US010259970B2

(12) United States Patent ( 10 ) Patent No.: US 10 ,259,970 B2

Chen et al. (45) Date of Patent: Apr. 16 , 2019
(54 ) POLYETHER COMPOUNDS HAVING EPOXY OTHER PUBLICATIONS
HYDROXYL URETHANE GROUPS AND
WATERBORNE EPOXY RESIN Kihara et al.,“ Synthesis and Properties of Poly(hydroxyurethane)s,”
COMPOSITION Journal of Polymer Science: Part A : Polymer Chemistry , vol.
31(11), pp . 2765- 2773 ( 1993 ) (Year: 1993 ).*
(71 ) Applicant: CHANG CHUN PLASTICS CO ., * cited by examiner
LTD ., Taipei ( TW )
Primary Examiner — Randy P Gulakowski
( 72 ) Inventors: Gai - Chi Chen, Taipei (TW ) ; Chia- En Assistant Examiner — Ha S Nguyen
Wu, Taipei (TW ) ; An - Pang Tu , Taipei (74 ) Attorney, Agent, or Firm — Muncy , Geissler , Olds &
( TW ); Kuen - Yuan Hwang, Taipei Lowe, P .C .
( TW )
(57 ) ABSTRACT
(73 ) Assignee: CHANG CHUN PLASTICS CO ., The present invention is to provide polyether compounds
LTD ., Taipei (TW ) having epoxy hydroxyl urethane group , as the following
formula (I), (II) or (III) shows:
( * ) Notice : Subject to any disclaimer, the term of this
patent is extended or adjusted under 35
U .S .C . 154 (b ) by 210 days.
OH
(21) Appl. No.: 15/487,158
N. LO
(22) Filed : Apr. 13, 2017 R3 R3 R3
(65 ) Prior Publication Data LOH
US 2017 /0321080 A1 Nov. 9 , 2017
(30 ) Foreign Application Priority Data RE

May 9, 2016 (TW ) . ..... 105114294 A

Oct. 26 , 2016 ( TW ) . . .. . . . .. . ................ 105134507 A
(51) Int. CI.
C09D 163 / 00 ( 2006 .01)
C08G 65 / 331 ( 2006 .01)
CO8G 59/ 06 ( 2006 .01) OH
OH
C08G 59/22 ( 2006 .01)
C08L 63 /00 (2006 .01)
C08G 59/ 10 ( 2006 . 01) Rai
(52) U .S . CI. OH
CPC . ... C09D 163 /00 (2013.01); C08G 59 /063 (III)
( 2013 .01) ; C08G 59 /066 (2013.01); C08G
59/ 10 (2013 .01) ; C08G 59/ 226 (2013 .01) ;
C08G 65/3318 (2013 .01); C08L 63/ 00
(2013.01); CO8L 2201/54 (2013.01); COEL R3 - R2
2205/025 (2013 .01)
(58 ) Field of Classification Search ??

None

(56 )
See application file for complete search history .
References Cited
HO
olyfenotiNRz;
U .S . PATENT DOCUMENTS
2013 /0004677 A1 * 1/ 2013 Hwang .................. CO8G 71/04 and waterborne epoxy resin composition . Using the
427 /512 hydroxyl urethane as emulsifier, the obtained waterborne
epoxy resin composition of the present invention has better
FOREIGN PATENT DOCUMENTS stability and freeze - thaw resistance .
CN 104559681 A * 4 /2015 12 Claims, No Drawings
 US 10 ,259 ,970 B2
POLYETHER COMPOUNDS HAVING EPOXY epoxy resin , so as to allow the epoxy resin to be dissolved
HYDROXYL URETHANE GROUPS AND or dispersed in water. According to the different water -based
WATERBORNE EPOXY RESIN way , it can be classified into self -emulsifying waterborne
COMPOSITION epoxy resins and external-emulsifier emulsified waterborne
5 epoxy resins.
BACKGROUND OF THE INVENTION Therein , the method of using an external emulsifier for
emulsification involves adding a proper emulsifier, and
pulverizing and mixing the epoxy resin , water, and the
1 . Technical Field emulsifier by means of, for example , mechanical stirring ,
thereby forming an emulsion . This method is easy to operate
The present invention relates to novel polyether com - " and requires low costs. However, products so made have
pounds having epoxy hydroxyl urethane groups and water poor stability in water and relatively large dispersion phase ,
borne epoxy resin composition . while the film foul ing properties thereof are not good
enough . Hence , the industry is still in urgent need of a
2 . Description of Related Art suitable emulsifier that is able to improve epoxy resin
15 emulsions in terms of stability and freeze -thaw resistance .
A waterborne epoxy resin (WER ) is a stable dispersion
system wherein the continuous phase is water and the SUMMARY OF THE INVENTION
dispersion phase is epoxy resin particles or droplets , and one
of its main uses is application in waterborne epoxy paints. To solve the foregoing problem , one primary objective of
Waterborne epoxy paints are similar to solvent-based epoxy 20 the present invention is to provide a polyether compound
resin paints in the way they work . An epoxy resin before having epoxy hydroxyl urethane group , and has a structural
applied has a linear structure , and upon its application it formula (I), (II) or ( III):

vittly fryhenteet
R3 Rz
?? OH

R2 R3;

R3 R

OH OH

OH
HO

45
undergoes cross - linking reaction and forms a net- like thin wherein , n is 2 – 70 ;
film having excellent properties. For this to be achieved , a R? is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl, a polyether
curing agent has to be added just before the paint is used so group or the structural formula ( IV ) :
as to activate chemical cross - linking reaction of the water
borne epoxy at room temperature . Waterborne epoxy paints 50
have many advantages, such as good adaptability , and high (IV )
adhesion to many carrier materials . In addition , the cured
paint coating has less shrinkage, great hardness, high abra
sion resistance , good electrical insulation , high resistance to
corrosion and chemicals , superb environmental friendliness ,
low VOC contentmaking it unlikely to cause air pollution ,
good operability allowing it to be cured at room temperature
and in humid places, reasonable curing time, and ensured
55 fant
wherein , m is ( - 5 , and
OH

R , is one of the structural formulas as below :

cross -linking density . Besides, working with waterborne
epoxy paints is convenient because the tools used can be 60
easily cleaned with water .
Epoxy resins are insoluble to water, and only soluble to
organic solvents such as aromatic hydrocarbon and ketones .
Preparation of a waterborne epoxy resin means making the
original solvent- type epoxy become waterborne , and is 65
usually achieved by introducing a hydrophilic molecular
chain or a component acting as an emulsifier to the original
 US 10 ,259 ,970 B2
- continued wherein , p is 0 - 5 , and
R , is one of the structural formulas as below :

R , is C2- 4 alkyl ;
Rz is the structural formula ( V ) or (VI):

( V ) 30

n OH In a preferable embodiment, wherein the polyether com

pound having epoxy hydroxyl urethane group is an emulsi
(VI)
RO 35 fier of an epoxy resin .
Another primary objective of the present invention is to
provide a waterborne epoxy resin composition , which com
OH , prises : (a ) an epoxy resin , (b ) hydroxyl urethane, and (c )
water.
10 In a preferable embodiment, wherein the hydroxyl ure
wherein , Ro is C4 ~ 12 alkyl , alkenyl, alkynyl, cycloalkyl or thane is a polyether compound having epoxy hydroxyl
a polyether group ; urethane group . In a more preferable embodiment, it has a
structure as defined by Formula (I), ( II) or ( III) as stated
R4 is the structural formula (VII ) or ( VIII): above.
In another preferable embodiment, the hydroxyl urethane
43 having HLB value of 4 - 17 .
( VII) In another more preferable embodiment, the hydroxyl
urethane having HLB value of 12 ~ 15 .
voor OH
In a preferable embodiment, the waterborne epoxy resin
composition further comprises a solvent.
(VIII ) 50 In another more preferable embodiment, the epoxy resin
6 - R, W is in amount of 30 ~ 65 wt % based on the total weight of the
waterborne epoxy resin composition ; the hydroxyl urethane
is in amount of 3 ~ 15 wt % based on the total weight of the
waterborne epoxy resin composition ; the water is in amount
55 of 30 –65 wt % based on the total weight of the waterborne
epoxy resin composition ; the solvent is in amount of 1 - 20
wherein , R , is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl, a wt % based on the total weight of the waterborne epoxy resin
polyether group or the structural formula (IX ) as below : composition .
In another preferable embodiment, the solvent is any one
60 or more than one selected from the group consisting of
(IX ) alcohols , ethers , and ketones.
In a preferable embodiment, wherein the waterborne
epoxy resin composition is used as paint.
Another primary objective of the present invention is to
OH 65 provide a method for making an epoxy resin waterborne,
which comprises mixing the epoxy resin and hydroxyl
urethane , adding water, and performing emulsification .
 US 10 ,259,970 B2
5
In a preferable embodiment, the epoxy resin and hydroxyl - continued
urethane are mixed in a solvent.
In a preferable embodiment, mixing is conducted at an
elevated temperature , such as 50 – 80° C .
In another preferable embodiment, water is added at a 5
speed of 2 - 10 ml/min .
In another preferable embodiment, wherein the hydroxyl
urethane polyether compound has a structure as defined by
Formula (I), ( II) or ( III) as stated above .
10
DETAILED DESCRIPTION OF THE
INVENTION
Polyether Compound Having Epoxy Hydroxyl Urethane
Group of the Present Invention 15
One primary objective of the present invention is to
provide a polyether compound having epoxy hydroxyl ure
thane group , and has a structural formula (I), ( II) or (III) as
below :

with theConstantin
OH

N OJ?
R3
PRE DRE

witntly goingkatan
R3 Rz
LO
Rz
OH OH
NJ od
TRE LRE R3;
( II)

destymogla
wherein , n is 2 – 70 ;
OH
RIÓ
??

R is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl, a polyether 45

K
.

-continued
R3;
(III)

group or the structural formula ( IV ) as below : O

=

=
(IV) 50

OH
R , is C2 - 4 alkyl;
Rz is the structural formula (V ) or (VI) as below :
55
wherein , m is 0 - 5, and
R , is one of the structural formulas as below : R6- Ó
OH

?? .
?
 US 10 ,259,970 B2
wherein , Ro is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl or a polyether compound having epoxy hydroxyl urethane
a polyether group ; group . The reaction can produce compounds of Formulas
R4 is the structural formula (VII) or ( VIII) as below : (I ), ( II ) and ( III) of the present invention . The term AGE
refers to C12 ~ C14 alkyl glycidyl ether, which is an epoxy
5 resin have a single functional group .

Volony OH
( VII) Waterborne Epoxy Resin Composition of the Present
Invention
Another primary objective of the present invention is to
provide a waterborne epoxy resin composition , which com
(VIII ) 10 prises: (a ) an epoxy resin , ( b ) hydroxyl urethane, and ( c )
water. For the purpose of this specification , the waterborne
epoxy resin composition is also referred to as the epoxy resin
emulsion .
OH , The epoxy resin used in the present invention may be
15 conventional epoxy resins. Examples thereof include gly
cidyl ether epoxy resins , glycidyl ester epoxy resins, gly
wherein , R , is C4~ 12 alkyl, alkenyl , alkynyl, cycloalkyl, a cidyl
polyether group or the structural formula (IX ) as below : amine epoxy resins, linear aliphatic epoxy resins,
alicyclic epoxy resins, epoxy resins obtained from bisphenol
A , bisphenol For bisphenol sulfone , phenol phenolic
20 novolac resins, polyepoxy propyl ethers of cresol novolac

firyta OH
resins, polyepoxy propyl ether of oxyalkylene adducts of
bisphenol A , poly propylene glycol, 1,6 -hexanediol, trim
ethylol propane , polyepoxy propyl ethers of polyvalent
alcohols such as glycerol, adipic acid , phthalic acid , poly
25 epoxy propyl ester of poly carboxylic acids such as dimeric
acid , and polyepoxy propyl amine . Other epoxy resins also
wherein , p is 0 - 5, and comprise glycidyl ether , and may be prepared by making
Rg is one of the structural formulas as below : epichlorohydrin react with a compound having at least 1.5
aromatic hydroxyl groups under alkaline conditions. In
30 addition to the foregoing epoxy resins, other epoxy resins
suitable for the present invention are single epoxy resins,
diglycidyl ethers of dihydroxyl compounds, epoxy phenolic,
alicyclic epoxy resins , polyglycidyl esters of polycarboxylic
acids , acrylic resins containing glycidyl methacrylate, and
combinations thereof. Moreover, modified epoxy resins
made by modifying the epoxy resins with polyphenols such
as bisphenol A or bisphenol F , or poly carboxylic acid such
as adipic acid or decanedioic acid are also usable . Among
these , the epoxy resins obtained from epichlorohydrin and a
40 phenol compound containing two hydroxyl groups, and
particularly , the epoxy resins obtained from bisphenol A or
bisphenol F and epichlorohydrin , are more usable in the
present invention . These epoxy resins preferably each have
an epoxy equivalent weight of 100 to 700 g/eq, such as
45 125- 130 g/eq, 170 - 180 g/eq, 490 -500 g/eq, and 275 -290
g /eq .
In the present invention , the term “ HLB value” refers to
the hydrophilic lipophilic balance value, which indicates the
degree to which a surfactant is hydrophilic or lipophilic . The
50 higher the HLB value is , the more hydrophile the surfactant
is . The smaller the HLB value is , the more lipophilic the
surfactant is. The value may be determined using an empiri
cal formula ofHLB = 7 + 11.7 log Mø/Mo, where Mwand M .
are respectively the molecular weights of the hydrophilic
55 group and the lipophilic group in the surfactant . The HLB
value may be alternatively estimated using the water disso
lution method , which involves adding the test subject to
water and determining its HLB value according to the
In one aspect , the polyether compound having epoxy observed appearance of the resulting dispersion according to
hydroxyl urethane group is an improved epoxy functional 60 the scale shown in Table 1 :
surfactant. The improved epoxy functional surfactant makes
a hydroxyl -urethane - group -containing polyether to react TABLE 1
with AGE at 50° C .~ 90° C ., preferably 60 - 70° C ., andmore
preferably 65° C ., for 1 - 3 hr, and preferably 2 hours before Estimation of HLB values Test subject in water
addition of an epoxy resin and heating to 60 - 120° C ., 65 1- 4 Not dispersed at all
preferably 90 - 110° C ., and more preferably 100° C ., for 3~6 Not well dispersed
reaction for 1 to 3 hours , and preferably 2 hr, so as to obtain
 US 10 , 259,970 B2
10
TABLE 1 -continued preferably 5 ~ 7 wt % , based on the total weight of the
waterborne epoxy resin composition .
Estimation of HLB values Test subjectin water In a more preferred example , the water is in amount of
6~ 8 Forming emulsive dispersion after strong 30 – 65 wt % , preferably 40 – 60 wt % , and more preferably
agitation 5 45 - 50 wt % , based on the total weight of the waterborne
8 - 10 Forming stable milky dispersion epoxy resin composition .
10 - 13 Forming translucent to transparent dispersion To the disclosed waterborne epoxy resin composition ,
> 13 Forming clear solution other resins, such as ester waterborne resins or acrylic
waterborne resin may be incorporated as needed provided
In one preferred embodiment, the disclosed hydroxyl 10 that the incorporation brings no adverse impact on the
urethane is a polyether compound having epoxy hydroxyl properties of the resulting waterborne epoxy resin . Further
urethane group , and is the Structural Formula (I ) , ( II) or ( III) more , in the disclosed waterborne epoxy resin composition ,
as defined previously . In another preferred embodiment, the various additives may be considered according to practical
HLB value of the disclosed hydroxyl urethane is estimated needs, such as anti-cissing agents, anti-sagging agents , flow
using the water dissolution method . For an emulsifier of a 15 leveling agents , defoamants , curing aid agents , UV absorb
waterborne epoxy resin composition , an excessively large or e rs , and photostabilizers . The use of the disclosed water
small HLB value cannot achieve preferred emulsifation . The borne epoxy resin composition is not limited herein , and
HLB value of the disclosed hydroxyl urethane may be may include, for example , paints , adhesives , fiber gathering
adjusted using the content of hydrophilic ethylene oxide agents , and concrete primers.
(EO ) in the starting material, polyether amine. Where the 20 The waterborne epoxy resin of the present invention may
identical polyether amine is used , the adjustment may be be extensively used in waterborne paints for indoor and
accomplished by controlling its [CCV ]/[NH ] mole ratio . outdoor applications, waterborne paints for inorganic build
For example, the [CC ]/[NH2] mole ratio may be controlled ing materials, waterborne anticorrosive paints for iron parts,
at 0 . 5 - 0 .75 , such as 0 .5 , 0 .6 , 0 .66 , 0 . 7 or 0 .75 . According to and waterborne paints for car repair, and may be also used
experiments, hydroxyl urethane having HLB value of 4 - 17 , 25 for industrial applications such as automotive painting and
and epoxy resin emulsion stability of 6 ~ 16 , or more pref- beverage cans . Among the foregoing applications, with its
erably 12 ~ 15 , is able to endow the resulting waterborne excellent anticorrosive properties and dry feeling by finger
epoxy resin composition with desired stability and freeze - touch , it is suitable for anticorrosive waterborne paints
thaw resistance . applied to iron parts of steel structures or bridges for
In one preferred embodiment of the present invention , the 30 multilayer anticorrosive purposes , and particularly suitable
waterborne epoxy resin composition may further comprise a for anticorrosive waterborne paints applied to iron parts as
solvent if necessary . Herein , the term " solvent” refers to a a primer .
substance that adjusts the softening point of the epoxy resin . Where the disclosed waterborne epoxy resin composition
Therefore, people skilled in the art may add the solvent in an is used in a paint, various dyes or various additives such as
appropriate amount according to the properties of the epoxy 35 anticorrosive colors, coloring agents , and extenders are
resin used . While insufficient addition may lead to failure in preferably incorporated as needed . Examples of the anticor
adjusting the resin 's softening point, excessive addition may rosive colors include scale - like colors, such as zinc powder,
cause undesirable increase of volatile organic compounds aluminium phosphomolybdate , zinc phosphate , aluminum
(VOCs) in the waterborne epoxy resin . Therefore, the using phosphate , barium chromate , aluminum chromate , and
amount of the solvent is preferably 1 ~ 20 wt % , more 40 graphite . Example of the coloring agents includes carbon
preferably 3 - 10 wt % , and most preferably 3 - 7 wt % of the black , titanium oxide, zinc sulfide, and red iron oxide.
total amount of the waterborne epoxy resin composition . Of Example of the extenders includes barium sulfate , calcium
course , if the epoxy resin has a proper softening point, the carbonate, talcum , and kaolin .
addition of a solventmay be omitted . Where the disclosed waterborne epoxy resin composition
Solvents usable in the present invention may be any 45 is used as a paint, the applied way is not limited , and may
solvents that can uniformly disperse the epoxy resin and include roller coating, spraying, brushing, blade applying,
hydroxyl urethane , and are inert to them , without limitation . using a rod coater, dipping coating , and electrodeposition
Examples include esters such as ethyl acetate , 3 -methoxy - coating . Post- coating processing may be air drying, and then
butyl acetate ,methoxypropyl acetate , and cellosolve acetate ; thermal curing. For thermal curing , the temperature is pref
alcohols such as methanol, ethanol, and isopropanol; cello - 50 erably 50 to 250° C ., and more preferably 60 to 230° C ., and
solves such as methyl cellosolve , ethyl cellosolve , propyl the heating time is preferably 2 to 30 minutes, and more
cellosolve, butyl cellosolve , isobutyl cellosolve , and tert- preferably 5 to 20 minutes.
butyl cellosolve; glymes such as monoethylene glycol dim - Where the disclosed waterborne epoxy resin composition
ethyl ether, diglyme, and triglyme; propylene glycol mono is used as an adhesive, the way how it is used is not limited
alkyl ethers such as propylene glycol monomehtyl ether, 55 herein . The waterborne epoxy resin composition may be
propylene glycol monoehtyl ether, propylene glycol applied to the adhesive surface of a substrate by means of
monobutyl ether, propylene glycol monoisobutyl ether, and spraying, brushing, or blade applying. After the joint is
propylene glycol monotertbutyl ether ; and ketones such as peripherally fixed or pressed , a strong adhesive layer can be
acetone , and methyl ethyl ketone , among which propylene formed . For this purpose , suitable substrate may include
glycol monoalkyl ethers are most preferable , such as pro - 60 steel sheets , concrete, mortar , wood , resin laminates , and
pylene glycolmethyl ether. resin thin films, and may preciously receive physical pro
In another more preferred example , the epoxy resin is in cessing such as polishing, electrical processing such as
amount of 30 – 65 wt % , preferably 40 – 60 wt % , and more corona treatment, and chemical processing such as chemical
preferably 45 - 55 wt % , based on the total weight of the conversion treatment for easy coating.
waterborne epoxy resin composition . 65 Method for Making the Waterborne Epoxy Resin
In a more preferred example , the hydroxyl urethane is in Another objective of the present invention is to provide a
amount of 3 ~ 15 wt % , preferably 3 ~ 7 wt % , and more method for making an epoxy resin waterborne, which com
 US 10 ,259, 970 B2
11 12
prisesmixing the epoxy resin and hydroxyl urethane , adding Preparation Examples
water, and performing emulsification .
In one preferred embodiment, the epoxy resin and Preparation Example 1 -1 : Synthesis of BDGE125
hydroxyl urethane are first mixed in a solvent before water Cyclic Carbonate
is added and emulsification is performed .
In the method for making the epoxy resin waterborne , 100 g of BDGE125 epoxy resin , and 0 . 1 – 5 % of quater
hydroxyl urethane is an emulsifier used in an aqueous nary ammonium salt were placed in a reactor, stirred and
dispersion of the epoxy resin . The good properties of the heated to 150° C . CO , was introduced and reaction was
waterborne epoxy resin emulsion as observed include performed BDGE125
under 5 kg/cm² for 4 hr, thereby obtaining
cyclic carbonate . By calculating the consumption
desired resin emulsion stability and resin emulsion freeze - 10 of CO2, the conversion was determined as 95 % .
thaw resistance .
In one preferred embodiment, mixing is conducted at an Preparation Example 1-2 : Synthesis of BE180
elevated temperature, such as 50 - 80° C ., and preferably Cyclic Carbonate
mixing is conducted at 60 – 80° C .
In another preferred embodiment, water is added at a 15 100 g of BE180 epoxy resin , and 0 .1 ~ 5 % of quaternary
speed of 2 ~ 10 ml/min . While a speed slower than 2 ml/min ammonium salt were placed in a reactor, stirred and heated
can make emulsification unnecessarily prolonged , a speed to 150° C . CO , was introduced and reaction was performed
faster than 10 ml/min may lead to poor emulsification. under 5 kg/cm² for 4 hr, thereby obtaining BE180 cyclic
In another preferred embodiment, the hydroxyl urethane carbonate . By calculating the consumption of CO2, the
is a polyether compound having epoxy hydroxyl urethane 20 conversion was determined as 93 % .
group, and has a structure as defined by Formula (I), (II) or
(III) as stated above . Preparation Example 2 : Synthesis of Hydroxyl
The preparation examples and examples described below Urethane Polyether
are intended to illustrate the principles of present invention
but not to limit the scope of the present invention . Materials 25 BDGE125 cyclic carbonate of Preparation Example 1 - 1
used in the following preparation examples and examples and BE180 cyclic carbonate of Preparation Example 1 - 2
have the following definitions: were respectively put into reaction with the polyether
BDGE125 : poly (glycidyl ether ) of 1,4 -butanediol, with amines of different types shown in Table 2 as below at 160°
an epoxy equivalent weight of 125 to 130 g /eq , produced by C . for 7 hr, thereby obtaining hydroxyl urethane polyethers .
ChangChun Plastics Co . Ltd . The experimental formulas are shown in Table 2 as below :
TABLE 2
Sample No.
si S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12
[CC ] [NHz] 0 .5 0 .5 0 .5 0. 5 0 .5 0. 5 0 .5 0 .5 0.66 0.75 0.66 0.75
BDGE cyclicg 00 100.00 100.00 100.00 100.00 100 .00 100 .00
carbonate
BE180 cyclic g 100 .00 100 .00 100.00 100 .00 100 .00 100 .00
carbonate
Jeffamine 00 165 . 37 107.78
D230
Jeffamine 00 317 . 95 206 .57
D400
Jeffamine 00 1416 .67 923. 30
D2000
Jeffamine 00 1584 .78 1032 . 87 1200 .60 1056 . 52 782 .48 688. 58
ED2003
Note :
[CC ]/ [NH2] is the mole ratio of cyclic carbonate group /amine group .
50
BE180 : poly (glycidyl ether ) of bisphenol A , with an Preparation Example 3 : Synthesis of Hydroxyl
epoxy equivalent weight of 170 to 180 g/ eq , produced by Urethane Polyether Having Epoxy Functional
ChangChun Plastics Co . Ltd . Groups
BE501: poly (glycidyl ether) of bisphenol A , with an 55 The hydroxyl urethane polyethers of Sample No.
epoxy equivalent weight of 490 to 500 g/ eq, produced by S01 - S12 as synthesized previously were put into reaction
ChangChun Plastics Co . Ltd . with a certain amount of AGE at 65° C . for 2 hr. BE180
epoxy resin was added and the mixture was heated to 100°
AGE: C12 - C14 alkyl glycidyl ether , with an epoxy C . for reaction for 2 hr, thereby obtaining hydroxylurethane
equivalent weight of 275 to 290 g/ eq , produced by Chang- 60 polyethers having epoxy functional groups (Sample No.
S13 - 524 , wherein S13 - S18 correspond to the compounds
Chun Plastics Co . Ltd . of Formulas (I ), (II) and (III) of the present invention , R , is
Jeffamine D230 : produced by Huntsman . a butane group ; R , is ethane and a propane group ; Rz is a
Jeffamine D400 : produced by Huntsman . group derived from AGE , R4 is a group derived from BE180 ;
65 S19 - S24 correspond to the compounds of Formulas (I), ( II)
Jeffamine D2000 : produced by Huntsman . and ( III ) of the present invention , R , is a group derived from
Jeffamine ED 2003: produced by Huntsman . BE180 ; R2 is ethane and a propane group; Rz is a group
 US 10 ,259,970 B2
13 14
derived from AGE, R4 is a group derived from BE180 ). The freezer, and set at the atmospheric temperature for 7 hr. The
experimental formulas are shown in Tables 3 and 4 as below . test was repeated for 5 times . Observation was conducted to
The HLB values were estimated using the water dissolution determine whether emulsion was settling , gelation or coagu
method . lation .
TABLE 3
Hydroxyl urethane polyethers with BDGE epoxy functional groups
Sample No.
S13 S14 S15 S16 917 918
[S01
epoxy ]/[AHEW ] g 1.1
100 .00
1.1 1.1 1.1 1.1 1.1
SO2 100 .00
S03 100 .00
S04 100.00
S09 09 100 .00
S10 100 .00
AGE 99.24 58 .25 14 .57 13.07 8 .63 5 .85
BE180 63 . 35 37 .18 9 . 30 8 . 35 5 .51 4 . 11
HLB value 15 17 Gelation
Unanalyzable

TABLE 4
Hydroxyl urethane polyether with BE180 epoxy functional groups
Sample No.

$ 19 S20 821 322 323 324

[ epoxy ]/[AHEW ]
S05
1. 1
100 .00
1 .1 1.1 1.1 1. 1 1.1
S06 100 .00
S07 100 .00
SO8 100.00
S11 60 100 .00
S12 100 . 00
AGE 88 .29 54 . 29 14. 31 12 . 86 8 .45 5 .72
BE180 56 .36 34 .66 9 . 14 8 .21 5 . 39 4 .01
HLB Value g6411214 Gelation
Unanalyzable

40
Note 1: [ANEW ] is amine hydrogen equivalent weight. The results of the experiments are shown in Table 5 as
Note 2 : “Gelation : shown in the field of the HLB value below :
indicates that the molecular weight of the product
during reaction was so high that gelation appeared . 45 Sample
EXAMPLES
S25 S26 S27 928 929 S30 S31
Experiments about making epoxy resins waterborne were
conducted using hydroxyl urethane polyethers having epoxy BE501 org 43 43 43 43 43 35 55
functional groups: 50 S13 g 5
BE501 epoxy resin , a hydroxyl urethane polyether having S14 g 5
epoxy functional groups (Sample No. S13 - S24 ) as the S15 co
on
emulsifier, propylene glycolmethyl ether as the solvent, and S16
AGE as the thinner for adjusting the viscosity of the system S17
were placed into a 100 ml glass reactor at a certain propor - 55 Propylene gggg 5 5 5 5 5 7
tion . The reactor was heated to 70° C ., and the components Glycol
were stirred and mixed . Pure water of a certain proportion Methyl Ether
was added at a speed of 2 ~ 10 ml/min for emulsification , AGE 5 5 5 5 5 5 5
thereby obtaining a waterborne epoxy resin composition
(Sample No. S25 - S36 ). 60 Pure Water g 42 42 42 42 42 50 30
The waterborne epoxy resin compositions were obtained , Emulsion OK OK NG OK OK OK OK
and tested for emulsion stability using the centrifugal sedi Stability
mentation method . The test was conducted with the cen Emulsion A A X 0 X A O
trifugal force = 1600 G * 5 min . The levels of stability were Freeze - Thaw
compared . 65 Resistance
The waterborne epoxy resin compositions were obtained ,
and placed in a - 18° C . freezer for 17 hr, removed from the
 US 10 ,259 ,970 B2
15 16
-continued - continued
Sample
NO
S32 S33 S34 S35 S36 MRE , RE * R33
BE501 | 43 43 43 OH
S19

vodity you
S20 ( III)
S21 50
S22
S23 10
Propylene
Glycol
5 un RZ O
R,
Methyl Ether
AGE 5 5 ??
OH
Pure Water g 42 42
OK OK NG OK 15

Ter
Emulsion
Stability
Emulsion
o
abu -O
LR2 R3;
Freeze- Thaw
Resistance
HO
Note 1:
Emulsion stability is determined by whether the emulsion was layered or showed resin 20
coagulating. Where the emulsion was not layered and showed no resin coagulating, OK
was recorded ; otherwise, NG was recorded .
Note 2:
wherein , n is 2 – 70 ;
O : the emulsion remained unchanged after five times of freeze - thaw cycles ; A : the
emulsion remained unchanged after three times of freeze -thaw cycles; X ; the emulsion was
R is C4 - 12 alkyl, alkenyl, alkynyl, cycloalkyl, a
layered or showed resin gathering after a single freeze -thaw cycle. polyether group or the structural formula (IV ) as below :
25
According to the above results , when the hydroxyl ure
thane is used as an emulsifier, the epoxy resin composition (IV)
can be waterborned . When the hydroxyl urethane has its
HLB of 4 ~ 17, an epoxy resin emulsion with desired stability
can be obtained . When the hydroxyl urethane has its HLB of 30 OH
12 - 15 , an epoxy resin emulsion with good stability and
freeze-thaw resistance can be obtained .
The waterborne epoxy resin composition of the present
invention contains hydroxyl urethane as the emulsifier, so 28
that it can be waterborned , and further obtained the epoxy
resin emulsion having preferred stability and freeze - thaw
puteren son ambasasbelow
wherein , m is 0 - 5, and
R , is one of the structural formulas as below :
resistance .
What is claimed is: 40
1. A waterborne epoxy resin composition , comprising : (a )
an epoxy resin , (b ) hydroxyl urethane , and (c ) water,
wherein the hydroxyl urethane is a polyether compound
having epoxy hydroxyl urethane group , and has a structural
formula (I), ( II ) or (III): 45

ON

what ly Layan LO
50

adio
R1 R2
55

IR TRE
60

N. LO .
R; \R \ ' RET . 65.
OH
 US 10 ,259, 970 B2
17 18
R2 is C2 - 4 alkyl; -continued
Rz is the structural formula ( V ) or (VI) as below :

(V ) 5

OH
(VI)
R6 10

OH ,

wherein , Ro is C4~ 12 alkyl, alkenyl, alkynyl , cycloalkyl 15

or a polyether group ;
R4 is the structural formula (VII) or (VIII) as below :
(VII) 20
R1- O
??
(VIII ) 2 . The waterborne epoxy resin composition of claim 1 ,
25 wherein the hydroxyl urethane having its HLB value of
Lo OH ,
4 - 17 .
3 . The waterborne epoxy resin composition of claim 2 ,
wherein the hydroxyl urethane having HLB value of 12 - 15 .
4 . The waterborne epoxy resin composition of claim 1 ,
wherein , R , is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl. 30 which further comprises a solvent.
a polyether group or the structural formula (IX ) as wherein 5 . The waterborne epoxy resin composition of claim 1,
below : the epoxy resin is in amount of 30 – 65 wt % based
on the total weight of the waterborne epoxy resin compo
sition .
(TX 35 6 . The waterborne epoxy resin composition of claim 1 ,

fhios y otros OH
wherein the hydroxyl urethane is in amount of 3 - 15 wt %
based on the total weight of the waterborne epoxy resin
composition .
7 . The waterborne epoxy resin composition of claim 1,
40 wherein the water is in amount of 30 65 wt % based on the
wherein , p is ( ~ 5 , and total weight of the waterborne epoxy resin composition .
Rg is one of the structural formulas as below : 8 . The waterborne epoxy resin composition of claim 4 ,
wherein the solvent is in amount of 1 – 20 wt % based on the
total weight of the waterborne epoxy resin composition .
45 9 . The waterborne epoxy resin composition of claim 4 ,
wherein the solvent is any one or more than one selected
from the group consisting of alcohols, ethers, and ketones .
10 . The waterborne epoxy resin composition of claim 1 ,
which is used as paint.
50 11 . A polyether compound having epoxy hydroxyl ure
thane group, which has a structural formula (I), (II ) or (III) :

OH

N. LO
R3 R R2 R2 Rz;
( II )

RN R2 R2
OH
OR
OH
R2 R2 R3;
 US 10,259, 970 B2
19 19 - continued
20
vittyy ylitty
N.
" RET
Lo

??
HO

10
R3;

wherein , n is 2 – 70 ; wherein , Ro is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl

R is C4 - 12 alkyl, alkenyl, alkynyl, cycloalkyl, a or a polyether group ;
polyether group or the structural formula (IV ) as below : R4 is the structural formula (VII ) or (VIII):
15
(IV) (VII)

OH
nonoy OH
(VIII)

r
20

en in die
wherein , m is 0 - 5, and
R is one of the structural formulas as below :
25
OH ,

wherein , R , is C4 ~ 12 alkyl, alkenyl, alkynyl, cycloalkyl,

a polyether group or the structural formula ( IX ):
30 (IX )
fes n otes
OH

35
wherein , p is 0 - 5, and
R , is one of the structural formulas as below :

R2 is C2~ 4 alkyl;
Rz is the structural formula (V ) or (VI):

??

R6
 US 10 ,259 ,970 B2
21
12 . The polyether compound having epoxy hydroxyl
urethane group of claim 11 , which is an emulsifier of an
epoxy resin .
* * * * *