23
Using Controlled Release and High Throughput Capabilities to Address Technology Trends in Agricultural Formulations 应用控释技术和高通量平台引领农药制剂开发新潮流 Dr. Rui Vogt Alves da Cruz R&D Director, Dow Industrial Solutions 2017 China International Agrochemical Conference Shanghai February 28 – March 2, 2017 DOW RESTRICTED ® ™Trademark of The Dow Chemical Company 2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Embed Size (px)

Citation preview

Page 1: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Using Controlled Release and High Throughput Capabilities to Address Technology Trends in Agricultural Formulations

应用控释技术和高通量平台引领农药制剂开发新潮流

Dr. Rui Vogt Alves da CruzR&D Director, Dow Industrial Solutions

2017 China International Agrochemical ConferenceShanghaiFebruary 28 – March 2, 2017

DOW RESTRICTED

® ™Trademark of The Dow Chemical Company2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 2: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

We Enable Manufacturing

Our ImpactPart of Dow’s $11.9B Performance Materials

& Chemicals portfolio comprised of

three technology-driven, customer-centric

global businesses.

我们隶属于功能材料与化学部门(119亿美金年销售额),在全球范围内开展技术驱

动、以客户为导向的业务

Markets We Serve

Our Six Core Competencies• Minimizing friction and heat in mechanical processes

• Managing the oil and water interface

• Delivering active ingredients for maximum effectiveness

• Facilitating dissolvability

• Providing the foundational building blocks for the

development of chemical technologies

• Enabling product authentication

PerformanceLubricants

CropDefense

ElectronicsMfg.

Energy

Technologies that help the

world’s manufacturers make what the

world wants and needs技术旨在助力制造商满足世界的需要和需求

Better.

Faster.

Cleaner.更好、更快、更清洁

DetergentsCleaners

Adhesives& Inks

Coatings Infrastructure

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 3: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Controlled Delivery and Release 控制释放技术

HTR & CDR Activities Take Place Around the Globe

陶氏在全球具备高通量和控制释放开发能力

3

DOW RESTRICTED

Shanghai, CN

Midland, MI

Collegeville, PA

Terneuzen, ND

• Polymers 聚合物

• Catalysts 催化剂

• Surfactants and dispersants

表面活性剂和分散剂

• Solubility and phase behavior

溶解与相行为

• Transport phenomena 转移现象

• Film formation 成膜

• Accelerates new product

development and launch

加速新产品开发和上市

• Broadly map variables vs.

performance properties

广泛研究不同变量与功能特

性的关系

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 4: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

High Throughput Research & Controlled Delivery and Release高通量研究与控制释放

Dow Commercial Successes in Advanced Formulation & Encapsulation Technologies陶氏化学在先进配方和包覆技术上的商业成功案例

4

DOW RESTRICTED

Pharma 医药:

• Controlled release tablets/ Safe dose

over time 可控释放的片剂/安全剂量

• Taste and odor masking of actives

有效成分味道和气味遮盖

• Enhanced bioavailability 生物利用率高

Food 食品:

• Oxidative stability of food ingredients 保证食物氧化稳定性

• Taste and odor masking 味道和气味遮盖

Household/ Personal Care

家庭与个人护理:

• Stability of volatile ingredients 提升可挥发

物质的稳定性

• Dose control of actives 活性物剂量控制

• Efficacy of active ingredients 高效活性物

Biocides生物杀菌:

• Safety/ Exposure to actives

接触安全性高的活性物

• Efficacy of actives

高效活性物

Agriculture农业:• Enhanced formulation stability 增强配方稳定性

• Targeted delivery of actives 活性物定向传导

• Improved compatibility 改善兼容性

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 5: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

High Throughput Research & Controlled Delivery and Release高通量研究与控制释放

Why do customers need high throughput research & controlled delivery technology?

5

DOW RESTRICTED

Improved

performance

Consumer demands

Product

differentiation

Formulate new

actives

Access to new

markets

Reduced product

costs

Compatibility/

stability

Formulation

complexity

Controlled

Delivery and

Release

High throughput & controlled delivery and release are the next generation of capabilities to address trends in

formulated products, specifically designed to enhance performance

高通量和控制释放是新一代的技术平台,用以推动配方产品的升级,提升产品性能

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 6: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

High Throughput Research at Dow陶氏的高通量研究平台

6

DOW RESTRICTED

Sample

Preparation Properties Performance70

60

50

40

30

Su

rfa

ce

Te

nsio

n (

mN

/m)

0.001 0.01 0.1

Concentration (wt%)

Tergitol A

Tergitol B

Tergitol C

Tergitol D

Tergitol E

Tergitol F

Tergitol G

Tergitol H

Tergitol I

Tergitol J

Dow

Cle

anin

g I

nde

x

12

13

14

15

16

17

2-EH - 10% 2-EH - 15% 2-octanol - 10%

2-octanol - 15%

Dowanol PnB - 10%

Dowanol PnB - 15%

PnHex - 10%

PnHex - 15%

Tide-Snow

Solvent

All Pairs

Tukey-Kramer

0.05

Rsquare

Adj Rsquare

Root Mean Square Error

Mean of Response

Observations (or Sum Wgts)

0.397577

0.359328

0.821269

14.49079

135

Summary of Fit

Solvent

Error

C. Total

Source

8

126

134

DF

56.08695

84.98491

141.07186

Sum of Squares

7.01087

0.67448

Mean Square

10.3944

F Ratio

<.0001

Prob > F

Analysis of Variance

2-EH - 10%

2-EH - 15%

2-octanol - 10%

2-octanol - 15%

Dowanol PnB - 10%

Dowanol PnB - 15%

PnHex - 10%

PnHex - 15%

Tide-Snow

Level

15

15

15

15

15

15

15

15

15

Number

14.4771

14.2851

15.2826

14.3529

14.2351

13.9370

13.3073

15.4482

15.0918

Mean

0.21205

0.21205

0.21205

0.21205

0.21205

0.21205

0.21205

0.21205

0.21205

Std Error

14.057

13.865

14.863

13.933

13.815

13.517

12.888

15.029

14.672

Lower 95%

14.897

14.705

15.702

14.773

14.655

14.357

13.727

15.868

15.511

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

3.15644

q*

0.05

Alpha

PnHex - 15%

2-octanol - 10%

Tide-Snow

2-EH - 10%

2-octanol - 15%

2-EH - 15%

Dowanol PnB - 10%

Dowanol PnB - 15%

PnHex - 10%

-0.9466

-0.7809

-0.5902

0.0245

0.1487

0.2165

0.2666

0.5647

1.1944

-0.7809

-0.9466

-0.7558

-0.1411

-0.0169

0.0509

0.1009

0.3990

1.0287

-0.5902

-0.7558

-0.9466

-0.3319

-0.2077

-0.1398

-0.0898

0.2083

0.8380

0.0245

-0.1411

-0.3319

-0.9466

-0.8224

-0.7546

-0.7045

-0.4064

0.2233

0.1487

-0.0169

-0.2077

-0.8224

-0.9466

-0.8787

-0.8287

-0.5306

0.0991

0.2165

0.0509

-0.1398

-0.7546

-0.8787

-0.9466

-0.8965

-0.5984

0.0313

0.2666

0.1009

-0.0898

-0.7045

-0.8287

-0.8965

-0.9466

-0.6485

-0.0188

0.5647

0.3990

0.2083

-0.4064

-0.5306

-0.5984

-0.6485

-0.9466

-0.3169

1.1944

1.0287

0.8380

0.2233

0.0991

0.0313

-0.0188

-0.3169

-0.9466

Abs(Dif)-LSD

PnHex - 15% 2-octanol - 10% Tide-Snow2-EH - 10% 2-octanol - 15%2-EH - 15% Dowanol PnB - 10% Dowanol PnB - 15% PnHex - 10%

Positive values show pairs of means that are significantly

different.

PnHex - 15%

2-octanol - 10%

Tide-Snow

2-EH - 10%

2-octanol - 15%

2-EH - 15%

Dowanol PnB - 10%

Dowanol PnB - 15%

PnHex - 10%

Level

A

A

A

B

B

B

B

C

C

C

C

C

D

D

D

D

D

E

E

E

15.448209

15.282564

15.091841

14.477128

14.352936

14.285111

14.235070

13.936983

13.307269

Mean

Levels not connected by same letter are significantly different

PnHex - 15%

2-octanol - 10%

Tide-Snow

PnHex - 15%

2-octanol - 10%

PnHex - 15%

2-EH - 10%

PnHex - 15%

Tide-Snow

PnHex - 15%

2-octanol - 10%

2-octanol - 15%

2-octanol - 10%

2-EH - 15%

PnHex - 15%

2-octanol - 10%

Dowanol PnB - 10%

Tide-Snow

Tide-Snow

2-octanol - 10%

Tide-Snow

Dowanol PnB - 15%

Tide-Snow

2-EH - 10%

2-octanol - 15%

PnHex - 15%

2-EH - 15%

Dowanol PnB - 10%

2-EH - 10%

2-EH - 10%

2-octanol - 10%

PnHex - 15%

2-EH - 10%

2-octanol - 15%

2-octanol - 15%

2-EH - 15%

Level

PnHex - 10%

PnHex - 10%

PnHex - 10%

Dowanol PnB - 15%

Dowanol PnB - 15%

Dowanol PnB - 10%

PnHex - 10%

2-EH - 15%

Dowanol PnB - 15%

2-octanol - 15%

Dowanol PnB - 10%

PnHex - 10%

2-EH - 15%

PnHex - 10%

2-EH - 10%

2-octanol - 15%

PnHex - 10%

Dowanol PnB - 10%

2-EH - 15%

2-EH - 10%

2-octanol - 15%

PnHex - 10%

2-EH - 10%

Dowanol PnB - 15%

Dowanol PnB - 15%

Tide-Snow

Dowanol PnB - 15%

Dowanol PnB - 15%

Dowanol PnB - 10%

2-EH - 15%

Tide-Snow

2-octanol - 10%

2-octanol - 15%

Dowanol PnB - 10%

2-EH - 15%

Dowanol PnB - 10%

- Level

2.140940

1.975295

1.784572

1.511226

1.345580

1.213139

1.169859

1.163098

1.154858

1.095273

1.047493

1.045667

0.997453

0.977842

0.971081

0.929628

0.927802

0.856771

0.806730

0.805436

0.738905

0.629715

0.614713

0.540145

0.415953

0.356368

0.348128

0.298087

0.242058

0.192017

0.190723

0.165645

0.124192

0.117866

0.067825

0.050041

Difference

1.19437

1.02872

0.83800

0.56466

0.39901

0.26657

0.22329

0.21653

0.20829

0.14870

0.10092

0.09910

0.05088

0.03127

0.02451

-0.01694

-0.01877

-0.08980

-0.13984

-0.14113

-0.20766

-0.31686

-0.33186

-0.40643

-0.53062

-0.59020

-0.59844

-0.64848

-0.70451

-0.75455

-0.75585

-0.78092

-0.82238

-0.82870

-0.87874

-0.89653

Lower CL

3.087510

2.921865

2.731142

2.457796

2.292150

2.159709

2.116429

2.109668

2.101428

2.041843

1.994063

1.992237

1.944023

1.924412

1.917651

1.876198

1.874372

1.803341

1.753300

1.752006

1.685475

1.576285

1.561283

1.486715

1.362523

1.302938

1.294698

1.244657

1.188628

1.138587

1.137293

1.112215

1.070762

1.064436

1.014395

0.996611

Upper CL

Comparisons for all pairs using Tukey-Kramer HSD

Means Comparisons

Oneway Analysis of Dow Cleaning Index By Solvent

Symyx XCM

Har

dwar

eS

oftw

are

Design of Experiments (DOE) 实验设计

Robotic formulating/characterization

Dow has various Information Research

groups that work to develop and integrate the

best hardware and software options for HTR陶氏拥有多领域的信息研发小组,协同开发并整合硬件和软件资源,为高通量平台提供最优化的选择

Statistical Experimental

Design, “State of the Art”

High Throughput Tools,

Informatics for Data Handling

and Predictive Modeling

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 7: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

High Throughput Research in Agriculture高通量平台用于农药制剂开发

7

DOW RESTRICTED

Solubility of Polymers and Small Molecules

Instructed

Volume

Experimental Design

Ternary Phase DiagramOutput

• Number of phases

• Volume fraction of

each phase

• Optical clarity of each

phase

Visualization Software

Automated Liquid Handler Phase Characterization

Phase Diagrams

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 8: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Controlled Delivery and Release Expertise and Capabilities 控制释放技术实力

8

DOW RESTRICTED

Particle Design & Engineering Expertise粒子设计及工程专家

Colloid & Interface Science

Polymer Matrix Micro-capsules Colloid synthesis and

characterization Powder Isolation Solubility control

Trigger

Encapsulation /

Process Expertise包覆与工艺专家

Controlled Gelation Interfacial Polymerization Particle Agglomeration Spray Drying Fluidized Bed/Pan

Coating Extrusion Vesicles / Polymersomes

Materials &

Polymer Science Expertise材料学与聚合物科学专家

Polymer Synthesis & Derivatization

Food & Pharma Grade CE Polymers

Stabilizers Dispersants Polymer selection

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 9: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Controlled Release Profiles 控制释放过程

Active release generally has three stages:

活性物释放通常分为三个阶段

• Initial Release (A) (起始阶段)

• Release immediately following trigger event

• Controlled Release (B) (控制释放)

• Release dependent on pathway or mechanism of

active migration

• Equilibrium Release (C) (均衡释放)

• Release which occurs when concentration of active

at destination approaches concentration in structure

Control of all three stages generates any release

profile required (调控三个阶段可以生成各种所需的释放模式)

9

DOW RESTRICTED

• Numerous factors contribute to release rate at

each stage in profile

• Factors dependent on encapsulation scheme

used:

• Particle morphology

• Trigger event

• Release mechanism

100

90

80

70

60

50

40

30

20

10

0

Time

Act

ive

Rel

ease

d (

wt

%)

Typical Active Release Profile

A

B

C

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 10: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Examples of HTR & CDR 高通量与控制释放应用实例

• Solvent replacement in an agrochemical formulation

农化配方里的溶剂替代

• Micro-encapsulation of antimicrobial agent for marine antifouling

抗菌剂微包覆用于海洋防污

• 2,4-D ester formulation with reduced volatility

2,4-D酯配方减小挥发性

10

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 11: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

HTR Solvent Replacement 高通量用于溶剂替代

Challenge 面临的挑战

• Solvents are key components in pesticide and fertilizer additive formulations. There is currently

no universal solvent that works in every formulation – solvent combinations are often optimized

around active ingredients for maximum solubility and emulsifiers to ensure proper emulsification

溶剂是农药和肥料添加剂配方里的主要组分。目前没有一只通用型溶剂可以适用于每一个配方。

通常采用溶剂组合匹配原药以达到最佳的溶解性,并选用乳化剂组合确保合适的乳化效果。

Technical Approach to the Solution: 技术路线

• HTR was used to test the solubility profile for 2 active agricultural compounds for all solvents

established in one round of experiments, versus multiple benchtop iterations

高通量技术被用来评估两种农药原药在大量溶剂里的溶解性,只需一轮实验即可完成,区别于常

规的多批次重复性工作。

11

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 12: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

HTR Solvent Replacement 高通量用于溶剂替代

HTR workflow 高通量流程• 1-2 Active ingredients 1-2个活性物

• 75 single solvents, 125 solvent blends, 4 concentration levels 800 experiments! • 75个单一溶剂,125个复配溶剂,4个浓度梯度 800多个实验

• Solubility determined through PICA digital imaging 溶解度测试通过PICA数字成像技术

• Emulsification determined through clarity analysis 乳化性能评估通过透明度分析

• Selected formulations scaled up on bench for validation 筛选出的配方进行放大实验做二次验证

12

DOW RESTRICTED

Results: New solvents or solvent combinations allowed for fast formulation development in a competitive market

space, crowded with patent protections, and constrained by regulatory restrictions.

A.I. in increasing amounts of solvent

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 13: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Micro-encapsulation of antimicrobial agent for marine antifouling抗菌剂微包覆用于海洋防污

1. Hard fouling 硬污垢

• Barnacles, etc. 藤壶

2. Soft fouling 软污垢

• Algae, etc . 海藻类3. Role of antifoulants 防污的重要性

• Reduce fuel usage 减少燃油使用• Shorten dry-docking intervals 缩短进入船坞间隔• Reduce maintenance 减少维护

4. DCOIT: 4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one 异噻唑啉酮类• Broad spectrum activity 广谱杀菌活性• Excellent eco-toxicological profile 优异的生态毒性• Received US EPA Green Chemistry Challenge award 美国绿色化学奖

13

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 14: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Micro-encapsulation of antimicrobial agent for marine antifoulingBenefits Desired(期望利好):

• Improve service lifetime

延长服役时间

• Improve active handling safety改善活性物处理安全性

• Create higher performing films形成更好性能的防护膜

Approach:

• Capsule based on aminoplast chemistry• Insoluble in formulation solvent (不会溶于配方溶剂)

• Design allows release rate control (释放速率可控设计)

• Active present as a solid (固态活性成分)

• Release triggered by sea water (海水激发释放)

14

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 15: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Micro-encapsulation of antimicrobial agent for marine antifouling抗菌剂微包覆用于海洋防污

Adjustable Release in Sea Water海水中释放可调控

15

DOW RESTRICTED

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200

% o

f T

ota

l Ac

tiv

e R

ele

as

ed

Days

Active Release Comparison of Three Different Capsule Types in Artificial Seawater

Type 1 Capsule

Type 2 Capsule

Type 3 Capsule

Type 3 Capsule for Complete Cu Replacement

Copper-free SPC Coating; 10 months (% active level)

45% Cu2O+ 3% CPT

5% Type 3Encapsulated DCOIT

6% Active C+ 4% Active D

三种不同类型的胶囊在模拟海水中的释放曲线

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 16: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Micro-encapsulation of antimicrobial agent for marine antifouling抗菌剂微包覆用于海洋防污

Desired Performance Achieved (所达到的期望性能)1. Good formulation in-can stability without premature release (良好的配方稳定性,不会提前释放)

2. Controlled release of active in sea water (海水中可控释放)

3. High active loading by weight (活性成分含量高)

4. Readily and evenly disperses in paint and film (极易在油漆和漆膜里均匀分散)

5. Robust to let down tank mixing conditions (50-60˚C at moderate shear rates) (在桶混搅拌时稳定性强)

6. Minimal impact on paint stability & viscosity (对油漆的稳定性和粘度影响极低)

7. Normal film drying & hardness (不会影响漆膜干燥和最终硬度)

8. Acceptable film appearance (可接受的漆膜外观)

9. Compatible with paint components (与油漆其他组分兼容性好)

10. Product complies with all global regulatory requirements

(产品符合全球法规要求)

16

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 17: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

2,4-D Ester Formulation With Reduced Volatility 2,4-D酯配方减小挥发性

Model System: 2,4-D Ethylhexyl Ester (EHE) (2,4-D异辛酯)

• Liquid with low water solubility (0.1 ppm) (低水溶性液体)

• Vapor pressure: 0.480 mPa @ 25C (reference dimethylamine salt: 0.013 mPa)

• Volatility of the ester formulation may result in vapor movement and plant injury outside of field borders

(配方里酯类的挥发所产生的蒸汽易引起地块以外区域的植物受到损害)

17

DOW RESTRICTED

2,4-D EHE

Target: Reduce the ester volatility with minimum impact on efficacy 目标:不降低药效的情况下尽可能减小酯的挥发

Technical Approach 技术方案

• Series of capsule formulations at various size with various shell thickness were prepared

(制备一系列不同尺寸不同壳厚度的胶囊)

• Fast screening: TGA (Thermal Gravimetric Analysis) was used to screen volatility rate (TGA被用来做挥发速率的快速筛选)

• Solvent free formulations were prepared to eliminate solvent effect (无溶剂配方消除溶剂影响)

• Confirm the results with volatility bio-assay (通过生测来确认挥发性结果)

• Extrapolate experimental observations to field scale to predict field performance(外推田试观察结果来预测田试性能)

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 18: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

2,4-D Ester Formulation With Reduced Volatility 2,4-D酯配方减小挥发性

18

DOW RESTRICTED

With ≥20 nm wall, the capsules were

stable up to a certain temperature

Gradual weight loss indicates

leaking of volatiles from capsules

Active:Solvent = 1:1 for all formulations

2,4-D EHE 18.8

Shell Thickness

(nm)

Weight Loss

Rate (µ g/min)

10 18.08

20 12.44

40 7.119

100 3.153

2,4-D DMA 3.012

Fast Screen: Is Encapsulation Reducing Volatility? (快速筛选:通过包覆能降低挥发吗?)

Screening data indicated reduction of volatility with increased shell thickness, approaching profile of 2,4-D

dimethylamine salt 评估结果表明:通过增加胶囊壳层的厚度可以降低挥发,接近2,4-D二甲胺盐的性能

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 19: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

2,4-D Ester Formulation With Reduced Volatility 2,4-D酯配方减小挥发性

19

DOW RESTRICTED

Volatility Comparison (挥发性比较)

• Confirmed that increased shell thickness significantly reduced formulation volatility

(增加壳层厚度被证实可以极大地降低配方的挥发性)

• 100nm capsules reduce the ester volatility to a negligible level

(100纳米壳层厚度的胶囊使2,4-D酯的挥发性降低到可以忽略的水平)

0

10

20

30

40

50

60

70

80

90

100

10 nm1D

10 nm8D

10 nm15D

40 nm1D

40 nm8D

100 nm1D

100 nm5D

100 nm11D

Pla

nt In

jury

(%

)

Volatility Effect on Grapes (Vitis sp.)

Green House

40 Degree C

0

10

20

30

40

50

60

70

80

90

100

10 nm1D

10 nm8D

10 nm15D

40 nm1D

40 nm8D

100 nm1D

100 nm5D

100 nm11D

Pla

nt In

jury

(%

)

Volatility Effect on Tomatoes (Solanum sp.)

Green House

40 Degree C

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 20: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

2,4-D Ester Formulation With Reduced Volatility 2,4-D酯配方减小挥发性

20

DOW RESTRICTED

Weed Control Efficacy (除草效果)

• Efficacy of 100nm capsules was inferior to that of emulsifiable concentrates in green house

(温室实验表明100纳米壳层厚度的胶囊除草效果比相对应的2,4-D异辛酯乳油要差)

0

10

20

30

40

50

60

70

80

90

100

Average ofSIDSP

Average ofCASOB

Average ofABUTH

Average ofCHEAL

Average ofAMBEL

Wee

d C

ontr

ol%

Average Weed Control% Over 5 Use Rates Comparison

2,4-D EHE EC

100 nm

0

10

20

30

40

50

60

70

80

90

100

100 200 400 600 800

Wee

d C

ontr

ol%

Use Rate (g ae/ha)

Average Weed Control% Over 5 Broad Leaf Weeds

2,4-D EHE EC

100 nm

SIDSP: Sida spinosa; CASOB: Senna obtusifolia; ABUTH: Abutilion theophrasti; CHEAL: Chenopodium album; AMBEL: Ambrosia artemisiifolia

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 21: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

2,4-D Ester Formulation With Reduced Volatility 2,4-D酯配方减小挥发性

21

DOW RESTRICTED

Weed Control Efficacy (除草效果)

• Efficacy was maintained for up to 40 nm shell with volatility reduction >50%

(壳层厚度低于40纳米的胶囊除草效果和相对应的乳油类似,但是挥发性降低大于50%)

Pricky Sida: Sida spinosa; Sicklepod: Senna obtusifolia; Velvetleaf: Abutilion theophrasti; Ragweed: Ambrosia artemisiifolia

0

10

20

30

40

50

60

70

80

90

100

200 400 800

Con

trol

%

Use Rate (g ai/ha)

Average Weed Control Over Four Weed Species

20 nm40 nmEC Control

0

10

20

30

40

50

60

70

80

90

100

Ragweed Prickly Sida Sicklepod Velvetleaf

Con

trol

%

Average Weed Control Over Three Rates

20 nm40 nmEC Control

2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 22: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

Controlled Delivery and Release 控制释放

Summary & Conclusions

• High throughput formulation tools are utilized to accelerate research in a variety of application areas

高通量配方开发工具可以加速许多领域的研究工作

• High throughput technique allows formulators to cover more experiments and fast systematic screening of components, addressing unpredictability

associated with active ingredients characteristics

高通量技术可以通过更多实验进行系统地配方组分筛选,发现与活性成分关联的许多不可预见的特性

• Demonstration that microencapsulation can be utilized to control the release and delivery: 微胶囊可以进行有效控制释放

• Shell thickness affects efficacy of certain actives 壳壁厚度影响活性物药效

• Timely release in sea water 海水中释放

• Reduced volatility 降低挥发性

• Through a careful design of materials and the controlled delivery & release profile, capsule formulation can maintain efficacy with proper release profile

and viable manufacturing process 通过材料设计和控制释放,胶囊配方能够在保持药效的同时提供缓释性能

• The combination of HTR & CDR is a powerful formulation development capability to address technology trends in

agrochemicals

高通量平台与控制释放技术相结合,能够提供强有力的配方开发能力,解决农化产品的许多技术热点和难题。

22

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用

Page 23: Using advanced formulation development capabilities to … · Address Technology Trends in Agricultural Formulations ... 2017 China International Agrochemical Conference ... •Received

ThankYou

Product Stewardship

Dow has a fundamental concern for all who make, distribute, and use its products, and for the environment in which we live. This concern is the basis for our product stewardship philosophy by which we assess the safety, health, and environmental information

on our products and then take appropriate steps to protect employee and public health and our environment. The success of our product stewardship program rests with each and every individual involved with Dow products - from the initial concept and

research, to manufacture, use, sale, disposal, and recycle of each product.

Customer Notice

Dow strongly encourages its customers to review both their manufacturing processes and their applications of Dow products from the standpoint of human health and environmental quality to ensure that Dow products are not used in ways for which they are not

intended or tested. Dow personnel are available to answer your questions and to provide reasonable technical support. Dow product literature, including safety data sheets, should be consulted prior to use of Dow products. Current safety data sheets are

available from Dow.

NOTICE II: No freedom from infringement of any patent owned by Dow or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, Customer is responsible for determining whether

products and the information in this document are appropriate for Customer's use and for ensuring that Customer's workplace and disposal practices are in compliance with applicable laws and other government enactments. The product shown in this literature

may not be available for sale and/or available in all geographies where Dow is represented. The claims made may not have been approved for use in all countries. Dow assumes no obligation or liability for the information in this document. References to "Dow" or

the "Company" mean the Dow legal entity selling the products to Customer unless otherwise expressly noted. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE

EXPRESSLY EXCLUDED.

® ™Trademark of The Dow Chemical Company

DOW RESTRICTED2017中国国际农化会议周(CACW2017)资料仅供参会代表学习,禁止随意传播和商用