CA2141538A1 - Process for obtaining antistatic polymer compounds - Google Patents

Abstract

A B S T R A C T
A method for production of antistatic polymer materials includes an introduction of antistatic agent in a form of a solution of the antistatic agent in an organic solvent, compatible with a polymer matrix, into a polymer composition during processing thereof. The antistatic agent is at least one compound from the group consisting of organic and inorganic salts, complex compounds and bases. The composition is processed at temperatures not exceeding the least of the boiling and decomposition temperatures of antistatic and solvent.
An organic acid is additionally introduced into the composition.
The organic solvents are glycols, esters and their derivatives.

Description

j . . ..
r~ 2 3L ~ 1 5 3 8 ~; ",','~,""'',',.,',',",',, Field of the Invention '~,'',~,,',,' The present invention, relates to chemical ',,'~,';,.:, 5 ~technology, and partic-]larly, to methods for production -,,.,',',' ,' of antistatic ~poly~er mater:ials ~y introducing '.'~i.,',,'.'antistatic addi~tives into their volu~e, and can be .~,"'','',''', utilized for:production;of~various Polymer coatin~s. ,~
Background of the I~nvention , .,,"',:.;;,',,,', 10~t is a ~co~mmon knowledge~that a reduction of ; "'~,',', ',, electrostatic polarization; of polymer coatings provides ,~
an~iDprovement~ of envl~ronmental,~ conditions: ~or human ~,.... ....
activity. The:re~fo~re, a considerable;numbe:r of inventions ~',.'- ',, s~alm~ed:~:at: d~evelopment ~:of ::method~s ~ for :~lmproving ~.
15 antis~tatic charlcter;istics~of polyme;r;materials. ''~
Qrie of t~he~most,aldely u~sed~ methods for reducing '~'' :sta~tic~el~ectri;z~àt~ion~of,~po~lymer~materlals:and~composlons . ,~
b~ased~t~hereon,~is~t~o~intr~odo~ce~an:ti:i~st~atic ~agents 1nto 20;,~ ;Part,lcularly,~'hnown~ ln~ th'è ~:~.'ar:t lS a method for ~: '~.-j,~
redu~c:i;ng ~s:tati~c~ e:l;ectr~iz~ation~ o~f.~:poly~er~:materlals~by ntroduotlon~o~f va:rious ~a~lne.~ deriYat~lves~ :into~ their .'r'' ~,'~'~`."..'.:~`'. v'lume~(SU:~A,:~ 84238 However,;'us~e~:of~;nit;rogen-conta~inlng~: additiv;es:;~in~
25~,'said prl~o~r~'à;rt;~ hàs~ a~n,~ Z:dv'erse~ e t~ ;upon ~thermhl;~
stabil~it~y~;of:~polyme,r~m~ate;rials,~ a~nd~c;:oat~i~ngs;;~on 'their~
,.bas~ls~ fo'r ~ e'~ le,~ oor:~ `oa ` s,~p~ossess lou `' Also,~'knlown ~t t ~ od~for oduotlon ~:Z,,~of;~aZt~ist t' ~'~olyZe~r coZposit~' n~;bY~:~ tr'duc~tion:;into~a~ ' ''''.' statlc~a ~ t, ;Synta~5 ~ Standard~ Teohnolo~ica; ~
u~: t~ ~n, for:"~Pjlyv~ de~ Llno~leum P~oduct~lon, ~ -:All-union~'Rès~ea:rc ~ an~d~ esi~ ns~itute~for ~P~olYmer~
rr~Rn~ erials,.~npsoow,~la~6, pp.6 ~ ~ 21~538 ; .,`,.. , . , ;
: .:

The basic disadvantage of said prior art is an : ~essentially limited:antistatic effect achieved by use thereof. This is caused by the fact that an insufficient ~ , .
quantity of antistatic agent:does;not ensure appropriate ~-: 5 : antistatic p~roperties, whereas the excessive ''introd~uction of: Syntamide-5 into:a co~position results ';
n~a~h1gh;~"sweatine out" of the~ antistatic agent and .- ' reduces~a;prooessab11ity of sa`1d~oo~position. ~ '.' ~' The closest~ prior art with respect to the present ~ lO~ inven;t~ion~is ~a ~method;~for ~production of antistatic '~
`~ n`~ po~ly~e~r~ ateria1~s~ nc1ud1ng: an .1ntroduction of an antistatic~;agent~: i`n ~a ~for~: of: an antistatic agent so1ution~into~a~po~ly~er ~co~posit1on ~dur~ing process'ing~ '.:-'''ther~eof ~(SU,~A,:~l39023~0):.~:In said: prior art, the ;'--~
15~ :antlstati;c~agents~a:re;:~a~ueous ~solutions~ o~ ~substances `.~ .
capa~le`~to',~hyd~r~ate~ 'wate~r~o`f~ory`sta 1iza;t1on~ 1n~a~solid~
state~.~Su:c:h'~substancès can:::be~solid~:c'onductive :~ineral . f ~ n ~ àgènts.
Sai.d~p~r~io:r:~ar:t~allows~to:~:pr~od~uce~po~ly~er~ coatings ' :~
~3.~ 2'0~:~p~0s:essIng~: sufficientl:y~ .;hig~h~:~ant~istati'c .properties. i~
Ho ~ e~r,~ app1icati~on~o~f~sa1d~coati~ngs~ is~:1imited~bY~the ''''-fa~t~`'that~on~ly~`~a:~na~rr'ow~class~of;~s~ub:`t~ancesJ~capable to ~: : '''''"' ` ~ àte~water:~'o~f~c~rystall~i~zation::~in~:so1~idj.state,~ can~be y e~r:oo~posit1on at,~the~stage of ther=al~

','vap~ou~r~envi~ron~;ent~result~ in~'~a:~qui:ck:~corrosive~ wear of rc~du~e a~ corro ' '~`~ 'e ~''.of~¢~' p~ent~h11e~=ainta1n1ng-~d Deohan~oa1 p~ro-erti~s aE~the 21~1538 ;., ,~, ./3 ,,':. ',' ' ' ; The further object of the invention is to extend a range of substances utilized as antistatic agents and to provide an improvement of decorative properties of ' ~ antistatic materials produced (including production of transparent polymer coatings).
Sald obJect ~is attalned by a method for production of antistatic polymer ~materials, ;including an introduction of an~antistatlc agent in a for~ of a solotion into a polymer~ composition~ ~during processing ther~eofj~ wherein is'used~a~solution of antistatic agent n aD ~organic~ solvent~ compatible ~w1th the poly~er matrix~, the antistatic agent being at least;~one compound from ~the group c~nsisting of organic salts, inorganic ~salts,~ co~plex co~p~ounds,~ bases; the co~position being ; 15~ proaessed~at~temperatures~'nor~ exceedlng the least of the temperatu~res Tp~ Tpz,~ Tkl,~ Tk2,~wher~e Tpl and Tp2'are antistatic~and solvent~deco~posi~tion ~tempe~ratures,~ and T~h~ and~ Tk2~;are~antlstatic~;and~ solvent; bollina temrepatu~res,~respective~ly~

2~0~Alterna~tively;, àccordlng~ to the'~present invention, an''`~organlc~acid ls~;add~l;tlonally introduced~;into the solution of antistatic agent.
Also~,~acco~rding t~o~the lnvent~on,~ the solutlons of àntistatic agent~are~homogeneous solutions.
' 2$"~ ;Add~lt~lonallg~,~`the organ1c~ solvent ls at least one oo~p~ound~Er~o~ ~the~;~group~oonslstlng~of~glyools, esters and derivatives thereof.
"~ The~pre,sent.~ nventi~on differs~froi ~ thle olosest~
prior art by the ;~Pact that~an ant~istatic agent is used 3;0~ n`à~ orm ~of~ solutlon~ ~of~ t~he~a t-st~atlo aaent~1n h~igh-bo~iling organi~o~solvent~ compa~tiblle with a polYmer matri~x~ Term~ "co~pat}bl~e"~ is ~intended to i~Ply an absen~c~e~of~boi~l~ing:aw~ay~and~decomposltion of~ antlstatic agent ~during~ the oomposition~pr`Qcessing and production of~poly~er ~mater~ials~;under~ the~ process~ temperature "
2 1 ~ 1 5 3 8 ,..~t~
:~ :;?~ 4 ~

r~anges ment:lored~ ,above. This allows to reduce ~
considerably~a re:lease: of~ i~n agressive mediu~, i,e. , ,', antistatic agent, from ~ a~p:olymer mitit r iX J during its '-pr,~cessing, while maitaining hig~ ntistatic ,,:
5 ~characteristics of: po:ly~er ~aterials being produced, :-an~d,~thus,~ to;provide~ a,~ reductlon of the equip~ent , ,,,~
corrrQsive wear:. ;~
Ow,ing to~e~limin~a!tion o~the~ evaporization~:;losses, "''~ '',, inheren~t,~to the~close:st~ ior~art,-~d~ur:ing ua er IO ~ph~se: t:rans~ltion,~ ~ ~ a or'di~ng to: the~:present ,' '' inv ~ ~}on~ ensure~s a~,reduct~lon~of~enè~rjy consu~ptlon per `pr.od t:c~t :~unit~ wi~th:,othe~r~con`d~i-t~ions~'being~equil. --''~ '' ;Said advantages~ a's~ well~as~peculiarities of the : .
pr-èsent':in,ven~tion~w~ ;;"~co e,~ ore ~'o~viou frolm the ~ ~ 21~538 - ,, :Fil~ spec:imens are produced by rolling through : rollers at tenperature 150C durin~ 5 nlin :, . ": -Exa~ple 2 ~-. ~':;
5 ~ Differs~from Exa~ple 1 by the fact that before i~
ixing, into:tetraethylene glycol there are additionallY -, '.. -introduced 2 parts by ~ass of kaliu~ salt of di-(alkYl ;p~olyethylene; glycol~ ester of phosphorous aaid having the~fol:lowing~structural formula: ~ -O~CHzCH20)~ z~ P ~ ,.where . .

R~is~alkyl group containing~8-10 a~toms of carbon, an .-average. value~of~n being:6.

A~co~posI~tion Is~prepared :by ~ixIng~ iat a~bient . `
~6~= ture~of the~ olIo~Ing ooDPonents, ~taken In;parts d i o c t ~ l P h t h a l a b e ( A ~ 4 0 tr~I~ohIorethy ph spha e ;~ 15 ch y ot ~le~.asbest~ s:~ 75 grade~:.7 450 hex`~hy~ u~ bro~Ide~

Y t MeBr2 ôH:O~ is 30~ d~issolved~ und ~ gita i n in d~i ethyl diethylene glycol iJ~ :~este~r to~abtain. ~ ene~ous~ (olear~j~so~lution~
The`~ sa~ple~s~;are~obtaIned~by:rolIinB through roll~e s~at~te~peratu~re~I40~:C~;fo~r;~three~Inutes ~

2 1 ~ 8 - 6 - . " ",.:,, ,Exa~ple 4~
; A co~posltion lS;prepared by mixing i~t i~ient ^,~,''.,.,',:
te~perature of the following co~ponents, t~ken in pi~.rts '~
` by mass~
n - C-70~ 0 , . . .

: n~ triethylene~glycol,~dicapryl~ate~ lS ,.",'.'':
An:tlstatic~agèn~t~

~0~ tri~vle~ yr~ fft~hyl~e3~-r ~ ~7 0 Pr or to ~ x~n ~ ~ n n~s~ LiCl is d ssolved prod~uce~;~a,~ho~ ~ene,ous~ clear3~ solution~

--` 21~1~38 ~ 7 _ . . .
Example 6 Differs fro~ Example 6 by introduction of 7 parts of glycerin by mass, instead of kalium bromide (KBr), at the stage of filling agent introduction.
'i' .
- ' Example 7 Differs from Exa~ple 6 by addition of 0.8 parts of kaliu~ bromide by mass to the composition.
Prior to introduction to the composition, kalium 10 bromide i5 dissolved, under agi~tation, in glycerin to ' ' ;obtain a ho~ogeneous (clear) solutlon.
In the Exa~ples above, the antistatic agent is - -' produced under agitation at temperature ~ithin a range of fro~ 80C'to 100C.
lS ~
Example 8 ~ -In this Example, ~characteristics of a method for produotlon of antlstatic poly~er compo~ition, including '~;' an introduction of Syntamide-5 into a polymer matrix are given for co~parison.
A composition is prepa~red by mixing at ambient '~
temperature of the following conponents, taken in parts by mass: ;
BX~- C-70 100 ' `-~
~0~ 50 ':
~ . ~
chrysotile asbestos (grade 7-450~ 100 Synt~a~ide-5, ; ~ ~~0.8 --Syntamide-5 for~ula~is ~-~
3 0 ~ rCnH 2n~ lC0 N HC 2H 40 ( C ~H~O ) m where n;= 8-18; m =~5-6. ~
The film samples are ~produced by rolling throu~h rollers at temperature 150 C for five~inutes.

:: : : .
, ~

2~ 41~38 Exa~ple 9 A co~position prepared has the following content, expressed in parts by ~ass:
nBX - C-70 10~ ~
~0~ 3U -Antistatic agent~
kaliu~ hexafluorophosphate (KPFG) 1.0 triethylene glycol diethY1 ester 5.0 trichloroethyl phosphate 10.0 : -Liguid stabilizer ~ -' (Ba - Zn~ 2.0 : -:
Prior to ~ixing the co~ponents~ KPFG is dissolved in a ~ixture of triethylene glycol diethyl ester and trichloroethyl phosphate under heating at approxi~atelY ; -~-15 8D-100C and agitation to obtain a ho~ogeneous (clear) -~
solution.
The fil~ sa~ples are produced by rolling through ' r~ollers at te~perature 180 C for five ~inutes.
his Exa~ple illustrates a utilization o~ a co~plex co~pound in the antistatic agent.

Exa~ple 10 Differs fro~ Exa~ple 9 by usine an organic salt, suoh as trifluoro~ethan~e sulphonyl litiu~ (CF3S 03Li~, ` ~ ,`-2S as an antistatic agent.

Example 11 `-!`-A co~position prepared has the following content, eXpressed in parts by mass~
30~ ~BX - C-70 ~ 100 Ant~l~static agen~t:
trioctyla~ine 2.0 trichloroethyl phosphate 12.0 `~

.; -: : :;- .

21~15~8 - , .
g . - , ., Liquid stabilizer (Ba - Zn) 1.0 Prior to mixing the components, trioctyla~ine is dissolved in trichloreothyl phosphate at ambient te~perature to obtain a homogeneous solution.
The film samples are produced by rolling through -rollers at temperature 150 C for five minutes. -~ -', -~ Exa~ple 12 - 10A co~position prepared has the follouing content, -~
expressed in parts by mass~
~BX - C-70 100 ~0~ 30 Antistatic agent:
trifluoromethane sulphonic acid 1.5 (C~13S 03H~
litiu~ chloride (LlCl~ ~ 0.4 trichloroethyl phosphate 10.0 triethylene glycol diethyl ester 3.0 Liquid stabilizer (Ba - Zn) ~ ~ l.0 ~;~
Prior to ~ixing the components, trifluoro~ethane sulphonic acid and litium chloride are dissolved in a `~
ixture of triethylene glycol diethyl~ ester and 25~ trichloroethyl phosphate~ under heating at approximately :: ~
~ 100C and agitation~ to obtain a ~homogeneous clear ~ ~
, solution.

Example ~3 A poly~er Go~positiOn is prepared according to the closest prior art, by mixing at ambient temperature of the following ço~ponents, taken in parts by mass~
; nBx- C-70 ~ - ~ 100 ~0~ ~ ~5 separated ohalk 60 2141~
o -Antistatic agent: ~
kaliu~ carbonate (K2CO3) 15 - -distilled water 30 ~ .:
Liquid stabilizer ~Ba - Zn) 1.5 Prior to ~ixing the components, Xzc03 iS dissolved ~ -in distilled water at ambient temperature.
The film samples are produced by rolling through . :~
rollers at te~perature 125 C for five minutes. . ,;~v 10 - Specific surfaoe resistivity of the resulting '~
antistatic polymer ~aterials was- defined using flat, circular (diameter 50~1mj :sa~ples of film having a : thickness of 0.2-1.5 mm in accordance with standard rOCT
;~ 8433.2-71 "Methods of Defining Resistivity under Direct --:; 15 Voltage".
:: The tests were~ conducted using the instrument :TEPAOMMETP~E-13A. A :number of sa~ples in each test was ~ x-:not less than 3.
Results of testing the film~sa~ples are given in Table be~low.

21~ 38 T A B L E
.
Antist.agent Anti- Boiling Solvent Solvent Max. Specif. - :
.p per 100 static (deco~p) boiling process resist. -m.p of poly agent t of (decomp~ t of ~er ~atrix antistatic t ~ate-(antistic agent rials N agent.incl.~ (C) (oC) (C) (o~) . -1 4.2 (0.7) LiNO3 254H(-OCH2CH2-)40H 327.3150 3.2 lO1o 2 6.2 (2.7)~ ~ixture of 254H(-OCH2CH2-)40H 327.3150 8.1 10 LiNO~ with kalium di-alkyl polyethylene glycol ester sulfonate*
3 8.0 (1.0) MgBr2 6HxO 165~CH30CH3CH2)20 162 140 2.7 10 4 7.8 (0.8) LiCl 610 G2HsO(C2H40)3H 255.4 155 4.1 1O1o 5 0.8 (0.8~ KBr 730 - - 30 3.1 10 ô 7.0 (O) - - HOCH2CH(OH)CH20H 290 30 1.3 10 . .
7 7.8 (0.8) RBr 730 HOCHzCH(OH)CH20H 290 30 3 3 10 8 8.0 (8.0) Syntamide-5** - - - 150 4.1 1012 9 16.0 (1.0) RPFs >250 ~ixture of >250 180 1.4 C2HsO(C2H40)3C~Hs with (Cl CHzCH20)3PO
10 16.0 (1.0) CF3SO3Li >250 mixture of >250 180 1.1 1011 ,~
C2HsO(C2HsO)3C~Hs , . . .. .
with (Cl CH2CHz0)3PO
11 14.0 (2.1) (C~Hl7)aN >250 (ClCHzCH20)3PO >250 150 8.4 12 14.9 (1.9) ~ixture of >250 ~ixture of >250 150 5.1 101l : -~
; LiCl with CzHsO(C H~0)3C2Hs CF3SO3H with (Cl CH2CH20)3PO
3 45.0 (15) R2CO3 >250 H20 100 125 4.~ 10 : : . ~.. .:
:~.: ~ ~ ''.: ' "

.: ~ - :

- :.....

--~ 2 ~ 8 * structural ~or~lula: -~
,, O ,, : ";,,, ', ~RO(CH2CH20~nl2 P ~ . ' ,' ` O~
where R is alkyl group containing 8-10 atoms of carbon;
an average value of n is 6.
** structural for~ula~
~CnH2~1CONHC2H40(C2H40)~H
where n = 8-18, m = 5-6. -Samples of Test 13 resulted in a considerable .
corrosion of the surfaces of processing shafts. The remaining tests did not demonstrate such effects.
Fro~ Table above, it is obvious that an implementation of the present invention ensures high 15 antistatic properties of the~resulting poly~er materials ~ .-.` .
for various polymer types. The significant feature is , that an agressive, corrosive vapour atmosphere is not established, andJ therefore, a corrosive wear of equipment is reduced.
The invented distribution of an antistatic agent in a polymer matrix at a molecular level (owing to use of homogeneous, clear solutions of antistatic a~ent) provides a possibility to produce poly~er coatings having improved antistatic propertles (including clear .~
25 ones, i.e. without a filling agent). `~.
The~organic solvents can be tetraethylene glycol, triethylene glycol monoethyI ester, diethylene glycol ,"j dimethy~l ester, triethylene glycol~ diethyl est~er, trichloroethyl phosphate, or combinations thereof. , .i.
The antistatic agents can be, for instance, kalium .
bro~ide, magnesiu~ bro~ide, litiu~ nitrate, litiu~
chlorideJ litium trifluoro~ethane sulfonate, kaliu~
hexafluorophosphate, trioctylamine, and co~binations ~ thereof : ' ~ - `. .~ ' ~ 13 - , 21~1538 The organic acid, additionally introduced into the co~position, ean be, for example, tri~luoro~lethane sulphonie aeid.
Industri21 .Applicability The present ~ethod for produetion of antistatic : poly~er materials ean be ~ost sueeessfully utilized in ehe~ieal and petroleu~ ehemieal teehnologies for produetion of antistatie poly~er eoatlngs.

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Claims (7)

1. A method for production of antistatic polymer materials, including an introduction of antistatic agent in a form of a solution into a polymer composition during processing thereof, c h a r a c t e r i z e d in that said solution is a solution of an antistatic agent in an organic solvent, compatible with a polymer matrix, the antistatic agent being at least one compound from the group consisting of organic salts, inorganic salts, complex compounds, bases, the composition being processed at temperatures not exceeding the least of the temperatures Tp1, Tp2, Tk1, Tk2, where Tp1 and Tp2 are decomposition temperatures of antistatic and solvent, and Tk1 and Tk2 are boiling temperatures of antistatic and solvent, respectively.

2. A method as set forth in claim 1, characterized in that an organic said is added to said solution of an antistatic agent.

3. A method as set forth in claim 1, characterized in that said solutions of antistatic agent are homogeneous soutions.

4. A method as set forth in claim 1, characterized in that said organic solvent is at least one compound from the group consisting of glycols, esters and their derivatives.

5. A method as set forth in claim 1, characterized in that said antistatic agent is at least one compound from the group consisting of potassium bromide, magnesium bromide, litium nitrate, litium chloride, litium trifluoromethane sulphonate, potassium hexafluorophosphate, potassium salt of di-(alkyl polyethylene glycol) ester of phosphorous acid, trioctylamine.

6. A method as set forth in claim 2, characterized in that said organic acid is trifluoromethane sulphonic acid.

7. A method as set forth in claim 4, characterized in that said organic solvent is at least one compound from the group consisting of tetraethylene glycol, monoethyl ester, triethylene glycol, diethyl glycol dimethyl ester, triethylene glycol diethyl ester, trichlorophosphate.