Packaged ABS Resin Technology Resin ABS Packaged

oration P Cor Petroleum ational n China

ABS 树脂成套技术

2011 年

2011 Science & Technology Management Department Management Technology & Science Packaged ABS Resin Technology Resin ABS Packaged

中国石油天然气集团公司科技管理部

我们愿携手业界同仁，共同发展，繁荣Team Expert ABS 技术产业！

21 Standard and Qualification

19 Equipment R&D

prosperity of ABS! of prosperity

18 Cases Typical

peers for the common development and and development common the for peers

6 Technologies Unique

We would like to cooperate with industry industry with cooperate to like would We

3 Introduction Contents Contents

Introduction 3

Unique Technologies 6

Typical Cases 18

R&D Equipment 19

Qualification and Standard 21

Expert Team 22 1InTRoDUCTIon

China National Petroleum Corporation (CNPC) 2010 and 5th among global top 50 oil companies. 1.1 ABS Resin team consisting of over 100 senior talents in resin is a state-authorized investment agency and a state CNPC strictly follows by the combined strategies development and over 300 specialists for professional ABS resin (Acrylonitrile Butadiene Styrene) is the holding company. As an integrated oil company of of increasing resource capacity, expanding market services. These talents and specialists have abundant graft copolymer of three monomers—acrylonitrile, cross-regions, cross-industries and cross-countries, shares and consolidating the international role, and experience in many fields (e.g. ABS resin production 1,3-butadiene and styrene. As a thermoplastic high it adopts modern enterprise system to realize the persists in regarding technical innovation as a key technology, new product development) and made molecular material with high strength, high toughness, integration of upstream and downstream operations, framework to advance technological progress. To substantial achievements. The early 21st century excellent processability, this copolymer combines the internal and external trade and production and develop its core businesses, focuses will be placed witnessed CNPC’s dedication to the production and impact resistance of butadiene, rigidity and chemical marketing. CNPC has 17 upstream companies, 33 on the solutions of key bottleneck technologies R&D of ABS resin, and now CNPC has become an resistance of acrylonitrile, glossiness and mouldability downstream companies and 36 large-scale marketing and key proprietary technologies. Thanks to indispensable manufacturer and technical service of styrene. companies. It is China’s largest producer and supplier continuously improving of the technical innovation supplier in ABS resin industry. The Packaged ABS Resin Technology of oil and gas, and also one of the largest refined system, optimizing the configuration of technological independently developed by CNPC: Emulsion oil products and petrochemicals. In 2010 CNPC resources and strengthening the construction of 1.2 Advantages of CNPC ABS Resin polymerization is adopted to synthesize small produced 105 million tons of crude oil and 72.5 billion strong talent teams, CNPC’s technological creativity Technology particle-sized polybutadiene latex that transforms cubic meters of natural gas, while crude processing has been considerably upgraded. Consequently, a to large particle-sized polybutadiene latex through The Emulsion Graft Technology, namely the volume reached 135 million tons. The total revenue large number of technologies have been developed chemical agglomeration. Then the large particle- Packaged Technology of SAN Mixing independently of RMB1, 720 billion with a profit of RMB172.7 billion independently, with its own intellectual property. sized polybutadiene latex undergoes the reaction developed by CNPC delivers the combination of the had been achieved the same year. Its profit is among The Packaged ABS Resin Technology is one of of emulsion graft polymerization with styrene and two-stage process for forming large particles latex the highest of the domestic enterprises in China. representatives for major innovations of CNPC. monomers of acrylonitrile to produce ABS graft and high rubber content graft polymerization, which CNPC was ranked 10th in Fortune Global 500 in latex. Graft latex is made into ABS powder through solves the conflict between the rapid polymerization coagulation, dewatering and drying. ABS powder, SAN reaction and particle size control, as well as the particles that are produced by bulk polymerization and conflict between the high conversion rate and gel various additives are mixed in proportion, extruded content to improve the production efficiency by 2~3 and granulated before ABS resin forms. times compared with similar equipment. CNPC introduced technology of ABS resin from ● The Technology of Polymerization of Small abroad in early 1960s. CNPC’s scientific research Particle-sized Butadiene is featured by short personnel have hammered at the production, polymerization time, high conversion rate, research and development of ABS resin. With over 40 optimally controlled particle size, low system years of endeavors, CNPC has become an important CLEAN ENERGY SUPPLY FOR BETTER ENVIRONMENT viscosity, excellent polymerization stability and manufacturer and main driving force in scientific research of ABS resin. It owns the well-equipped resin stable latex with a storage period of over 2 synthesization laboratories and a national top R&D years.

3 1InTRoDUCTIon

3 InTRoDUCTIon Packaged aBS ReSin Technology BRochuRe

Technology of Polymerization of Small ● ● The chemical agglomeration period is short and Highly safe Nitrogen Drying Technology Particle-sized Butadiene

the storage period of agglomerated latex with sufficiently ensures a safe powder drying Technology of PB Latex Agglomeration sound stability can reach over 1 year; process; Technology of PB Latex Agglomeration ● ● ABS Powder Synthesization The Graft Polymerization Technology ensures The SAN Synthesization Technology boasts Graft Polymerization Technology Technologies that graft polymerization process takes short good operation flexibility, high safety factor, Latex Coagulation Technology time, rubber content may be adjusted between high conversion rate, low residue monomer

40%~75%, graft percentage and conversion rate content, few “three wastes” and little pollution to Powder Drying Technology are high and latex can be easily coagulated and environment; Technology of Continuous Proportioning and ● Packaged ABS Resin Technology dried; The Cavitation Air Flotation (CAF) Technology Mixing ● Coagulant with low cost is used in coagulation featured by simple operation and high Bulk Polymerization Technology process that is carried out under low temperature processing efficiency is introduced in wastewater SAN Polymerization Technologies and the coagulated latex powder in uniform treatment system; Technology of Two-stage Devolatilization particle size ensures stable operation of the ● Compared with that of the similar units, its Technology of SAN Resin Granulation dewaterer with long-time cycle; consumption of energy and material is relatively low.

Technologies of “Three Wastes” Cavitation Air Flotation Technology Treatment

General-purpose ABS Resin

High Impact-resistance ABS Resin

Sheet ABS Resin Unique new Products Flame Retardant ABS Resin

ABS Alloy

SAN Resin

CNPC R&D Base for ABS Resin

CNPC Marketing Area of ABS Resin

Place of Origin of CNPC ABS Resin

4 5 InTRoDUCTIon Packaged aBS ReSin Technology BRochuRe

Technology of Polymerization of Small ● ● The chemical agglomeration period is short and Highly safe Nitrogen Drying Technology Particle-sized Butadiene the storage period of agglomerated latex with sufficiently ensures a safe powder drying Technology of PB Latex Agglomeration sound stability can reach over 1 year; process; Technology of PB Latex Agglomeration ● ● ABS Powder Synthesization The Graft Polymerization Technology ensures The SAN Synthesization Technology boasts Graft Polymerization Technology Technologies that graft polymerization process takes short good operation flexibility, high safety factor, Latex Coagulation Technology time, rubber content may be adjusted between high conversion rate, low residue monomer

Technologies of “Three Wastes” Cavitation Air Flotation Technology Treatment

General-purpose ABS Resin

High Impact-resistance ABS Resin

Sheet ABS Resin Unique new Products Flame Retardant ABS Resin

ABS Alloy

SAN Resin

CNPC R&D Base for ABS Resin

CNPC Marketing Area of ABS Resin

Place of Origin of CNPC ABS Resin

4 5 Packaged aBS ReSin Technology BRochuRe

UnIqUE TECHNOlOGIES 2 Technical Features and Advantages: 2) Chemical Agglomeration Technology (1) With short polymerization time, the same Chemical agglomeration which takes small particle- polymerization equipment allows PB latex production sized PB latex (80~120nm) as base latex is used The “high rubber content by two-stage” ABS 2.1 ABS Powder Synthesization Tech- to increase by 2~3 times; the polymerization time to produce grafting trunk latex with particle size of Powder Synthesization Technology independently nologies is shortened by 50%~70% compared with similar 120~400nm. During the agglomeration, anhydride developed by CNPC can solve the conflict between technologies; agglomerant is added under certain conditions and high reaction speed and optimum latex particle size as 1) Technology of Polymerization of Small (2) Conversion rate of polymerization is high and agitation while reaction temperature and time are well as the conflict between high conversion rate and Particle-sized Butadiene recovery system for butadiene is not needed; controlled; besides, the particle size, particle size optimum gel content. This technology can also realize (3) Compound emulsifying system improves the distribution and PH viscosity can be effectively As a main stage of ABS resin production and the the proper combination of rapid polymerization, high stability of polymerization and agglomeration process; controlled to ensure the stability and practicability of most critical technology in the two-stage production of conversion rate, high rubber content and optimum (4) Multifunctional additives lessen the types and agglomerated latex. ABS resin, the emulsion polymerization process used particle size, shorten the synthesization time of dosage of additives, shorten induction period and Compared with similar technologies, Chemical for production of small particle-sized PB employs ABS powder, and optimize the overall performance improve stability of system; Agglomeration Technology independently developed water solvent, butadiene and a small amount of of ABS resin. As a result, the production efficiency (5) Unique technology of heat-removing during PB by CNPC may allow agglomerated latex with styrene monomers together with compound emulsifier, exceeds that of the similar technologies by 60% polymerization accelerates heat release during early properties within optimum range required by different multifunctional additives, and molecular weight and the conversion rate of butadiene is higher than and later polymerization process while subduces heat types of ABS resins. In addition, little latex is regulator, all of which are dispersed into emulsion 98%. Moreover, fewer monomer recovery units are release during middle stage to ensure the safety of precipitated during the agglomeration process and the by mechanical agitation and react under effect of used, the equipment investment is cut down and the polymerization; concentration of agglomerant is high to enable more inorganic peroxide as initiator. pollution to environment is decreased. Besides, the (6) Without coagulum, polymerization proceeds stable agglomerated latex and improve the stability of The ABS Resin Butadiene Polymerization unit waste water discharge is lessened by 5%~7% with high stability and long reactor cleaning interval grafting reaction. Technology independently developed by CNPC and the raw material consumption is reduced. The that can be up to over 2 months; solves the conflict between high conversion rate and Technical Features and Advantages technology is characterized by mature and simple (7) The gel content may be adjusted between optimum gel content to allow the proper combination techniques, stable device operation, long operation 40%~75% while high conversion rate is ensured. ● Continuous and precise control on latex particle of rapid polymerization, high conversion rate and cycle as well as safety and eco-friendliness. optimum gel content, which reduces production cost Application of Technology size allows the production of any kind of latex Meanwhile, this technology can be used to produce and decrease “three wastes” discharge. Compared The technology is generally used for the production with the particle size between 120nm and ABS powder with rubber content varying from 40% to with similar technologies, this innovative technology of rubber latex during the production of General- 400nm; 75% and can deliver ABS products with high added- has outstanding characteristics and significant purpose ABS Resin, Special ABS Resin and ABS ● Both agglomeration process and equipment are value and production techniques to customers with advantages. Alloy, as well as for the production of polybutadiene various demands. simple and easy to operate. Particle size is easy and styrene butadiene latex. to control;

6 7 Packaged aBS ReSin Technology BRochuRe

6 7 UNIQUE TECHNOlOGIES Packaged aBS ReSin Technology BRochuRe

● Rapid agglomeration reaction, agglomeration by 34.6%; cost is cut down, “three wastes” discharge decreased refresh nitrogen timely. time < 1h and latex precipitated <0.03%. The ● High conversion rate (>98%) and low pollution and water content and debris in the dewatered and Nitrogen Recycling Drying Technology is used for agglomeration cycle is 60% shorter and the latex to environment; high rubber content (>60%), washed powder reduced. ABS Powder Drying Technology developed by CNPC where the nitrogen which can dry the powder by precipitated is 70% less than those of similar production cost for ABS resin reduced, overall Technical Features and Advantages successively taking away moisture and other volatiles technologies; performance of ABS resin improved and (1) Simple process, easy operation and continuous in the powder through direct-contact type sieve ● Agglomerated particle size is stable (may be production capacity of ABS resin production coagulation process; plate tower. Compared with similar technologies, stored for over 1 year) and particle size, particle equipment increased; (2) Coagulant with low cost, little corrosion and little this technology can be used to increase drying dosage is used to effectively reduce production cost size distribution, PH, and viscosity can be ● Subsequent coagulation and drying processes temperature, shorten drying time, reduce moisture and decrease pollution to environment; effectively controlled. can be ensured to proceed smoothly; contained in powder and accumulated powder in (3) Optimum agitation speed under low temperature ● the drying tower, improve safety factor during drying Application of Technology Ensure ABS products to have pleasant is used to produce uniform coagulated particles with process to ensure safe and stable drying operation appearance. The latex particle size, particle size distribution and stable structure, and water content in the dewatered and prolong the operation cycle of the dryer. In additives may be adjusted to produce grafting trunk Application of Technology wet powder is low; addition, this technology can be used for drying other (4) Deflocculation method with excellent latex required by different types of ABS resin. The technology is generally used for the production flammable and explosive powders. coagulation effect is used, which enables rapid of graft latex specially used for the General- 3) Graft Polymerization Technology particle formation, even particle size distribution, rigid Technical Features and Advantages purpose ABS Resin, Special ABS Resin and ABS As for the graft polymerization, main latex PB, particles, easy washing, and environment friendliness. (1) The technology of recycling nitrogen in the Alloy. Different technical support and technical styrene and acrylonitrile monomers are taken into This method eliminates the effect by coagulant drying process is used to reduce consumption of follow-up service may be provided according to the emulsion graft polymerization reaction under the dripping speed in deflocculation method to particle nitrogen and improve safety by eliminating the hazard requirements by customers. function of additives such as emulsifier and initiator sizes and distribution; of detonation of air drying system; while the free styrene-acrylonitrile copolymer is 4) Coagrulation Technology (5) Long cleaning interval for coagulation reactor; (2) Prolonged cleaning interval for the dryer; produced. CNCP developed unique continuous three- (6) Little corrosion by coagulant to equipment (3) The dryer operation temperature raised, high CNPC has innovated to combine the compound reactor coagulation process innovatively. The prolongs service life of the equipment; drying rate and moisture contained in powder less emulsifying system and the highly efficient oxidation- coagulation process mainly includes two stages, (7) Product quality is improved with little debris than 1%. reduction system for high gel graft polymerization. namely, coagulation and maturation. After coagulation content in dewatered and washed powder. Application of Technology Compared with similar technologies, this technology and maturation, the graft latex is put in a dryer Application of Technology This technology can be generally used for drying features short reaction time, high rubber content, for dewatering. Latex coagulation is one of the Generally used to the flocculation of graft latex and different types of powders, especially flammable less coagulum, high conversion rate, safety and indispensable processes of emulsion polymerization. relative emulsion. and explosive materials, to ensure safe production environment friendliness, stable heat release and The latex coagulation conditions are critical for process. simple reaction operation. Meanwhile, high added- subsequent processes. 5) Powder Drying Technology value ABS resin products may be produced based on Different from similar technologies, this process Drying Technology with nitrogen circulating this technology. 2.2 SAN Polymerization Technologies uses sulfate as coagulant, which generates low fluidized bed used to dry ABS powder takes nitrogen Technical Features and Advantages cost and has less corrosion effect on equipment. In as the drying medium. Nitrogen heated by heater SAN Polymerization Technologies cover the mature addition, the operation temperature is low, maturation enters the dryer and takes away moisture in the Technology of Continuous Monomer Proportioning ● Innovative compound emulsifying system; duration is short and the coagulated particle size is powder. Moisture and heat contained in nitrogen are and Mixing, Bulk Polymerization Technology, ● Short graft polymerization reaction time (<6h) uniform. Tripping times of dewaterer are reduced, washed away by water. Split range control is used to Technology of Two-stage Devolatilization and and production capacity of grafting unit improved and operation cycle is prolonged while coagulation maintain system pressure as well as supplement and Technology of SAN Resin Granulation.

8 9 UNIQUE TECHNOlOGIES Packaged aBS ReSin Technology BRochuRe

1) Technology of Continuous Proportioning ● Heat remove from gas phase to allow stable polymer with high viscosity. Cavitation Air Flotation and Mixing temperature; 4) Technology of SAN Resin Granulation Waste water from ABS unit is treated by processes ● of flocculation, air flotation, and scum dewatering and As for the continuous proportioning and mixing Short process flow and high production capacity; Underwater Granulation Technology and the treated water satisfies requirements of drainage. process, two monomers with preset flow rate ● Stable product quality; Centrifugal Drying Technology are used to produce Features of this technology include high treatment controlled by the regulating valve and flow gauge ● Little “three wastes” discharge, safe and eco- SAN resin particles which are delivered by fans. efficiency, integrated equipment (rational structure realize the cascade and split range control through friendly; Logic programs are made according to requirements and easy maintenance) and low energy consumption. flow ratio control system. The monomers are mixed by ● Long operation cycle. of process and switching of end product tanks is ● pipe static mixer while onsite chemical analysis and sequentially controlled by DCS. Aerator produces highly efficient bubbles in Application of Technology timely adjustment are performed to ensure uniform During SAN granulation process, the melted waste water without blockage. monomer mixture with stable proportion. Applicable to the continuous SAN resin production. polymer is boosted by high viscosity gear pump and ● Easy operation and high treatment efficiency. Technical Features and Advantages 3) Technology of Two-stage Devolatiliza- extruded into strip bundle through die plate. After ● Integrated equipment with rational structure and passing the guide plate, polymer strips are cooled ● Continuous proportioning, short surge time; tion easy maintenance. down by spray water, and then cut into SAN particles ● Low liquid mixture temperature to facilitate heat- During the two-stage SAN resin devolatilization, ● Low energy consumption and high efficiency. by granulator. The speeds of pressure roller and slitter removing from reactor; unreacted styrene and acrylonitrile monomers of can be regulated to control particle size. 2.4 Unique New Products ● Precise control with narrow proportion fluctuation the polymer as well as the ethylbenzene solvent are removed from the devolatilizers in different operation Technical Features and Advantages range; CNPC is armed with an R&D team for development conditions to obtain SAN resin. The removed ● Stable operation, the proportion may be timely ● Spray water may be recycled to allow low and technological innovation of new ABS products. monomers are condensed, and return back to With independently developed Packaged Technology adjusted according to production load; material consumption; polymerization system for repeated reaction. of Emulsion Graft −SAN Mixing, a series of new ● Easy maintenance. ● Underwater granulation emits little dust and Compared with similar technologies, this ABS products are further developed and marketed Application of Technology technology boasts better devolatilization result, less gives little pollution to environment; nationwide. monomers left in product, lower product yellowness, ● The particle is uniform with smooth appearance; This technology is applicable to the production higher SAN heat resistance, safer performance and ● with continuous proportioning and strict components Effective dryness delivers low moisture content General- more eco-friendliness. purpose requirements. in particles. ABS Resin Technical Features and Advantages Application of Technology 2) Bulk Polymerization Technology ABS Alloy ● Two-stage devolatilization to allow reuse of During SAN resin polymerization process, This technology is applicable to granulation and condensed liquid and lower down material new Unique monomers of styrene and acrylonitrile are thermally delivery of all types of melted resin. Products initiated to continuous polymerization reaction and consumption; ● Sheet ABS molecular weight regulator is continuously added. The Acrylonitrile is removed at a relatively low 2.3 Technologies of “Three Wastes” Resin reacted mixture will be sent to devolatilization system temperature from the first devolatilizer to yield Treatment by a discharge pump when solid content in the reactor low-yellowness product; Cavitation Air Flotation Technology is used by Flame gets up to 55%~65%, and conversion rate up to 70%. ● Retardant Styrene is removed from the second devolatilizer CNPC to treat “three wastes” with treated water SAN ABS Resin Resin High Technical Features and Advantages at a relatively high temperature and vacuum. satisfying emission requirements of Grade I GB 8968- Impact ABS Resin ● 1996. Polymerization in reactor; Application of Technology 1) Technology of “Three Wastes” Treatment by ● Easy control and flexible operation; It is applicable to remove unreacted monomers of

10 11 UNIQUE TECHNOlOGIES Packaged aBS ReSin Technology BRochuRe

1) General-purpose ABS Resin 2) High Impact ABS Resin The General-purpose ABS resin independently developed by CNPC has outstanding overall performance High Impact ABS Resin independently developed by CNPC has high impact strength with excellent rigidity, with high impact strength, excellent mechanical property, chemical resistance, mouldability, space stability and processability, dyeing property and chemical resistance. dyeing property. Application Application ● Electrical machinery enclosures ● Electronic and electrical ● Toys components ● Motorcycle parts ● Automobile parts ● Bicycles ● Toys ● Helmets ● Cameras ● Pipes

Performance Indexes of General-purpose ABS Resin Performance Indexes of High Impact ABS Resin

Indexes Grades and Index Values Test Method Indexes Grades and Index Values Test Method

750A 750 750SW 740A

Izod impact strength 200 200 200 ASTM D256-2006 Izod impact strength J/m ≥ 280 ASTM D256-2006 J/m ≥

Tensile strength MPa 42 45 40 ASTM D638-2003 Tensile strength MPa ≥ 40 ASTM D638-2003 ≥

Rockwell hardness 100 98 95 ASTM D785-2003 Rockwell hardness(R scale) 95 ASTM D785-2003 (R scale)

Melt mass-flow rate ċ ċ ċ Melt mass-flow rate (MFR) ċ (MFR) g/10min 25 36 36 50 45 60 GB/T 3682-2000 g/10min 15 27 GB/T 3682-2000

Heat distortion 78 80 80 ASTM D648-2006 Heat distortion temperature 80 ASTM D648-2006 temperature ņ ≥ ņ ≥

Bending strength MPa 60 60 60 ASTM D790-2003 Bending strength MPa ≥ 63 ASTM D790-2003

Modulus of elasticity in 1900 1900 1900 ASTM D790-2003 Modulus of elasticity in 2000 ASTM D790-2003 bending MPa bending MPA

12 13 UNIQUE TECHNOlOGIES Packaged aBS ReSin Technology BRochuRe