Next Generation of International Chemical Additives

553 Pages·2013·10.46 MB·English

Next Generation
of International
Chemical Additives
A Critical Review of Current US Patents
Thomas F. DeRosa
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ISBN: 978-0-444-53788-1
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This Book is Dedicated to My Mother and Mother-In-Law
Gloria DeRosa
and
Marguerite Schuster
Preface
Within a typical week, approximately 3,000 US Patents are issued and 7,000 US Pat-
ent Applications filed. Within the 9,000 issued patents, 1,800 are directly involved
with chemical sciences associated with new synthetic methods, preparation of bio-
logically active agents, polymers, chemical additives, plastics, and improved or
enhanced chemical or polymer processes. It was the objective of this treatise to focus
our efforts on new and novel or improved chemical additives.
A chemical additive is broadly defined as an agent that can impede, enhance, or
stabilize a chemical process through a unique and anticipated chemical reaction or
physical interaction. Moreover, the amount of additive needed to achieve a specified
goal is completely immaterial.
By contrast additive mixtures or additive packages are defined as the mixture of
two or more chemical agents that achieve the identical objectives as a single addi-
tion but do so by (a) forming an insitu intermediate; (b) become synergistic in the
presence of each other; or (c) act as individual chemical additives. The description
of chemical additives in this text has been separated into 31 categories including:
1 Adhesives; 2 Antioxidants; 3 Automotive Additives; 4 Automotive Tire Additives;
5 Battery And Charge Extenders; 6 Carpets; 7 Colorants; 8 Composites; 9 Cosmet-
ics; 10 Dental Adhesives; 11 Disinfectants; 12 Dispersants; 13 Drilling Additives;
14 Drug Delivery; 15 Electronic Additives; 16 Extreme Pressure Additives; 17 Films;
18 Fire Retardants; 19 Flame Suppressants; 20 Food Additives; 21 Ink; 22 Laundry;
23 Medical; 24 Ophthalmology; 25 Paint Additives; 26 Photography; 27 Polymers;
28 Powder Coating Additives; 29 Surfactants; 30 Textile Additives; 31 Water Treatment.
I urge the reader not to limit their review of chemical additives to sections they
are currently actively involved. In many instances chemical additives described in an
unrelated industrial may be potentially useful agents in your own field. Casual bros-
ing throughout this text is also strongly encouraged since each entry within every
category is accompanied by at least four similar (or dissimilar) chemical additives
along with easy to access references. It is my belief that by reviewing this book in
areas unrelated to your own to identify next generation chemical additives will pay
off handsomely.
Thomas F. DeRosa
ix
Introduction
In order to make a useful polymer product, a variety of additives must be added to
the polymer itself. The commercial success and usefulness is determined by the addi-
tives required for processing, enhancement of specific properties, lifetimes control,
and particular use requirements and forms. Thus the great importance of additives
in polymer systems. This book has great interests for scientists and engineers doing
research and development on additives and to individuals involved in modifying poly-
mers for specific end use requirements. This book alerts all to the latest developments
and possibilities for improvements in all of these areas. Those involved in these areas
should have this book on their desk! The author has done a most useful service to all.
Eli M. Pearce, PhD
University Research Professor
Herman Mark Polymer Research Institute
Polytechnic Institute of NYU
2005 American Chemical Society President
xi
Chapter 1
Adhesives
A.  CROSSLINKABLE ADDITIVE PACKAGE
Trimethoxysiloxane Copolymers
Title: Curable composition
US Patent: 7,772,332 (August 10, 2010)
Author: Katsuyu Wakabayashi
Assignee: Kaneka Corporation (Osaka, JP)
Significance: Curable resins having high mechanical strength, good
adhesive strength and rubber elasticity as well as good
workability without the use of organotin reagents were
prepared. The method entails reacting polypropylene
oxide containing propenyl and trimethoxysilyl termini
with a crosslinkable siloxy and 3-(diethylamino)propyl
amine.
Additive Components The additive composition consists of three components
Adhesive Additive Polypropylene oxide containing propenyl and
trimethoxysilyl terminus (I)
CAS Number Unreported
Safety Concerns Unreported
Additive Component DMSV-42 (II)
CAS Number 68083-19-2
Safety Concerns Mild-to-moderate skin irritant
Additive Component 3-Aminopropyltriethoxysilane (III)
CAS Number 68083-19-2
Safety Concerns Causes eye and skin burns. May cause severe respiratory
tract irritation with possible burns. May cause severe
digestive tract irritation with possible burns. May be
harmful if swallowed.
Additive Structure The crosslinked adhesive resin is the reaction product
comprising
Next Generation of International Chemical Additives. DOI: http://dx.doi.org/10.1016/B978-0-444-53788-1.00001-2
Copyright © 2013 Elsevier B.V. All rights reserved. 1
2 Next Generation of International Chemical Additives
CH
H CO OCH H CO OCH 3
3 3 3 3
Si O Si Si
H3CO O 300 O H O
CH
3
(I)
Adhesitive Component
Adhesive Additive
(II)
OC H
2 5
H N Si OC H
2 2 5
OC H
2 5
Adhesitive Component
(III)
Safety Concerns Since no purification was used in the final preparation of the
curable additive, residual amounts of the following chemical
reagents may be present in varying amounts in the product.
Name Polypropylene oxide diol
CAS Number 25322-69-4
Safety Concerns May be harmful by inhalation, ingestion, and through
skin absorption. May act as an irritant.
Name Zinc hexacyanocobaltate glyme complex
CAS Number 116912-63-1
Safety Concerns Residual zinc hexacyanocobaltate glyme is a moderate
skin irritant.
Name Trimethoxy silane
CAS Number 2487-90-3
Safety Concerns Very toxic. May be fatal if inhaled. May cause blindness.
Corrosive. Harmful if swallowed and in contact with the
skin. Very destructive of mucous membranes.
Name Allyl chloride
CAS Number 107-05-1
Safety Concerns While there is evidence that exposure to allyl chloride may
result in reversible enzymatic evidence of liver damage,
one report described impaired kidney function in workers
exposed to allyl chloride in unknown concentrations.
Name Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
CAS Number 68478-92-2
Safety Concerns Contact with the eyes and the skin may cause irritation.
In susceptible persons, skin reactions may occur. This is a
short-term effect and should go away after washing with
soap and water.
Additive Preparation Commercial supplies of reagent grade additive components
can be obtained from the following suppliers:
Chapter | 1  Adhesives 3
Polypropylene Oxide Diol. Allyl Chloride
Lone Star Chemical Nanjing Fubang Chemical Co., Ltd.
214 E. College Street 5F Tianzheng International Square
Grapevine, TX 76051 No. 399 Zhongyang
888-575-9195 Nanjing of Jiangsu, China
86-25-83179277
Trimethoxy Silane Platinum (0)-1,3-divinyl-1,1,3,3-tetra-
Voster Chemicals methyldisiloxane
415 Huguenot Street United Technical Technologies
New Rochelle, NY 10801 2731 Bartram Road
800-282-3982 Bristol, PA 19007
800-541-0559
Zinc Hexacyanocobaltate Glyme DMSV-42
Bayer Material Sciences Limited Gelest, Inc.
Berthold Alfes 11 East Steel Road
Hong Kong, China Morrisville, PA 19067
852-2894-7357 215-547-1015
Additive Preparation
O
HO OH
50
Zinc Hexacyanocobaltate glyme
CH 0Na, CH =CHCH C1
3 2 2
O
HO O
300
Trimethoxy Silane
Platinum (0)-1,3-divinyl-
1,1,3,3-tetramethyldisiloxane
H CO OCH
3 3
Si O
H CO O O
3 300
Additive Synthesis
1.  Preparation of high molecular polypropylene oxide containing 
an allyl and hydroxyl terminus
A mixture containing polyoxypropylene diol, Mn of approximately 2000 Da,
propylene oxide, and zinc hexacyanocobaltate glyme was reacted at ambient
4 Next Generation of International Chemical Additives
temperature to produce polypropylene oxide having hydroxyl groups at the termini
with an Mn of approximately 25,500 Da. The reaction product was then treated
with 1.2 equivalents of sodium methoxide dissolved in methyl alcohol and then
heated to a sufficient temperature to distill off methyl alcohol. The solution was
then treated with 1.5 equivalents of allyl chloride, and unreacted allyl chloride was
distilled from the reaction vessel. The allyl intermediate was then isolated by dis-
solving 300 parts by weight of n-hexane and water, and water was subsequently
removed by centrifuging. Hexane and any remaining water were then removed by
distillation at a reduced pressure and the product isolated had an Mn of approxi-
mately 26,200 Da.
2.  Preparation of high molecular polypropylene oxide containing 
a trimethoxysilyl terminus and allyl terminus
A reactor containing 100 parts by weight of the Step 1 product was treated with
1.1 parts by weight of trimethoxy silane in a solution of 150 ppm platinum(0)-1,3-
divinyl-1,1,3,3-tetramethyldisiloxane dissolved in isopropyl alcohol, and the mixture
was heated to 90 °C for 2 h. The product that was then isolated had trimethoxysilyl
groups at one end of the termini.
Optimum Treatment Level
Optimum silane coupling entailed using five parts by weight of DMSV-42, 100 parts
by weight of the Step 2 experimental additive and 2–3 parts by weight based of
3-amino-1-triethoxysilyl-propane. Using this weight ratio, the blend can be expected
to cure in approximately 15 min.
Advantages over Prior Art
The curable additive composition of the current invention contains a reactive sili-
con hydrolyzable group bonded to a silicon atom which is curable without the use
of dibutyltin bis(acetylacetonate). The absence of organotin as the curing catalyst
provides a less toxic adhesive and a resin with improved strength and enhanced
adhesiveness.
Notes
1. In an earlier investigation by Wakabayashi,1 the reaction product of trifluoro-
propyl dimethoxy silane and bis(pentafluorophenyl)dimethoxysilane was used
in preparing organotin-free adhesive resins for use in water-resistant applica-
tions.
2. Nishiwaki2 developed a high yielding and general method for silylating nonsi-
lanol hydroxyl groups by dehydrative condensation using t-butyldimethylsilanol
with ytterbium(III) trifluoro-methanesulfonate and obtained conversions exceed-
ing 95%.
3. The silane coupling chemical additive (IV) was used by Tsumura3 to prepare
adhesive resins and light-shielding pastes when blended with titanium oxide.
Chapter | 1  Adhesives 5
SiH
O O
SiH HSi
O O
Si
O N O
N N
SiHO O OHSi
Si Si
O O
O O
SiH HSi
OHSi SiHO
(IV)
4. Saito4 prepared adhesive compositions containing γ-methacryloxypropyltrimethoxy-
silane (V), which were very workable, had excellent adhesion, rubber-like properties,
good storage stability, and were quick curing.
O
OCH
3
O Si OCH
3
OCH
3
(V)
REFERENCES
1. Katsuyu Wakabayashi, US Patent Application 20070265409 (November 15,2007)
Kaneka Corporation (Osaka, JP)
2. Hiromi Nishiwaki et al, US Patent 6,875,880 (April 5, 2005)
Shin-Etsu Chemical, Co., Ltd. (Tokyo, JP)
3. Manabu Tsumura et al, US Patent 7,785,715 (August 31, 2010)
Kaneka Corporation (Kita-ku, Osaka-shi, JP)
Nichia Corporation (Anan-shi, Tokushima, JP)
4. Atsushi Saito et al, US Patent 7,781,559 (August 24, 2010)
Cemedine Co., Ltd. (Shinagawa-ku, Tokyo, JP)
B.  GLASS ADHESIVES
Poly(Acrylic Acid-co-4-Vinylpyridine N-oxide)
Title: Glass Adhesion Promoter
US Patent: 7,829,627 (November 9, 2010) 627
Author: Klin A. Rodrigues et al.
Assignee: Akzo Nobel N.V. (Arnhem, NL)