Recommeded Additives for Polyvinyl Alcohol*
| Type | Brand or Generic Name | Manufacturer | Suggested Use Level |
| | | | |
| Crosslinkers | Sunrez 700 resins | Sequa | 1-4% d/d |
| | — Bacote-20 | Hopton Technology | 2-10% d/d |
| | — Glyoxal | Clariant | 5-15% d/d |
| | — Polycup 172 | Hercules Inc. | 5-10% d/d |
| | | | |
| Defoamers | Foamaster V | Henkel | < 1% d/d |
| | Foamaster KB | Henkel | < 1% d/d |
| | Drewplus L474 | Drew Industrial Div. of | < 1% d/d |
| | | Ashland Chemical Co. | |
| | Colloid 698 | Rhone-Poulenc | < 1% d/d |
| | | | |
| Biocides | Kathon LX | Rohm & Haas | < 50 ppm |
| | Dowicil 75 | Dow Chemical | 1000-2000 ppm |
| | | | |
| Plasticizers | Glycerine | — | 2-5% |
| | Ethylene Glycol | — | 2-5% |
| | Urea | | 1-5% |
Note: *
The FDA compliance status of the recommended
additives should be verified with the respective manufacturer.
Crosslinking
All
polyvinyl alcohol grades are crosslinkable through their secondary hydroxyl functionality. Even lower
hydrolysis grades—which are so exceptional on paper surfaces for oil, grease and organic solvent resistance
and Gurley porosity—can be made water resistant. Degrees of water resistance vary from grade to grade.
The table below shows the effect of glyoxal, a commonly used and favored crosslinker for polyvinyl alcohol.
When glyoxal was added to Celvol grades 540, 350 and 165 polyvinyl alcohol at 20% dry-on-dry, significant
water resistance improvements resulted. Note that the wet tensile of Celvol 540 polyvinyl alcohol increased
from no measurable wet strength uncrosslinked to 6.1 pli when crosslinked. Also, the wet tensile of
crosslinked Celvol 350 polyvinyl alcohol was more than double that of uncrosslinked Celvol 350, and
crosslinked Celvol 165 polyvinyl alcohol was 28% higher than uncrosslinked Celvol 165.
A
vast array of crosslinkers or insolubilizers are available. They include several classes: (1) aldehydes,
of which glyoxal, a simple dialdehyde, is the most common, along with higher aldehydes, such as gluteraldehyde
and hydroxyadipaldehyde; (2) thermosetting resins, such as urea-formaldehyde and melamineformaldehyde;
and (3) salts of multivalent anions, such as zirconium ammonium carbonates.
More
recently, there has emerged a growing interest in zero-formaldehyde, or low-formaldehyde-type crosslinkers.
Two such products are Polycup 172, a water soluble, polyamide-epichlorohydrin-type resin, and Bacote-20,
a zirconium ammonium carbonate salt. The results in the table below indicate that the addition of Polycup
172 to Celvol 165 polyvinyl alcohol at 5% dry/dry parts was as effective as glyoxal added at 20%, both
resulting in a 26% wet tensile improvement. The addition of 5% Bacote-20 resulted in an 11% wet tensile
improvement.
Effect of Glyoxal on Polyvinyl Alcohol Wet
Tensile Strength Chromatography Base Paper*
| Celvol Grade | % Hydrolysis Spec. Range | % Glyoxal Dry/Dry | Wet Tensiles, pli (3 Min in 1% Aerosol OT Solution) |
| | | | |
| 540 | 87-89 | None | 0.0 |
| | | | |
| 540 | 87-89 | 20 | 6.1 |
| | | | |
| 350 | 98-98.8 | None | 3.2 |
| | | | |
| 350 | 98.98.8 | 20 | 6.6 |
| | | | |
| 165 | 99.3+ | None | 6.7 |
| | | | |
| 165 | 99.3+ | 20 | 8.6 |
Note:*
9 add-on level based on fiber; cure 5 min @ 149°C.
Effect
of Crosslinker Type on Wet Tensile of Celvol 165 Polyvinyl Alcohol-Saturated Paper*
| Crosslinker | % Dry/Dry | Instron Wet Tensile (CMD) pli |
| | | |
| None | — | 6.4 |
| | | |
| Glyoxal | 20 | 8.0 |
| | | |
| Bacote-20 | 5 | 7.1 |
| | | |
| polycup 172 | 5 | 8.1 |
Note:*
Whatman No. 4 chromatography paper
10% Celvol 65 add-on
Drying Conditions
were 5 min @ 149°C.