general equally by simple modification such as pulverizing, chain extension enhancing, can only be used for some low side fields, added value is low.4) selective dissolution is purified, and this scheme exists waste to discharge in a large number equally, and has the certain molecular weight reduction in purification process, thereby influences its later stage use.
The present invention mainly is by respectively waste and old PC material, waste PET material being carried out chain extension, then these two kinds of waste and old material are carried out modification by alloying process, thereby obtain a kind of PC/PET recycled material that can be used for the mechanical property and the processing characteristics excellence in fields such as trolley part, household electrical appliance, the present invention its when having excellent properties its production cycle and cost lower, the more environmental protection and have better economic benefit and social benefit of whole process.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of preparation technology rationally, production cycle and lower polycarbonate/pet resin composition and the preparation method of cost.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of polycarbonate/pet resin composition is characterized in that, said composition comprises following component and content (wt%):
Waste and old polycarbonate resin (PC) 60-75;
Waste and old polyethylene terephthalate (PET) 20-30;
Impact modifying agent 4-15;
Chainextender 0.5-1.5;
Processing aid 0.1-1.5.
Described waste and old polycarbonate resin derives from the consumption market, comprises PC scuttlebutt, PC sheet material or the PC CD of recovery, needs through thorough cleaning broken.
Described waste and old pet resin derives from the consumption market, comprises the PET bottle embryo of recovery, needs through thorough cleaning broken.
Described impact modifying agent is selected from one or more among ABS, MBS, body ABS, ACR, ASA or the AES, preferred ACR impact modifying agent.
Described chainextender is for containing the polymkeric substance of glycidyl methacrylate (GMA).
The described polymkeric substance that contains glycidyl methacrylate (GMA) is the terpolymer that aromatic vinyl monomer, acrylic monomer and glycidyl methacrylate (GMA) copolymerization form.
Described processing aid is selected from one or more in lubricant, oxidation inhibitor, ester exchange inhibitor, releasing agent or the tinting material.
Described lubricant comprises pentaerythritol stearate or polyethylene wax, described oxidation inhibitor comprises phosphite ester kind antioxidant or Hinered phenols antioxidant, described ester exchange inhibitor comprises phosphite ester compound, described releasing agent comprises silicone powder releasing agent, and described tinting material comprises carbon black, Fe
2O
3Red or TiO
2
A kind of polycarbonate/pet resin preparation of compositions method is characterized in that this method may further comprise the steps:
(1) prepare raw material according to following component and content (wt%):
Waste and old polycarbonate resin (PC) 60-75,
Waste and old polyethylene terephthalate (PET) 20-30,
Impact modifying agent 4-15,
Chainextender 0.5-1.5,
Processing aid 0.1-1.5;
(2) use chainextender that waste and old polycarbonate (PC), waste and old ethylene glycol terephthalate (PET) are carried out the chain extension granulation, then with the PC behind the chain extension, PET and impact modifying agent and processing aid by proportioning premix 3-10min in super mixer, twin screw extruder is passed through in the Preblend that obtains, melt extrude under 230-300 ℃, last cooling granulation obtains polycarbonate/pet resin composition.
Compared with prior art, preparation technology of the present invention is reasonable, by respectively waste and old PC material, waste PET material being carried out chain extension, carry out modification with alloying process again, thereby obtain a kind of PC/PET recycled material that can be used for the mechanical property and the processing characteristics excellence in fields such as trolley part, household electrical appliance, the present invention its when having excellent properties its production cycle and cost lower, the more environmental protection and have better economic benefit and social benefit of whole process.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1-4
A kind of polycarbonate/pet resin preparation of compositions method, this method may further comprise the steps:
(1) material is formed
Component A: waste and old polycarbonate (PC), from PC scuttlebutt and the PC sheet material that reclaim the consumption market, broken after thoroughly cleaning;
B component: waste and old polyethylene terephthalate (PET), from the PET bottle that reclaim the consumption market, broken after thoroughly cleaning;
Component C: impact modifying agent EXL2691A, from Rohmhaas;
Component D: chainextender SAN-g-GMA, wherein GMA content is 5%, molecular weight is 50000, self-control;
Component E: processing aid comprises lubricant pentaerythritol stearate (PETS), phosphite ester kind antioxidant IRGAFOS
168, hindered phenol IRGANOX245, triphenyl phosphite (TPP-i) and silicone releasing agent DOW CORNING MB-50, its weight ratio is 2: 2: 2: 1: 1, each components contents was as shown in table 1.
(2) use chainextender that waste and old polycarbonate (PC), waste and old ethylene glycol terephthalate (PET) are carried out the chain extension granulation, then with the PC behind the chain extension, PET and impact modifying agent and processing aid by proportioning premix 5min in super mixer, twin screw extruder is passed through in the Preblend that obtains, melt extrude under 270 ℃, last cooling granulation obtains polycarbonate/pet resin composition.
Comparative Examples 1-2
(1) material is formed
Component A: waste and old polycarbonate (PC), from PC scuttlebutt and the PC sheet material that reclaim the consumption market, broken after thoroughly cleaning;
B component: waste and old polyethylene terephthalate (PET), from the PET bottle that reclaim the consumption market, broken after thoroughly cleaning;
Component C: impact modifying agent EXL2691A, from Rohmhaas; Each components contents is as shown in table 1.
(2) use chainextender that waste and old polycarbonate (PC), waste and old ethylene glycol terephthalate (PET) are carried out the chain extension granulation, then with the PC behind the chain extension, PET and impact modifying agent and processing aid by proportioning premix 5min in super mixer, twin screw extruder is passed through in the Preblend that obtains, melt extrude under 270 ℃, last cooling granulation obtains contrast material.
Table 1
| Component (kg) | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Component A | ?60 | ?60 | ??60 | ??75 | ??65 | ??60 |
| B component | ?40 | ?30 | ??30 | ??20 | ??25 | ??25 |
| Component (kg) | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Component C | ?/ | ?10 | ??10 | ??5 | ??10 | ??15 |
| Component D | ?/ | ?/ | ??1.0 | ??1.0 | ??1.5 | ??0.5 |
| Component E | ?/ | ?/ | ??1.0 | ??1.0 | ??1.0 | ??1.0 |
Performance test
Use a sea day injection moulding machine to inject all kinds of test bars and colour table.
Elongation test: according to the ISO527 standard testing, draw speed is 50mm/min;
Flexural strength and modulus in flexure: according to ISO178 standard testing, speed 2mm/min, span 64mm;
The Izod shock strength: according to the ISO180 standard testing, 23 ℃;
The Vicat softening temperature: according to the ISO306 standard testing, 5Kg, 50 ℃/h.
MFR: according to ISO1183 test, 260 ℃, 5Kg.
The test result of embodiment and Comparative Examples products obtained therefrom is as shown in table 2.
Table 2
| Test event | Comparative Examples 1 | Comparative Examples 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Tensile strength (Mpa) | ??60.4 | ??55.2 | ??58.5 | ??65.7 | ??60.2 | ??56.5 |
| Modulus in flexure (Mpa) | ??1916 | ??1884 | ??2041 | ??2315 | ??2110 | ??1989 |
| Izod shock strength (KJ/m2) | ??16.1 | ??25.3 | ??45.6 | ??51.0 | ??52.1 | ??55.6 |
| The Vicat softening temperature (℃) | ??119.5 | ??116.4 | ??124.4 | ??134.0 | ??130.9 | ??122.8 |
| ??MFR(g/10min) | ??105.6 | ??95.3 | ??41.0 | ??22.1 | ??33.2 | ??45.2 |
From a series of correlation datas of Comparative Examples and embodiment as can be seen, by waste and old PC, waste PET are carried out chain extension, then by after the alloying process modification, material MFR is more stable, the degraded of waste and old PC, PET is controlled in explanation well by the utilization of above technology, and suitably improve the molecular weight of material by chain extension, and thereby all being had, the performances such as heat-resisting, impact of PC/PET alloy improve significantly, can be used as high performance material and be applied to fields such as automobile, household electrical appliances.
Embodiment 5
A kind of polycarbonate/pet resin preparation of compositions method, this method may further comprise the steps:
(1) prepares raw material according to following component and content: waste and old polycarbonate resin (PC) 60kg, waste and old polyethylene terephthalate (PET) 30kg, impact modifying agent 4kg, chainextender 0.5kg, processing aid 0.1kg, wherein waste and old polycarbonate resin derives from the consumption market, be the PC scuttlebutt that reclaims, and it is broken through thoroughly cleaning, waste and old pet resin derives from the consumption market, for PET film and the warp that reclaims thoroughly cleans broken, impact modifying agent is body ABS, chainextender is an aromatic vinyl monomer, the terpolymer that acrylic monomer and glycidyl methacrylate (GMA) copolymerization forms, processing aid is lubricant pentaerythritol stearate and oxidation inhibitor 168, and weight ratio is 1: 2;
(2) use chainextender that waste and old polycarbonate (PC), waste and old ethylene glycol terephthalate (PET) are carried out the chain extension granulation, then with the PC behind the chain extension, PET and impact modifying agent and processing aid by proportioning premix 3min in super mixer, twin screw extruder is passed through in the Preblend that obtains, melt extrude under 300 ℃, last cooling granulation obtains polycarbonate/pet resin composition.
Embodiment 6
A kind of polycarbonate/pet resin preparation of compositions method, this method may further comprise the steps:
(1) prepares raw material according to following component and content: waste and old polycarbonate resin (PC) 75kg, waste and old polyethylene terephthalate (PET) 20kg, impact modifying agent 15kg, chainextender 1.5kg, processing aid 1.5kg, wherein waste and old polycarbonate resin derives from the consumption market, be the PC scuttlebutt that reclaims, and it is broken through thoroughly cleaning, waste and old pet resin derives from the consumption market, for PET film and the warp that reclaims thoroughly cleans broken, impact modifying agent is ACR, ASA, weight ratio is 1: 1, chainextender is an aromatic vinyl monomer, the terpolymer that acrylic monomer and glycidyl methacrylate (GMA) copolymerization forms, processing aid is the ester exchange inhibitor phosphorous acid ester, releasing agent silicone powder and tinting material Fe
2O
3Red, weight ratio is 1: 2: 1;
(2) use chainextender that waste and old polycarbonate (PC), waste and old ethylene glycol terephthalate (PET) are carried out the chain extension granulation, then with the PC behind the chain extension, PET and impact modifying agent and processing aid by proportioning premix 10min in super mixer, twin screw extruder is passed through in the Preblend that obtains, melt extrude under 230 ℃, last cooling granulation obtains polycarbonate/pet resin composition.
Claims (9)
1. polycarbonate/pet resin composition is characterized in that, said composition comprises following component and content (wt%):
Waste and old polycarbonate resin (PC) 60-75;
Waste and old polyethylene terephthalate (PET) 20-30;
Impact modifying agent 4-15;
Chainextender 0.5-1.5;
Processing aid 0.1-1.5.
2. a kind of polycarbonate according to claim 1/pet resin composition, it is characterized in that, described waste and old polycarbonate resin derives from the consumption market, comprises PC scuttlebutt, PC sheet material or the PC CD of recovery, needs through thorough cleaning broken.
3. a kind of polycarbonate according to claim 1/pet resin composition, it is characterized in that, described waste and old pet resin derives from the consumption market, comprises the PET bottle embryo of recovery, needs through thorough cleaning broken.
4. a kind of polycarbonate according to claim 1/pet resin composition, it is characterized in that, described impact modifying agent is selected from one or more among ABS, MBS, body ABS, ACR, ASA or the AES, preferred ACR impact modifying agent.
5. a kind of polycarbonate according to claim 1/pet resin composition is characterized in that, described chainextender is for containing the polymkeric substance of glycidyl methacrylate (GMA).
6. a kind of polycarbonate according to claim 5/pet resin composition, it is characterized in that the described polymkeric substance that contains glycidyl methacrylate (GMA) is the terpolymer that aromatic vinyl monomer, acrylic monomer and glycidyl methacrylate (GMA) copolymerization form.
7. a kind of polycarbonate according to claim 1/pet resin composition is characterized in that described processing aid is selected from one or more in lubricant, oxidation inhibitor, ester exchange inhibitor, releasing agent or the tinting material.
8. a kind of polycarbonate according to claim 7/pet resin composition, it is characterized in that, described lubricant comprises pentaerythritol stearate or polyethylene wax, described oxidation inhibitor comprises phosphite ester kind antioxidant or Hinered phenols antioxidant, described ester exchange inhibitor comprises phosphite ester compound, described releasing agent comprises silicone powder releasing agent, and described tinting material comprises carbon black, Fe
2O
3Red or TiO
2
9. polycarbonate/pet resin preparation of compositions method is characterized in that this method may further comprise the steps:
(1) prepare raw material according to following component and content (wt%):
Waste and old polycarbonate resin (PC) 60-75,
Waste and old polyethylene terephthalate (PET) 20-30,
Impact modifying agent 4-15,
Chainextender 0.5-1.5,
Processing aid 0.1-1.5;
(2) use chainextender that waste and old polycarbonate (PC), waste and old ethylene glycol terephthalate (PET) are carried out the chain extension granulation, then with the PC behind the chain extension, PET and impact modifying agent and processing aid by proportioning premix 3-10min in super mixer, twin screw extruder is passed through in the Preblend that obtains, melt extrude under 230-300 ℃, last cooling granulation obtains polycarbonate/pet resin composition.
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| CN 201010121459 CN101857716A (en) | 2010-03-10 | 2010-03-10 | Polycarbonate/polyethylene terephthalate resin composition and preparation method |
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| CN102432988A (en) * | 2011-10-31 | 2012-05-02 | 东莞劲胜精密组件股份有限公司 | Method for preparing polycarbonate (PC) regrind material through recovering and modifying |
| CN102604352A (en) * | 2012-01-18 | 2012-07-25 | 上海锦湖日丽塑料有限公司 | Recycled PC (Polycarbonate) and recycled PET (polyethylene terephthalate)-containing halogen-free flame retardant resin composition and preparation method thereof |
| CN103131138A (en) * | 2011-11-23 | 2013-06-05 | 合肥杰事杰新材料股份有限公司 | Thermoplastic polyester composition and preparation method thereof |
| CN103214808A (en) * | 2012-01-18 | 2013-07-24 | 柯尼卡美能达商用科技株式会社 | Copier or printer external part using halogen-free flame-retardant resin composition containing regenerated PC and regenerated PET |
| CN104559115A (en) * | 2014-12-31 | 2015-04-29 | 上海锦湖日丽塑料有限公司 | PC/PET halogen-free flame retarding alloy containing regenerative resin, and preparation method of PC/PET halogen-free flame retarding alloy |
| CN104559110A (en) * | 2014-12-29 | 2015-04-29 | 浙江俊尔新材料股份有限公司 | PC/PET (polycarbonate/polyethylene terephthalate) alloy material and preparation method thereof |
| CN104877323A (en) * | 2014-02-28 | 2015-09-02 | 汉达精密电子(昆山)有限公司 | Recovered PC/recovered PET composite material and product thereof |
| CN105176045A (en) * | 2015-10-27 | 2015-12-23 | 上海锦湖日丽塑料有限公司 | PC-PA alloy material with outstanding heat resisting stability and preparation method thereof |
| CN107446337A (en) * | 2017-09-30 | 2017-12-08 | 界首市远航织带有限公司 | A kind of method of modifying of waste and old polycarbonate plastic |
| CN111978686A (en) * | 2020-08-25 | 2020-11-24 | 广州大学 | Regenerated polyester material and preparation method thereof |
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| CN102432988A (en) * | 2011-10-31 | 2012-05-02 | 东莞劲胜精密组件股份有限公司 | Method for preparing polycarbonate (PC) regrind material through recovering and modifying |
| CN103131138A (en) * | 2011-11-23 | 2013-06-05 | 合肥杰事杰新材料股份有限公司 | Thermoplastic polyester composition and preparation method thereof |
| CN103131138B (en) * | 2011-11-23 | 2016-05-11 | 合肥杰事杰新材料股份有限公司 | A kind of thermoplastic polyester composition and preparation method thereof |
| CN102604352B (en) * | 2012-01-18 | 2016-05-18 | 上海锦湖日丽塑料有限公司 | Containing regeneration PC and regenerative PET halogen-free fire-proof resin composition and preparation method |
| CN102604352A (en) * | 2012-01-18 | 2012-07-25 | 上海锦湖日丽塑料有限公司 | Recycled PC (Polycarbonate) and recycled PET (polyethylene terephthalate)-containing halogen-free flame retardant resin composition and preparation method thereof |
| CN103214808A (en) * | 2012-01-18 | 2013-07-24 | 柯尼卡美能达商用科技株式会社 | Copier or printer external part using halogen-free flame-retardant resin composition containing regenerated PC and regenerated PET |
| EP2617767A1 (en) * | 2012-01-18 | 2013-07-24 | Konica Minolta Business Technologies, Inc. | Copier/printer exerior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
| JP2013147651A (en) * | 2012-01-18 | 2013-08-01 | Konica Minolta Business Technologies Inc | Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
| CN103214808B (en) * | 2012-01-18 | 2016-12-14 | 柯尼卡美能达商用科技株式会社 | Use containing regenerating PC and the photocopier of regenerative PET halogen-free fire-proof resin composition or the exterior member of printer |
| CN104877323A (en) * | 2014-02-28 | 2015-09-02 | 汉达精密电子(昆山)有限公司 | Recovered PC/recovered PET composite material and product thereof |
| CN104559110A (en) * | 2014-12-29 | 2015-04-29 | 浙江俊尔新材料股份有限公司 | PC/PET (polycarbonate/polyethylene terephthalate) alloy material and preparation method thereof |
| CN104559115A (en) * | 2014-12-31 | 2015-04-29 | 上海锦湖日丽塑料有限公司 | PC/PET halogen-free flame retarding alloy containing regenerative resin, and preparation method of PC/PET halogen-free flame retarding alloy |
| CN105176045A (en) * | 2015-10-27 | 2015-12-23 | 上海锦湖日丽塑料有限公司 | PC-PA alloy material with outstanding heat resisting stability and preparation method thereof |
| CN107446337A (en) * | 2017-09-30 | 2017-12-08 | 界首市远航织带有限公司 | A kind of method of modifying of waste and old polycarbonate plastic |
| CN111978686A (en) * | 2020-08-25 | 2020-11-24 | 广州大学 | Regenerated polyester material and preparation method thereof |
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Application publication date: 20101013 |