CN101265351B - Thermoplastic elastomer resin and its preparing and forming method - Google Patents

Thermoplastic elastomer resin and its preparing and forming method Download PDF

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Publication number
CN101265351B
CN101265351B CN2008100255096A CN200810025509A CN101265351B CN 101265351 B CN101265351 B CN 101265351B CN 2008100255096 A CN2008100255096 A CN 2008100255096A CN 200810025509 A CN200810025509 A CN 200810025509A CN 101265351 B CN101265351 B CN 101265351B
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Prior art keywords
thermoplastic elastomer
elastomer resin
speed
stirring
temperature
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Expired - Fee Related
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CN2008100255096A
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Chinese (zh)
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CN101265351A (en
Inventor
李茁实
张学全
龚宜彤
马晶
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JIANGSU QIONGHUA HIGH SCIENCE AND TECHNOLOGY Co Ltd
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JIANGSU QIONGHUA HIGH SCIENCE AND TECHNOLOGY Co Ltd
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Abstract

The invention provides a thermoplastic elastomer resin, and a preparation and forming method thereof. The invention relates to a preparation and forming process of the thermoplastic elastomer resin for special purpose of the coating of a toothbrush holder. Hydrogenated styrene-butadiene-styrene block copolymer, polypropylene, accessory additive, an inorganic filler and white oil are mixed at high speed, and are extruded and pelleted, dried, wind cooled, and are deposited in a bunker for more than one hour. Finally, the mixture are packaged and formed. The thermoplastic elastomer resin for special purpose of injection molding of the coating of the toothbrush holder can completely substitute for the imported elastomer product in the prior market, has no toxicity and no pollution, and can be recycled with high process versatility and low cost.

Description

A kind of thermoplastic elastomer resin and preparation thereof, forming method
Technical field
The present invention relates to preparation and product forming process that a kind of handle coats the special-purpose thermoplastic elastomer resin of material.
Background technology
Thermoplastic elastomer (TPE) can be summarized as general TPE and two types of engineering TPE, and oneself develops into more than 30 kind of 10 big classes at present.Find polyurethanes TPE the earliest from German Bayer in 1938,1963 and nineteen sixty-five U.S. Phillips and Shell, develop styrene-butadiene-styrene block polymer TPE, since various countries begin to produce in batches olefines TPE to the USA and Europe day seventies, technology is constantly brought forth new ideas, new TPE kind continues to bring out, and has constituted the huge system of current TPE, makes rubber industry combine marriage with plastics industry and has striden forward a step greatly.Over nearest more than 30 years, thermoplastic elastomer has been obtained very swift and violent development as third generation rubber all over the world.Now, the output of thermoplastic elastomer is gone beyond the fluid rubber of the s-generation already, becomes the another type material of current rubber industry.
The TPE of suitability for industrialized production has in the world: styrenic (SBS, SIS, SEBS, SEPS), olefines (TPO, TPV), diene class (TPB, TPI), polyvinyl chloride-base (TPVC, TCPE), ammonia ester class (TPU), ester class (TPEE), amides (TPAE), organic fluorine class (TPF), silicone based and vinyl etc., almost contained all areas of present synthetic rubber and synthetic resins.Now, TPE is the center with TPS and TPO, has obtained all over the world to develop rapidly, and both product consumptions have accounted for about 80% of whole TPE.Diene class TPE and polyvinyl chloride-base TPE also become the important kind of general TPE.Other has then turned to based on engineering as TPU, TPEE, TPAE, TPF etc.
The country of world TPS production capacity maximum is the U.S., and its production technology is also gathered around by states such as France, Germany, Italy, Belgium, Spain, Japan, Australia in addition, and the Taiwan of China also possesses certain throughput.China is the maximum country of consumption of world TPS, is the center since 1980 with SBS, is accompanied by developing rapidly of China's shoe industry, construction industry, to TPS need be with average annual speed increment more than 12%.Along with TPS class elastomerics range of application enlarges gradually, TPS class elastomerics has been widely used in fields such as daily necessities, footwear material, toy, wrapping material, medical device, sports equipment, automotive material.Along with the fast development of TPS analog thermoplastic elastomer, elastomerics coating material demand is very big, and is badly in need of adopting homemade material to replace expensive elasticity of import body material.
Summary of the invention
The present invention's first purpose provides a kind of novel toothbrush handle and coats the special-purpose thermoplastic elastomer resin of material.
The present invention is become to be grouped into by following weight percent: hydrogenated polystyrene-butadiene-styrene triblock copolymer (SEBS) 15.4%~36.9%, white oil 22.2~63.7%, polypropylene (PP) 3.2%~16.6%, mineral filler 10%~47.5% and interpolation auxiliary agent 0.12%~0.3%.
Hydrogenated polystyrene among the present invention-butadiene-styrene triblock copolymer (SEBS), white oil, polypropylene (PP), lime carbonate and interpolation auxiliary agent all can use the raw material of the homemade trade mark, have substituted expensive import material, greatly reduce cost; Trial state feedback through breadboard detection sign and downstream producer shows, elasticity, tint permanence, wear resistance, performances such as cementability reach the service requirements that handle coats material fully, and good fluidity, flexibility of operation is strong, but equal processing and manufacturing goes out product on the general injection-moulding device of handle coating material.In addition, all recyclable utilization of the defective material in the extruding pelletization process, waste material, the scrap stock in the injection moulding process are also recyclable to be utilized again, has further reduced cost.
Hydrogenated polystyrene of the present invention-butadiene-styrene triblock copolymer (SEBS) is a linear structure, and styrene content wherein is 33%, and not oil-filled.
White oil of the present invention is that kinematic viscosity is 30~40mm 2The paraffinic base white oil of/s (envrionment temperature is under 40 ℃ of conditions).
Polypropylene of the present invention (PP) melt flow rate (MFR) is 8g/10min ± 0.5g/10min.
Mineral filler of the present invention is 800~1200 purpose lime carbonate or superfine talcum powders.
Interpolation auxiliary agent of the present invention comprises promoting agent stearic acid, antioxidant and anti ultraviolet agent, and the mass ratio of promoting agent stearic acid, antioxidant and anti ultraviolet agent is 5: 5: 3.
The present invention's second purpose provides the preparation method that a kind of above-mentioned handle coats the special-purpose thermoplastic elastomer resin of material.
May further comprise the steps:
A, high mixing:
Weight percent is respectively hydrogenated polystyrene-butadiene-styrene triblock copolymer (SEBS) of 15.4%~36.9%, 3.2%~16.6% polypropylene (PP), 0.12%~0.3% interpolation auxiliary agent, 10%~47.5% mineral filler and 22.2~63.7% white oil puts into high mixer successively, stirring at low speed 2~3 minutes, high-speed stirring 0.5~1 minute; The temperature of stirring at low speed is 35~45 ℃, and the temperature of high-speed stirring is 55~65 ℃.
B, extruding pelletization:
Temperature: 60~90 ℃ of die heads, 90~130 ℃ of metering zones, 150~190 ℃ of fluxing zones, 120~160 ℃ of feeding sections;
Screw speed: 60~100r/min;
Feeding rotating speed: 40~60r/min;
Pelletizing mode: the fervent granulation of water ring die face;
C, drying;
D, air-cooled;
E, in feed bin, deposit more than 1 hour;
F, packing.
Wherein, stirring at low speed speed is 480~500r/min, and high-speed stirring speed is 950~1000r/min.
This technology is simple, and handled easily is easy to control, and product stability is good, and production process is pollution-free, environmental protection.
The present invention's the 3rd purpose is to provide a kind of forming method for above-mentioned handle coats the special-purpose thermoplastic elastomer resin of material injection moulding.
Moulding on general injection moulding machine, injection temperature are that 180 ℃~230 ℃, injection pressure are that 25~40MPa, dwell time (cycle) are 2~3 seconds.
In addition, the injection moulding machine nozzle temperature is higher than 5~10 ℃ of other sections.
This moulding process need not increase new installation, only needs to adjust slightly on original equipment to form handle according to design, and this handle has very strong cementability, good elasticity, good tint permanence and wear resistance.In addition, waste material that produces in the production process (effusion burr, extrude scrap rubber) and the final waste product that occurs can directly return and utilize, and can significantly reduce environmental pollution like this, enlarge the resource recovery source.
Embodiment
Describe the present invention in detail below by preferred embodiment, but do not limit the scope of the invention.The ordinary skill of this area is according to content of the present invention, and some nonessential improvement and adjustment to the present invention has done still belong to protection scope of the present invention.
One, feed composition:
Can choose hydrogenated polystyrene-butadiene-styrene triblock copolymer (SEBS) account for gross weight 15.4%~36.9%, white oil accounts for 22.2~63.7% of gross weight, polypropylene (PP) accounts for 3.2%~16.6% of gross weight, mineral filler accounts for 10%~47.5% of gross weight, adds auxiliary agent and accounts for 0.12%~0.3% of gross weight.
In this routine A# prescription, each component is:
1, linear structure, styrene content be 33%, not oil-filled SEBS (hydrogenated polystyrene-butadiene-styrene triblock copolymer) 19.97kg.
2, white oil: kinematic viscosity is 30~40mm 2The paraffinic base white oil 35.94kg of/s (40 ℃ envrionment conditions under), or kinematic viscosity is 160~180mm 2The naphthenic base white oil 35.94kg of/s (40 ℃ envrionment conditions under).
3, melt flow rate (MFR) is PP (polypropylene) 3.99kg of 8g/10min ± 0.5g/10min
4, mineral filler: 800~1200 purpose lime carbonate 39.94kg, or the superfine talcum powder about 1000 orders.
5, add auxiliary agent: 0.16kg.
The mass ratio that adds promoting agent stearic acid, antioxidant and anti ultraviolet agent in the auxiliary agent is 5: 5: 3.
Two, preparation technology:
A. fs: the high technology of mixing
Each resin dedicated component is put into high mixer successively, and order of addition(of ingredients) is SEBS → PP → auxiliary agent → mineral filler → white oil, and stirring at low speed 2-3 minute, high-speed stirring 0.5-1 minute to stirring fully; The temperature of stirring at low speed is controlled at 35-45 ℃, and the temperature of high-speed stirring is controlled at 55-65 ℃.Wherein, stirring at low speed speed is 490r/min, and high-speed stirring speed is 980r/min.
B. subordinate phase: double-screw extruding pelletizing technology
1. temperature: 60~80 ℃ of die heads, 90~120 ℃ of metering zones, 150~180 ℃ of fluxing zones, 120~140 ℃ of feeding sections,
Preferable: 70~80 ℃ of die heads, 100~140 ℃ of metering zones, 160~180 ℃ of fluxing zones, 120~140 ℃ of feeding sections.
2. screw speed: 60~80r/min, preferable 65~75r/min.
3. main frame electric current: 100~120A, preferable 100~110A.
4. feeding rotating speed: 40~50r/min, preferable 40~45r/min.
5. pelletizing mode: the fervent granulation of water ring die face.
6. granulation material process dries, and is air-cooled, deposits in feed bin more than 1 hour, then the blowing packing.
Three, moulding process:
The handle that above technology is obtained coats the machine-shaping on injection moulding machine of the special-purpose thermoplastic elastomer resin of material injection moulding.
Injection temperature is that 180 ℃~230 ℃ (can set each section and nozzle temperature respectively according to practical situation, nozzle temperature is higher 5~10 ℃ than other section), injection pressures are that 25~40MPa, dwell time (cycle) are 2~3 seconds, can be injection molded into handle and coat material.
Four, performance, index:
Adopt above-mentioned complete processing to obtain handle and coat special-purpose thermoplastic elastomer resin of material injection moulding and injection moulded products, its physicals, sanitary index are:
Density 1.18g/cm 3
Hardness Shao Shi A22
Melting index 13.2g/10min (230 ℃, 3.8Kg)
Tensile strength 3.28Mpa
Elongation at break 853%
300% stress at definite elongation 0.69Mpa
Sanitary index belongs to actual nontoxic level.
The through performance parameter as seen, the handle that the present invention produces coats expects that the special-purpose thermoplastic elastomer resin product of injection moulding can replace elasticity of import body product in the market fully, nontoxic, pollution-free, recyclable recycling, and Technological adaptability is strong, cost is low, has more market competition advantage.

Claims (7)

1. thermoplastic elastomer resin, become to be grouped into by following weight percent: hydrogenated polystyrene-butadiene-styrene triblock copolymer 15.4%~36.9%, white oil 22.2~63.7%, polypropylene 3.2%~16.6%, mineral filler 10%~47.5% and interpolation auxiliary agent 0.12%~0.3%, it is characterized in that described hydrogenated polystyrene-butadiene-styrene triblock copolymer is a linear structure, styrene content wherein is 33%, and not oil-filled.
2. according to the described thermoplastic elastomer resin of claim 1, it is characterized in that described white oil is 30~40mm for kinematic viscosity under 40 ℃ of envrionment temperatures 2The paraffinic base white oil of/s.
3. according to the described thermoplastic elastomer resin of claim 1, it is characterized in that described mineral filler is 800~1200 purpose lime carbonate or 1000 purpose superfine talcum powders.
4. according to the described thermoplastic elastomer resin of claim 1, it is characterized in that described interpolation auxiliary agent comprises promoting agent stearic acid, antioxidant and anti ultraviolet agent, the mass ratio of promoting agent stearic acid, antioxidant and anti ultraviolet agent is 5: 5: 3.
5. preparation method of thermoplastic elastomer resin according to claim 1 is characterized in that may further comprise the steps:
A, high mixing:
Weight percent is respectively hydrogenated polystyrene-butadiene-styrene triblock copolymer of 15.4%~36.9%, 3.2%~16.6% polypropylene, 0.12%~0.3% interpolation auxiliary agent, 10%~47.5% mineral filler and 22.2~63.7% white oil puts into high mixer successively, stirring at low speed 2~3 minutes, high-speed stirring 0.5~1 minute; The temperature of stirring at low speed is 35~45 ℃, and the temperature of high-speed stirring is 55~65 ℃; Described stirring at low speed speed is 480~500r/min, and high-speed stirring speed is 950~1000r/min;
B, extruding pelletization:
Temperature: 60~90 ℃ of die heads, 90~130 ℃ of metering zones, 150~190 ℃ of fluxing zones, 120~160 ℃ of feeding sections;
Screw speed: 60~100r/min;
Feeding rotating speed: 40~60r/min;
Pelletizing mode: the fervent granulation of water ring die face;
C, drying;
D, air-cooled;
E, in feed bin, deposit more than 1 hour;
F, packing.
6. forming method of thermoplastic elastomer resin according to claim 1 is characterized in that: moulding on general injection moulding machine, injection temperature are that 180 ℃~230 ℃, injection pressure are that 25~40MPa, dwell time are 2~3 seconds.
7. according to the forming method of the described thermoplastic elastomer resin of claim 6, it is characterized in that the injection moulding machine nozzle temperature is higher than 5~10 ℃ of other sections.
CN2008100255096A 2008-05-07 2008-05-07 Thermoplastic elastomer resin and its preparing and forming method Expired - Fee Related CN101265351B (en)

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CN101376733B (en) * 2008-09-28 2011-06-22 深圳市科聚新材料有限公司 Shock absorption thermoplastic elastomer material for cars and preparation thereof
CN101747554B (en) * 2008-12-22 2012-05-23 上海日之升新技术发展有限公司 Thermoplastic elastomer for suction disc and preparation method thereof
CN102094328B (en) * 2009-12-15 2012-12-19 银禧工程塑料(东莞)有限公司 Thermoplastic elastomer material for replacing PVC coated polyester yarns and preparation method thereof
CN101999796B (en) * 2010-11-23 2012-06-20 武汉市今晨实业有限公司 Tooth brush holder and stirring process of raw material thereof
CN103385599B (en) * 2013-08-05 2015-09-16 高秀娟 A kind of monoblock type antibacterial toothbrush and forming manufacture technique thereof
CN103589026B (en) * 2013-10-19 2016-08-17 安徽荣盛橡塑科技有限公司 A kind of Medical elastic pad and preparation method thereof
CN104403253A (en) * 2014-11-10 2015-03-11 苏州新区枫盛塑料制品厂 Anti-aging TPE plastic formula
CN104403255A (en) * 2014-11-12 2015-03-11 苏州新区枫盛塑料制品厂 Thermoplastic elastomer formula
CN106496917A (en) * 2016-11-09 2017-03-15 深圳市普特美橡塑原料有限公司 A kind of modified form of resistance to toluene TPE plastic cement
CN109082063A (en) * 2018-08-02 2018-12-25 苏州騳骉新材料科技有限公司 Thermoplastic elastomer (TPE) for court runway

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CN1466509A (en) * 2000-10-09 2004-01-07 采夫创造股份公司 Method for the production of at least one body and a pourable mixture for use in such a method
CN1772807A (en) * 2005-08-05 2006-05-17 东莞银禧塑胶有限公司 High flame retardance heat resistant low smoke no-halogen cable sheath and its production process
CN1772808A (en) * 2005-08-05 2006-05-17 东莞银禧塑胶有限公司 Low smoke no-halogen wire and plug material
ES2257128A1 (en) * 2003-10-07 2006-07-16 Victor Javier Boldova Hernandez (Titular Al 50%) Plastic cork material, especially for wine bottle corks, comprises SEBS copolymer, white oil and polypropylene
CN1970604A (en) * 2006-10-27 2007-05-30 上海应用技术学院 Method for improving compression-resistant permanent deformation property of SEBS/PP elastomer material
CN101288991A (en) * 2007-04-16 2008-10-22 李彬 Manufacturing technique of makeup grade material secondary injection moulding cordwood system plastic floor

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29911193U1 (en) * 1999-06-26 1999-09-02 Schaefer Polymer Gmbh Plucking finger
CN1466509A (en) * 2000-10-09 2004-01-07 采夫创造股份公司 Method for the production of at least one body and a pourable mixture for use in such a method
ES2257128A1 (en) * 2003-10-07 2006-07-16 Victor Javier Boldova Hernandez (Titular Al 50%) Plastic cork material, especially for wine bottle corks, comprises SEBS copolymer, white oil and polypropylene
CN1772807A (en) * 2005-08-05 2006-05-17 东莞银禧塑胶有限公司 High flame retardance heat resistant low smoke no-halogen cable sheath and its production process
CN1772808A (en) * 2005-08-05 2006-05-17 东莞银禧塑胶有限公司 Low smoke no-halogen wire and plug material
CN1970604A (en) * 2006-10-27 2007-05-30 上海应用技术学院 Method for improving compression-resistant permanent deformation property of SEBS/PP elastomer material
CN101288991A (en) * 2007-04-16 2008-10-22 李彬 Manufacturing technique of makeup grade material secondary injection moulding cordwood system plastic floor

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