TOMNOMA UUT TURUTDI PANTAI

US010040878B2

(12) United States Patent (10) Patent No.: US 10 ,040,878 B2

Youk et al. (45) Date of Patent : Aug . 7 , 2018
(54) VINYL CHLORIDE POLYMER AND
PREPARATION METHOD THEREOF
(58 ) Field of Classification Search
CPC ...... C08F 14 /06 ; C08F 114 /06 ; C08F 214 /06 ;
COSF 8 / 32 ; CO8F 8 /40
(71) Applicant: LG CHEM , LTD ., Seoul (KR ) See application file for complete search history.
(72 ) Inventors : Kyung Seog Youk , Daejeon (KR ); (56 ) References Cited
Hyun Min Lee, Daejeon (KR ); Chan
Hee Lee, Daejeon (KR ); Heung Kwon U .S . PATENT DOCUMENTS
Bae, Daejeon (KR ); Kwang Jin Lee,
Daejeon (KR ); Kyung Hyun Kim , 2 ,482,038 A 9 /1949 Temple
Daejeon (KR ); Jung Rae Lee, Daejeon 2003 /0027881 A1 2 /2003 Sunagawa et al.
2006 / 0025552 A1 2 / 2006 Kaiser et al.
(KR ) 2012/0226000 A1 * 9 /2012 Percec .................. C08F 214/06
525 /419
(73 ) Assignee : LG CHEM , LTD ., Seoul (KR )
( * ) Notice : Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS
patent is extended or adjusted under 35 CN 1156156 A 8/ 1997
U . S .C . 154 (b ) by 92 days. CN 1756777 A 4 /2006
CN 103119073 A 5 /2013
DE 2125586 Al 12 /1972
(21) Appl. No.: 15 / 101 ,803 EP 0107063 A1 5 / 1984
06 - 192523 A 7 / 1994
(22 ) PCT Filed : Sep . 14 , 2015 06184220 A 7 / 1994
2501322 B2 5 / 1996
-
mm 09137023 A 5 / 1997
(86 ) PCT No .: PCT/KR2015 /009641 09 - 241309 A 9 /1997
$ 371 (c )( 1), KR 10 - 2002- 0037769 A 5 /2002
(2 ) Date : Jun . 3, 2016 KR 20040050468 A 6 / 2004
KR 10 -2010 -0005283 A 1 /2010
( 87 ) PCT Pub. No.: WO2016 /047953 KR 20110006224 A 1 / 2011
KR 20120007227 A 1 /2012
PCT Pub . Date :Mar. 31 , 2016 KR 10 - 2012 -0130801 A 12/ 2012
* cited by examiner
(65) Prior Publication Data
US 2016/0304636 A1 Oct. 20, 2016 Primary Examiner - Roberto Rabago
(74 ) Attorney, Agent, or Firm — Dentons US LLP
(30) Foreign Application Priority Data
(57 ) ABSTRACT
Sep . 23 , 2014 (KR ) ......... ..... .... ..... 10 - 2014 -0127047 The present invention relates to a vinyl chloride polymer
Sep . 23, 2014 (KR ) . . . . . . . . . . . . . 10 -2014 -0127048 having good thermal stability due to the restraint of dehy
Sep . 23 , 2014 (KR ) 10 -2014 -0127049 drochlorination by heat or ultraviolet rays, and a method of
Aug . 27, 2015 (KR ) ... ..................... 10 - 2015 -0121273 preparing the same . The generation of the dehydrochlorina
tion of the vinyl chloride polymer due to heat or ultraviolet
(51) Int. Ci. rays may be markedly restrained , the thermal stability
C08F 14 / 06 ( 2006 .01) thereof may be improved , and the discoloration thereof or
C08F 14 / 06 (2006 .01) the modification of the physical properties thereof may be
C08F 8732 ( 2006 .01) prevented . In addition , a modifier may be introduced to a
C08F 8 /40 ( 2006 .01) polymerization process at the end of the polymerization , and
U .S . CI. high thermal stability may be attained without generating the
CPC . ...... C08F 114 /06 (2013.01); C08F 14/06 transformation of the vinyl chloride polymer.
( 2013 .01 ); C08F 8/ 32 ( 2013. 01); C08F 8/40
(2013.01) 13 Claims, 4 Drawing Sheets
U . S . Patent Aug. 7 , 2018 Sheet 1 of 4 US 10 ,040,878 B2

[ Fig . 1A ]
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U . S . Patent Aug. 7 , 2018 Sheet 2 of 4 US 10 ,040 ,878 B2

[Fig . 2 )

Overlaid Relative Distribution

1. 10 cer v enant 100 . 00
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U . S . Patent Aug. 7 , 2018 Sheet 3 of 4 US 10 ,040,878 B2

[Fig . 3 ]
COMPARATIVE EXAMPLE EXAMPLE EXAMPLE
EXAMPLE 1
. .. . . . . . . . . . . . . .

60 SECONDS
80 SECONDS

100 SECONDS

120 SECONDS

150 SECONDS

180 SECONDS
U . S . Patent Aug. 7 , 2018 Sheet 4 of 4 US 10 ,040,878 B2

[Fig . 4 ]
COMPARATIVE EXAMPLE EXAMPLE EXAMPLE
EXAMPLE 1

2050
60 SECONDS

80 SECONDS

100 SECONDS

120 SECONDS

150 SECONDS
* * * ** * * * * * ** * * 7 !

180 SECONDS
 US 10 ,040 ,878 B2
VINYL CHLORIDE POLYMER AND polymer and to control the thermal decomposition rate of a
PREPARATION METHOD THEREOF resin . Recently , a method of using a thermal stabilizer of
diverse types such as a metallic material or an organic
CROSS -REFERENCE TO RELATED compound has been introduced . However , the use thereof is
APPLICATIONS 5 limited due to environmental problems caused by the use of
a heavy metal stabilizer and high price .
This application is a National Stage Entry of International A method of blending a polymer having good heat resis
Application No. PCT/KR2015 / 009641, filed on Sep . 14 , tance with a vinyl chloride polymer has been suggested to
2015 , and claims the benefit of and priority to Korean complement weak physical properties however is not easily
Application No . 10 - 2014 -0127047, filed on Sep . 23 , 2014 , 10 used due to low miscibility with the vinyl chloride polymer
Korean Application No. 10 - 2014 -0127048 , filed on Sep . 23 , and difficulty in processing.
2014 , Korean Application No . 10 - 2014 -0127049, filed on With such a background, the inventors of the present
Sep . 23 , 2014 , and Korean Application No. 10 - 2015 - disclosure studied on a method of improving the thermal
0121273 , filed on Aug. 27 , 2015, all of which are hereby stability of a vinyl chloride polymer by effectively restrain
incorporated by reference in their entirety for all purposes as 15 ing a dehydrochlorination reaction (a dehydrochloric acid
if fully set forth herein . reaction ), prepared a vinyl chloride polymer by adding at
least one modifier of oxycarboxylates, inorganic phosphates,
TECHNICAL FIELD or ethylenediamine tetraacetates to a vinyl chloride mono
mer and emulsion polymerizing , measured the generation
The present invention relates to a vinyl chloride polymer 20 degree of scale, the amount of dehydrochloric acid and
having good thermal stability due to the restraint of dehy thermal stability ( Yellowness Index ), found that the genera
drochlorination by heat or ultraviolet rays , and a method of tion degree of the scale is extremely small , the amount of
preparing the same. dehydrochloric acid is decreased , and the thermal stability
(Yellowness Index ) is improved , and achieved the present
BACKGROUND ART 25 invention .
A vinyl chloride polymer is a polymer including 50 % or DISCLOSURE OF THE INVENTION
more of vinyl chloride , is cheap , allows easy control of
hardness , is applicable in most processing equipments and Technical Problem
has diverse application fields . In addition , the vinyl chloride 30
polymer may provide a molded product having good physi The present invention provides a vinyl chloride polymer
cal and chemical properties such as mechanical strength , having improved thermal stability by restraining the dehy
climate resistance and chemical resistance , and is widely drochlorination reaction of a vinyl chloride polymer due to
used in diverse fields. heat or ultraviolet rays .
However, the vinyl chloride polymer may induce dehy- 35 The present invention also provides a method of preparing
drochlorination due to the defects of chemical structures, the vinyl chloride polymer.
generated during a polymerization reaction by heat or ultra
violet rays applied during processing and may induce the Technical Solutions
discoloration of a resin or the deterioration of physical
properties . 40 According to an aspect of the present invention , there is
Particularly , in a vinyl chloride polymer, chemical defects provided a vinyl chloride polymer including modifier-de
generated during a polymerization reaction , i.e., the defects rived unit , wherein the modifier is at least one selected from
of the chemical structures of allyl chloride and tertiary the group consisting of oxycarboxylates , inorganic phos
chloride are present. Due to the defects of the chemical phates , and ethylenediamine tetraacetates , wherein a poly
structure , the binding energy of carbon with chlorine in the 45 dispersity index (PDI) of the vinyl chloride polymer is from
vinyl chloride polymer may be much lower than that of 2 . 1 to 2 .4 .
carbon with chlorine in a normal molecular structure , and According to another aspect of the present invention ,
the bonding between carbon and chlorine may be easily there is provided a method of preparing the vinyl chloride
broken due to external radical transfer during processing the polymer including a step of adding a modifier to a vinyl
vinyl chloride polymer. Separated hydrogen chloride from a 50 chloride monomer, and polymerizing, wherein the modifier
polymer chain accelerates other side reactions through an is at least one selected from the group consisting of oxy
auto -catalyst reaction to produce another hydrogen chloride carboxylates, inorganic phosphates, and ethylenediamine
continuously. In addition , a double bond may be formed at tetraacetates.
the site from where the hydrogen chloride has been
removed , and a number of double bondsmay be overlapped 55 Effects of the Invention
to generate the discoloration of a resin and the deterioration
of physical properties. That is, in a vinyl chloride polymer According to the vinyl chloride polymer of the present
or a molded product processed therefrom , a dehydrochlori - invention , the generation degree of scale may be markedly
nation reaction may be generated due to heat or ultraviolet low , the generation of dehydrochlorination due to heat or
rays, thereby generating the discoloration defects of a vinyl 60 ultraviolet rays may be markedly restrained , the thermal
chloride polymer or the deterioration or change of physical stability thereof may be improved , and the discoloration
properties . thereof or themodification of the physicalproperties thereof
In order to improve the limitations of the vinyl chloride may be prevented .
polymer, an organometallic compound containing a metal In addition , according to the preparation method through
such as Ba, Zn , Ca and Pb has been mixed with the vinyl 65 emulsion polymerization , the transformation of the vinyl
chloride polymer to restrain the generation of radicals or chloride polymer may not be generated , and high thermal
ions during thermal decomposition of the vinyl chloride stability thereof may be attained .
 US 10 ,040 ,878 B2
Accordingly, the vinyl chloride polymer and the method molecular weight by the samemethod as that for measuring
of preparing the same through the emulsion polymerization the weight average molecular weight and obtaining the ratio
may be readily applied to an industry requiring the vinyl (Mw /Mn ) of the weight average molecular weight (Mw ) and
chloride polymer , for example , industries concerning a vinyl the number average molecular weight (Mn).
chloride resin and a molded product thereof. 5 The vinyl chloride polymer includes the vinyl chloride
monomer- derived unit and the modifier- derived unit as
BRIEF DESCRIPTION OF THE DRAWINGS described above , and the vinyl chloride polymer includes the
modifier- derived unit in an amount ratio from 0 . 001 to 10
The accompanying drawings in the present disclosure parts by weight relative to 100 parts by weight of the vinyl
illustrate preferred embodiments of the present invention , 10 chloride monomer - derived unit. If the vinyl chloride poly
and serve to further understanding of the principles of the mer includes the modifier -derived unit in an amount of less
present invention together with the description . The present than 0 .001 parts by weight, the restraining effect of the
invention should not be construed as limited to the descrip - dehydrochlorination reaction would be trivial, and the
tion in the drawings . improving effect of the thermal stability of the vinyl chloride
FIG . 1A , FIG . 1B , FIG . 1C and FIG . 1D respectively 15 polymer may be deteriorated , and if the vinyl chloride
illustrates PNMR analysis results of a vinyl chloride poly - polymer includes the modifier- derived unit in an amount of
mer of Example 1 prepared according to an embodiment of greater than 10 parts by weight, the viscosity of a plastisol
the present invention ; would increase during processing the vinyl chloride polymer
FIG . 2 is a graph illustrating analysis results of polydis - thus prepared , and the processability thereof may be dete
persity index of a vinyl chloride polymer of Example 2 20 riorated , thereby deteriorating the coloring property of a
prepared according to an embodiment of the present inven - molded product processed therefrom .
tion and vinyl chloride polymers prepared in Comparative Particularly , the vinyl chloride polymer may include the
Examples 1 and 2 ; vinyl chloride monomer -derived unit and the modifier
FIG . 3 illustrates color changes of vinyl chloride poly - derived unit, and at least a portion of the modifier- derived
mers of Examples 5 to 7 prepared according to embodiments 25 unit is bonded with the vinyl chloride monomer-derived
of the present invention and a vinyl chloride polymer unit. That is, the vinyl chloride polymer according to an
prepared according to Comparative Example 1 with respect embodiment of the present invention may include a vinyl
to time; and chloride monomer-derived unit bonded with the modifier
FIG . 4 illustrates color changes of vinyl chloride poly - derived unit together with that not bonded with the modifier
mers of Examples 10 to 12 prepared according to embodi- 30 derived unit. For example , the vinyl chloride polymer may
ments of the present invention and a vinyl chloride polymer include a vinyl chloride monomer - derived unit combined
prepared according to Comparative Example 1 with respect with a modifier -derived unit as represented by the following
to time. Formula 1 together with a separate modifier- derived unit.
BEST MODE FOR CARRYING OUT THE 35
35
INVENTION ? ?
[Formula 1]
Hereinafter, the present invention will be explained in unt
more detail to assist the understanding of the present inven /
Finn
11111
tion . 40
40
It will be further understood that terms or words used in Liu
the description and claims should not be interpreted as
having a meaning such as those defined in commonly used
dictionaries , however should be interpreted as having a In Formula 1, M represents a modifier -derived unit .
meaning and concept that is consistent with the technical 45 Here , the expression of " derived unit” may represent a
spirit of the present invention on the basis of a principle that structure or a component produced from a certain material
an inventor may define the concept of terms appropriately to and may represent a material itself. For example , the vinyl
explain his invention by the best way. chloride monomer -derived unit may be a structure or a
The present invention provides a vinyl chloride polymer component produced from the vinyl chloride monomer or a
having good thermal stability , and low discoloration degree 50 vinyl chloride monomer itself.
due to heat and ultraviolet rays. In addition , the expression of at least one ” means a
In an embodiment according to the present invention , a portion of the whole , and may represent at least one where
vinyl chloride polymer includes a vinyl chloride monomer- the whole is ten .
derived unit and modifier -derived unit, wherein the modifier Particularly , in a vinyl chloride monomer - derived unit
is at least one selected from the group consisting of oxy - 55 bonded with the modifier -derived unit, represented by the
carboxylates, inorganic phosphates and ethylenediamine tet- above Formula 1 and included in the vinyl chloride polymer,
raacetates, and a polydispersity index (PDI) of the vinyl themodifier- derived unit may be bonded with one side of the
chloride polymer is from 2 . 1 to 2 . 4 . vinyl chloride monomer-derived unit by electrostatic attrac
In an embodiment, the vinyl chloride polymer may have tion , and a modification ratio due to the modifier -derived
a weight average molecular weight from 10 , 000 g /mol to 60 unit may be from 0 .01mol % to 2 . 5 mol % . Themodification
20 ,000 g /mol. ratio may represent the ratio of at least a portion of the
The weight average molecular weight of the vinyl chlo - modifier - derived unit bonded with the vinyl chloride mono
ride polymer was measured using gel permeation chroma- mer- derived unit .
tography (GPC ) after completely dissolving 0 . 02 g of the The combination of the vinyl chloride monomer- derived
vinyl chloride polymer in 20 ml of tetrahydrofuran (THF) 65 unit and the modifier -derived unit by the electrostatic attrac
and filtering (using a filter of 0 .45 um ). The polydispersity tion may be changed into a covalent bond according to the
index was obtained after measuring a number average application of heat. In this case , a dehydrochlorination
 US 10 ,040 ,878 B2
reaction generated due to the application of the heat may be crosslinking monomer such as diallyl phthalate . The vinyl
restrained . Therefore , the dehydrochlorination reaction of monomers may be used alone or as a mixture of two or more.
the vinyl chloride polymer including the vinyl chloride The oxycarboxylate is not specifically limited , however
monomer-derived unit bonded with the modifier-derived may be citric acid or trisodium citrate .
unit may be restrained , and good heat resistance may be 5 The ethylenediamine tetraacetate is not specifically lim
attained . ited , however may be disodium ethylenediamine tetraacetic
More particularly, the vinyl chloride polymer according to acid or tetrasodium ethylenediamine tetraacetic acid , and
may particularly be the tetrasodium ethylenediamine tet
an embodiment of the present invention may include an
inorganic phosphate modifier-derived unit, and in this case , raacetic acid .
may satisfy the following Mathematical Formula 1. 10 The inorganic phosphate is not specifically limited , how
ever may be disodium diphosphate or tetra -sodium diphos
0 .01sB /As0.5 [Mathematical Formula 11 phate , and may particularly be the tetra -sodium diphosphate .
The vinyl chloride polymer according to the present
in Mathematical Formula 1, invention may have a glass transition temperature from 70°
A is an integral value of peaks appeared in a range from 15 C . to 90° C . and an average particle diameter from 0 .01 um
5 ppm to 10 ppm in phosphorus -31 solid state nuclear to 10 um . Particularly, the glass transition temperature of the
magnetic resonance (PNMR ), and
B is an integral value of peaks appeared in a range from vinyl
the
chloride polymer may be from 75° C . to 85° C ., and
average particle diameter thereofmay be from 0 .1 um to
- 5 ppm to 5 ppm in PNMR . 5 um . The vinyl chloride polymer according to the present
In addition , in the case where the vinyl chloride polymer 20 invention may be polymerized by the following polymer
includes the inorganic phosphate modifier -derived unit , the ization process , and may have uniform and minute average
structure may be changed by forming a covalent bond
according to the application of heat to the polymer. In this particle diameter, good viscosity property and molding
processability .
case, the following Mathematical Formula 2 may be satis There is provided a method of preparing a vinyl chloride
fied . 25 polymer having good thermal stability and a low discolor
0.01sD /C50.8 [Mathematical Formula 2 ] ation degree due to heat and ultraviolet rays.
The preparation method according to an embodiment of
in Mathematical Formula 2 , the present invention is characterized in including a step of
C is an integral value of peaks appeared in a range from adding a modifier to a vinyl chloride monomer and polym
2 .5 ppm to 7 .5 ppm in PNMR after leaving the polymer at 30 erizing themonomer ( step A ), and the modifier is at least one
205º C . for 210 seconds, and selected from the group consisting of oxycarboxylates,
D is an integral value of peaks appeared in a range from inorganic phosphates and ethylenediamine tetraacetates.
- 5 ppm to 2 . 5 ppm in PNMR after leaving the polymer at Step A is for preparing a vinyl chloride polymer including
205° C . for 210 seconds. a vinyl chloride monomer-derived unit and a modifier
In the present invention , PNMR is measured using an 35 derived unit by polymerizing a vinyl chloride monomer in
Agilent 600 MHz DD2 solid state NMR apparatus . In this the presence of a modifier.
case , the measurement was conducted using a 3 . 2 mm The polymerization may be emulsion polymerization, and
HFXY solid probe with a pulse width of 6 .8 sec , a recycle particularly, micro - seed emulsion polymerization , micro
delay of 20 sec, a scan number of 1024 , and a spinning rate emulsion polymerization or pure emulsion polymerization .
of 10 kHz 40 Hereinafter, the micro -seed emulsion polymerization , the
The vinyl chloride monomer according to an embodiment microemulsion polymerization and the pure emulsion
of the present invention may mean a pure vinyl chloride polymerization will be explained in detail item by item .
monomer or a mixture of a vinyl chloride monomer and a Micro -Seed Emulsion Polymerization
vinyl monomer copolymerizable therewith . If the polymerization is the micro -seed emulsion polym
That is , the vinyl chloride monomer -derived unit may 45 erization , the emulsion polymerization may include a step of
include the pure vinyl chloride monomer -derived unit and a preparing a seed mixture including a first seed and a second
derived unit by the copolymerization of the vinyl chloride seed ( step i); and a step of adding a vinyl chloride monomer
monomer as a main component with the vinyl monomer and a modifier to the seed mixture and conducting polym
copolymerizable with the vinyl chloride monomer. In the erization (step ii). In this case , the seed mixture may be used
case where the vinyl chloride monomer-derived unit is 50 in an amount ratio from 1 to 20 parts by weight relative to
derived from the copolymerization of the vinyl chloride 100 parts by weight of the vinyl chloride monomer. In
monomer with the vinyl monomer, vinyl chloride may addition , the micro -seed emulsion polymerization may be
preferably be included in the copolymer in a ratio of 50 % or conducted by continuously adding a first emulsifier during
more . polymerization .
The vinyl monomer copolymerizable with the vinyl chlo - 55 Step i is a step of preparing a seed mixture by mixing a
ride monomer is not specifically limited , however may first seed and a second seed , which have different average
include an olefin compound such as ethylene, propylene, and diameters to increase the binding force of a vinyl chloride
butane ; vinyl esters such as vinyl acetate, vinyl propionate , monomer and to impart the vinyl chloride polymer finally
and vinyl stearate ; unsaturated nitriles such as acrylonitrile ; produced with bimodal effect . The seed mixture may be
vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl 60 obtained by mixing the first seed and the second seed in an
ether , vinyl octyl ether, and vinyl lauryl ether ; vinylidene appropriate weight ratio according to purpose , without spe
halide such as vinylidene chloride, unsaturated fatty acid cific limitation . The first seed may have an average particle
and anhydrides of the fatty acid such as acrylic acid , diameter from 0.5 um to 1.0 um , and the second seed may
methacrylic acid , itaconic acid , maleic acid , fumaric acid , have an average particle diameter from 0 .05 um to 0 . 5 um .
maleic anhydride, and itaconic anhydride ; unsaturated fatty 65 Hereinafter, the first seed will be explained in particular.
acid esters such as methyl acrylate , ethyl acrylate , monom - The first seed may be prepared by adding 100 parts by
ethylmaleate , dimethylmaleate , and butylbenzylmaleate ; a weight of a vinyl chloride monomer and 0 . 1 to 5 parts by
 US 10 ,040 ,878 B2
weight of a first emulsifier to a reactor filled with a polym - of the vinyl chloride monomer, and the average particle
erization initiator and homogenizing , followed by emulsion diameter of the second seed finally formed may be con
polymerizing at from 30° C . to 70° C . trolled by the amount used of the first emulsifier. For
The reactor filled with the polymerization initiatormay be example , the average particle diameter of the finally formed
a reactor containing a mixture solution including the polym - 5 second seed may increase according to the increase of the
erization initiator , and the mixture solution may further amount used of the first emulsifier .
include polymerization water, a separate emulsifier, a reac The polymerization initiator may preferably be a water
tion inhibitor, and a dispersant other than the polymerization soluble initiator and may be at least one selected from the
initiator, without limitation . group consisting of potassium persulfate, ammonium per
The polymerization initiatormay preferably be used in an 10 sulfate , and hydrogen peroxide .
amount ratio from 0 .01 to 3 parts, or 0 .01 to 2 parts by The second emulsifier in step b ) may be continuously
weight on the basis of 100 parts by weight of the vinyl added to the reactor during emulsion polymerizing and may
chloride monomer, and the average particle diameter of the be used in an amount ratio from 0 .01 to 6 parts by weight on
first seed finally produced may be controlled by the amount the basis of 100 parts by weight of the vinyl chloride
used of the polymerization initiator. For example , as the 15 monomer .
amount used of the polymerization initiator increases , the The first emulsifier and the second emulsifier used for
average particle diameter of the first seed finally produced preparing the first seed and the second seed may be the same
may decrease . material, and may preferably be differentmaterials. Particu
The kind of the polymerization initiator is not specifically larly , the first emulsifier and the second emulsifiermay be at
limited , and at least one of a water soluble initiator and an 20 least one selected from the group consisting of sodium lauryl
oil soluble initiator may be used . For example , at least one sulfate, laurylbenzene sulfonic acid , alpha - olefin sulfonate ,
selected from the group consisting of peroxy carbonates , sodium lauryl ethoxylated sulfate , sodium octadecyl sulfate ,
peroxy esters , and azo compounds may be used . Particularly , sodium lauryl ether sulfate , and linear alkylbenzene sul
diisopropyl peroxy dicarbonate, t-butyl peroxy pivalate , fonate .
t -butyl peroxy neodecanoate , 2 , 2 -azobisisobutyronitrile , etc . 25 Step ii is a step of adding a vinyl chloride monomer to a
may be used , or a mixture of two or more thereof may be seed mixture of the first seed and the second seed prepared
used as the polymerization initiator. Particularly, the polym - in step i, and emulsion polymerizing. The emulsion polym
erization initiator may be lauryl peroxide (LPO ), di- 2 - erization may include a step of injecting a modifier and a
ethylhexyl peroxycarbonate (OPP ) , or a mixture thereof. first emulsifier.
The emulsifier may be a known material in this art or the 30 The emulsion polymerization in step ii is not limited
same material as the first emulsifier to be described below . thereto , however may be conducted by adding a vinyl
The reaction inhibitor may be paraquinone, etc . In addition , chloride monomer, a modifier, and a first emulsifier to a
the dispersant is not specifically limited , however may vacuum reactor including a mixture of the seed mixture and
include , for example , a higher alcohol such as lauryl alcohol, polymerization water, and conducting a reaction . The modi
myristic alcohol, and stearyl alcohol, or a higher fatty acid 35 fier may be added together with the vinyl chloride monomer
such as lauric acid , myristic acid , palmitic acid , and stearic before initiating polymerization or particularly at an appro
acid . priate time according to polymerization conversion ratio ,
The homogenization is not specifically limited and may and more particularly at a point when a polymerization
be conducted by homogenizing at a temperature of 20° C . or conversion ratio is 50 % or more. Still more particularly , the
less , particularly at a temperature from 5° C . to 15º C . for 1 40 modifier may be added at a point when a polymerization
to 3 hours using a homogenizer. In this case , the homog - conversion ratio is from 80 % to 95 % . In addition , the first
enizer is not specifically limited and a commonly known one emulsifier may be continuously added during emulsion
in this art, for example , a rotor- stator type homogenizer,may polymerization , and the emulsion polymerization may be
be used . conducted by additionally adding an additive such as a
The polymerization may be conducted at a temperature 45 polymerization initiator, a molecular weight controller, and
from 30° C . to 70° C . as described above , and may particu - an electrolyte as occasion demands.
larly be conducted by elevating the homogenizing tempera - Particularly , the polymerization may be conducted by a
ture to a temperature from 40° C . to 50° C . to initiate method including steps of adding 100 parts by weight of a
emulsion polymerization and conducting polymerization for vinyl chloride monomer to a vacuum reactor including 70 to
5 to 15 hours . 50 120 parts by weight of polymerization water and 1 to 20
Hereinafter, the second seed will be explained in particu - parts by weight of a seed mixture on the basis of 100 parts
lar. by weight of the vinyl chloride monomer, initiating polym
The second seed may be prepared by the following erization at a temperature from 30° C . to 70° C ., and adding
method : 0 . 001 to 10 parts by weightof a modifier on the basis of 100
a ) a step of adding 100 parts by weight of a vinyl chloride 55 parts by weight of the vinyl chloride monomer. The modifier
monomer to a reactor filled with a first emulsifier and may be added before initiating polymerization as described
initiating polymerization at a temperature from 30° C . to 70° above , according to the polymerization conversion ratio . In
C ., and addition , 0 .2 to 2.5 parts by weight ofa first emulsifier on the
b ) continuously adding a second emulsifier during polym - basis of 100 parts by weight of the vinyl chloride monomer
erization and emulsion polymerizing for 4 to 10 hours . 60 may be continuously added during the reaction , and 0 . 1 to
The reactor filled with the first emulsifier in step a ) 1 .5 parts by weight of a polymerization initiator, 0 .5 to 2
represents a reactor including an emulsion solution contain parts by weight of an electrolyte , and 0 . 1 to 1 parts by weight
ing the first emulsifier, and the emulsion solution may of a molecular weight controller on the basis of 100 parts by
include polymerization water, a polymerization initiator, etc . weight of the vinyl chloride monomer may be additionally
other than the first emulsifier. 65 added as additives as occasion demands.
The first emulsifier may be used in an amount ratio from In this case , the modifier and the polymerization initiator
0 .01 to 1 parts by weight on the basis of 100 parts by weight may be the same as those described above , and the emul
 US 10 ,040 ,878 B2
10
sifier may be the same as the first emulsifier and the second The water soluble polymerization initiator may be used in
emulsifier as described above . an amount ratio from 0 .01 to 2 parts by weight on the basis
The molecular weight controller is not specifically lim of 100 parts by weight of the vinyl chloride monomer, and
ited , however may be , for example, n -butyl mercaptan , the water soluble polymerization initiator may be the same
n -octylmercaptan , n -dodecylmercaptan , t- dodecylmercap - 5 as those described above.
tan , etc . In addition , the second emulsifier may be continuously
The electrolyte is not specifically limited , however may added to the reactor during polymerizing and may be used
be at least one selected from the group consisting of potas - in an amount ratio from 0 . 01 to 6 parts by weight on the
sium chloride , sodium chloride , potassium bicarbonate , basis of 100 parts by weight of the vinyl chloride monomer,
sodium carbonate , potassium carbonate, potassium hydro - 10 and the second emulsifier may be the same as those
gen sulfite , sodium hydrogen sulfite, potassium pyrophos described above.
phate, sodium pyrophosphate, tripotassium phosphate , dipo ization The modifier may be added at a point when a polymer
tassium hydrogen phosphate, and disodium hydrogen larly , atconversion ratio is 50 % or more , and more particu
a point when a polymerization conversion ratio is
phosphate .
Microemulsion Polymerization 15 from 80 % to 95 % .
If the polymerization is microemulsion polymerization , tionThe may
preparation method according to the present inven
further include a step of washing , flocculating, and
the polymerization may be conducted by the steps of inject drying after emulsion polymerizing . The drying is not spe
ing an oil soluble polymerization initiator, and a vinyl cifically limited and may be conducted by a commonly
chloride monomer to a reactor filled with a first emulsifier, 20 known method to a person skilled in the art.
homogenizing , injecting a modifier, and polymerizing. According to the method of preparing a vinyl chloride
The reactor filled with the first emulsifier represents a polymer via the emulsion polymerization , the modifier may
reactor including a mixture solution containing a first emul be included in the vinyl chloride polymer without inducing
sifier, and the mixture solution may include an additive such the modification of the vinyl chloride polymer finally pro
as polymerization water, a reaction inhibitor, and a disper - 25 duced . Therefore , the thermal stability of the vinyl chloride
sant other than the first emulsifier, without limitation . The polymer may be markedly increased by restraining the
additive may be the same as those described above. dehydrochlorination reaction in case of exposing the vinyl
The first emulsifier may be injected in an amount ratio of chloride polymer to heat or ultraviolet rays. Thus, the
0 . 1 to 5 parts by weight on the basis of 100 parts by weight discoloration and the modification of the vinyl chloride
of the vinyl chloride monomer, and the particular kind of the 30 polymer due to heat or ultraviolet rays may be prevented .
first emulsifier may be the same as those described above . Hereinafter , the present invention will be explained in
The oil soluble polymerization initiator may be added in more detail referring to the following examples and experi
an amount ratio of 0 .01 to 2 parts by weight relative to 100 mental examples . However, the examples and the experi
parts by weight of the vinyl chloride monomer, and may mental examples are for illustrating the present invention ,
include , for example, at least one selected from the group 35 and the scope of the present invention is not limited thereto .
consisting of cumene hydro peroxide, diisopropyl benzene
hydroperoxide, azobisisobutyronitrile , tertiary butylhydrop Preparation Example 1
eroxide, paramentane hydro peroxide, benzoylperoxide , and
di- 2 - ethylhexyl peroxydicarbonate, known in the art, with 110 parts by weight (73 kg ) of de -ionized water, 1 .83 parts
out limitation . 40 by weight ( 1.21 kg) of lauryl peroxide (LPO ), and 0 .001
The modifier may be added at a point when a polymer- parts by weight (0 .9 g ) of paraquinone were injected to a 200
ization conversion ratio is 50 % and more , and may more L , high pressure reactor, followed by making the inner side
particularly be added at a point when a polymerization of the reactor vacuous by reducing the pressure to -730
conversion ratio is from 80 % to 95 % . mmHg. To the reactor in a vacuum state , 100 parts by weight
The homogenization may be conducted by the same 45 (66 kg ) of a vinyl chloride monomer and 11.8 parts by
method described above , and the additives such as polym - weight (7 . 8 kg ) of sodium dodecyl benzene sulfonate ( 15 % )
erization water, a reaction inhibitor, and a dispersant, and the were injected , followed by stirring for 15 minutes . The inner
amounts thereof are the same as those described above . temperature of the reactor was decreased to 20° C . or less ,
Pure Emulsion Polymerization and homogenization was conducted for 2 hours using a
If the polymerization is pure emulsion polymerization , the 50 rotor -stator type homogenizer. After completing homogeniz
polymerization may be conducted by adding a vinyl chloride ing, the inner temperature of the reactor was controlled to
monomer to a reactor filled with a first emulsifier and a water 42° C . to allow polymerizing reaction . After 558 minutes ,
soluble polymerization initiator, and conducting a polymer - the pressure in the reactor reached 3 .5 kg/ cm ' , and the
ization reaction , and the polymerization reaction may be reaction was finished . Unreacted vinyl chloride monomer
conducted while continuously adding a second emulsifier. 55 was recovered and removed to obtain a first seed having an
The reactor filled with a mixture of the first emulsifier and average particle diameter of 0 .68 um .
the water soluble polymerization initiator represents a reac
tor including a mixture containing the first emulsifier and the Preparation Example 2
water soluble polymerization initiator. The mixture may
further include an additive such as polymerization water, a 60 124 parts by weight ( 230 kg) of polymerization water,
dispersant, and a reaction inhibitor other than the first 0 .54 parts by weight of a first emulsifier ( lauric acid 790
emulsifier and the water soluble polymerization initiator, g /NaOH 240 g ), and 0 .059 parts by weight ( 110 g ) of
and the additives may be the same as those described above . potassium persulfate (KPS) were injected to a 500 L , high
The first emulsifier may be used in an amount ratio of pressure reactor, followed by stirring and making the reactor
from 0 .02 to 0 .4 parts by weight on the basis of 100 parts by 65 vacuous. 100 parts by weight ( 185 kg ) of a vinyl chloride
weight of the vinyl chloride monomer, and the kind of the monomer was injected to the reactor in a vacuum state ,
first emulsifier may be the same as those described above. followed by elevating the temperature in the reactor to 56°
 US 10 ,040 , 878 B2
12
C . to initiate polymerization . After initiating polymerization , Example 7
6 parts by weight ( 11 . 1 kg ) of a second emulsifier ( sodium
dodecyl benzene sulfonate ) was continuously injected to the A vinyl chloride polymer was obtained by conducting the
reactor for 5 hours. After the pressure in the reactor reached same procedure described in Example 5 except for injecting
4 kg/cm², the reaction was finished . Unreacted vinyl chlo - 5 0 .5 parts by weight of tetrasodium diphosphate (TSDP ).
ride monomer was recovered and removed to obtain a
second seed having an average particle diameter of 0 . 12 um . Example 8
Example 1 A vinyl chloride polymer was obtained by conducting the
10 same procedure described in Example 5 except for injecting
70 parts by weight ( 150 kg ) of de -ionized water, 7 parts 0 .005 parts by weight of tetrasodium ethylenediamine tet
by weight (15 kg ) of the first seed prepared in Preparation raacetate (EDTA - 4Na ) instead of tetrasodium diphosphate
Example 1 , and 2 .8 parts by weight (6 kg ) ofthe second seed ( TSDP).
prepared in Preparation Example 2 were injected to a 500 L ,
high pressure reactor, followed by stirring and making the Example 9
reactor vacuous. 100 parts by weight ( 215 kg) of a vinyl
chloride monomer was injected to the reactor in a vacuum A vinyl chloride polymer was obtained by conducting the
state , followed by elevating the temperature in the reactor to same procedure described in Example 5 except for injecting
58° C . to initiate emulsion polymerization . After initiating 0 .01 parts by weight of tetrasodium ethylenediamine tet
polymerization , 0 .7 parts by weight ( 1. 5 kg ) of sodium raacetate ( EDTA -4Na ) instead of tetrasodium diphosphate
dodecyl benzene sulfonate was continuously injected to the ( TSDP).
reactor, followed by stirring for 300 minutes to allow the
reaction . 5 parts by weight of tetrasodium diphosphate Example 10
(TSDP ) relative to 100 parts by weight of the vinyl chloride
monomer was injected and introduced to the reaction after 25 A vinyl chloride polymer was obtained by conducting the
initiating polymerization and at a point when a polymeriza same procedure described in Example 5 except for injecting
tion conversion ratio was 50 % . After the pressure in the 0 . 1 parts by weight of tetrasodium ethylenediamine tetraac
reactor reached 4 .0 kg/cm², the reaction was finished , and etate (EDTA -4Na) instead of tetrasodium diphosphate
unreacted vinyl chloride monomer was recovered and 30 (TSDP ).
removed to obtain a vinyl chloride polymer.
Example 11
Example 2
A vinyl chloride polymer was obtained by conducting the
A vinyl chloride polymer was obtained by conducting the 35 same procedure described in Example 5 except for injecting
same procedure described in Example 1 except for injecting 0 .3 parts by weight of tetrasodium ethylenediamine tetraac
0 .1 parts by weight of tetrasodium diphosphate ( TSDP). etate (EDTA -4Na) instead of tetrasodium diphosphate
( TSDP ).
Example 3
40
40 Example 12
A vinyl chloride polymer was obtained by conducting the
sameprocedure described in Example 1 except for injecting A vinyl chloride polymer was obtained by conducting the
0 .1 parts by weight of tetrasodium ethylenediamine tetraac - same procedure described in Example 5 except for injecting
etate (EDTA - 4Na ) instead of tetrasodium diphosphate 0 .5 parts by weight of tetrasodium ethylenediamine tetraac
( TSDP) . etate instead of tetrasodium diphosphate ( TSDP ).
Example 4 Example 13
A vinyl chloride polymer was obtained by conducting the
A vinyl chloride polymer was obtained by conducting the 50 same procedure described in Example 5 except for injecting
same procedure described in Example 1 except for injecting 0 .1 parts by weight of trisodium citrate instead of tetraso
0 .1 parts by weight of trisodium citrate instead of tetraso dium diphosphate
dium diphosphate ( TSDP). ( TSDP ).
Example 5 55
Example 14
A vinyl chloride polymerwas obtained by conducting the
A vinyl chloride polymer was obtained by conducting the same procedure described in Example 5 except for injecting
same procedure described in Example 1 except for injecting 0 .3 parts by weight of trisodium citrate instead of tetraso
0 .1 parts by weight of tetrasodium diphosphate ( TSDP) at a dium diphosphate ( TSDP) .
point when a polymerization conversion ratio was 80 % .
Example 15
Example 6
A vinyl chloride polymer was obtained by conducting the
A vinyl chloride polymer was obtained by conducting the 65 same procedure described in Example 5 except for injecting
same procedure described in Example 5 except for injecting 0 .5 parts by weight of trisodium citrate instead of tetraso
0 .3 parts by weight of tetrasodium diphosphate ( TSDP). dium diphosphate ( TSDP ).
 US 10 ,040 ,878 B2
13 14
Comparative Example 1 where tetrasodium diphosphate was dissolved well in water
and did not make a covalent bond with the vinyl chloride
A vinyl chloride polymer was obtained by conducting the monomer-derived unit but remain , the PNMR peak would
same procedure described in Example 1 except for not rarely appear after washing. However, the PNMR peak was
injecting tetrasodium diphosphate ( TSDP ). 5 observed after washing for the vinyl chloride polymer
according to an embodiment of the present invention , and
Comparative Example 2 this result meant that the tetrasodium diphosphate -derived
unit and the vinyl chloride monomer -derived unit made a
A vinyl chloride polymer was obtained by conducting the covalent bond .
same procedure described in Example 2 except for injecting 10
tetrasodium diphosphate ( TSDP ) together with a vinyl chlo Experimental Example 2
ride monomer not at a point when a polymerization conver
sion ratio was 50 % but before initiating polymerization . For comparing physical properties of each vinyl chloride
spolymer prepared in Example 2 and Comparative Examples
Comparative Example 3 1 and 2 , the weight average molecular weight and the
polydispersity index of each polymer were measured . The
A vinyl chloride polymer was obtained by conducting the
same procedure described in Example 3 except for injecting results are shown in the following Table 1 and FIG . 2 .
tetrasodium ethylenediamine tetraacetate (EDTA -4Na ) not TABLE 1
at a point when a polymerization conversion ratio was 50 % 20
but before initiating polymerization . Number average Weight average
molecular molecular weight Polydispersity
Comparative Example 4 Division weight (Mn) (Mw ) index
Example 2 71,458 161,129 2 .26
A vinyl chloride polymer was obtained by conducting the 25 Comparative 69 ,319 141,425 2 .31
sameprocedure described in Example 4 except for injecting Example 1
trisodium citrate not at a point when a polymerization Comparative
Example 2
65 ,567 160 ,554 2.54
conversion ratio was 50 % but before initiating polymeriza
tion .
30 As shown in Table 1 and FIG . 2, the vinyl chloride
Comparative Example 5 polymer of Example 2 according to an embodiment of the
present invention have the similar degree of polydispersity
A vinyl chloride polymer was obtained by conducting the index as that of the vinyl chloride polymer of Comparative
same procedure described in Example 2 except for injecting Example 1. However, the vinyl chloride polymer of Com
tetrasodium diphosphate ( TSDP ) not at a point when a 35 parative Example 2 showed increased polydispersity index .
polymerization conversion ratio was 50 % but at a point Particularly , the vinyl chloride polymer of Example 2
when a polymerization conversion ratio was 30 % . polymerized by injecting themodifier at a point of a specific
Experimental Example 1 polymerization conversion ratio showed the similar degree
of polydispersity as that of the common vinyl chloride
PNMR was measured for the vinyl chloride polymer polymer of Comparative Example 1 prepared without using
prepared in Example 1, and the results are shown in FIG . 1 . a modifier. However, the vinyl chloride polymer of Com
PNMR was measured at a state where the heat was not parative Example 2 prepared by injecting the same amount
applied to the vinyl chloride polymer, after applying the heat of the modifier as in Example 2 but injecting the modifier
at 205° C . for 60 seconds and 210 seconds, and after 45 together with a vinyl chloride monomer before initiating
applying the heat at 205° C . for 210 seconds and washing in polymerization , showed increased polydispersity index .
order to observe the change of the vinyl chloride polymer Therefore , the vinyl chloride polymer prepared by the prepa
according to the degree of the application of heat . ration method according to an embodiment of the present
As shown in FIG . 1 , it was confirmed that the main peak invention has even molecular weight and has been easily
of PNMR moved by degrees according to the application of 50 prepared . In addition , thermal stability may be attained due
heat. After washing, the original main peak was disappeared to the modifier without seriously affecting the physical
while remaining a moved peak . properties of a common vinyl chloride polymer.
A partially moved peak ( 2 ppm ) was appeared beside a Meanwhile , with respect to the time required for com
main peak (7 ppm ) due to a tetrasodium diphosphate -derived pleting polymerization , the polymerization time of the vinyl
unit via the combination of a portion of the tetrasodium 55 chloride polymer of Example 2 according to an embodiment
diphosphate -derived unit with a vinyl chloride monomer- of the present invention was similar to that of the vinyl
derived unit present in the vinyl chloride polymer according chloride polymer of Comparative Example 1, however the
to the present invention (refer to FIG . 1A ). In addition , the polymerization time of the vinyl chloride polymer of Com
tetrasodium diphosphate - derived unit and the vinyl chloride parative Example 2 was at least 1. 5 times . From the results ,
monomer-derived unit made a covalent bond by applying 60 the preparation method according to an embodiment of the
heat, and the main peak was moved by degrees, thereby present invention is found to be effective in consideration of
weakening the peak strength thereof and enlarging a par- productivity and economy.
tially moved peak beside thereof ( refer to FIGS. 1B and 1C ) .
From the results of PNMR after washing ( FIG . 1D ), it Experimental Example 3
would be found that a portion of the tetrasodium diphos - 65
phate - derived unit made a covalent bond with the vinyl Physical properties of vinyl chloride polymers prepared in
chloride monomer-derived unit. Particularly, in the case Examples 2 to 15 and Comparative Examples 1 to 5 were
 US 10 ,040 ,878 B2
15 16
measured , compared and analyzed , and the results are shown low yellowness index ) when compared to the vinyl chloride
in the following Table 2 , and FIGS. 3 and 4 . polymers prepared in Comparative Examples 1 to 5.
1) Viscosity Particularly, the vinyl chloride polymer of Comparative
The viscosity of the vinyl chloride polymers of Examples Example 1 prepared by not adding any modifier suggested in
2 to 15 and Comparative Examples 1 to 5 were compared 5 the present invention has an increased amount of dehydro
and analyzed . chlorination and markedly deteriorated thermal stability
For the vinyl chloride polymers prepared in Examples 2 when compared to those of the vinyl chloride polymers of
to 15 and Comparative Examples 1 to 5 , 100 g of each vinyl Examples 2 to 15 .
chloride polymer and 60 g of dioctyl phthalate (DOPminutes
) were In addition , by adding the modifier, the vinyl chloride
stirred using a Werke mixer ( Eurostar IKA) for 10 minutes 10 polymers of Examples 2 to 15 according to an embodiment
of the present invention has a decreased amount of dehy
at 800 rpm to prepare a plastisol.
The viscosity of each plastisol thus prepared was mea drochlorination
to the vinyl
and better thermal stability when compared
chloride polymers of Comparative Examples 2
sured using a viscometer (AR2000EX peltier plate , 40 mm to 5 prepared by adding the modifier not at a point when a
parallel plate , gap 500 um ). 15 polymerization conversion ratio was 50 % or more but at the
2 ) Thermal Stability initiating point of polymerization (polymerization conver
The thermal stability of each vinyl chloride polymer
prepared in Examples 2 to 15 and Comparative Examples 1 sion ratio of 0 % ) or at a point when a polymerization
conversion ratio was 30 % . The results mean that the physi
to 5 were compared and analyzed .
Particularly, thermal stability was measured using eachof 20 cal properties of the vinyl chloride polymers may be
improved by adding the modifier, and vinyl chloride poly
plastisol prepared in 1 ) for each vinyl chloride polymer of 20 mers having more preferable physical properties may be
Examples 2 to 15 and Comparative Examples 1 to 5 . Each
plastisol was spread on a release paper and coated using a obtained by controlling the injection time of the modifier.
0 .5 mm rod , and then , dried at 150° C . for 45 seconds using The invention claimed is :
a Mathis oven to manufacture a pregelling sheet. Heat was 1 . A vinyl chloride polymer, comprising:
applied at 205° C . to each sheet thus manufactured , and 23 a vinyl chloride monomer -derived unit; and
change was observed with respect to time lapse of 60 a modifier-derived unit,
seconds, 80 seconds , 110 seconds , 120 seconds, 150 sec wherein the modifier is selected from the group consisting
onds , 180 seconds, and 210 seconds . The results are shown of citric acid , trisodium citrate , inorganic phosphates ,
in FIGS. 3 and 4 . In addition , yellowness index was mea 3030 and ethylenediamine tetraacetates,
sured at 120 seconds using a colorimeter. wherein a polydispersity index ( PDI) of the vinyl chloride
3 ) Dehydrochlorination Amount polymer is from 2 .1 to 2 . 4 .
10 g of each vinyl chloride polymer of Examples 2 to 15 2 . The vinyl chloride polymer of claim 1 , wherein a
and Comparative Examples 1 to 5 was injected to a small wej weight average molecular weight of the vinyl chloride
reactor and washeated to 180° C . The hydrochloric acid thus
produced was collected in 200 mL of distilled water and the 3335 polymer is from 10 ,000 g/mol to 20 ,000 g /mol.
3 . The vinyl chloride polymer of claim 1 , wherein at least
pH thereof was measured to calculate the amount of hydro a portion of the modifier -derived unit is bonded with the
chloric acid produced . vinyl chloride monomer -derived unit.
4 . The vinyl chloride polymer of claim 3 , wherein the
TABLE 2 an vinyl chloride monomer- derived unit has a modification
Thermal ratio by the modifier -derived unit from 0 .01 mol % to 2 .5
Viscosity stability Dehydrochlorination mol % .
Division (Pa · s ) ( Y.I) amount (mol/L , X10 - ) 5 . The vinyl chloride polymer of claim 1, wherein the
Example 2 3 .6 1 .4 inorganic phosphate is disodium diphosphate , or tetraso
Example 3 1.5 45 dium diphosphate.
Example 4 3.4 1.6 6 . The vinyl chloride polymer of claim 1 , wherein the
Example 5 3.0 1. 3 ethylenediamine tetraacetate is disodium ethylenediamine
Example 6 3. 1
i tetraacetate , or tetrasodium ethylenediamine tetraacetate .
Example
Example
Example
Example
Example 11
7
8
9
10
3.1
3. 2
3 .2
3. 9
8. 8
8avoguos 1 .9
1. 8
1.5
1 .4
7 . The vinyl chloride polymer of claim 1 , wherein the
50 polymer comprises an inorganic phosphate modifier - derived
unit and satisfies the following Mathematical Formula 1 :
Example 12 12 . 0 1.2 0 .01sB /A50 .5 Mathematical Formula 1 ]
Example 13 2.9 1 . 35
Example 14 3 .1 1 . 31 in Mathematical Formula 1,
Example 15 3.1 1. 3 55 A is an integral value of peaks appeared in a range from
Comparative 124 2.4
Example 1 5 ppm to 10 ppm in PNMR , and
Comparative 3.6 116 2 .2 B is an integral value of peaks appeared in a range from
Example 2
Comparative 3 .3 105
- 5 ppm to 5 ppm in PNMR.
Example 3
2 .0
8 . The vinyl chloride polymer of claim 1 , wherein the
Comparative 3 .4 108 2.2 60 polymer comprises an inorganic phosphate modifier - derived
Example 4 unit and satisfies the following Mathematical Formula 2 :
Comparative 3. 4 110
äne
2.2
Example 5 0 .015D /C50.8 [Mathematical Formula 2 ]
in Mathematical Formula 2 ,
As shown in Table 2, the vinyl chloride polymers of 65 C is an integral value of peaks appeared in a range from
Examples 2 to 15 have a decreased amount of dehydrochlo 2 .5 ppm to 7 .5 ppm in PNMR after leaving the polymer
rination and markedly improved thermal stability (markedly at 205° C . for 210 seconds , and
 US 10 ,040 , 878 B2
17
D is an integral value of peaks appeared in a range from
- 5 ppm to 2.5 ppm in PNMR after leaving the polymer
at 205° C . for 210 seconds .
9 . A method of preparing the vinyl chloride polymer of
claim 1 , the method comprising adding a modifier to a vinyl 5
chloride monomer, and polymerizing the monomer,
wherein the modifier is at least one selected from the
group consisting of citric acid , trisodium citrate , inor
ganic phosphates , and ethylenediamine tetraacetates.
10 . The method of preparing a vinyl chloride polymer of 10
claim 9 , wherein the modifier is injected in an amount ratio
from 0 .01 to 10 parts by weight relative to 100 parts by
weight of the vinyl chloride polymer.
11 . The method of preparing a vinyl chloride polymer of
claim 9 , wherein the polymerizing is conducted by an 15
emulsion polymerization , and the emulsion polymerization
is micro - seed emulsion polymerization , micro emulsion
polymerization , or pure emulsion polymerization .
12 . The method of preparing a vinyl chloride polymer of
claim 9 , wherein the polymerizing is conducted in the 20
presence of a polymerization initiator, and
the polymerization initiator is used in an amount ratio
from 0 .01 to 3 parts by weight relative to 100 parts by
weight of the vinyl chloride monomer.
13 . The method of preparing a vinyl chloride polymer of 25
claim 9 , wherein the polymerizing is conducted at a tem
perature ranging from 30° C . to 70° C .
* * * * *