the role of polymers in cosmetics formulations: november ......is a polymer made of two different...
TRANSCRIPT
The R
ole o
f Pol
ymer
s in
Cosm
etics
For
mul
atio
ns:
Robe
rt Lo
chhe
ad, P
rofe
ssor
Em
eritu
s of P
olym
er S
cienc
eNo
vemb
er 13
, 201
8. S
CC S
outhw
est C
hapte
r
Poly
mer
?
•Pol
y=
man
y •M
er =
mem
ber
•Pol
ymer
s are
form
ed b
y lin
king
man
y sm
all m
olec
ules
toge
ther
into
ve
ry la
rge
mol
ecul
es
•Th
is gi
ves r
ise to
new
phy
sical
pro
pert
ies
•Et
hyle
ne is
a g
as :
poly
ethy
lene
is a
toug
h so
lid
•Gl
ucos
e is
wat
er-s
olub
le: c
ellu
lose
is w
ater
-inso
lubl
e
•Cop
olym
eris
a po
lym
er m
ade
of tw
o di
ffere
nt m
onom
ers i
n th
e sa
me
mol
ecul
ar ch
ain.
•T
erpo
lym
eris
a po
lym
er co
nsist
ing
of 3
diff
eren
t mon
omer
s in
the
sam
e m
olec
ular
chai
n.
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
2
Poly
mer
Pro
duct
For
ms
•Pol
ymer
solid
s •
Pow
der,f
lake
s, pr
ills,
pelle
ts, f
oils,
chun
ks,
•Am
orph
ous,
crys
talli
ne o
r sem
i-cry
stal
line
•Po
rous
par
ticle
s •P
olym
er so
lutio
ns
•Pol
ymer
latic
es
•Reg
ular
and
Inve
rse
em
ulsio
ns a
nd m
icro
emul
sions
•D
isper
sions
•S
elf a
ssem
bled
ord
ered
stru
ctur
es
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
3
Poly
mer
Cla
ssifi
catio
n
•Sol
ubili
ty
•W
hich
sol
vent
s?•I
onic
char
ge :
•An
ioni
c.no
nion
ic, ca
tioni
c.
•Pol
ymer
izatio
n m
etho
d •
Cond
ensa
tion
(ste
p-gr
owth
) •
Addi
tion
(cha
in g
row
th -f
ree
radi
cal o
r ion
ic p
olym
eriza
tion
•Nat
ural
or s
ynth
etic
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
4
Poly
mer
Fun
ctio
ns
in C
osm
etic
For
mul
atio
ns
•Fi
lm-fo
rmer
s•
Hair
fixat
ives
, Mas
cara
, Nai
l ena
mel
s,Tra
nsfe
r-res
istan
t col
or co
smet
ics•
Thic
kene
rs a
nd R
heol
ogy-
mod
ifier
s.
•Em
ulsio
n-st
abili
zers
, Gel
s, Bi
nder
s, Ha
ir co
lora
nts,
Hair-
rela
xers
•
Emul
sifie
rs
•Lo
tions
, Sun
scre
en, H
air-C
olor
•
Cond
ition
ers
•M
oist
urize
rs
•Em
ollie
nts
•Di
sper
sers
•
Wat
erpr
oofe
rs•
Mic
ropo
re sp
onge
s SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
5
Film
For
mer
s.
•Non
ioni
c •
PVP
[Pol
y(vi
nylp
yrol
idon
e)],
PVP/
VAC
opol
ymer
•Po
lyvi
nylc
apro
lact
am•
Poly
(vin
ylal
coho
l),Po
ly(v
inyl
alco
hol-c
o-vi
nyla
ceta
te)
•Po
lyur
etha
ne-2
,Pol
yure
than
e-5
•PP
G-1
7/IP
DI/
DM
PAC
opol
ymer
•PV
P/D
imet
hico
nyla
cryl
ate/
Poly
carb
amyl
Poly
glyc
olE
ster
•PE
G-2
00 H
ydro
gena
ted
Cas
tor
Oil/
IPD
I Cop
olym
er
•Po
lygl
ycer
yl-2
Diis
oste
arat
e/IP
DI C
opol
ymer
•V
inyl
capr
olac
tam
/PV
P/D
imet
hyla
min
oeth
ylm
etha
cryl
ate
Cop
olym
er [p
oly-
(vin
ylpy
rrol
idon
e-vi
nylc
apro
lact
am-d
imet
hyla
min
oeth
ylm
etha
cryl
ate)
]•
VP/
Vin
yl C
apro
lact
am/D
MA
PA A
cryl
ates
Cop
olym
er•
Cellu
lose
Ace
tate
, Cel
lulo
se A
ceta
te B
utyr
ate,
Cel
lulo
se A
ceta
te P
ropi
onat
e•
Nitr
ocel
lulo
se
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
6
Film
For
mer
s •
Ani
onic
•Sh
ella
c •
Acr
ylat
es C
opol
ymer
•Ac
ryla
tes/
C 1-2S
ucci
nate
s/Hy
drox
yacr
ylat
es C
opol
ymer
•A
cryl
icE
ster
s(an
d)M
etha
cryl
icE
ster
sCop
olym
er•
AM
P-A
cryl
ates
/Ally
l Met
hacr
ylat
e Cop
olym
er•
Dig
lyco
l/Cyc
lohe
xane
dim
etha
nol/I
soph
tala
tes/S
ulfo
isoph
tala
tes C
opol
ymer
D
igly
col/I
soph
tala
tes/
Sulfo
isop
htal
ates
Cop
olym
er•
Isob
utyl
ene
Eth
ylm
alei
mid
e/H
ydro
xyet
hylm
alei
mid
eCop
olym
er•
Gly
ceri
n an
d D
igly
col/C
yclo
hexa
nedi
met
hano
l/Iso
phta
late
s/Su
lfoiso
phta
late
s Cop
olym
er•
Met
hacr
ylat
eAci
d/So
dium
Acr
ylam
idom
ethy
lPro
pane
Sulfo
nate
Cop
olym
er•
Oct
ylac
ryla
mid
e/A
cryl
ates
/But
ylam
inoe
thyl
met
hacr
ylat
eC
opol
ymer
•Po
lyur
etha
ne (a
nd) A
cryl
ates
Cop
olym
er•
PVM
/MA
Cop
olym
er•
PVP/
Eth
ylM
etha
cryl
ate/
Met
hacr
ylic
Aci
dT
erpo
lym
er•
PVP/
Poly
carb
amyl
Poly
glyc
olE
ster
•A
mph
oter
ic•
Acry
late
s/La
uryl
Acry
late
/Ste
aryl
Acry
late
/Eth
ylam
ine
Oxi
deM
etha
cryl
ate
Met
hacr
yloy
lEth
ylBe
tain
e/Ac
ryla
tesC
opol
ymer
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
7
Film
For
mer
s A
nion
ic•
VA/C
roto
nate
sCop
olym
er•
VA/C
roto
nate
s/Vin
yl N
eode
cano
ate
Cop
olym
er
VP/
Acr
ylat
es/L
aury
l Met
hacr
ylat
e C
opol
ymer
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
8
Thic
kene
rs
•N
onio
nic
•H
ydro
xyet
hylc
ellu
lose
,Hyd
roxy
met
hylc
ellu
lose
•M
ethy
lhyd
roxy
ethy
lcel
lulo
se,H
ydro
xypr
opyl
cellu
lose
•H
ydro
xypr
opyl
met
hylc
ellu
lose
•C
etyl
Hyd
roxy
ethy
lcel
lulo
se•
Cor
nSt
arch
,Hyd
roxy
prop
ylSt
arch
Phos
phat
e•
Dis
tarc
hPh
osph
ate,
Dis
tarc
hdi
met
hyle
neur
ea•
Alu
min
umSt
arch
Oct
enyl
Succ
inat
e•
Gua
rgu
m,H
ydro
xypr
opyl
Gua
r•
Loc
ustB
ean
Gum
•R
osin
,Scl
erot
ium
Gum
•M
alto
dext
rin,
Dex
tran
•Po
ly(a
cryl
amid
e)•
PEG-
150
Dist
eara
te,P
EG-1
50/D
ecyl
Alco
hol/
SMDI
Copo
lym
er•
PEG-
150/
Stea
rylA
lcoho
l/SM
DICo
poly
mer
,•
PEG-
180/
Laur
eth-
50/T
MM
GCo
poly
mer
,Pol
yeth
er-1
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
9
Thic
kene
rs
•An
ioni
c •
Acr
ylic
Aci
d/A
cryl
amid
omet
hylP
ropa
neSu
lfoni
cAci
dC
opol
ymer
•Ac
ryla
tes/
C 10-3
0Al
kylA
cryl
ate
Cros
spol
ymer
•A
cryl
ates
/Beh
enet
h-25
Met
hacr
ylat
eC
opol
ymer
•A
cryl
ates
/Ste
aret
h-20
Met
hacr
ylat
eC
opol
ymer
•Ac
ryla
tesC
opol
ymer
(and
)Ste
aret
h-20
•Ac
ryla
tes/
VACr
ossp
olym
er•
Acr
ylic
Aci
d/A
cryl
onitr
ogen
sCop
olym
er•
Am
mon
ium
Acr
yloy
ldim
ethy
ltaur
ate/
Beh
enet
h-25
Met
hacr
ylat
e C
opol
ymer
•A
mm
oniu
mA
cryl
oyld
imet
hylta
urat
e/V
PC
opol
ymer
•C
apry
lic/C
apri
cTri
glyc
erid
e(a
nd)S
odiu
mA
cryl
ates
Cop
olym
er•
Car
bom
er•
PVM
/MA
Dec
adie
neC
ross
poly
mer
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
10
Thic
kene
rs
•Ani
onic
•
Alg
inic
aci
d •
Prop
ylen
e G
lyco
l Alg
inat
e•
Car
agee
nan
gum
(Kap
pa,I
ota,
Lam
bda)
•C
ellu
lose
Gum
(Car
boxy
met
hylc
ellu
lose
)•
Gum
Ara
bic/
Gum
Aca
cia
•K
aray
agu
m•
Xan
than
gum
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
11
Oil
Thic
kene
rs
•D
imet
hico
ne (a
nd) D
imet
hico
ne C
ross
poly
mer
•
Silic
a D
imet
hyl S
ilyla
te
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
12
Emul
sifie
rs
•Tr
agac
anth
gum
•Po
ly(a
cryl
amid
e-b-
acry
licac
id)(
Hyp
anSS
201)
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
13
Cond
ition
ers
•C
hito
san
•C
ocod
imon
ium
Hyd
roxy
prop
ylH
ydro
lyze
dC
olla
gen
•C
ocod
imon
ium
Hyd
roxy
prop
yl H
ydro
lyze
d H
air
Ker
atin
•C
ocod
imon
ium
Hyd
roxy
prop
yl H
ydro
lyze
d K
erat
in•
Coc
odim
oniu
m H
ydro
xypr
opyl
Hyd
roly
zed
Whe
at P
rote
in•
Coc
odim
oniu
m H
ydro
xypr
opyl
Oxy
ethy
l Cel
lulo
se•
Stea
rdim
oniu
mH
ydro
xyet
hylC
ellu
lose
•St
eary
ldim
oniu
mH
ydro
xypr
opyl
Hyd
roly
zed
Oxy
ethy
lCel
lulo
se•
Gua
r H
ydro
xypr
opyl
trim
oniu
m C
hlor
ide
•St
arch
Hyd
roxy
prop
yltr
imon
ium
Chl
orid
e•
Lau
ryld
imon
ium
Hyd
roxy
prop
ylH
ydro
lyze
dC
olla
gen
•L
aury
ldim
oniu
mH
ydro
xypr
opyl
Hyd
roly
zed
Whe
atpr
otei
n•
Stea
ryld
imon
ium
Hyd
roxy
prop
ylH
ydro
lyze
dW
heat
Prot
ein
•Po
lyqu
ater
nium
-4,
Poly
quat
erni
um-1
0,Po
lyqu
ater
nium
-24
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
14
Cond
ition
ers
•A
cryl
amid
e/A
mm
oniu
mA
cryl
ateC
opol
ymer
•Po
ly(m
etha
cryl
oxye
thyl
trim
ethy
lam
mon
ium
met
hosu
lfate
)
•Po
ly(N
-met
hylv
inyl
pyri
dini
umch
lori
de)
•O
nam
erM
(pol
yqua
tern
ium
-1),
PEI-
1500
(Pol
y(et
hyle
nim
ine)
•Po
lyqu
ater
nium
-2
•Po
lyqu
ater
nium
-5-p
oly(
acry
lam
ide-
co-m
etha
cryl
oxye
thyl
trim
ethy
lam
mon
ium
etho
sulfa
te)]
•Po
lyqu
ater
nium
-6po
ly(d
imet
hyld
ially
lam
mon
ium
chlo
ride
)
•Po
lyqu
ater
nium
-7•
poly
(acr
ylam
ide-
co-d
imet
hyld
ially
lam
mon
ium
chlo
ride
)
•Po
lyqu
ater
nium
-8
•Po
lyqu
ater
nium
-11
•[p
oly-
(N-v
inyl
-2-p
yrro
lidon
e-m
etha
cryl
oxye
thyl
trim
ethy
lam
mon
ium
etho
sulfa
te)]
•Po
lyqu
ater
nium
-16
[Co(
viny
lpyr
rolid
one-
viny
lmet
hylim
idaz
olin
ium
chlo
ride
)
•Po
lyqu
ater
nium
-17
•Po
lyqu
ater
nium
-18
•Po
lyqu
ater
nium
-22
•po
ly(s
odiu
mac
ryla
te–
dim
ethy
ldia
llyla
mm
oniu
mch
lori
de)
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
15
Cond
ition
ers
•
Poly
quat
erni
um–2
7•
Poly
quat
erni
um-2
8_•
poly
viny
lpyr
olid
one-
met
hacr
ylam
idop
ropy
ltrim
ethy
lam
mon
ium
chlo
ride
)•
Poly
quat
erni
um-3
1•
Poly
(N,N
-dim
ethy
lam
inop
ropy
lacr
ylat
e-N
-acr
ylam
idin
e-ac
ryla
mid
e-ac
ryla
mid
ine-
acry
licac
id-
acry
loni
trile
)eth
osul
fate
•Po
lyqu
ater
nium
-39
•po
ly(d
imet
hyld
ially
lam
mon
ium
chlo
ride
–so
dium
acry
late
–ac
ryla
mid
e)•
Poly
quat
erni
um-4
3•
poly
(acr
ylam
ide-
acry
lam
idop
ropy
ltrim
oniu
mch
lori
de-2
-acr
ylam
idop
ropy
lsul
fona
te-D
MA
PA)
•Po
lyqu
ater
nium
-44
•Po
ly(v
inyl
pyrr
olid
one-
co-im
idaz
olin
ium
met
hosu
lfate
)•
Poly
quat
erni
um-4
6•
Poly
(vin
ylca
prol
acta
m-v
inyl
pyrr
olid
one-
imid
azol
iniu
mm
etho
sulfa
te)
•Po
lyqu
ater
nium
-47
•po
ly(a
cryl
icac
id-m
etha
cryl
amid
opro
pyltr
imet
hyla
mm
oniu
mch
lori
de–
met
hyla
cryl
ate)
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
16
Cond
ition
ers
•Po
lyqu
ater
nium
-53
•Po
lyqu
ater
nium
-55
•po
ly(v
inyl
pyrr
olid
one-
dim
ethy
lam
inop
ropy
lmet
hacr
ylam
ide-
laur
yldi
met
hylp
ropy
lmet
hacr
ylam
ido
amm
oniu
mch
lori
de)
•PV
P/D
imet
hyla
min
oeth
ylM
etha
cryl
ate
Cop
olym
er•
VP/
DM
APA
Acr
ylat
eC
opol
ymer
•PV
P/D
imet
hyla
min
oeth
ylm
etha
cryl
ate
Poly
carb
amyl
Poly
glyc
olE
ster
•PV
P/D
imet
hico
nyla
cryl
ate/
Poly
carb
amyl
Poly
glyc
olE
ster
•Q
uate
rniu
m-8
0(D
iqua
tern
ary
poly
dim
ethy
lsilo
xane
)•
Poly
(vin
ylpy
rrol
idon
e-co
-dim
ethy
lam
idop
ropy
lmet
hacr
ylam
ide)
•V
P/V
inyl
Cap
rola
ctam
/DM
APA
Acr
ylat
esC
opol
ymer
•A
mod
imet
hico
ne
•PE
G-7
Am
odim
ethi
cone
•Tr
imet
hylsi
loxy
amod
imet
hico
ne
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
17
Cond
ition
ers
•Io
nene
s•
Poly
(adi
pic
acid
-dim
ethy
lam
inoh
ydro
xypr
opyl
diet
hyle
netr
iam
ine)
•po
ly(a
dipi
cac
id-e
poxy
prop
yldi
ethy
lene
tria
min
e)(D
else
tte
101)
•Si
licon
eQ
uate
rniu
m-8
•Si
licon
eQ
uate
rniu
m-1
2
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
18
Hum
ecta
nts
•PE
G-p
oly(
ethy
lene
oxid
e)•
PPG
-po
ly(p
ropy
lene
oxid
e)•
Poly
(eth
ylen
eox
ide-
co-p
ropy
lene
oxid
e)•
Hya
luro
nic
acid
•Po
lygl
ycer
ylm
etha
cryl
ate
•G
lyce
rylP
olym
etha
cryl
ate
•G
lyce
rylp
olym
etha
cryl
ate
and
Prop
ylen
egl
ycol
•G
lyce
rylp
olym
etha
cryl
ate
and
prop
ylen
egl
ycol
and
PVM
/MA
Cop
olym
er•
Gly
cery
lpol
ymet
hacr
ylat
e(a
nd)C
yclo
pent
asilo
xane
(and
)Cyc
lote
tras
iloxa
ne(a
nd)
Poly
sorb
ate
81(a
nd)P
EG
-51
Coc
oam
ine
(and
)Dim
ethi
cono
l(an
d)L
aure
th-9
•G
lyce
rylP
olym
etha
cryl
ate
(and
)But
ylen
eG
lyco
l(an
d)PV
M/M
AC
opol
ymer
•Po
lype
rflu
oroe
thox
ymet
hoxy
Difl
uoro
ethy
lPE
GPh
osph
ate
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
19
Hum
ecta
nts
•Am
phot
eric
and
Zw
itter
ioni
c Po
lym
ers
•H
ydro
lyze
d C
olla
gen,
Sol
uble
Col
lage
n•
Hydr
olyz
edEl
astin
•So
lubl
eKe
ratin
,Hyd
roliz
edKe
ratin
PG-P
ropy
lmet
hylsi
lane
diol
•Hy
drol
ized
Milk
Prot
ein,
Hydr
olize
dPr
otei
n(a
nd)H
yalu
roni
cAci
d•
Hydr
olize
dSi
lk,H
ydro
lized
Silk
PG-P
ropy
lmet
hylsi
lane
diol
•Hy
drol
ized
Soy
Prot
ein/
Dim
ethi
cone
PEG-
7Ac
etat
e•
Hydr
olize
dSo
yPr
otei
nPG-
Prop
ylm
ethy
lsila
nedi
ol•
Solu
ble
Whe
atPr
otei
n•
Hydr
olize
dW
heat
Prot
ein/
Dim
ethi
cone
PEG-
7Ac
etat
e•
Hydr
olize
dW
heat
Prot
ein/
PEG-
20Ac
etat
eCo
poly
mer
•Hy
drol
ized
Whe
atPr
otei
nPG
-Pro
pylm
ethy
lsila
nedi
ol•
Hydr
olize
dW
heat
Prot
ein
(and
)Whe
atO
ligos
acch
arid
es•
Hydr
olize
dW
heat
Prot
ein
Poly
silox
ane
Copo
lym
er•
Hydr
olize
dW
hole
Oat
s•
Isos
tear
oylH
ydro
lized
colla
gen
•So
dium
Lau
royl
Hyd
roly
zed
Silk
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
20
Emol
lient
s •
Bis
-PE
G-1
5 M
ethy
l Eth
er D
imet
hico
ne, B
is-P
EG
/PPG
-20/
20 D
imet
hico
ne•
Dim
ethi
cone
Cop
olyo
l, D
imet
hico
ne C
opol
yol A
ceta
te•
Dim
ethi
cone
Cop
olyo
l N-A
ceta
te T
aura
te (a
nd) S
odiu
m S
alt
•D
imet
hico
ne C
opol
yol P
hosp
hate
, Dim
ethi
cone
PE
G-7
Pho
spha
te•
Dim
ethi
cone
PE
G/P
PG-7
/4 P
hosp
hate
•
Dim
ethi
cone
PE
G-7
Pht
hala
te, D
imet
hico
ne P
ropy
l PG
-Bet
aine
•M
etho
xy P
EG/P
PG-7
/3 A
min
opro
pyl D
imet
hico
ne
•PE
G-12
Dim
ethi
cone
, PEG
/PPG
-17/
18 D
imet
hico
ne•
PEG/
PPG-
20/6
Dim
ethi
cone
, PEG
/PPG
-25/
25 D
imet
hico
ne•
PVP/
Eico
sene
Cop
olym
er•
Beh
enox
y D
imet
hico
ne
•
Bis
-PE
G/P
PG-1
4/14
Dim
ethi
cone
(and
) Cyc
lope
nta-
Silo
xane
•B
is-P
EG
/PPG
-16/
16 P
EG
/PPG
-16/
16 D
imet
hico
ne (a
nd) C
apry
lic/C
apri
c Tri
glyc
erid
e
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
21
Emol
lient
s •
C24
-28
Alk
yl M
ethi
cone
, C30
-45
Alk
yl M
ethi
cone
, C24
-28
Met
hico
ne
•C
etyl
Dim
ethi
cone
•C
etyl
Dim
ethi
cone
Cop
olyo
l
•C
etyl
Met
hico
ne
•C
etyl
PE
G/P
PG-1
0/1
Dim
ethi
cone
•C
etyl
PE
G/P
PG-1
5/15
But
yl E
ther
Dim
ethi
cone
•C
yclo
hexa
silo
xane
•C
yclo
met
hico
ne
•C
yclo
met
hico
ne (
and)
Dim
ethi
cone
Cro
sspo
lym
er
•C
yclo
met
hico
ne (
and)
Tri
met
hylsi
loxy
silic
ate
•C
yclo
pent
asilo
xane
•C
yclo
pent
asilo
xane
(an
d) C
apry
lyl D
imet
hico
ne E
thox
y G
luco
side
•C
yclo
pent
asilo
xane
(an
d) D
imet
hico
ne/V
inyl
trim
ethy
lsilo
xysi
licat
e C
ross
poly
mer
•C
yclo
pent
asilo
xane
(an
d) D
imet
hico
nol
•C
yclo
pent
asilo
xane
(an
d) P
EG
-12
Dim
ethi
cone
Cro
sspo
lym
er
•C
yclo
pent
asilo
xane
(an
d) P
EG
/PPG
-18/
18 D
imet
hico
ne
•D
imet
hico
ne
•D
imet
hico
ne (a
nd) T
rim
ethy
lsilo
xysi
licat
e
•D
imet
hico
ne C
opol
yol
•D
imet
hico
ne (a
nd) D
imet
hico
nol
•D
imet
hico
ne N
F
•D
imet
hico
ne P
EG
-6 A
ceta
te
•D
imet
hico
ne P
EG
-1 I
sost
eara
te
•D
imet
hico
ne P
EG
-7 C
ocoa
te
•D
imet
hico
ne P
EG
-7 O
livat
e
•D
imet
hico
ne P
EG
-8 B
eesw
ax
•D
imet
hico
ne (a
nd) T
rim
ethy
lsilo
xysi
licat
e
•D
imet
hico
ne/V
inyl
dim
ethi
cone
Cro
sspo
lym
er
•D
imet
hico
nol (
and)
Cyc
lom
ethi
cone
(an
d) D
imet
hico
ne
•D
imet
hico
nol (
and)
Cyc
lope
ntas
iloxa
ne
•D
imet
hico
nol (
and)
Dim
ethi
cone
•D
imet
hico
nol F
luor
oalc
ohol
Dili
nole
ic A
cid
•D
imet
hico
nol/I
PDI
Cop
olym
er
•D
isilo
xane
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
22
Emol
lient
s •
Dim
ethi
cone
, Dim
ethi
cone
(and
) Tri
met
hylsi
loxy
silic
ate
•D
imet
hico
ne C
opol
yol,
Dim
ethi
cone
(and
) Dim
ethi
cono
l
•D
imet
hico
ne N
F
•D
imet
hico
ne P
EG
-6 A
ceta
te, D
imet
hico
ne P
EG
-1 I
sost
eara
te
•D
imet
hico
ne P
EG
-7 C
ocoa
te, D
imet
hico
ne P
EG
-7 O
livat
e
•D
imet
hico
ne P
EG
-8 B
eesw
ax
•D
imet
hico
ne (a
nd) T
rim
ethy
lsilo
xysi
licat
e
•D
imet
hico
ne/V
inyl
dim
ethi
cone
Cro
sspo
lym
er
•D
imet
hico
nol (
and)
Cyc
lom
ethi
cone
(an
d) D
imet
hico
ne
•D
imet
hico
nol (
and)
Cyc
lope
ntas
iloxa
ne, D
imet
hico
nol (
and)
Dim
ethi
cone
•D
imet
hico
nol F
luor
oalc
ohol
Dili
nole
ic A
cid,
Dim
ethi
cono
l/IPD
I C
opol
ymer
•D
isilo
xane
•L
aury
l Dim
ethi
cone
•L
aury
l PE
G/P
PG-1
8/18
Met
hico
ne, P
EG
-7 D
imet
hico
ne A
voca
doat
e
•Ph
enyl
Dim
ethi
cone
, Phe
nyl T
rim
ethi
cone
•Po
lym
ethy
lsils
esqu
ioxa
ne
•St
earo
xy D
imet
hico
ne
•St
earo
xy D
imet
hico
ne (a
nd) D
imet
hico
ne
•St
earo
xy T
rim
ethy
lsila
ne (
and)
Ste
aryl
Alc
ohol
•St
eary
l Dim
ethi
cone
•St
eary
l Met
hico
ne
•G
raft-
copo
ly(d
imet
hyls
iloxa
ne/i-
buty
l met
hacr
ylat
e)
• •
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
23
Emol
lient
s •
Stea
roxy
Dim
ethi
cone
•St
earo
xy D
imet
hico
ne (a
nd) D
imet
hico
ne•
Stea
roxy
Tri
met
hyls
ilane
(and
) Ste
aryl
Alc
ohol
•St
eary
l Dim
ethi
cone
•St
eary
l Met
hico
ne•
Gra
ft-c
opol
y(di
met
hyls
iloxa
ne/i-
buty
l met
hacr
ylat
e)•
Graf
t-cop
oly
(IBM
A; M
eFO
SEA/
PDM
S) P
erflu
oron
onyl
Dim
ethi
cone
•Pe
rflu
oroe
ther
s•
Poly
perf
luor
oeth
oxym
etho
xy D
ifluo
rohy
drox
yeth
yl E
ther
•Po
lype
rflu
oroe
thox
ymet
hoxy
Difl
uoro
met
hyl D
iste
aram
ide
•H
ydro
gena
ted
Poly
dece
ne, H
ydro
gena
ted
Poyi
sobu
tene
•Po
lyde
cene
/Pol
ybut
ene
Cop
olym
er
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
24
Emol
lient
Pow
ders
•Si
lk P
owde
r•
Nyl
on –
6, N
ylon
-6/1
2, N
ylon
-12
•Po
lyet
hyle
ne, O
xidi
zed
Poly
ethy
lene
•Tr
imet
hyls
iloxy
silic
ate
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
25
Disp
ersi
ng A
gent
s
•Sod
ium
pol
ysty
rene
sulfo
nate
•Sod
ium
poly
met
hacr
ylat
e•S
odiu
mpo
lyna
phth
alen
esul
phon
ate
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
26
Wat
erpr
oofe
rs
•A
cryl
ates
/Oct
ylac
ryla
mid
e Cop
olym
er•
Acr
ylic
/Acr
ylat
e C
opol
ymer
•Ac
ryla
tes/
C 12-2
2Al
kylm
etha
cryl
ate
Copo
lym
er•
Ethy
lene
/Acr
ylat
e Co
poly
mer
, Eth
ylen
e/Vi
nyl A
ceta
te C
opol
ymer
•PV
P/Ei
cose
ne C
opol
ymer
, PV
P/H
exad
ecan
e C
opol
ymer
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
27
Mic
ropo
re sp
onge
s •
Met
hyl M
etha
cryl
ate
Cro
sspo
lym
er (a
nd) D
imet
hico
ne•
Met
hyl M
etha
cryl
ate
cros
spol
ymer
(and
) Gly
ceri
n•
Met
hyl M
etha
cryl
ate
Cro
sspo
lym
er (a
nd) V
itam
in A
Pal
mita
te (a
nd)
Cor
n O
il
•
Styr
ene/
DV
B C
opol
ymer
(and
) Min
eral
Oil
•La
uryl
Met
hacr
ylat
e/Gl
ycol
Dim
etha
cryl
ate
Copo
lym
er
•La
uryl
Met
hacr
ylat
e/Gl
ycol
Dim
etha
cryl
ate
Copo
lym
er (a
nd)
Cycl
omet
hico
ne•
Laur
yl M
etha
cryl
ate/
Glyc
ol D
imet
hacr
ylat
e Co
poly
mer
(and
) Di
met
hico
ne•
Laur
yl M
etha
cryl
ate/
Glyc
ol D
imet
hacr
ylat
e Co
poly
mer
(and
) Di
met
hico
ne
(and
) Pet
rola
tum
•La
uryl
Met
hacr
ylat
e/Gl
ycol
Dim
etha
cryl
ate
Copo
lym
er (a
nd)
Min
eral
Oil
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
28
Pion
eers
of P
olym
er S
cien
ce
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
29
“I am
incl
ined
to th
ink
that
the
deve
lopm
ent o
f po
lym
eriza
tion
is pe
rhap
s the
big
gest
thin
g th
at c
hem
istry
ha
s don
e, w
here
it h
as h
ad th
e bi
gges
t im
pact
on
ever
yday
life
”
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
30
“Pla
stic
s”
•It’s
a w
onde
rful l
ife –
plas
tic:
•htt
ps:/
/ww
w.y
outu
be.c
om/w
atch
?v=P
GLeM
dlYN
60•T
he G
radu
ate;
•htt
ps:/
/ww
w.y
outu
be.c
om/w
atch
?v=P
Sxih
hBzC
jk
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
31
Her
man
n St
audi
nger
•Cha
lleng
ed F
ritz H
aber
on
‘gas
war
fare
”•C
halle
nged
the
idea
that
pol
ymer
s wer
e m
erel
y ag
greg
ated
–•
Publ
ished
evi
denc
e in
192
0’s f
or la
rge
cova
lent
ly b
onde
d m
olec
ules
and
term
ed
them
‘mac
rom
olec
ules
’•1
926:
Hab
er d
ebat
ed th
e id
ea o
f m
acro
mol
ecul
es; M
ark
supp
orte
d th
e id
ea:
HABE
R W
ON
•Sta
udin
ger o
stra
cized
dur
ing
WW
II•1
953
: Nob
el P
rize
in ch
emist
ry
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
32
Her
man
Fra
ncis
Mar
k 18
95-1
992
•M
ost d
ecor
ated
Aus
tria
n of
ficer
in W
W I
•Do
ctor
ate
from
U. V
ienn
a 19
21•
Mem
ber o
f Kai
ser W
ilhel
m In
stitu
t•
Join
ed IG
Farb
enin
192
7•
X-ra
y cr
ysta
llogr
aphy
“ •
cellu
lose
is a
gia
nt m
olec
ule”
•De
velo
ped
the
met
hod
to m
easu
re p
olym
er m
olec
ular
size
fro
m E
inst
ein’
s visc
osity
theo
ry. [
ή] =
KM
a•
Pion
eere
d PV
C, p
olys
tyre
ne a
nd sy
nthe
tic ru
bber
s•
1936
; ret
reat
ed to
Vie
nna
•19
38 e
scap
ed to
Sw
itzer
land
and
then
Can
ada
and
then
USA
•Es
tabl
ished
the
poly
mer
pro
gram
at B
rook
lyn
Poly
tech
nic
Inst
itute
•M
any
Amer
ican
poly
mer
chem
ists c
an tr
ace
thei
r aca
dem
ic or
igin
s to
this
prog
ram
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
33
Wer
ner K
uhn
Swiss
Phy
sical
Che
mist
–18
99-1
963
•193
0 –
Karls
ruhe
Tech
nica
l Uni
vers
ity
•Fi
rst a
pplic
atio
n of
stat
istica
l the
ory
to p
olym
er sc
ienc
e•
Show
ed th
at ce
llulo
se m
acro
mol
ecul
ar ch
ains
in so
lutio
n ar
e co
iled
rath
er
than
rigi
d•
Appl
ied
stat
istica
l the
ory
to e
xpla
in ru
bber
ela
stici
ty
•Pr
edict
ed th
e M
ossb
auer
effe
ct 2
9 ye
ars b
efor
e M
ossb
auer
disc
over
ed it
.
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
34
Wal
lace
Hum
e Ca
roth
ers 1
896-
1937
•Rec
ruite
d to
Du
Pont
from
Har
vard
In
stru
ctor
ship
•To
inve
stig
ate
poss
ibili
ty o
f syn
thet
ic ru
bber
from
ace
tyle
ne ch
emist
ry
•19
30 A
rnol
d Co
llins
disc
over
ed
chlo
ropr
ene
•Sp
onta
neou
s pol
ymer
izatio
n to
Ne
opre
ne•
Julia
n Hi
ll sy
nthe
sized
firs
t pol
yest
ers
•19
34: d
iscov
ered
Nyl
on (
“New
York
Lo
ndon
”)
•19
37 B
olto
n co
mm
ercia
lized
nyl
on a
s a
fash
ion
fiber
•W
W II
–Ny
lon
Para
chut
es
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
35
Poly
(vin
ylpy
rrol
idon
e) th
e w
orld
’s fir
st
synt
hetic
wat
er-s
olub
le p
olym
er•I
nven
tion
of th
e el
ectr
ic lig
ht•
deva
stat
ed th
e ac
etyl
ene
indu
stry
•I.G
. Far
benf
abrik
en sc
ient
ists s
ough
t oth
er u
ses
for a
cety
lene
•I.G
. Far
benf
abrik
en p
osse
ssed
the
Habe
r Pro
cess
fo
r the
synt
hesis
of a
mm
onia
from
nitr
ogen
and
hy
drog
en•
In 1
938
Paul
Rep
pe sy
nthe
sized
N-2
-vi
nylp
yrro
lidon
e fro
m a
cety
lene
and
am
mon
ia
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
36
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Rep
pe w
ent h
ome
and
left
the
flask
with
the
viny
lpyr
rolid
one
on
the
win
dow
sill
•On
his r
etur
n he
foun
d a
whi
te
solid
in th
e fla
sk•T
he su
nlig
ht h
ad p
olym
erize
d vi
nylp
yrro
lidon
e to
PVP
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
37
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Thi
s am
azin
g po
lym
er d
issol
ved
in w
ater
and
the
solu
tion
was
ve
ry v
iscou
s SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
38
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Thi
s am
azin
g po
lym
er d
issol
ved
in w
ater
and
the
solu
tion
was
ve
ry v
iscou
s SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
39
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Thi
s am
azin
g po
lym
er d
issol
ved
in w
ater
and
the
solu
tion
was
ve
ry v
iscou
s•U
nlik
e na
tura
l gum
s thi
s pol
ymer
ha
d a
wid
e ra
nge
of so
lubi
lity
in
orga
nic s
olve
nts
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
40
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Thi
s am
azin
g po
lym
er w
as
foun
d to
be
safe
in th
e bo
dy•i
t cou
ld b
e ad
ded
to th
e bl
ood
with
out a
ny o
bser
vabl
e ill
effe
cts
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
41
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Dur
ing
Wor
ld W
ar II
•G
erm
an R
ussia
n Fr
ont
•PVP
use
d as
a b
lood
pl
asm
a su
bstit
ute
to sa
ve
man
y Ge
rman
sold
iers
’ liv
es
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
42
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•194
5 GA
F re
ceiv
ed th
e rig
hts t
o PV
P up
on
cess
atio
n of
hos
tiliti
es
•The
y bu
ilt a
pro
duct
ion
facil
ity in
Cal
vert
City
KY
-to
prov
ide
PVP
for K
orea
n W
ar
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
43
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•Kor
ean
War
ceas
ed•
Mar
ket f
or P
VP d
ried
up•
Wha
t to
do?
44SC
C S
W C
HA
PTER
111
8 P
olym
ers
in C
osm
etic
s
Poly
(vin
ylpy
rrol
idon
e) [
PVP]
•195
0’s -
Hairs
tyle
s asc
end
•Hai
rspr
ay b
ecom
es n
eces
sary
•She
llac i
s use
d as
the
fixat
ive
poly
mer
•bu
t she
llac i
s ins
olub
le in
wat
er
•ca
nnot
be
rem
oved
by
sham
poos
45SC
C S
W C
HA
PTER
111
8 P
olym
ers
in C
osm
etic
s
Euge
ne G
uth
1905
-199
0•H
unga
rian
–Na
tura
lized
US
1942
•Pro
fess
or U
. Vie
nna
1932
-37
•Dire
ctor
, Offi
ce o
f Rub
ber R
esea
rch
Proj
ect 1
943-
44•O
RNL P
rofe
ssor
of P
hysic
s-No
tre
Dam
e •D
evel
oped
mod
ern
theo
ry o
f rub
ber
elas
ticity
•Ru
bber
is a
n ‘e
ntro
py sp
ring’ SC
C SW
CHA
PTER
111
8 P
olym
ers i
n Co
smet
ics46
Paul
J. F
lory
191
0-19
85
•Ph
D Ph
otoc
hem
istry
Ohi
o St
ate
U. 1
934
•19
34 -1
937
Du P
ont
•W
orke
d un
der C
arot
hers
•19
43-4
8 Go
odye
ar T
ire &
Rub
ber C
o.•
1948
–In
vite
d by
Deb
ye to
Cor
nell
U.•
Laid
dow
n pr
incip
le o
f exc
lude
d vo
lum
e•
Intr
oduc
ed th
e id
ea o
f The
ta co
nditi
ons
•W
rote
“ Pr
incip
les o
f Pol
ymer
Che
mist
ry”
•19
57 M
ello
n In
stitu
te•
1961
–St
anfo
rd U
. •
Deve
lope
d th
eorie
s of c
hain
stat
istic
s.
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
47
Mau
rice
Loya
l Hug
gins
189
7-19
81
•191
9; C
once
ived
the
idea
of h
ydro
gen
bond
ing
•W
hile
doi
ng P
hD u
nder
G.N
.Lew
isat
UC
Berk
eley
•Pro
duce
d th
e m
odel
of t
he a
lpha
-hel
ix in
194
3•F
lory
–Hu
ggin
s The
ory
1948
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
48
Wat
er S
tock
may
er19
14-2
004
•Lai
d fo
unda
tions
for t
he
stat
istica
l the
ory
of p
olym
er
solu
tions
•Fou
nded
the
jour
nal
‘Mac
rom
olec
ules
’
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
49
Robe
rt S
imha
1912
-200
8
•Doc
tora
te –
U. V
ienn
a 19
37•
Exte
nded
Ein
stei
n’s v
iscos
ity
theo
ry to
elli
psoi
ds a
nd h
ighe
r co
ncen
trat
ions
•M
ajor
cont
ribut
ions
to th
e st
atist
ical t
heor
y of
pol
ymer
s •
Broo
klyn
, NIS
T, US
C, C
ase-
Wes
tern
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
50
Pier
re-G
illes
de
Gen
nes
•Pro
fess
or a
t the
Col
lege
de
Fran
ce•L
iqui
d Cr
ysta
ls•C
ritica
l ove
rlap
conc
entr
atio
n•“
Blob
” The
ory
•i.e
. Cor
rela
tion
Leng
th
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
51
Sam
Edw
ards
Cam
brid
ge U
.•D
evel
oped
theo
ries f
or
poly
mer
s, ge
ls, co
lloid
s and
gl
asse
s•
The
impo
rtan
ce o
f cor
rela
tion
leng
th
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
52
Sum
mar
y
•The
idea
s tha
t wer
e in
trod
uced
in th
is le
ctur
e•
Poly
mer
s dom
inat
e m
ater
ials
in o
ur m
oder
n w
orld
•Th
e in
trod
uctio
n of
the
conc
ept o
f gia
nt m
olec
ules
•Po
lym
er co
nfor
mat
ion
in so
lutio
n •
Coile
d m
olec
ules
•Ho
w to
mea
sure
mol
ecul
ar si
ze
•Co
nden
satio
n an
d ad
ditio
n po
lym
eriza
tion
•Th
e in
trod
uctio
n of
synt
hetic
wat
er-s
olub
le p
olym
ers
•Ru
bber
ela
stici
ty•
The
impo
rtan
ce o
f exc
lude
d vo
lum
e an
d in
tram
olec
ular
forc
es•
Corr
elat
ion
leng
th a
nd o
ur u
nder
stan
ding
of t
he se
mi-d
ilute
dom
ain.
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
53
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
54
Boltz
man
n
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
55
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
56
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
mer
Sol
ubili
ty
Poly
mer
solu
bilit
y an
d in
solu
bilit
y ar
e of
ten
not a
bsol
ute
Phas
e Se
para
tion:
Bin
odal
sand
Spi
noda
ls
57
Poly
mer
Sol
utio
n Th
eory
Flor
y Hu
ggin
s an
d So
lubi
lity
Para
met
er
58
Solu
bilit
y Pa
ram
eter
•
On
the
basis
of “
like
diss
olve
s lik
e”,
Hild
ebra
nd h
ypot
hesiz
ed th
at so
lven
ts
diss
olve
d so
lute
s whe
n th
e fo
rces
be
twee
n th
e m
olec
ules
mat
ched
•Ho
w to
com
pare
the
‘cohe
sive
forc
es’
betw
een
liqui
ds•
Com
pare
thei
r hea
ts o
f vap
oriza
tion
•O
n th
e ba
sis o
f ene
rgy
per u
nit v
olum
e•
Not m
olec
ular
size
.
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
59
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Solu
bilit
y Pa
ram
eter
•Hild
ebra
nd In
trod
uced
the
conc
ept t
hat s
pont
aneo
us m
olec
ular
m
ixin
g oc
curs
whe
n th
e co
hesiv
e en
ergy
den
sitie
s mat
ched
. •
Ener
gy p
er u
nit v
olum
e•
Joul
es/c
ubic
met
reor
jou
les/
cubi
c cm
.
•Hild
ebra
nd d
efin
ed th
e so
lubi
lity
para
met
er a
s the
squa
re ro
ot o
f the
co
hesiv
e en
ergy
den
sity.
•=c
1/2
= (U
/V) ½
= (
g lU/V
) ½
•=
[(g lH
-RT
) /V½
]
•Thi
s wor
ks w
ell f
or m
ater
ials
with
onl
y di
sper
sion
forc
es•
Such
as a
lkane
s.
60
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Solu
bilit
y Pa
ram
eter
•Hild
ebra
nd S
olub
ility
doe
s not
wor
k so
wel
l for
subs
tanc
es th
at a
re
pola
r or L
ewis
acid
s and
Lew
is ba
ses
•Be
caus
e it
does
not
acc
ount
for t
he e
ntro
py lo
ss d
ue to
orie
ntat
iona
l or
derin
g in
thes
e m
ater
ials
•G
=H
-TS
•To
acc
ount
for t
his H
anse
n in
trod
uced
thre
e co
mpo
nent
s of t
he so
lubi
lity
para
met
er:
•Di
sper
sion
•Po
lar
•H-
bond
ing
61
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Solu
bilit
y Pa
ram
eter
•Ho
y in
trod
uced
the
Idea
of f
ract
iona
l sol
ubili
ty p
aram
eter
s •
f disp
ersig
n=
disp
ersig
n/to
tal
•f po
lar
= po
lar /
tota
l•
f H-b
ondi
ng =
H-
bond
ing /
tota
l
•He
show
ed th
at m
olec
ular
mix
ing
was
spon
tane
ous w
hen
the
thre
e fra
ctio
nal r
atio
s mat
ched
•
Solu
bilit
ies o
f pol
ymer
s cou
ld b
e m
appe
d •
Mat
chin
g co
uld
even
be
achi
eved
by
mix
ing
two
non-
solv
ents
•
Raisi
ng th
e m
olec
ular
wei
ght o
f the
solu
te
•Re
stric
ts th
e so
lubi
lity
scop
e
•
62
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Disp
ersio
n Fo
rces
Pola
r For
ces
Hydr
ogen
Bon
ding
100 80
20
60
40
2010
0
80
60
40
4060
8010
020
= Al
kane
s
Hans
en-H
oy S
olub
ility
Par
amet
ers
63
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Solu
bilit
y Di
agra
ms
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
0.0
0.2
0.4
0.6
0.8
1.0
f pf h
f d
Solv
ents
sel
ecte
d
Wat
erKe
tone
s
Alco
hols
Hyd
roca
rbon
sH
alog
enat
ed H
ydro
carb
ons
DM
SO
DM
F
Barto
n, A
.F.M
. H
andb
ook
of S
olub
ility
Par
amet
ers
and
Oth
er C
ohes
ion
Par
amet
ers.
C
RC
Pre
ss: B
oca
Rat
on, F
lorid
a (1
983)
.64
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
PCL
Solu
bilit
y in
Pur
e So
lven
ts
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Hig
hly
Swol
len
Lig
htly
Sw
olle
n In
solu
ble
Car
bon
Tetra
chlo
rideTo
luen
eBe
nzen
eD
ioxa
ne
Chl
orof
orm
Die
thyl
Eth
er
THF
Ethy
l Ace
tate
Met
hyle
ne C
hlor
ide
Pyrid
ine
MEK
Acet
one
DM
F
DM
SO
Prop
ylen
e G
lyco
lAc
etic
Aci
d
Gly
cerin
eFo
rmic
Aci
dM
etha
nol
Wat
erPoly
(Cap
rola
cton
e) 2
5°C
Hydrogen Bonding
Polar Forces
Dis
pers
ion
Forc
es65
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
PVAm
-11
Solu
bilit
y in
Pur
e So
lven
ts
0.00
0.25
0.50
0.75
1.00
0.00
0.25
0.50
0.75
1.00
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Hig
hly
Swol
len
Lig
htly
Sw
olle
n In
solu
ble
Car
bon
Tetra
chlo
rideTo
luen
eBe
nzen
eD
ioxa
ne
Chl
orof
orm
Die
thyl
Eth
er
THF
Ethy
l Ace
tate
Met
hyle
ne C
hlor
ide
Pyrid
ine
MEK
Acet
one
DM
F
DM
SO
Prop
ylen
e G
lyco
lAc
etic
Aci
d
Gly
cerin
eFo
rmic
Aci
dM
etha
nol
Wat
erPoly
(Vin
ylam
ine-
pH 1
1.04
) 25°
C
Hydrogen Bonding
Polar Forces
Dis
pers
ion
Forc
es
66
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
(-C
apro
lact
one)
So
lubi
lity
Diag
ram
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Sw
olle
n In
solu
ble
f hf p
f d
OO
n
67
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
(4-V
inyl
phen
ol)
Solu
bilit
y Di
agra
m
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Sw
olle
n In
solu
ble
f hf p
f d
OH
n
68
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
(Eth
ylen
e ox
ide)
Solu
bilit
y Di
agra
m
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Sw
olle
n In
solu
ble
f hf p
f d
On
69
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
(Vin
ylpy
rrol
idon
e)So
lubi
lity
Diag
ram
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Sw
olle
n In
solu
ble
f hf p
f d
NO
n
70
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Com
posit
e So
lubi
lity
Diag
ram
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Sol
uble
Sw
olle
n In
solu
ble
f hf p
f d
NO
n
OO
n
OO
n O
H
n
On
71
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Hyd
roge
n Bo
ndin
g Pa
ram
eter
(C)
•Spe
ctru
m o
f CH 3
OD in
sa
mpl
e liq
uid
com
pare
d w
ith re
fere
nce
spec
trum
•CH
3OD
in b
enze
ne•
OD
stre
tch:
268
1 cm
-1
•is
the
OD
stre
tch
abso
rptio
n sh
ift (c
m-1
)•N
itrob
enze
ne:
•26
53 cm
-1
•C
= 2.
8
C10
Barto
n, A
.F.M
. H
andb
ook
of S
olub
ility
Par
amet
ers
and
Oth
er C
ohes
ion
Par
amet
ers.
C
RC
Pre
ss: B
oca
Rat
on, F
lorid
a (1
983)
.72
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
H-B
ondi
ng P
aram
eter
(C)
Dia
gram
1214
1618
2022
2426
2830
05101520
C
(MPa
1/2 )
Hyd
roca
rbon
sH
alog
enat
ed H
ydro
carb
ons
Este
rs
Keto
nes
Alco
hols
DM
FD
MSO
CH
3CN
Solv
ents
sel
ecte
d
Barto
n, A
.F.M
. H
andb
ook
of S
olub
ility
Par
amet
ers
and
Oth
er C
ohes
ion
Par
amet
ers.
C
RC
Pre
ss: B
oca
Rat
on, F
lorid
a (1
983)
.73
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
(-C
apro
lact
one)
H
-bon
ding
Inte
ract
ion
Diag
ram
1214
1618
2022
2426
2830
05101520
c
(MPa
1/2 )
Sol
uble
Sw
olle
n In
solu
ble
OO
n
74
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Poly
(Lac
tic a
cid)
H
-bon
ding
Inte
ract
ion
Diag
ram
1214
1618
2022
2426
2830
05101520
c
(MPa
1/2 )
Sol
uble
Sw
olle
n In
solu
ble
OO
n
75
…bu
t we
also
mus
t con
side
r the
ent
ropy
of
mix
ing…
…
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
76
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
77
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
78
Conf
igur
atio
nsSC
C SW
CHA
PTER
111
8 P
olym
ers i
n Co
smet
ics79
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
The
Flor
y-H
uggi
ns In
tera
ctio
n Pa
ram
eter
•Flo
ry-H
uggi
ns ca
lcul
ates
the
conf
igur
atio
nal e
ntro
py o
f pla
cing
the
poly
mer
s in
solu
tion
(on
a la
ttice
)•
Then
F-H
det
erm
ines
the
enth
alpi
cco
ntrib
utio
n re
quire
d fo
r m
olec
ular
mix
ing
•Th
is En
thal
py is
the
Flor
y-Hu
ggin
s Int
erac
tion
Para
met
er,
•=i V
(i-j
)2 /RT
•If
<0.5
, the
syst
em w
ill b
e co
mpa
tible
•
If >2
.0 th
e sy
stem
will
be
inco
mpa
tible
80
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
The
Flor
y-H
uggi
ns In
tera
ctio
n Pa
ram
eter
•Flo
ry-H
uggi
ns ca
lcul
ates
the
conf
igur
atio
nal e
ntro
py o
f pla
cing
the
poly
mer
s in
solu
tion
(on
a la
ttice
)•
Then
F-H
det
erm
ines
the
enth
alpi
c co
ntrib
utio
n re
quire
d fo
r m
olec
ular
mix
ing
•Th
is H
is th
e Fl
ory-
Hugg
ins I
nter
actio
n Pa
ram
eter
, •
=i V(i
-j)2 /
RT•
If <0
.5, t
he sy
stem
will
be
com
patib
le
•If
>2.0
the
syst
em w
ill b
e in
com
patib
le
81
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Flor
y H
uggi
ns T
heor
y
•Th
e th
erm
odyn
amic
s of p
olym
er so
lubi
lity
are
class
ically
des
crib
ed b
y th
e Fl
ory-
Hugg
ins e
quat
ion:
ΔGm
ix/R
T =
x sol
vent
lnΦ
solv
ent+
x pol
ymer
ln Φ
poly
mer
+ χ
x sol
vent
Φpo
lym
er
•w
here
; ΔGm
ix is
the
free
ener
gy o
f mix
ing
of th
e po
lym
er a
nd so
lven
t•
xsol
vent
is th
e m
ole
fract
ion
of so
lven
t in
the
solu
tion
•xp
olym
er is
the
mol
e fra
ctio
n of
pol
ymer
in th
e so
lutio
n•
Φso
lven
t is t
he v
olum
e fra
ctio
n of
solv
ent i
n th
e so
lutio
n•
Φpo
lym
er is
the
volu
me
fract
ion
of p
olym
er in
the
solu
tion
•χ
is th
e Fl
ory-
Hugg
ins i
nter
actio
n pa
ram
eter
for p
olym
er-s
olve
nt
inte
ract
ion.
82
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Flor
y-H
uggi
ns T
heor
y
ΔG m
ix/R
T =
x sol
vent
lnΦ
solv
ent
+ x p
olym
erln
Φpo
lym
er
+χ
x sol
vent
Φpo
lym
erM
ixin
g En
trop
y co
ntrib
utio
n:Al
way
s fa
vora
ble
to
mix
ing
Mix
ing
Enth
alpy
co
ntrib
utio
n83
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Flor
y-H
uggi
ns T
heor
y
+χ
x sol
vent
Φpo
lym
erM
ixin
g En
thal
py
cont
ribut
ion
poly
mer
and
solv
ent a
re co
mpl
etel
y m
iscib
le o
ver t
he e
ntire
com
posit
ion
rang
e if[
i],[ii
],[iii
], [iv
]:
χ<
½( 1
+ (V
poly
mer
/ Vso
lven
t) -1
/2)2
[i]Fl
ory,
P. J.
“The
rmod
ynam
ics o
f hig
h po
lym
er so
lutio
ns”,
J.Che
m. P
hys.,
194
2, 1
0, 5
1.[ii
]Flo
ry, P
.J.; “
Prin
ciple
s of P
olym
er C
hem
istry
,” Co
rnel
l Uni
vers
ity P
ress
, Ith
aca,
N.Y.
, 195
3.[ii
i]Pa
tters
on, D
; Mac
rom
olec
ules
, 196
9, 2
, 672
[iv]B
arto
n, A
llan,
F. M
.; “H
andb
ook
of S
olub
ility
Par
amet
ers a
nd O
ther
Coh
esio
n Pa
ram
eter
s;
CRC
Pres
s, Bo
ca R
aton
, Flo
rida,
198
3.84
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Flor
y-H
uggi
ns T
heor
y
•A p
olym
er a
nd so
lven
t sho
uld
be co
mpl
etel
y m
iscib
le if
the
valu
e of
the
Flor
y-Hu
ggin
s in
tera
ctio
n pa
ram
eter
, χ, i
s les
s tha
n 0.
5.
85
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Draw
back
s of t
he F
lory
-Hug
gins
The
ory
•χ
is no
t a co
nsta
nt; i
t var
ies w
ith p
olym
er co
ncen
tratio
n an
d te
mpe
ratu
re.
•χ
can
not b
e ea
sily
foun
d ex
perim
enta
lly.
•χ
is ch
arac
teris
tic o
f onl
y a
poly
mer
-sol
vent
pai
r and
it is
not
eas
ily e
xten
ded
to
mul
ticom
pone
nt fo
rmul
atio
ns.
•χ
is no
t a si
mpl
e te
rm; i
t has
to b
e m
odifi
ed to
inclu
de te
rms f
or m
olec
ular
or
ient
atio
n an
d sp
ecifi
c bin
ding
such
as h
ydro
gen
bond
ing.
•If
the
syst
em b
ecom
es m
ore
orde
red
whe
n a
solu
tion
is fo
rmed
, χca
n ha
ve
anom
alou
s lar
ge p
ositi
ve va
lues
.•
Fina
lly, c
lass
ical F
lory
-Hug
gins
theo
ry ca
n no
t exp
lain
the
fact
that
pol
ymer
so
lutio
ns ca
n se
para
te in
to tw
o ph
ases
upo
n he
atin
g or
cool
ing
beyo
nd ce
rtai
n cr
itica
l tem
pera
ture
s.3 [i][
ii]•
This
is es
peci
ally
per
tinen
t for
ther
mo-
asso
ciativ
e po
lym
ers.
•[i]
Patte
rson
, D.;
“The
rmod
ynam
ics o
f non
-dilu
tee
poly
mer
solu
tions
”; R
ubbe
r Ch
em. T
echn
ol.,
1967
, 40,
1.
•[ii
]Pat
ters
on, D
., De
lmas
, G.;
Som
cyns
ky, T
; “A
Com
paris
on o
f low
er cr
itica
l so
lutio
n te
mpe
ratu
res o
f som
e po
lym
er so
lutio
ns”,
Poly
mer
, 196
7, 8
, 503
.
86
Gen
eral
ized
Phas
e Di
agra
m fo
r a
Poly
mer
in S
olut
ion
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
87
Bin
odal
Tie
Line
s
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
88
XY
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Free
Ene
rgy
of M
ixin
g
•A sy
stem
reac
hes c
hem
ical e
quili
briu
m (a
nd th
is in
clud
es p
hase
eq
uilib
ria) w
hen
the
free
ener
gy o
f the
syst
em re
ache
s a m
inim
um.
•Th
e ch
ange
in G
ibbs
free
ene
rgy
(ΔG)
is re
late
d to
the
chan
ges i
n en
thal
py (Δ
H) a
nd e
ntro
py (Δ
S) o
f a p
roce
ss a
t tem
pera
ture
, T, b
y th
e fa
mili
ar e
quat
ion:
ΔG =
ΔH
–T
ΔS•P
hase
sepa
ratio
n be
low
the
UCST
requ
ires a
sign
ifica
nt n
egat
ive
enth
alpy
of m
ixin
g, a
nd p
hase
sepa
ratio
n ab
ove
the
LCST
requ
ires
both
a n
egat
ive
enth
alpy
and
ent
ropy
of m
ixin
g.
89
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Cond
ition
s for
M
iscib
ility
and
Pha
se S
epar
atio
n
The
Exc
ess
Free
Ene
rgy
and
Pha
se S
epar
atio
n
Pol
ymer
con
cent
ratio
n
exce
ssG
mix
One
-pha
se
Pol
ymer
con
cent
ratio
n
exce
ssG
mix
Two-
phas
eA
B
C1
C2
X
(a)
(b)
The
exce
ss fr
ee e
nerg
y as
a fu
nctio
n of
pol
ymer
conc
entr
atio
n fo
r (a)
a
misc
ible
solu
tion
and
(b)
a ph
ase-
sepa
rate
d sy
stem
90
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Met
asta
ble
Equi
libria
and
Ther
mal
Gel
ling
Diff
usio
n O
bsta
cles
to P
hase
Sep
arat
ion
Pol
ymer
co
ncen
trat
ion
exce
ssG
mix
Tw
o-ph
ase
AB
C 1
C 2X
Infle
ctio
n po
int
Diffu
sion
to p
hase
sepa
ratio
ndi
sfav
ored
Diffu
sion
to p
hase
sepa
ratio
nfa
vore
d
Expl
oded
vie
w o
f a se
gmen
t of t
he fr
ee e
nerg
y cu
rve
show
ing
the
infle
ctio
n po
int.
91
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Spin
odal
s an
d Bi
noda
ls S
pino
dalD
ecom
posi
tion
Poly
mer
Con
cent
ratio
n
Tem
p.
LCS
T
UC
ST
This
locu
s of
po
ints
defin
esth
e sp
inod
al
Spi
noda
lD
ecom
posi
tion
Reg
ions
92
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Spin
odal
s an
d Bi
noda
ls S
pino
dalD
ecom
posi
tion
Poly
mer
Con
cent
ratio
n
Tem
p.
LCS
T
UC
ST
This
locu
s of
po
ints
defin
esth
e sp
inod
al
Spi
noda
lD
ecom
posi
tion
Reg
ions
Diffu
sion
driv
en
phas
e se
para
tion
favo
red
Diffu
sion
has
to g
o up
hill
agai
nst
Chem
ical
pote
ntia
l
93
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
Sum
mar
y of
Po
lym
er S
olub
ility
The
orie
s
•Flo
ry –
Hugg
ins a
ttem
pts t
o in
clude
ent
ropy
of m
ixin
g•
It is
diffi
cult
to ca
lcula
te th
e to
tal e
ntro
py o
f mix
ing
for p
olym
er so
lutio
ns a
nd
blen
ds•
But F
lory
-Hug
gins
The
ory
is us
eful
for c
once
ptua
l und
erst
andi
ng
•Sol
ubili
ty P
aram
eter
theo
ry co
nsid
ers o
nly
enth
alpy
of m
ixin
g•
But i
t is u
sefu
l pra
ctica
lly a
nd re
lativ
ely
easy
to u
se•
if th
e in
tera
ctio
ns a
re d
ivid
ed in
to d
isper
sion,
pol
ar a
nd h
ydro
gen
bond
ing
94
Poly
mer
Cha
ins
The
Basic
s
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
95
The
Fund
amen
tal P
aram
eter
s
C1
C2
C3
C4
(RO
TAT
ION
AL
AN
GL
E)
( hin
dran
ce a
ngle
)
aB
ond
leng
th
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
96
The
Fund
amen
tal P
aram
eter
s
C1
C2
C3
C4
(RO
TAT
ION
AL
AN
GL
E)
( hin
dran
ce a
ngle
)
aB
ond
leng
th
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
97
The
Fund
amen
tal P
aram
eter
s
C1
C2
C3
C4
(RO
TAT
ION
AL
AN
GL
E)
( hin
dran
ce a
ngle
)
aB
ond
leng
th
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
98
Dilu
te S
olut
ions
, c’
•The
pol
ymer
chai
n be
have
s as a
smal
l sph
ere
•a
singl
e bl
ob, w
ith ra
dius
, r•E
xam
ple:
•Ea
ch p
olym
er ch
ain
is an
isol
ated
chai
n at
c’•
The
leng
th sc
ale
Lis r
epre
sent
ed b
y th
e ra
dius
rand
is e
qual
to th
e co
rrel
atio
n le
ngth
, •
ther
efor
e, r
=
•th
e co
ils a
re se
para
te fr
om o
ne a
noth
er
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
99
Sem
idilu
te S
olut
ions
•As c
once
ntra
tion
incr
ease
s•
blob
s ove
rlap
•ch
ains
inte
ract
and
inte
rpen
etra
te•A
bove
c*•
coils
bec
ome
enta
ngle
d an
d fo
rm a
net
wor
k of
mes
h •
isth
e di
stan
ce b
etw
een
two
enta
ngle
men
t poi
nts
SCC
SW C
HAPT
ER 1
118
Pol
ymer
s in
Cosm
etics
100