CYLINK® NBMA Monomer
N-Butoxymethyl Acrylamide for Non-Wovens and Other Applications
A p p l i c a t i o n B u l l e t i n |
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| Introduction |
N-butoxymethyl acrylamide (NBMA), a homolog of
N methylolacrylamide (NMA), is the n-butyl ether of NMA.
It contains a readily polymerizable vinyl group as well as a
crosslinkable n-butoxymethyl group. The n-butyl group
imparts organic solubility to NBMA permitting the
preparation of three general classes of polymers:
- Organic soluble or solvent based polymers which, on
application can be thermoset or crosslinked through
either self or external crosslinking mechanisms.
- Water based or emulsion polymers which, can also
be either self or externally crosslinked at the point
of application.
The presence of the N-butoxymethyl group offers
several advantages in emulsion polymers.
- The organic solubility of NBMA enhances its compatibility
with other vinyl monomers permitting the
incorporation of larger quantities into the polymer
backbone relative to NMA.
- The alkyl ether stabilizes the methylol group,
thus providing greater resistance to premature
crosslinking.
- The N-butoxymethyl group in NBMA provides
a more controllable cure rate, thus minimizing
cracking and checking of the final thermoset
polymers.
- In radiation curing systems, NBMA can be used as
a reactive diluent. All of the components present
in NBMA with the exception of a small amount of
n-butanol are radiation polymerizable through the
vinyl double bond. Upon further heating of
the NBMA-containing radiation-cured polymer,
additional crosslinking can take place through the
N-butoxymethyl group.
The major polymer properties imparted by NBMA include:
- Improved water and solvent resistance
- Improved adhesion
- Improved tensile strength
- Higher impact resistance
- Flexibility
- Resistance to blocking
- Good hand properties
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PRODUCT INFORMATION |
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| Solubility, @ 25°C |
Stability
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Chemical Reactions and Properties
Reactions of the Vinyl Group
NBMA copolymerizes readily with most vinyl monomers
such as acrylates, styrene, vinyl chloride, acrylonitrile,
acrylamide and vinyl acetate.
Reaction of the N-Butoxymethyl Group
Copolymers made with NBMA can be crosslinked utilizing
the reactivity of the N-butoxymethyl group. The cross-linking
reaction can occur via condensation reaction of the
N-butoxymethyl groups with hydroxyl, carboxyl, amine
or amide groups that may be present in the copolymer
system or in the substrates (e.g. cellulosic products) to
which the NBMA-containing copolymer is applied. While
heat alone can affect post cure (cross-linking), generally a
combination of acid catalyst and one or more of the
above mentioned groups in the polymer reduces the time
and temperature of cure. Such groups will also tie up the
hydroxymethyl group as part of the polymer or as part of
the polymer-to-substrate linkage.
The crosslinking (cure) mechanism of the N-butoxymethyl
moiety in such polymers or in polymer-to-substrate
linkages is obviously a very complex chemical reaction
that can only be depicted in a general way by chemical
equations. n-butanol is usually generated during the
crosslinking reaction. |
These reactions can be illustrated generally by chemical equations as follows:
Curing by Heat |
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In the first step, thermal condensation yields the alcohol
as the only cleavage product, yielding Structure 1.
This intermediate can be hydrolyzed in the presence of
water and heat to yield Structure 2, n-butyl alcohol and
formaldehyde.
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Crosslinking with Hydroxyl Groups
The use of an acid catalyst in the presence of a hydroxyl containing compound minimizes or eliminates the release of formaldehyde. |
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Reaction with Carboxyl and Amine Groups
Reaction with these groups follows the same pattern of
crosslinking shown for the hydroxyl group. These reactions
are depicted below showing only the reactive groups of
the polymer backbone. |
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Polymerization: Recipes, Procedures and Properties for Non-Woven Applications
NBMA can be readily copolymerized with most monomers by either solution or emulsion polymerization. Much work has
been done with this monomer and many examples are available from the literature, including application test data related to
the use of the resulting polymers.
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POLYMERIZATION OF BUTYLACRYLATE - METHYLMETHACRYLATEN-
BUTOXYMETHYL ACRYLAMIDE TERPOLYMER
Solids: 51% SAA level: AEROSOL 501 surfactant- 2.7 phm; SAA level: AEROSOL 103 surfactant- 0.6 phm
Ratio: BA/MMA/MAA/NBMA = 46.6/49.7/0.6/4 |
I. RECIPE: 245A
| A) Kettle charge: |
parts per weight |
| B) Monomer charge: |
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| C) Catalyst charge: |
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II. Glass Transition Temperature:
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III. Procedure:
| A)Preparation of kettle charge: |
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Dissolve 6.0 parts AEROSOL 501 surfactant in 260 parts
deionized water. Purge with nitrogen and heat to 65ºC.
Mix 26.2 parts methylmethacrylate and 21 parts
butylacrylate and add into kettle. Slow down the nitrogen
purge and wait for temperature to requilibrate.
Dissolve 0.8 parts of KPS in 30 parts of Deionized water
and place aside with name initial catalyst. |
| B)Preparation of monomer charge: |
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Dissolve 20 parts AEROSOL 501 surfactant and 8 parts
AEROSOL A103 surfactant in 100 parts deionized water.
Add to this solution under sufficient stirring a mix of
210 parts butylacrylate, 220 parts methylmethacrylate,
3 parts of methacryllic acid and 24.4 parts 80%
n-butoxymethylacrylamide-801. This pre-emulsion is
placed in an addition vessel under continuous stirring. |
| C) Preparation of catalyst charge: |
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Dissolve 0.8 parts potassiumpersulphate in 60 parts
deionized water and place in an addition vessel. |
| D)Preparation of latex: |
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When the contents of the polymerization kettle reach
65ºC, add the initial catalyst while raising the
temperature to 75ºC. After initiation start addition of the
pre-emulsion and catalyst at a rate of 2.4 and 0.2 parts
per minute resp. Total addition time should require
4 hours. After finishing the addition hold at 75ºC for
another 1 hour to complete the reaction and cool to
room temperature. Neutralize the polymer to 8.5 pH
with 30 % ammonium hydroxide and filter. |
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IV. Results:
| Parameter |
Poly(BA/MMA/MAA/NBMA-2) |
Poly(BA/MMA/MAA/NBMA-4) |
| Solids (%) |
50.1 |
50.3 |
| pH |
8.5 |
8.4 |
| PS (nm) |
176 |
176 |
| Viscosity (#1, 60RPM) |
48.0 |
63.2 |
| Grit 100# (%) |
0.15 |
0.07 |
| Reactor coat (%) |
0.3 |
0.9 |
| Gel Content (%) |
10.5 |
11.2 |
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V. Film Characteristics:
| MEK Swelling @ 130ºC, 5 minutes
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Poly(BA/MMA/MAA/NBMA-2) |
Poly(BA/MMA/MAA/NBMA-4) |
| Uncatalyzed |
3.05 |
3.40 |
| Catalyzed, pH-3 |
3.38 |
1.97 |
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POLYMERIZATION OF VINYL ACETATE - BUTYL ACRYLATE -
N-BUTOXYMETHYL ACRYLAMIDE -TERPOLYMER
Solids: 50% SAA level: AEROSOL 102 surfactant- 2.0 phm
Ratio: Vinyl Acetate-85/Butyl Acrylate-13/N-Butoxymethyl Acrylamide-4
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I. RECIPE: 952B
| A) Kettle charge: |
parts per weight |
| B) Monomer charge: |
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| C) Catalyst charge: |
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II. Glass Transition Temperature:
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III. Procedure:
| A)Preparation of kettle charge: |
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Dissolve 6.7 parts of AEROSOL A102 surfactant,
1.0 parts sodium bicarbonate and 2.0 parts ammonium persulphate in 110 parts of deionized water. Purge the solution with nitrogen while stirring and heat to 65ºC. |
| B)Preparation of monomer charge: |
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Dissolve 0.4 parts sodium metabisulphite and 6.7
parts AEROSOL A102 surfactant in 75 parts deionized
water. Add under sufficient stirring a mix of 175 parts
vinylacetate, 25 parts Butylacrylate. Place this monomer
pre-emulsion in an addition vessel equiped with stirrer.
10.4 parts NBMA 801 is placed aside. |
| C) Addition of pre-emulsified monomer to polymerization flask: |
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When the contents of the polymerization kettle reach
65ºC, the nitrogen flow is reduced to a minimum and
15% of the monomer is added to the reactor. After
initiation and maximum exotherm, the NBMA solution
is added to the monomer emulsion and the addition
of monomer emulsion is started at a rate of 1.4 parts per
minute. Total addition time requires about 3 - 31/2 hours.
Following monomer addition, the addition line is flushed
with 15 parts of D.I. water and the latex is held at 65ºC
for 1 hour, then cooled to room temperature and filtered
into a suitable container. |
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IV. Results:
| Parameter |
Poly(VA/BA/NBMA-2) |
Poly(VA/BA/NBMA-4) |
| Solids (%) |
48.1 |
48.3 |
| pH |
5.0 |
4.9 |
| PS (nm) |
159 |
155 |
| Viscosity (#1, 20RPM) |
57.0 |
81.5 |
| Grit 60# (%) |
0.01 |
0.01 |
| Grit 150# (%) |
0.001 |
0.001 |
| Reactor coat (%) |
0.02 |
0.02 |
| Gel Content (%) |
1.6 |
0 |
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V. Film Characteristics:
| MEK Swelling @ 130ºC,
5 minutes
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Poly(VA/BA/NBMA-2) |
Poly(VA/BA/NBMA-4) |
| Uncatalyzed |
7.9 |
5.12 |
| Catalyzed, pH-3 |
6.9 |
5.15 |
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Health and Safety Information
Toxicity
Acute oral (rat) and acute dermal (rabbit) LD50 values
are 630 mg /kg and estimated 200-1000 mg / kg,
respectively. Mild skin irritation and mild eye irritation
were produced during primary irritation studies with rabbits.
This material is slightly toxic and the standard precautions
normally exercised in handling toxic materials should be
followed.
CYLINK NBMA Monomer contains materials which may
cause nervous system damage. It also contains formaldehyde
and other materials which caused cancer in
laboratory animals. Acrylamide caused male reproductive
disorders in laboratory animal tests. Refer to the Cytec
Material Safety Data Sheet (MSDS) before using this
product.
Handling, Waste Disposal, Spill
and Leak Procedures
Utilize a closed system process where feasible.
Where a closed system is not used, good enclosure and
local exhaust ventilation should be provided to minimize
exposure. After Acrylamide is in solution, exposure to liquid
and mist must be controlled. Food, beverages and tobacco
products should not be carried, stored or consumed where
this chemical is in use. Before eating, drinking or smoking,
wash face and hands with soap and water. Shower after
completion of workshift. Launder work clothing at end of
workshift prior to reuse. Store street clothing separately
from work clothing and protective equipment. Work clothing
and shoes must not be taken home. Where adequate
engineering controls are in effect, and measurements
confirm airborne concentrations are below the Permissible
Exposure Level, no respiratory protection is required.
NIOSH does not approve a cartridge respirator for use with
Acrylamide. However, tests conducted show that organic
vapor cartridges provide protection from airborne levels up
to 2.5 mg /M3. THE CARTRIDGES MUST BE CHANGED AT
THE BEGINNING OF EACH SHIFT. Full facepiece, positive
pressure, supplied air respirators or self-contained breathing
apparatus must be used for higher or for unknown
concentrations. Full facepiece respirators provide additional
eye protection where handling makes it desirable. |
Note that Acrylamide exhibits no warning properties at concentrations at or below the Permissible Exposure Level. Wear the following to prevent skin contact: impervious rubber or plastic gloves, rubber shoes and long sleeved coveralls, which are provided clean daily. For operations where eye and face contact with Acrylamide solution can occur, wear chemical splash-proof goggles, a faceshield and headcovering. WASH GLOVES THOROUGHLY BEFORE
REMOVING AND DISCARD GLOVES THAT ARE
CONTAMINATED ON THE INSIDE. When solutions are
used, provide eyewash fountain and safety shower in
close proximity to points of potential exposure.
Steps To Be Taken in Case Material is
Released or Spilled
- Remove sources of ignition.
Where exposure level is not known, wear NIOSH
approved, positive pressure, self-contained
respirator.
- Where exposure level is known, wear NIOSH
approved respirator suitable for level of exposure.
In addition to the protective clothing / equipment,
wear impervious boots. Cover spills with some
inert absorbent material; sweep up and place in a
waste disposal container. Flush area with water.
TSCA Information
This product is manufactured in compliance with all
provisions of the Toxic Substances Control Act, 15 U.S.C.
IMPORTANT NOTICE
The information and statements herein are believed to
be reliable but are not to be construed as a warranty
or representation for which we assume legal responsibility
or as an assumption of a duty on our part. Users
should undertake sufficient verification and testing
to determine the suitability for their own particular
purpose of any information, products or vendors
referred to herein. NO WARRANTY OF FITNESS FOR A
PARTICULAR PURPOSE IS MADE. Nothing herein is to be
taken as permission, inducement or recommendation to
practice any patented invention without a license. |
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