How thick is the pad? Could it be folded and sewn together to make a slip cover?

This one is pretty thick. There is a 6' X 6' whelping pad that is just a thin layer of rubberized backing with a thin top layer of soft fabric. I think you would be far better off getting one of the very inexpensive padded sofa covers/chair covers/loveseat covers that you can find on Amazon, Wayfair, zulily, or in most home goods stores. I have spilled water and cups oft coffee, andy (small) dog licks herself interminably, and the furniture hasn't gotten wet with one of these. Some are as inexpensive as $15.- some more. You'll save yourself a ylotofwork and disappointment, as sewing the rubberized backing removes the waterproofing pretty much and opens it to tears/gaps/holes.

Is there any padding in this? I just need something for my older Dane to lay on while out on the wooden deck.

Not much. This is primarily to keep liquids from seeping through to the floor. It is not much thicker than a thin quilt. It is great for it's intended use but not for bony dogs who need padded rest areas.

Does it shrink when washed ?

No doesn't shrink...we have washed it several times...holds up great

What is the waterproofing material on this mat?

This mat adopts human-grade fabrics that have passed OEKO-TEX safety fabric certification to provide the highest level of waterproof protection

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🐾 Stay dry, stay stylish—because your pet deserves the best!

SPACIOUS COMFORT ZONE - Extra-large 72" x 72" size fits crates, sofas, and trunks with ease.
SOFT NON SLIP DESIGN - Thick polyester layers provide warmth and prevent slips, perfect for puppies and senior dogs.
CERTIFIED SAFE FOR PETS - Human-grade OEKO-TEX certified polyester keeps your furry family members safe and cozy.
ECO FRIENDLY EASY CARE - Machine washable and reusable—save money and reduce waste without sacrificing convenience.
ULTIMATE LEAK PROTECTION - 100% waterproof TPU backing ensures zero leaks, safeguarding your floors and furniture.

The CoolShields Washable Puppy Dog Pee Pad offers an extra-large 72" x 72" waterproof surface with OEKO-TEX certified polyester for safe, soft comfort. Its leak-proof TPU backing protects floors and furniture, while the thick, non-slip layers keep pets warm and secure. Machine washable and reusable, this pad is perfect for puppies, senior dogs, and multi-pet households seeking a durable, eco-friendly solution.