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Overviews on PMMA Overviews on PMMA

MMA is;MMA is;Colorless and transparent liquid.Its polymer is hard and transparent resin like glassand has excellent weatherability, transparencyand high gloss.

Colorless and transparent liquid.Its polymer is hard and transparent resin like glassand has excellent weatherability, transparencyand high gloss.

CH

HC

CO

C

CH HH

HH H

O

MethylMethyl

MethaMethaAcrylateAcrylate

MMA process chartMMA process chart

CH

H

C

CO

C

CH HH

HH H

O

Naphtha CrackingNaphtha Cracking

Mixed C4Mixed C4

Butadiene ExtractionButadiene Extraction

Raffinate - 1Raffinate - 1

MTBE SythesisMTBE Sythesis

IsobutyleneIsobutylene

Isobutylene OxidationIsobutylene Oxidation

Methyacrylic AcidMethyacrylic Acid

EsterificationEsterification

MTBEMTBE

MeOHMeOH

MTBE CrackingMTBE Cracking

MAAMAA

MeOHMeOH

MMAMMA

PMMA(PolyMethylMethAcrylate) is an acrylic resin, which is made from MMA(MethylMethAcrylate) monomer mainly. Now LG PMMAs are manufactured through co-polymerization of MMA with MA or MMA with EA. PMMA is widely used for its high colorability, elegant appearance, good weatherability as well as excellent transmission of 93% among many other resins.

PMMA is;PMMA is;

C

H

H

C

C

O

C

CH H

H

H

H H

O

n

? Thermoplastics? Liner polymer? Amorphous? Excellent light transmission? Resistance to weathering? High surface hardness? Scratch resistance? Excellent colorability and elegant

appearance? Heat resistance? High rigidity? Chemical resistance? Recyclable

C

H

H

C

CO

C

CH HH

HH H

O

n

PMMA Process ChartPMMA Process Chart

Solution Make-upSolution Make-up

SlurrySlurry

Monomer Make-upMonomer Make-up

MMAMMA MAMA EAEA

BeadBead

ExtrusionExtrusion

PelletPellet

PolymerizationPolymerization

DryingDrying

PMMAPMMA

PMMA GRADESPMMA GRADES

TYPES OF PMMA GRADESTYPES OF PMMA GRADES

PMMAPMMA

INJECTIONGRADES

INJECTIONGRADES

HIGH IMPACTGRADES

HIGH IMPACTGRADES

IH830IH830

IG840IG840

IF850IF850

IF870IF870

EH910EH910

EG920EG920EXTRUSION

GRADESEXTRUSION

GRADES

HI835HI835

HI855HI855

HEAT RESISTANCEHEAT RESISTANCE

GENERAL-PURPOSE, HIGH IMPACT & WHITEGENERAL-PURPOSE, HIGH IMPACT & WHITE

FLUIDITYFLUIDITY

HIGH FLUIDITYHIGH FLUIDITY

HEAT/CHEMICAL RESISTANCEHEAT/CHEMICAL RESISTANCE

GENERAL-PURPOSEGENERAL-PURPOSE

HIGH IMPACTHIGH IMPACT

HIGH IMPACT & FLUIDITYHIGH IMPACT & FLUIDITY

GRADESGRADES

BEAD GRADESBEAD GRADESBASIC BEADBASIC BEAD

SPECIAL BEADSPECIAL BEAD

PROPERTIESPROPERTIES

GENERAL GRADES

GENERAL GRADES

SPECIALGRADESSPECIALGRADES

APPLICATIONSAPPLICATIONS

CO-MONOMER

HE

AT

DE

FL

EC

TIO

N

TE

MP

ER

AT

UR

E

MOLECULAR WEIGHT

HE

AT

DE

FL

EC

TIO

NT

EM

PE

RA

TU

RE

CO-MONOMER

FL

UID

ITY

MOLECULAR WEIGHT

FL

UID

ITY

CO-MONOMER

IMP

AC

T S

TR

EG

HT

H

MOLECULAR WEIGHT

IMP

AC

T S

TR

EG

HT

H

PMMA AND THE PHYSICAL PMMA AND THE PHYSICAL PROPERTISPROPERTIS

GENERAL GRADES OF GENERAL GRADES OF PMMAPMMA

Classification Standard of GRADESClassification Standard of GRADES

TypesTypes

Injection MoldingInjection MoldingGeneral

Grades

General

Grades

Extrusion Molding

Extrusion Molding

IH830

IG840

IF850

IF870

IH830

IG840

IF850

IF870

EH910

EG920

EH910

EG920

GradesGrades

Heat Resistance

General-Purpose

Good Fluidity

Excellent Fluidity

Heat Resistance

General-Purpose

Good Fluidity

Excellent Fluidity

Heat Resistance

General-Purpose

Heat Resistance

General-Purpose

PropertiesProperties RemarksRemarks

MFIMFI

MFIMFI

HighHigh

HighHigh

HDTHDT

HDTHDT

HighHigh

HighHigh

Characteristics of General GradesCharacteristics of General Grades

830 840 850 870

Flu

idit

y In

dex

VIC

AT

So

ften

ing

Po

int

Hea

t D

efle

ctio

n

Tem

per

atu

re

VIC

AT

So

ften

ing

Po

int

910 920

Flu

idit

y In

dex

Hea

t D

efle

ctio

n

Tem

per

atu

re

830 840 850 870

910 920

830 840 850 870

910 920

Characteristics of General GradesCharacteristics of General Grades

830 840 850 870

Imp

act S

tren

gth

Fle

xura

l Str

eng

th

RO

CK

WE

LL

Har

dn

ess

Fle

xura

l Str

eng

th

910 920 930

Impa

ct S

tren

gth

RO

CK

WE

LL

Har

dn

ess

830 840 850 870

910 920 930

830 840 850 870

910 920 930

SPECIAL GRADES OF PMMASPECIAL GRADES OF PMMA

HIGH IMPACT GRADESHIGH IMPACT GRADES

High Impact Grades has solved such problems as cracks by heat and so on, while they keep the excellent transmission and weatherability of the existing PMMA. They are, so to speak, enhanced High Impact Series.

◆ TypesHI835H, HI835M, HI835SHI855H, HI855M, HI855S, HI855HX

◆ TypesHI835H, HI835M, HI835SHI855H, HI855M, HI855S, HI855HX

Physical PropertiesPhysical Properties PMMA(855HX)PMMA(855HX)

Transparent ABSTransparent ABS

Impact StrengthImpact Strength 6 11 ASTM D256, IZOD Impact

FluidityFluidity 2.45 7.3 230℃ 3.8㎏

RemarksRemarks

TransmissionTransmission

HazeHaze

90

1.2

88

2.0

Characteristics of High Impact GRADESCharacteristics of High Impact GRADES

HI835 M S H

Impa

ct S

tren

gth

Flu

idit

y In

dex

RO

CK

WE

LL

Har

dn

ess

Flu

idit

y In

dex

HI855 M S H HX

Impa

ct S

tren

gth

HI835 M S H HI835 M S H

HI855 M S H HX HI855 M S H HX

RO

CK

WE

LL

Har

dn

ess

Characteristics of High Impact GRADESCharacteristics of High Impact GRADES

HI835 M S H

VIC

AT

So

ften

ing

Po

int

Hea

t Def

lect

ion

Tem

per

atu

re

HI855 M S H HX

VIC

AT

So

ften

ing

Po

int

HI835 M S H

HI855 M S H HX

Hea

t Def

lect

ion

Tem

per

atu

re

Flu

idit

y In

dex

M S H HX M S HHI855 HI835

M M S S H H HXHI835 HI855

Impa

ct S

tren

gth

RemarksRemarks

Artificial Marbles, Coatings

BEAD GRADESBEAD GRADESWe produce acryl powder for artificial marbles, acrylic coatings, acrylic adhesives and paints on the basis of unique polymerization technology.

BASIC BEAD GRADESBASIC BEAD GRADES

LGGrades

LGGrades

BasisMonomers

BasisMonomers

IH830BIH830B

IG840BIG840B

IF850BIF850B

IF870BIF870B

EH910BEH910B

EG920BEG920B

Coatings

Coatings

Coatings

Artificial Marbles, Coatings, Adhesives

Coatings, Adhesives

MethylmethacrylateCopolymer

BEAD GRADESBEAD GRADES

SPECIAL BEAD GRADESSPECIAL BEAD GRADES

LGGrades

LGGrades

BasisMonomers

BasisMonomers

BN490BBN490B

BN630BBN630B

BN890BBN890B

MethylmethacrylateCopolymer

MethylmethacrylateCopolymer

n-buthylmethacrylate/ mma polymer

n-buthylmethacrylate/ mma polymer

MethylmethacrylateCopolymer

MethylmethacrylateCopolymer

RemarksRemarks

Ink Binders, Coatings

PVC Leathers, Coatings

PVC Leathers, Coatings

Characteristics of Basic Bead GradesCharacteristics of Basic Bead Grades

830B 840B 850B 870B

V.N

Tg

V.N V.N

910B 920B

Tg Tg

630B 490B 890B

830B 840B 850B 870B 910B 920B 490B 630B 890B

◆ Artificial Marbles

Bead ApplicationsBead Applications

. Beads specifically IH830B and EH910B and MMA are applied to artificial marbles.

◆ PVC Coatings. PMMA is easy to process. It is applied to PVC coatings and solidifying agents,

while urethane resin is good to the touch but hard to process.

◆ Shrink Proofing Agent. PMMA beads prevent UPR ( FRP) from shrinkage by heat. PMMA is high glossy.

◆ Others. Paints, Inks, Sheet Costings and so on

◆ Analysis Standards◆ Analysis Standards

BEAD Analysis StandardsBEAD Analysis Standards

◆ VN (Viscosity Number)- Melt PMMA in chloroform solvent and measure relative viscosity of the solution.- Beads with higher VN have larger molecular weight.

For instance, a bead with VN of 52∼74 has 80∼120 thousand molecular weight.

◆ Moisture Contents- Measuring Device : karl-Fischer

◆ Tg (Glass Transition Temperature) - Measuring Device : DSC- Tg represents the elasticity of a polymer and it is equal to its softening

temperature.

◆ Acidity value- Melt PMMA in acetone and titrate it with KOH solution. ( Unit : mgKOH/g )

◆ MFI (Melt Flow Index)- MFI represents the fluidity of polymer. To get MFI, melt PMMA at 230 ℃, and

give a force of 3.8kg on the molten PMMA for ten minutes.- Bead with higher MFI has better fluidity.

Characteristics of PMMACharacteristics of PMMA

LIGHT TRANSMISSIONLIGHT TRANSMISSION◆ LIGHT TRANSMISSIN OF PMMA : 93% for colorless and transparent PMMA

(It transmits 93% of visible ray and reflects the rest of it. Thus it hardly absorb visible ray.)

200 240 300 400 500 1000 1500 2000 2800

100

80

60

40

20

0Tra

nsm

issi

on

%

Ultra violet Visible ray Infrared ray

Wave length (nm)

Ultra Violet AbsorptionUltra Violet Absorption◆By the difference of wavelength, Light is classified into;

Ultra-Violet : below 380 nm

Visible ray : 380 ~ 780nm,

Infrared ray : 780 nm and over

Therefore, LG PMMA contains some UV absorbent, if necessary.

LG PMMA UV Absorption

TypesTypes ApplicationsApplications

100% at 280nm (UVA-280)

100% at 360nm (UVA-360)

100% at 390nm (UVA-390)

IF850 and IF870 for internal application

IH830 and IG840 for external application

IH830U for sunglasses

WeatherabilityWeatherability◆ PMMA has outstanding weatherability among the plastic resins.

In spite of long exposure to UV, rain or wind , it keeps the initial physical properties.

(Typical application: Taillights of automotive vehicles)

◆ AMECA

•Test period (3yrs) : `89.4 ~ ‘92.4

•Test places : Florida (hot and humid), Arizona (hot and dry)

•Grade/ Color

- Grade : 4 types (IH830 etc.)

- Color : 19 types (Clear 2, Amber 7 and Red 10)

WeatherabilityWeatherability

2000

PC

Acrylic Rubber

PMMA

0 500 1000 1500Time of Exposure(hr)

Haze(%) 30

25

20

15

10

5

◆ PMMA has outstanding weatherability among the plastic resins◆ Haze test results after two thousand hours’exposure show that the haze for PMMA makes an steady and slight increase, while that for PC increases sharply on and after fifteen hundreds hours.

WeatherabilityWeatherability

Y.I 6.0

5.0

4.0

3.0

2.0

1.0

0 500 1000 1500 2000

Time of Exposure(hr)

PC

Acrylic Rubber

PMMA

◆ PMMA having low initial yellow index has excellent transparency. It hardly change despite of long-time exposure over 2000 hours, while PC makes sharp change in the beginning and shows relatively slight change afterwards.

Other Characteristics of PMMAOther Characteristics of PMMA◆ Colorability-Transparent/semi-transparent/opaque- It doesn’t discolor by heat during molding nor produce any substance to affect dyestuffs and pigments.

◆ Ease to Process- Such machine works as cutting, sewing, carving and grinding are

easy to be done.-Good to the adhesives, paints and dyestuffs.

◆ Lightweight-Specific Gravity 1.19 (1/2 of glass)

- Its strength is comparable to inorganic glass

◆ Innoxious- It doesn’t contain materials harmful to the body.- No relation to any of environmental hormone- food containers, artificial teeth, dental filling materials, artificial eyes and artificial

bones -Environmental Hormone: chemical substances exposed to the polluted environment come into the body and act like hormones. They are called environmental hormone or ‘endocrine disrupter scientifically.-Influences to the body; sperm count decrease, deformation of sexual organs and hormone-related cancer increase.

PMMA and moisturePMMA and moisture

The Influence of Moisture ContentThe Influence of Moisture Content

◆Moisture absorption of various resins: ASTM D570 (measure the weight of resin after steeping it in 23℃ water for 24 hours )

Moisture content over 5% Moisture content over 5%

Moisture content 1~5%Moisture content 1~5% Celluros Resin, Poly Vinyl Acetic Acid,Poly Vinyl Formalin, NylonCelluros Resin, Poly Vinyl Acetic Acid,Poly Vinyl Formalin, Nylon

Moisture content 0.1~1%Moisture content 0.1~1% PVC, Styrene Copolymer, PMMA, PC, PET,Phenolic Resin, Urea Resin, Melanin, PAPVC, Styrene Copolymer, PMMA, PC, PET,Phenolic Resin, Urea Resin, Melanin, PA

Polyvinylalcohol, CellophanePolyvinylalcohol, Cellophane

Moisture content under0.1%Moisture content under0.1% PE, PP, PolyChloroethylene, PS...PE, PP, PolyChloroethylene, PS...

* The molecular structure of resin with moisture content of 0.1 ~ 1% includes ester combination like PC,PET and PMMA, and ether combination like polyacetal, urea resin and phenol resin.

* Thus PMMA absorbs moisture easily because its molecular structure has ester combination and it is amorphous resin.

Moisture AbsorptionMoisture Absorption

◆ PMMA moisture absorption changes according to surrounding temperature and humidity.

Moisture Absorption with preservation temperature

0.8

Moisture Absorption

0.630℃,80%RH30℃,80%RH

(%)

0.4

0.2 23℃,80%RH23℃,80%RH

0

40 80 120 160 200 240Preservation period(Days)

Moisture AbsorptionMoisture Absorption

◆ PMMA absorbance characteristic curve (left alone) : change with surrounding temperature(80% RH is fixed)

Moisture Absorption

(%)

Days

1.4

1.2

1.0

0.8

0.6

0.4

0.2

01 2 3 4 5 6 7

60℃60℃

40℃40℃

20℃20℃

Moisture AbsorptionMoisture Absorption

◆ PMMA Moisture Absorption

characteristic curve(left alone) : change according to humidity

(20℃ is fixed)Moisture Absorption

(%)

Days

1.4

1.2

1.0

0.8

0.6

0.4

0.2

05 10 15 20 25 30 35

92% RH92% RH

60% RH60% RH

40% RH40% RH

Control of Moisture Content During the MoldingControl of Moisture Content During the Molding

◆ Safe and precise molding requires moisture content control.

◆ Moisture absorption and the quality of molding product

•Silver streaks and blowholes may appear.•Lower melt viscosity may cause;

-over filling, defective molding release and defective size-deterioration of mechanical physical property

◆ Environmental causes•Humidity difference between rainy season and winter time•Temperature difference between summer time and winter time•Humidity difference by weather•Temperature difference between the day and night time•Requiring time to final use after initial exposure

Necessity of Dehumidifying DryerNecessity of Dehumidifying Dryer

◆ Reasons to bring blowholes and silver streaks occupying most

of defects in PMMA in summer time are as follows;

. 80% of defective products is caused by moisture content

. Thermal degradation of resin due to poor heat stability and activation is one of the minor causes.

◆ Limit Moisture Absorption is 0.08~0.05% for general molding but

it is estimated to be under 0.03~0.01% for a safe and precise molding

of specific product.

ex) Especially, to control moisture content is important to the long-sized product as SANTAMO’s garnish panel.

Moisture AbsorptionMoisture Absorption◆ In summer time, as hot-air dryer using hot and humid air removes moisture of the pellet surface only, dehumidifying dryer using air below-40℃ is required to the safe and precise molding.

ex) In case of PC

While drying with hot-air dryer for 4 hours reduces the moisture content from 0.18% to 0.018%, drying with dehumidifying dryer reduces it from 0.18% to 0.006%.

◆ Note

Recently, Japan attaches importance to control moisture content of hydrolytic resins as well as resins with high moisture absorption like PMMA.

Pre-dryingPre-drying

◆ General Conditions for PMMA Pre-drying

GradesGrades Temperature(℃)Temperature(℃) Hrs

4 ~ 6

Hrs

4 ~ 6

70 ~ 8070 ~ 80

60 ~ 70

50 ~ 60

60 ~ 70

50 ~ 60

IH830A , IH830P, IG840 EG920, EG930,IH830A , IH830P, IG840 EG920, EG930,

IF850

IF870

IF850

IF870

IH830, IH830S, IH830C IH830HR, IH830G, EH910IH830, IH830S, IH830C IH830HR, IH830G, EH910

80 ~ 9080 ~ 90

Comparison with Other ResinsComparison with Other Resins

Light Transmission of Various Materials (ASTM D1003)Light Transmission of Various Materials (ASTM D1003)

PMMAPMMA

93%89% 87% 87%

84%

90%

PSPS SANSAN PCPC RigidPVCRigidPVC

GLASSGLASS

•PMMA has the highest light transmission among the plastics, especially its light transmission is superior to glass.

•Light transmission of PMMA is 93% between 380 nm ~ 780 nm but that of PC is only 87% between 480 nm ~ 680 nm.

89%

TransparentABS

TransparentABS

Other physical propertiesOther physical propertiesCoefficient of Linear Thermal

Expansion(ASTM D1003)

Rockwell Hardness(ASTM D785)

PMMAPMMA

PSPS

GlassGlass

7~8

Nylon6Nylon6

PEPE

PMMAPMMA

PSPS

ASAS

PCPC

85 ~ 105

65~80

80~90

75~85

10 ㎝/㎝ ℃ M Scale

6~8

0.84

PCPC

11 ~13

8~13

7

Other Physical PropertiesOther Physical Properties

Heat Deflection Temp.

(ASTM D648)

Flexural Strength

(ASTM D790)

PMMAPMMA

PSPS

ASAS

PCPC

PVCPVC

74~105

65~104

88~104

130~141

60~77

PMMAPMMA

PSPS

ASAS

PCPC

910~1330

560~980

980~1330

950950

℃ ㎏/ ㎠

Other Physical PropertiesOther Physical Properties

0

1

2

3

4

5

Transparency

Heat resistance

Rigidity

High impact

Scratch Resistance

Chemical Resistance

Weatherability

Workability

PMMAPMMA

PCPC

PVCPVC

PSPS

SANSAN

INTERNATIONAL INTERNATIONAL CERTIFICATIONS FOR PMMACERTIFICATIONS FOR PMMA

Int’l Certifications for LG PMMAInt’l Certifications for LG PMMA

Int’l Standard

UL (94HB)

CSA (0.6HB)

JHPC

AMECA

UL (94HB)

CSA (0.6HB)

JHPC

AMECA

GRADE

ALL GRADE

ALL GRADE

ALL GRADE

IH830, IG840, EH910, EG930

ALL GRADE

ALL GRADE

ALL GRADE

IH830, IG840, EH910, EG930

Remarks

US Flame Retardant Standard

Canada Flame Retardant Standard

JHPC Directive of Japan Ministry of Health

(Equivalent to FDA)

AMECA Standard

US Flame Retardant Standard

Canada Flame Retardant Standard

JHPC Directive of Japan Ministry of Health

(Equivalent to FDA)

AMECA Standard

☞ UL : Underwriters Laboratories

☞ CSA : Canada Standard Association

☞ JHPC : Japan High Polymer Center

☞ AMECA : Automotive Manufactureres Equipment Compliance Agency