sinopec and brici - chemspec europe · 2018. 9. 20. · (sinopec) 0 24.8 1.05 106.3 615 0.1 26.7...
TRANSCRIPT
•Sinopec and BRICI
•What is UFPR
•Why UFPR can improve the performance
•What Narpow® can do
•Key takeaway
In 2016• Crude oil 303.51 MMbbls,
Natural gas 766.12 Bcf
• Crude throughput 235.53 Mtons
• Ethylene 11,059 Ktons
Synthetic resin 15,201 Ktons
• Sales of refined oil 194.84 Mtons
Largest Integrated Energy Company in China,the 3rd in Fortune
Global 500, 2017.
Main Business
•Oil/gas field exploration and
production
•Refining
•Petrochemicals production
•Oil products sales and
distribution
• A R&D subsidiary of Sinopec Corp, also the leading polyolefin research
institute in China.
• Total Employee:~1100,including 1 academician of CAE
• Focusing on: Olefin Technology, Plastic Technology, Synthetic Rubber,
Chemical & Fine Chemicals, Environmental Protection
• Polyolefin technology: New polymerization, catalyst(PP,PE),new
products(PE/PP Grades )
UFPR: Ultrafine Full-vulcanized Powdered Rubber(ENP)
Narpow ®: Nano rubber powder
Independent intellectual property:150 patents in china(70
granted),11 foreign patents(5 granted in USA ,4 in Europe,3
in Korea,5 in Japan and 1 in Canada, Brazil, India and Taiwan
region)
Plant with capacity of 3000 tons/year.
rubber latex particlefully cured latex particle
premixing with cross -
linking agent or not
irradiated with g ray
or electron beam etc.
linear or light cross -
linked molecules
heavy cross -linked
molecules
ENP or UFPR
Spray
drying
rubber latex particlefully cured latex particle
premixing with cross -
linking agent or not
irradiated with g ray
or electron beam etc.
linear or light cross -
linked molecules
heavy cross -linked
molecules
Surface: heavy cross-linked
particles do not tend to agglomeratejust like ordinary rubber. So it is easyto disperse in polymers
Center: lightly cross-linked
keep the elasticity of rubber
SEM micrograph of full-vulcanized
styrene-butadiene powdered
rubber
TEM micrograph of rubber
particles in styrene-butadiene
rubber latex
AFM micrograph of
full-vulcanized styrene butadiene
powdered rubber in PP
Spray
Drying
1、Styrene-butadiene UFPR (Particle Size:<150nm),
2、Carboxylic styrene-butadiene UFPR (Particle Size : <150nm),
3、Acrylate UFPR (Particle Size : <150nm),
4、Nitrile-butadiene UFPR (Particle Size : <100nm),
5、Carboxylic nitrile-butadiene UFPR (Particle Size : <90nm),
6、Silicon UFPR (Particle Size : <100nm),
7、Butadiene vinylpyridine UFPR (Particle Size : <100nm),
8、EVA powdered elastomer (Particle Size : <250nm),
9、Chloroprene UFPR (Particle Size :<150nm),
10、A series of Narpow composite additive agents (composite nucleating agents,composite antibacterial agents)
Grade Name Application
VP-108,
VP-108(5) Styrene-butadiene UFPR Preparing friction materials
VP-121 Carboxylic styrene-butadiene UFPR Simply and efficiently preparing TPV
VP-301,
VP-362Acrylate UFPR
Toughening polyester, POM, Nylon, AS, PVC, PMMA etc., Blending
with rubber
VP-401 Nitrile-butadiene UFPR Toughening PVC, Preparing TPV,Blending with rubber
VP-401F,VP-402 VP-412 Nitrile-butadiene UFPR Preparing friction materials,toughening phenolic resin
VP-401E Nitrile-butadiene UFPR Modifying epoxy resin
VP-501 Carboxylic nitrile-butadiene UFPR Toughening PVC, Preparing TPV,Blending with rubber
VP-501F Carboxylic nitrile-butadiene UFPR Preparing friction materials,toughening phenolic resin
VP-501E Carboxylic nitrile-butadiene UFPR Modifying epoxy resin
VP-601 Silicon UFPRAdditives for paints ,printing ink, and cosmetics, Blending with
rubber such as PU
VP-701 Butadiene vinylpyridine UFPR Toughening plastics such as Nylon, polyester etc., Blending with rubber
VP-901 Chloroprene UFPRAdditives or binders for building, construction materials, automobile
industry and special applications
VP-101B Composite nucleating agents, α-nucleating agent, Used in PP to increase crystallization temperature,
stiffness and heat resistance, improve processing properties
VP-101T Composite nucleating agentsβ-nucleating agent, Used in PP to increase crystallization temperature,
toughness and heat resistance, improve processing properties
VP-101KJComposite antibacterial
agents
A type of composite antibacterial agents which can give plastics the
antibacterial function
TEM micrograph of rubber particles
in carboxylic styrene-butadiene
rubber latex
AFM micrograph of
Nylon-6/ Vp-201(20wt%) Blends
TEM micrograph of Epoxy/VP-501
PVC /VP-401 phenolic resin/VP-401
1.Plastics Toughening: Thermoplastic resins, Thermosetting resins
2.Preparation and application of Narpow composite materials and
composite additive agents
3. Preparing novel thermoplastic elastomer
4. Modifying rubber, especially vehicle tire treads, Improving rolling
resistance , abration and grip in the wet at the same time
5. Other application
Epoxy resin
Unsaturated polyester
Phenolic resin
• Phenolic resin molding
compoundPhenolic resin friction
materials
Disc break pads Drum break linings Industrial friction materials• Epoxy resin adhesive or power
coating
Promotion
Impact Strength
HDT
Tg
Delustering
Transparent
Viscosity
☞Promotion Impact Strength
HDT
Tg
Decomposition temperature
Viscosity
Improving the impact resistance
Increasing friction coefficient at higher temperature.
lowering wearing rate Lowing the hard Lowing noise when
braking, weight is light
Friction Materials
By now, Narpow has been sold to over 40 domestic manufacturers, also to Japan and Thailand to prepare high-performance friction materials
A schematic illustration of Narpow® helping additive
agent to disperse in plastics
VP101B Composite α nucleating agent
Using in PP to increase crystallization temperature, stiffness
and heat resistance, improve processing properties ,production
efficiency ,dimensional stability and thermal aging properties
VP101T Composite β nucleating agent
Using in PP to increase crystallization temperature, toughness
and heat resistance
01
02
-1 0 1 2 3 42.0
2.1
2.2
2.3
2.4
弯曲模量(GPa)
成核剂A含量( ‰)
-1 0 1 2 3 4
48
50
52
54
56 成核剂 A复合成核剂VP101B
弯曲强度 (MPa)
成核剂A含量( ‰) Content of NA-A(‰)
Content of NA-A(‰)
NA-AVP-101B
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5124
125
126
127
128
129
130
131
132
133
134
Tc (
℃)
NA-11含量(‰)
NA-11 成 核 剂 本 技 术 复 合 成 核 剂
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
122
124
126
128
130
132
HDT ( ℃
)
成核剂A含量( ‰)
-1 0 1 2 3 4
48
50
52
54
56
成核剂A 复合成核剂VP-101B
Nucleating agent A Compound nucleating agent VP-101B
弯 曲
强
度
(MPa)
Content of NA-A(‰)
NA-A
VP-101B
NA-AVP-101B
Content of NA-A(‰)
The effect of VP101B on the crystallization behavior of PP
Isothermal crystallization diagrams
show VP-101B can increase thecrystallization rate more greatly
than traditional nucleating agent
although the same dosage of
traditional nucleating agent is
used(0.3‰)
130 132 134 136 138 1400
2
4
6
8
10
12
t 1/2 (
min)
Tc ( ℃)
空白 PP +0.3‰ 成核剂A +1.5‰ VP101B(含 0.3‰ 成核剂A)
Pure PP0.3‰NA-A1.5‰VP-101B(Having 0.3‰NA-A)
a.+0.4‰NA-A(traditional
nucleating agent)
The PLM micrographs of PP modified by different nucleating agents
(b) +2.0‰ VP-101B
(Content of NA-A is 0.4 ‰)
VP-101B can fine the PP spherocrystals size better (dosage of
traditional nucleating
agent is used0.4‰
• Easily dispersed• Add less, the recommended dosage is 0.1%-0.3% of PP• Low cost
Adding VP101B in co-polypropylene
GRADE VP101B Content(%)
Tensile Strength
Flexual Modulus
HDT(0.45MPa) Izod Impact Strength
(23 ℃)
Unit / MPa GPa ℃ J/m
standard / ASTM D638 ASTM D790 ASTM D648 ASTM D256
J340
(SINOPEC)
0 28.3 1.15 102.6 115
0.1 29.6 1.44 120.5 122
0.2 30.5 1.58 130.7 160
K8003
(SINOPEC)
0 24.8 1.05 106.3 615
0.1 26.7 1.33 122.0 678
0.2 26.6 1.33 131.1 679
Flexual modulus and HDT raise with the increase of the VP101B
Adding VP101B in homo-polypropylene
GRADE VP101B Content(%)
Tensile Strength
Flexual Modulus HDT(0.45MPa) Izod Impact Strength
(23 ℃)
Unit / MPa GPa ℃ KJ/m2
standard / ASTM D638 ASTM D790 ASTM D648 ASTM D256
HC9012M
(SINOPEC)
0 35.8 1.78 122.3 26.5
0.12 40.2 2.43 141.6 26.8
HC9006M
(SINOPEC)
0 35.2 1.76 121.5 31.2
0.12 39.6 2.42 140.2 30.6
•19.3℃
•18.7℃
• 36.5%
• 37.5%
Flexual modulus and HDT raise with the increase of the VP101B at the same time
Adding VP101T in co-polypropylene
VP101T Content(%)
FlexualStrength
FlexualModulus
Izod Impact Strength(notched)
(23 ℃)
Charpy Impact Strength(notched)
(23 ℃)
Tensile Strength
HDT(0.45MPa)
Unit MPa GPa KJ/m2 KJ/m2 MPa ℃
standard ISO 178 ISO 178 ISO 180 ISO 179 ISO 527 ISO 75
0 24.2 0.81 25.6 28.3 24.9 66.9
0.05 25.3 0.85 33.1 24.1 26.0 72.4
0.1 25.0 0.85 37.7 34.0 26.3 68.3
0.15 24.9 0.84 42.9 32.8 25.3 71.8
0.2 23.3 0.79 64.3 77.6 24.0 66.5
0.25 23.7 0.79 74.2 87.4 24.0 72.5
Impact strength and HDT raise with the increase of the VP101B at the same time
Adding VP101T in homo-polypropylene
VP101T Content(%)
FlexualStrength
Flexual Modulus
Izod Impact Strength
(23 ℃ /-20 ℃)
Tensile Strength
HDT(0.45MPa)
Unit MPa GPa J/M MPa ℃
standard ASTM D790 ASTM D790 ASTM D256 ASTM D638 ASTM D648
0 36.3 1.30 58.6 20.0 84.7 133.2
0.1 37.2 1.37 239.7 25.6 83.9 131.9
0.15 38.0 1.40 336.6 30.9 88.4 133.2
0.2 38.6 1.44 410.0 32.9 96.4 134.4
0.25 39.4 1.47 300.0 31.3 101.7 134.0
0.3 39.0 1.46 256.3 32.5 103.1 134.3
0.4 40.4 1.50 249.1 31.6 104.5 134.3
Impact strength and HDT raise with the increase of the VP101B at the same time
60 80 100 120 140 160 180 200 220
-6
-4
-2
0
2
4
6
8
10
12
14
temperature(℃)
heat
flow
end
o up
(mW
)
pure PP
PP with 0.2wt% VP101T
modified PP with VP101T
Pure PP
The effect of VP101T on the crystallization behavior of PP
Experiment of VP101T’s stability
40 60 80 100 120 140 160 180 200 220 240
temperature(℃)
1
2
3
4
5
6
7
8
9
Endo
--In order to investigate the stability of VP101T, we designed
an experiment by using DSC.
--Scan PP sample 9 times to simulate the process of PP.
--The scan process include:
1.Heating from 50℃ to 210 ℃ at 50 ℃/min.
2.Staying at 210 ℃ for 3min.
3.Cooling from 210 ℃ to 50 ℃ at 10 ℃/min.
4.Stay at 50 ℃ for 1min.
5.Heating from 50 ℃ to 210 ℃ at 10 ℃/min.
--The result shows that even experienced scan for 9 times,
VP101T can still form βcrystallization efficiently and the
ability is almost as same as the first time.
VP101T IS QUITE STABLE!
A series of composite antibacterial agent has been developed
VP101KJ: Used in PP, PE, EVA, PS, ABS to give the antibacterial and antimildew
functions
•VP301KJ:Used in PA, PET, PVC, AS to give the antibacterial and antimildew
functions
•VP401KJ:Used in PVC, Epoxy resin, Phenolic resin to give the antibacterial and
antimildew functions
•VP601KJ:Used in Silicon rubber to give the antibacterial and antimildew functions
VP701KJ : Used in PA,PET,PBT, Epoxy resin to give the antibacterial and
antimildew functions
Platter of Stroller From Antibacterial PP
Washing machine base from antibacterial PP
Transparent Water Tank of Cooling Fan from Antibacterial PP
Antibacterial Plastic Products
Antibacterial Plastic Products Developed for Different Customers