Ethyleneimine Polymer for cross bridge of creation

For more detailed information,please contact to Coating Materials Business Unit of Performance Chemical Business Div.(Tokyo, Osaka)

Osaka Oﬃce
KoginBldg.
4-1-1 Koraibashi, Chuo-ku
Osaka 541-0043, Japan
Telephone : +81-6-6223-9235
Facsimile : +81-6-6223-9236
Tokyo Oﬃce
Hibiya Dai Bldg
1-2-2 Uchisaiwai-cho, Chiyoda-ku
Tokyo 100-0011, Japan
Telephone : +81-3-3506-7610
Facsimile : +81-3-3506-7597
URL http://www.shokubai.co.jp/
2014.2.28 200

Contents

Introduction

Production method of EPOMIN

P05

Product line of EPOMIN

P05

Viscosity of EPOMIN

P06

Chemical reactivity of EPOMIN

P07,P08

Functions and Applications of EPOMIN

P09,P10

Propertys of EPOMIN

P11

Regulatory status of EPOMIN

P12

Handling of EPOMIN

P12Specialty Polyethyleneimine

P13,P14

Production method of POLYMENT

P15Characteristic of POLYMENT

P16Speciﬁcation and property of POLYMENT

01

P03,P04

P17,P1802

Introduction

Polymerization
H2N-(CH2CH2N)x-(CH2CH2NH)y-

Ethyleneimine (EI) has high reactivity, and it is used
and well known as pharmaceutical intermediate

CH2CH2N＜

product and / or raw material of amine polymer.

(Polyethyleneimine)

Since we have commercialized EI in1969 using bySpecialty Polyethyleneimine

WENKER Method, NIPPON SHOKUBAI have pursued

PP-061 (PEl-Propylene oxide)

production method, which minimized waste disposal,

RP-20 (PEI-Octadecy lisocyanate)

and successfully developed “ The Vapor Phase Method",which ecologically materialize minimal resource. This
was the ﬁrst development in the world using by own
developed new catalyst technology in 1990.

As the result of making best eﬀorts to utilize highHN

Aminoethylation
R

Ethyleneimine（EI）

Rー(CH2C)xー(CH2C)y-reactivity of EI , NIPPON SHOKUBAI would develop

COOR

COO(CH2CH2NH)n-H

Ethyleneimine derivatives such as pharmaceutical(Aminoethylated Acrylic Polymers)

intermediate products, amine containing polymers
and cross-linking agents.

N ―R―R―N

We would like to present standard types of EI(Polyfunctional aziridine ring compounds)

derivatives,(Polyethyleneimine),(Aminoethylated acrylic polymer)
in this catalogue.

03

S

NH

CH3

CH3

×

(Dimethylthiazolizine), HSCH2CH2NH2 (Cysteamine)04

Viscosity of（Polyethyleneimine）
is the water soluble polymer which is made by polymerization of ethyleneimine.
is not aentirely linear polymer but a partly branched polymer containing
primary, secondary, and tertiary amine.
Characteristics

Viscosity of

SP-003shows a great dependence on its molecular

SP-006weight, temperature and concentration.

SP-012

Relation of viscosity to temperature and concentration of

SP-018is shown below.

SP-200P-1050▶The highest cation density among other existing materials.
▶Very high reactivity.

Temperature-Viscosity▶Water solubility.

1,000,000

NH2

H
N

H2C

H
N

N

100,000

10,000

1,000

N
NH2

HNH2
N

H2N

NH

H
N

N

N
H

CH2

Viscosity（mPa・s）

Production method of

H
N

NH

100

N

N

N

N
H

10

N
H

NH2

0

20

40

60

80

100

20

0

Ｔemperature（℃）

Concentration-Viscosity at 20℃
1,000,000

Product line ofSpec.

Product

SP-003SP-006SP-012SP-018

SP-200P-1050

Mw

300

600

1,200

1,800

10,00070,000Resin cont.
（wt%）

＞98

＞98

＞98

＞98

＞98

50±2

Viscosity

200
-500

500
-2,5003,500-7,5008,500-15,000

40,000-150,000

10,000-20,000（mPa·s-25℃）

10-12Appearance

Colorless or light yellow liquidCan（18kg）,Drum（200kg）

10,000

1,000

100

10

pH
（5%aq.）▶Packagetype

Viscosity（mPa・s）

100,000＊Molecular weight is not in speciﬁcation.

1
100

80

60

40

Concentration（wt%）

Please contact on other package types.
05

06

Chemical reactivity of
Having diversity in chemical reactivity like low molecular amine,chemically in variety. Typical examples of

1 Reaction with aldehydes and ketones
NH ＋ O ＝ C − R

can be modiﬁed

reactivity are illustrated below.

can formOH

6 Reaction with cyanamide, guanidine, ureaandetc.

cross-link throughN−C−R

reaction withO

O
NH ＋ H2N − C − Rwith cyanamide,

N − C − R ＋ NH3

dialdehyde.
Rreactsguanidine
and urea.

R

2 Reaction with alkyl halides

can formcross-link throughNH ＋ XR

with acid, acid anhydrides and7 Reaction
acylhalides

reaction withNR ＋ HX

alkylenedihalide.

O
NH ＋ HO − C − R

OOC − RN

N − C − R ＋ H2O

H

3 Reaction with isocyanates and thioisocyanates
O

NH ＋ O ＝ C ＝N − ROHreacts with

N − O − NHR

alkylisocyanate.
O
C−R

4 Reaction with acryloyl compounds

reacts withO

N ー O − R ーRCOH

NH ＋ O

fatty acid.

C−R

reactsNH ＋ CH2 ＝ CHCOORO

N − CH2CH2COORO

with acryl
monomers.
O

5

NH ＋ CIC − RO
N ー C − R ＋HCI

Reaction with epoxy compounds
RO
NH ＋ R2C

CR2R

N − C − C − OHreactswithepichlorohydrin.

R

07

R

08

Functions and Applications of1) Functions ofApplications

Recommended
Products

Dye ﬁxing agent

P-1050

Washing resistance and dyeing promoters

Surface modiﬁcationof tire cord

P-1050Adhesion improvement PET cord with rubber.

Sizing agent forglass ﬁber

P-1050

Lubricity

Fixing ofﬁrere tardantP-1050Retention agent for ﬁre retardant(phosphorous type)

Liquid clariﬁer

P-1050

Removal of chlorine and aldehydes.

Coagulant

P-1050Anionic trash scavenging, charge modiﬁcationand emulsion breaking

Bacterial cell
ﬂocculant agent

P-1050Bacteria removal

Chelatingagent

P-1050

Metal extraction

Gas cleaning

Gas scavenger

P-1050Absorb of C02, NOx, SOx, CI2 and aldehydes.

Dispersion

Dispersing agent

SP-012EPOMIN can disperse ceramic, carbon black, coal,cement, metal powder, pigment.

Metal plating
bath agent

SP-006Brightener, smooth agent for Zn plating.

Corrosion inhibitor
for acid pickling,
Primary rust inhibitor

P-1050Corrosion inhibitor for iron.

P-1050Fixation agent to carrier for enzyme,
microorganism.

P-1050

Fluid loss agent for cement slurry.

Antibacterial /Sanitization polymer

P-1050Ag, Cu complex PEl shows antibacterial.

Wood preservative,
Cut ﬂowers
preservative

SP-018PEl complex (Ag, Cu / PEI) shows antibacterial
and permeabillity.

Field▶High adhesion and absorption
Amino group form hydrogen bond with hydroxyl group.
Amino group form ionic bond with carboxyl group.
Amino group form an organic bond with carbonyl group.
has polar group(amino group)and hydrophobic group(-CH2CH2-) in a structure
and therefore has adhesion ability with diﬀerent materials.
They apply these total bonding strength, and it is used adhesives, inks, paints and pressure
sensitive adhesives.
▶Highcationicis present as polycation in water and they are neutralized every anionic material.
And
has chelation ability of heavy metal ions.
They used paper manufacturing, water treatment conditioning, plating bath agent anddispersing agent.
▶High reactivity
The primary and secondary amino group easily reacts with epoxy, aldehyde, isocyanate
compounds and acid gases. They used in hardening agent of epoxy resins, aldehyde adsorbents
and dye ﬁxing agents.

TextileLiquid cleaning

2) Industrial applications of
Field

Paper

Applications

Paper making agent

Recommended
Products

P-1050Characteristics
Neutralization of an anion charging material
Retention agent
Pitch controller
White water treatment
Dispersion and retention of ketene dimmer

Metal plating
Pressure sensitiveadhesion

SP-200P-1050

Improve in holding power

PVC sol adhesive

SP-018
SP-200Adhesion promoter

Water based adhesive

SP-200P-1050Adhesion promoter for EVA, Poly vinyl acetate,
PVA and Acryl emulsion.

P-1050Adhesion promoter for extrusion polyethylene
with Paper, Oleﬁn ﬁlm.

Adhesion
Anchor coat agent for
extrusion laminate
Anchor coat agent forgas barrier ﬁlm

Paint / ink

09

P-1050Adhesion promoter for PVA, EVOH with Oleﬁn ﬁlm

Release agent

RP-20

Backside release agent for the various tapes.

Polyvinylbutyral
based ink

SP-200Adhesion promoter.

Acryl emulsion
based paintSP-012SP-018

Fast drying, adhesion promoter andwater resistance

Enzymeimmobilization
Petroleum

Antimicrobe /preservation

Immobilized enzyme,
Microorganism
immobilized carrier
Petroleum emulsion
breaker,
Fluid loss agent

Characteristics※ In using our products () in relation to the application referred to in this booklet, please pay attention toexistence of the intellectual property rights (including patent and its application) owned by any third parties andavoid the possible infringement of such intellectual property rights. NIPPON SHOKUBAI shall in no event be
responsible for any damages or liabilities caused by infringement or alleged infringement of said intellectual
property rights due to the above-mentioned use of our products.

10

Propertys of

Use in the food ﬁeld and Handling of
Use in the food ﬁeld of

Product
Molecular weight

SP-003SP-006SP-012SP-018

SP-200P-1050

300

600

1,200

1,800

10,00070,000

When I use EPOMIN in the food field, please confirm
regulations / statute related to safety.

▶FDA information :Speciﬁc gravity

1.01

1.03

1.04

1.04

1.05

1.08

Amine value(mmol / g,solid)

21

20

19

19

18

18

Polyethyleneimine having CAS No .9002-98-6 is published by the following 1), 2), of 3).

＜ -20

PropetyFreezing point(℃)

Safety

FDA publication circumstance of Polyethyleneimine

In addition, polyethyleneimine having CAS No .68130-97-2 is published by thefollowing short-term work of 4).

＜ -15

Decomposition
Temperature(℃)

240

270

290

300

310

300

Flash point(℃)

188

263

262

264

262

−

Aminerate(%)
Primary
Secondary
Tertiary

45
35
20

Solubility（＊1）
Water
Alcohol
Ethyl acetate
THF
Toluenen-Hexane

○
○
△
△
△
×

○
○
△
△
△
×

○
○
△
△
△
×

○
○
△
△
△
×

○
○
△
△
×
×

○
○
×
×
×
×

Acute oral toxicity
LD50(ml/kg. mouse)

−

1.2

1.0

0.87

2.97

8.0(＊2)

Acute dermal toxicity
LD50(g/kg. rat)

1.6

1.8

＞2.0

＞2.0

＞2.0

＞2.0

Primary ski
irritation(rabbit)

Moderate

Moderate

Sight

Sight

Sight

Non

Ames test

Positive

Negative

Negative

Negative

Negative

Negative

Listed(9002-98-6)

Listed(9002-98-6
or 68130-97-2)

35
35
30

1)Adhesive industry

2)Paperboard industry

25
50
25

3)Food package

TSCA（CAS No.)

Listed(106899-94-9)

4) Enzyme industry

Handling precaution of
1)Storage stability▶SP series are stable for about one year when stored at a cool and dark place.
However, if they contact with air (oxygen) under high temperature (>80℃) may cause
their quality degradation such as coloring and surface filming.
▶SP series require careful handling because of their high hygroscopicity andabsorbency of carbondioxide in the air.
▶P Series are stable for about one year when stored at a cool and dark place.
However, if they contact with air (oxygen) under high temperature (>80'C) may cause
their quality degradation such as coloring.
▶P-Series require careful handling because of its absorbency of carbon dioxide in the air.

2)Heating of container

The container
is inner-coated with synthetic resin.
When heated long at high temperature, the container coating may come off and the
product may be colored.
If necessary, heating should be done with hot water at lower temperature than 80℃.

3)Applicable materials▶Suitable materials
Stainless steel, Synthetic resin (PVC,PE,PP), Synthetic resin coating (such as epoxy)▶Not Suitable materials
・Iron materials such as soft iron.
*Should be avoided to prevent coloring caused by rust.
*Such materials should not be used, particularly for
aqueous solution,
because iron rust tends to harden polyethyleneimine in the solution.
・Copper and copper-containing alloys such as brass*React with polyethyleneimine and forms bluish green complex salt4)Storage condition

Keep away from direct sunlight, rain, heat and flame. Keep container closed and store ina dark and cool place when not in use.

Regulatory information except U.S.A. please refer to SDS.

＊1 ○:Soluble，△:Partly soluble, ×:lnsoluble＊2As P-1000＊3 As P-1050▶Analysis methods
1.Mecular weight (1) SP series : Number average molecular weight (Mn) by ebullioscopic method.
(2) P series : Number average molecular weight (Mn) by osmotic pressure method.
2.Amine value:Acidimetry in non-qaueous system
3.Decomposition temperature : Differential scanning calorimetry (DSC) was used in N2 atmosphere.
4.Flash point : Cleveland open tester
5.Amine rate : NMR(13C)

Note

11

： Part 175 Indirect food additives:Adhesive coating and component.
・175.105 Adhesives
・175.320 Resinous and polymeric coatings for polyolefin films.
: Part 176 Indirect food additives: Paper and paperboard components.
・176.170 Components of paper and paperboard in contact with aqueousand fatty food.(Limited to use at a level not to exceed 5% by weight offinished dry paper or paperboard fibers.)
・176.180 Components of paper and paperboard in contact with dry food.
(Limited to use at a level not to exceed 5% by weight of finished dry paperor paperboard fibers.)： Part 177 Indirect food additives: Polymers
・177.1200 Cellophane
・177.1400 Water-insoluble hydroxyethyl cellulose film.
： Part 173 Secondary direct food additives permitted in food for human consumption.
・173.357 Materials used for fixing agent in the immobilization of enzyme preparations.

Please refer to the Safety Data Sheet (SDS) that provides details of the safety of the product.
Above-mentioned regulations are valid September, 2013.

12

Specialty Polyethyleneimine
The introduce specific modified polyethyleneimine.

1) Octadecyl isocyanate modiﬁcation polyethyleneimine
RP-20 is addition product of polyethyleneimine with octadecyl isocyanate, it has two functionalgroup polymers having hydrophilic amino group and lipophilic (C18).
RP-20 shows superior effects as release agent of pressure-sensitive adhesive tape, and canapply polyester, polyethylene, polypropylene, cellophane and paper for base material.

2) Propylene oxide modiﬁcation polyethyleneimine
PP-061 is the addition product of polyethyleneimine with propylene oxide,
it is the tertiary polyamine.

Chemical Formula : −(CH2CH2N)n 一一
Chemical Formula : −(CH2CH2N)n 一一
CH2CHOH
CONH(CH2)17CH3
CH3

Product

Spec.

Appearance

Slight yellow powder

Melting point(℃)

87.0~95.0

Product

Spec.

PP-61

Appearance

Viscosity transparence liquid

Resin content(wt%)

48.0-52.0

Toluene solubility (10℃)

Not muddiness

Viscosity(mPa.s-25℃)<200

Loss on drying (wt%)＜2.0

pH(5%aq.)

10.0-12.0

Recommended diluent solvent

TolueneOH value(mmol/g.solid)

9.9

Solubility

Dissolble in toluene, xylene
Insoluble in water, alcohol

Amine value(mmol/g.solid)

9.9

Molecular weight

Approx.1400

Mole ratio(OH/NH)

1.0

Speciﬁc gravity(20℃)

1.08

Property

SafetyRP-20

Acute oral toxicity LD50
(mg/kg.rat)>2000

Skin irritation (rabbit)

Not

Ames test

Negativity

Amine rate

All tertiary amine

Dust explosion

Lower explosive limit:40g/m3

Solubility

Dissolble in water, alcohol

TSCA (CAS No.)

Listed (68441-25-8)

Property

TSCA (CAS No.)

Not listed

Please refer to the Safety Data Sheet (SDS) that provides details of the safety of the product.
Above-mentioned regulations are valid September,2013.

13

14

Characteristic of(Aminoethylated Acrylic Polymers)
is the primary amino group component acrylic polymer which has

has water reducibility type (NK-100PM, NK-200PM), solvent type (NK-350，

polyethyleneimine in side chain.

NK-380) The adhesives, primers, paints which blended epoxy resin withis poly acryl amine having both characteristics of poly ethyleneimine andshow superior adhesion to plastics and metals.

acrylic polymer and is superior in high reactivity and adhesion of the primary aminogroup origin.
Generally, for cationic acrylic polymer, Dimethylaminoethyl acrylate polymer (DAA),
Dimethylaminoethyl methacrylate polymer (DAM) are known, However, they are the tertiaryamine or quarternary amine type. For polymer having primary amine,

COOCH2CH2NH2 ＋

COOCH2CH2NHCH2CH
OH

O

is

only one product in the world.

Production method ofis synthesized by reaction with ethyleneimine and carboxylic acid group.

R

Type

Water reducibility

Product

NK-100PM, NK-200PM

＋

n HN

NH2・HX
NH2・HX
HX:HCI 、
HBr

Aminoethylation
Characteristic

COOR

COOH

Acrylic acid copolymer

R

Ethyleneimine

R-(CH2C)x − (CH2C)yCOOR

COO(CH2CH2NH)n-H

NK-350, NK-380

Structure

R-(CH2C)x − (CH2C)y-Solvent

Application

NH2

NH2

•Water soluble polymer•Self emulsiﬁcation type
hardening agent of
epoxy resin•Room temperature
reactivity with epoxy
resin•Superior adhesion•Superior water
resistance andchemical resistance•Solvent soluble
polymer•Room temperature
reactivity with epoxy
resin•Superior adhesion•Superior water
resistance,
chemical resistanceand barrier•Water based for ﬂoor
paints•Primer for oleﬁn ﬁlms

•Primer for pressuresensitive adhesive tape
•Adhesive promoting
agents and primer for
ﬁlms•Adhesives of ﬂuorine
ﬁlm with Steel (NK-350)•Antimigration agent for
PVC ﬁlm (NK-380)※ In using our products () in relation to the application referred to in this booklet, please pay
attention to existence of the intellectual property rights (including patent and its application) owned by any
third parties and avoid the possible infringement of such intellectual property rights. NIPPON SHOKUBAI
shall in no event be responsible for any damages or liabilities caused by infringement or alleged
infringement of said intellectual property rights due to the above-mentioned use of our products.
15

16

Speciﬁcation and property of

SafetyPhysicalSpec.

NK-100PM
NK-200PM(Water reducibility) (Water reducibility)17

NK-350(Solvent)

NK-380(Solvent)

Solid cont.(wt％)

48.0-50.0

55.0-57.0

33.0-37.0

29.0-31.0

Viscosity(mPa・s/25℃)

4000-8000

20000-40000

400-1500

＜2000

pH

4.0-5.5

4.0-5.5−−

Appearance

Viscous,yellowish-brownliquidViscous,yellowish-brownliquidViscous,clear liquid

Viscous,light yellow liquid

Water solubility

Complate

Complate−−

Amino hydrogenequivalent weight(g-solid/eq.)＊1

350-450

350-450

1000-1800

800-1400

Amine value(mmol/g-solid)＊2

2.2-2.9

2.2-2.9

0.6-1.0

0.7-1.3

Tg(℃)

13

16

40

100

MW

10,000〜30,000

10,000〜30,000

100,000

100,000

Spec. grav.(25℃)

1.05

1.10

0.95

0.94

Product solvent

PM

PM

Toluene/lPA(7/3)

Toluene / MIBK
(3/1)

Solubility

Dissolble
in water,lower alcohol

Dissolble
in water,lower alcohol

Dissolble
in toluene, IPA
Insoluble
in water,

Dissolble intoluene, MIBK,
MEK, IPA
Insoluble in waterFlash point(℃)

36(Closed Cup)

36(Closed Cup)

4(Closed Cup)

4(Closed Cup)

Acute oral
toxicity
LD50(mg/kg. rat)

>5000

>5000

>5000

>5000

Acute dermal
toxicity
LD50(mg/kg. rat)

>2000

>2000

>2000

>5000

Primary skinirritation(rabbit)

SlightSlightSevereModerate

Acute eyeirritation(rabbit)

Moderate〜
SevereModerate〜
SevereModerate〜
Severe−Mutagenicity(AMES)

Positive

Positive

Positive−

Micronucleus
test(in vivo)

Negative

Negative

Negative

Negative

NK-100PM
NK-200PM(Water reducibility) (Water reducibility)
CAS No.

67970-17-6 or
449196-55-8103051-70-3

NK-350(Solvent)

NK-380(Solvent)

120363-55-5

178954-62-6

PM:Propylene glycol monomethyl ether, IPA:lsopropyl alcohol ,MIBK:Methyl isobutyl ketone, MEK:Methyl ethyl ketone＊1 Amino hydrogen equivalent weight:Solid weight equivalent to one amine mol.
＊2 Amine value:Amine mol number (mmol) contained in solid1g
Please refer to the Safety Data Sheet(SDS) that provides details of the safety of the product.
Above-mentioned regulations are valid September,2012.

18