CA1141893A - Sulfobetaine-modified olefinic copolymer, process for preparation thereof, and use thereof - Google Patents
Sulfobetaine-modified olefinic copolymer, process for preparation thereof, and use thereofInfo
- Publication number
- CA1141893A CA1141893A CA000315997A CA315997A CA1141893A CA 1141893 A CA1141893 A CA 1141893A CA 000315997 A CA000315997 A CA 000315997A CA 315997 A CA315997 A CA 315997A CA 1141893 A CA1141893 A CA 1141893A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- sulfobetaine
- copolymer
- group
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/16—Anti-static materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
Abstract
ABSTRACT OF THE DISCLOSURE
A sulfobetaine-modified olefinic copolymer useful as an antistatic agent for synthetic polymeric materials, which comprises an olefinic copolymer having a number average molecular weight of about 500 to about 100,000 derived from a major proportion of an .alpha.-olefin having 2 to 6 carbon atoms and a minor proportion of a comonomer selected from the group consisting of un-saturated carboxylic acids containing 3 to 12 carbon atoms, functional derivatives of said unsaturated carboxylic acids unsaturated esters of carboxylic acids containing 4 to 12 carbon atoms and unsaturated amines containing 3 to 9 carbon atoms, and chemically bound to the co-monomer-derived moiety of said olefinic copolymer, a sulfobetaine group of the formula
A sulfobetaine-modified olefinic copolymer useful as an antistatic agent for synthetic polymeric materials, which comprises an olefinic copolymer having a number average molecular weight of about 500 to about 100,000 derived from a major proportion of an .alpha.-olefin having 2 to 6 carbon atoms and a minor proportion of a comonomer selected from the group consisting of un-saturated carboxylic acids containing 3 to 12 carbon atoms, functional derivatives of said unsaturated carboxylic acids unsaturated esters of carboxylic acids containing 4 to 12 carbon atoms and unsaturated amines containing 3 to 9 carbon atoms, and chemically bound to the co-monomer-derived moiety of said olefinic copolymer, a sulfobetaine group of the formula
Description
~ his invention relates to novel sulfobetaine-modified olefinic copolymers which are useful as anti-static agents and when incorporated into olefinic polymers or copolymers and other synthetic polymeric materials, can impart superior and durable antistatic effects without the need for after-treating the polymeric materials such as corona discharge treatment and without any deleterious effect on the properties of the polymeric materials; a process for producing such copolymers; and to the use of such copolymers as antistatic agents.
As is well known, olefinic polymers and copoly-mers and other hydrophobic synthetic polymeric materials tend to accumulate static charges. Buildup of static charges causes various troubles such as dust collection or spar~ing when films, sheets, fibers and other shaped articles are produced from such polymeric materials, or when these shaped articles are further processed or treated, or when the resulting products are in use.
~umerous attempts have been made to prevent buildup of static charges on hydrophobic synthetic poly-meric materials, and various antistat~c agents have b~en suggested and used. However, none of these antistati~
agents have proved to ~e entirely satisfactory, and investigations are still bein~ undertaken to provide satisfactory antista~ic agents for such polymeric mate-rials~
Various suggestions have previously been made as to betaine-type antistatic agents (see, for example, 11~1893 Japanese Patent Publication Nos. 164~/65, 14654/73 and 29928/?~). Polymeric shaped articles containing these known betaine-type antistatic agents, however, did not show the desired antist~tic effect. In an attempt to obtain a satisfactory antistatic effect, it was suggested, for example, to ~ctivate the surface of a stretched film containing a betaine-type antistatic agent by, for ex-ample, corona discharge treatment (see, for example, Japanese Patent Publications Nos. 29757/69, 5746/74 and 33827/75). These suggested techniques, however, have the defect that the surface-activating treatment is complica-ted and disadvantageous, and the antistatic effect ob-tained does not last for a sufficient period of timeO
The present inventors worked extensively in order to develop antistatic agents which can obviate the need for surface-treating shaped articles of synthetic polymeric ~aterials containing the antistatic agents contrary to the case of using known betaine-type antista-tic agents, and show antistatic effects that last for a sufficient period of time.
As a result, the inventors found that the novel sulfobetaine-modified olefinic copolymers not described in the literature can be produced as will be described hereinbelow5 and these copolymers show excellent ability to prevent buildup of static charges, completely r~moving the defects of the conventional betaine-type antistatic agentsO It was specifically fo~nd that these sulfobetaine-modified olefinic copolymers show sufficient long-lasting ~ 41893 antistatic effects in synthetic polymeric materials with-out the need for a surface-aetivating treatment, and d~
not cause adverse effects on the desirable properties of the synthetic polymeric materials contrary to the conven-tional betaine-type antistatic agents. It has thus been found that these antistatic agents of the invention can impart excellent and long-lasting antistatic effects to synthetic polymeric materials without the need for a com-plicated and disadvantageous surface-activ~ting treatment, and have the ~dvantage that they do not degrade the anti-blocking properties of poly~eric shaped articles such as films or sheets nor their printability, gloss or other surface characteristics, and do not render their surfaces tacky.
It is an object of this invention therefore to provide novel sulfobetaine-modified olefinic copolymers.
Another object of this invention is to provide a process for producing such copolymers.
Still another object of this invention is to provide the use of such copolymers as antistatic agents for synthetic organic polymeric materials.
The above and other objects and advantages of this invention will become more apparent from the follow-ing description.
he sulfobetaine-modified olefinic copolymer of this invention is an olefinic copolymer having a number average molecular weight (~n) of ~bout 500 to about 100,000 and derived from a major proportion of an ~-olefin 11~1893 containing 2 to 6 carbon atoms and a minor proportion of a comonomer selected from the group consisting of unsat-urated carboxylic acids containing 3 to 12 carbon atoms, the functional derivatives thereof, unsaturated esters of carboxylic acids containing 4 to 12 carbon atoms and unsaturated amines containing 3 to 9 carbon atoms, with the moiety derived from the comonomer having chemically bound thereto a sulfobetaine group of the following formula -X-Rl _ N~-R2 _y -so3G~
wherein Rl represents an alkylene group containing 1 to 12 carbon atoms, R represents an alkylene group con*aining 1 to 3 carbon atoms, R3 and R4 each represent a member of the class consisting of a hydrogen atom, alkyl groups con-taining 1 to 10 carbon atoms, polyoxyalkylene groups con-taining 2 to 6 carbon atoms, hydroxyalkyl groups contain-ing 1 to 6 carbon atoms, carboxyalkyl groups containing
As is well known, olefinic polymers and copoly-mers and other hydrophobic synthetic polymeric materials tend to accumulate static charges. Buildup of static charges causes various troubles such as dust collection or spar~ing when films, sheets, fibers and other shaped articles are produced from such polymeric materials, or when these shaped articles are further processed or treated, or when the resulting products are in use.
~umerous attempts have been made to prevent buildup of static charges on hydrophobic synthetic poly-meric materials, and various antistat~c agents have b~en suggested and used. However, none of these antistati~
agents have proved to ~e entirely satisfactory, and investigations are still bein~ undertaken to provide satisfactory antista~ic agents for such polymeric mate-rials~
Various suggestions have previously been made as to betaine-type antistatic agents (see, for example, 11~1893 Japanese Patent Publication Nos. 164~/65, 14654/73 and 29928/?~). Polymeric shaped articles containing these known betaine-type antistatic agents, however, did not show the desired antist~tic effect. In an attempt to obtain a satisfactory antistatic effect, it was suggested, for example, to ~ctivate the surface of a stretched film containing a betaine-type antistatic agent by, for ex-ample, corona discharge treatment (see, for example, Japanese Patent Publications Nos. 29757/69, 5746/74 and 33827/75). These suggested techniques, however, have the defect that the surface-activating treatment is complica-ted and disadvantageous, and the antistatic effect ob-tained does not last for a sufficient period of timeO
The present inventors worked extensively in order to develop antistatic agents which can obviate the need for surface-treating shaped articles of synthetic polymeric ~aterials containing the antistatic agents contrary to the case of using known betaine-type antista-tic agents, and show antistatic effects that last for a sufficient period of time.
As a result, the inventors found that the novel sulfobetaine-modified olefinic copolymers not described in the literature can be produced as will be described hereinbelow5 and these copolymers show excellent ability to prevent buildup of static charges, completely r~moving the defects of the conventional betaine-type antistatic agentsO It was specifically fo~nd that these sulfobetaine-modified olefinic copolymers show sufficient long-lasting ~ 41893 antistatic effects in synthetic polymeric materials with-out the need for a surface-aetivating treatment, and d~
not cause adverse effects on the desirable properties of the synthetic polymeric materials contrary to the conven-tional betaine-type antistatic agents. It has thus been found that these antistatic agents of the invention can impart excellent and long-lasting antistatic effects to synthetic polymeric materials without the need for a com-plicated and disadvantageous surface-activ~ting treatment, and have the ~dvantage that they do not degrade the anti-blocking properties of poly~eric shaped articles such as films or sheets nor their printability, gloss or other surface characteristics, and do not render their surfaces tacky.
It is an object of this invention therefore to provide novel sulfobetaine-modified olefinic copolymers.
Another object of this invention is to provide a process for producing such copolymers.
Still another object of this invention is to provide the use of such copolymers as antistatic agents for synthetic organic polymeric materials.
The above and other objects and advantages of this invention will become more apparent from the follow-ing description.
he sulfobetaine-modified olefinic copolymer of this invention is an olefinic copolymer having a number average molecular weight (~n) of ~bout 500 to about 100,000 and derived from a major proportion of an ~-olefin 11~1893 containing 2 to 6 carbon atoms and a minor proportion of a comonomer selected from the group consisting of unsat-urated carboxylic acids containing 3 to 12 carbon atoms, the functional derivatives thereof, unsaturated esters of carboxylic acids containing 4 to 12 carbon atoms and unsaturated amines containing 3 to 9 carbon atoms, with the moiety derived from the comonomer having chemically bound thereto a sulfobetaine group of the following formula -X-Rl _ N~-R2 _y -so3G~
wherein Rl represents an alkylene group containing 1 to 12 carbon atoms, R represents an alkylene group con*aining 1 to 3 carbon atoms, R3 and R4 each represent a member of the class consisting of a hydrogen atom, alkyl groups con-taining 1 to 10 carbon atoms, polyoxyalkylene groups con-taining 2 to 6 carbon atoms, hydroxyalkyl groups contain-ing 1 to 6 carbon atoms, carboxyalkyl groups containing
2 to 4 carbon atoms and carboxylate alkyl groups containing 2 to 4 carbon atoms, X represents an oxygen atom, a carbonyl group, an ester bond, an amide bond or a methylene group, and Y represents an oxygen atom or a methylene group.
As antistatic compounds which most resemble the sulfobetaine-modified olefinic copolymers of this inven-tion, Japanese Laid-Open Patent Publication No. 31027j77 (laid open on March 9, 1977) discloses compounds formed 11~1893 by reacting a tertiary ~mine-containing vinyl monomer of the formula (cH2)n-l F~ Rlo I. CH2=C-CO-Y_A-N-R
(~12in-l R2 II. C~2=C-Z-CII2-N-R3 ( CH2 ~n-l III. CH2=C ~ ~
wherein Y represents -O- or -~I-, A re~resents an alkylene group containing 2 to 6 carbon atoms, Z represents -O-, an alkylene group containing 1 to 6 carhon atoms or ~ phenylene o~ Rl, R2, and R~ represents an alkyl group containing 1 to 4 carbon atoms, n is an integer of 1 to 4, and m is an integer of 2 to 4, with the reaction product formed between a mono-, di-, or 1~ trihalogenated acetate and a sultone of the following formula IV. 4CH2)m~o3 wherein m is as de~ined above.
It is stated in this Publication that portion of the final compound which contains a moiety derived from the sultone and bonded to the auaternary nitrogen atom has 1~4~893 any one of the following structuresO
~ CH2COO(CI~2~n~C~Me.
-N-cH-coo(cH2)n5 ~ c-coo(cH2)n5o3~Ie (Me represents a metal atom constituting the acetate).
~he sulfobetain~-modified oléfinic copolymers of this invention are distin~uished from these suggested compounds in that the corresponding portion of these copolymers has the following structures.
-N_(cl-C3 alkYlene)~CH2 S3 C~' (Cl-C~; alk91ene)_o_so3 ~
Furthermore, as will be shown in Comparative Example 11, the compounds suggested in the above-cited Publication do not show the excellent antistatic properties possessed by the sulfobetaine-modi~ied olefinic copolymers of this invention.
The sulfobetaine-modified olefinic copolymer of this invention has a sulfobetsine group of the above formula which is bonded chemically to the moiety derived from the comonomer of an olefinic copolymer having a number average molecular weight, measured by a vapor-11~1893 pressure osmometer, of about ~00 to about 100,000. Thecopolymer preferably has a number average molecular weight of about 800 to about 25,000. If the number average molecular weight is less than about 500, it will bleed out or become sticky on the surface of a shaped article prepared from a composition composed of a syn-thetic polymeric material and the sulfobetaine-modified olefinic copolymer. Or the sulfobetaine-modified olefinic copolymer tends to be dissolved easily when such a shaped article comes into contact with water or solvents. Hence, the durability of the antistatic effect is aggravated. Gn the other hand, when the number average molecular weight is higher than about 100,~00, it is difficult to disperse the sulfobetaine-modified olefinic copolymer uniformly in a synthetic polymeric material, or it does not easily impart a sufficient antistatic effect. Or the appearance of a shaped article containing it becomes poor.
Examples of the ~-olefin containing 2 to 6 carbon atoms from which the olefin copolymer having a number average molecular 1~eight of about 500 to about 100,000~ preferably about 800 to about 25,000, is derived are ethylene, propylene, l-butene, and 4-methyl-1-pentene.
~he~ can be used either singly or as a mixture of two or more D ~he comonomer includes, for example, unsaturated carboxylic ~cids containing 3 to 12 carbon atoms such as acrylic acid, methacrylic acid, ~-ethylacrylic acid, atropic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, undecylenic acid and 5-norbornene-2,3-dicarboxylic acid; and their functional derivatives. Examples of such functional derivatives include the anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; the mono- or di-alkyl esters (preferably C4-C18 alkyl esters) such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, dimethyl fumarate, monoethyl fumarate, diethyl itaconate, monomethyl itaconate, dimethyl citraconate, and 5-norbornene-2,3-dimethylcarboxylate; and aminoethyl esters, aminopropyl esters, mono- or di-alkyl aminoethyl esters and dihydroxyalkylamino ethyl esters of the aforesaid unsaturated carboxylic acids such as aminoethyl meth-acrylate, N-methylaminoethyl methacrylate, N,N-diethyl-aminoethyl methacrylate, N,N-dihydroxyethylaminoethyl methacrylate, aminoethyl acrylate, N-ethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dihydroxy-ethylaminoethyl acrylate, diaminoethyl maleate, di-N-ethylaminoethyl maleate, and di-N,N-diethylamino-ethyl maleate. The alkyl group of the alkylaminoethyl esters or hydroxyalkylaminoethyl esters preferably con-tains 1 to 6 carbon atoms.
Other examples of the comonomer include unsat-urated esters of carboxylic acids containing 3 to 12 carbon atoms such as vinyl aceta~e, allyl acetate and undecenyl acetate; and C3-Cg unsaturated amines selected from alkenylamines, N-alkylalkenylamines, N,N-dialkyl-il4~893 g alkenylamines, N-hy~roxyalkylalkenylamines ~nd N,N-dihydroxyall~ylalkenylamines, typified by allylamine, I~,N-dimethylallylamine, N,N-~iethylallylamine, I~-hydroxy-ethylallylamine, and N,N-dihydroxypropylallylamine.
Preferably, the hydroxyal~yl group contains 2 to 6 carbon atoms and the alkenyl group contains 3 to 9 carbon atoms.
Preferred comonomers are acrylic acid, its derivatives, methacrylic acid, its derivatives, and N,N-diethylallylamine.
These comonomers can be used either singly or as a mixture of two or more.
~ he olefinic copolymer which cor.stitutes the basic part of the sulfobetaine-modified olefinic copoly-mer of this invention may be any of random, block, and 1~ graft copolymers. Conveniently, a ma~or proportion of the basic part is a moiety derived fron an a-olefin con-taining 2 to 6 carbon atoms as exemplified hereinabove.
Preferably, for this purpose, the olefinic copolymer which constitutes the basic part comprises about 30 to about 99 mole~', more preferably about 40 to about 95 mole~, of a moiety derived from the a-olefin~ and the remainder consisting of a moiety derived from the comonomer.
~xamples of the basic part are olefinic copoly-mer portions havin~ a moiety resulting ~rom the graft-copolymerizing of the aforesaid comonomer with a homopoly-mer of an a_olefinc such as polyethylene, polypropylene7 polystyrene, poly-l-butene and poly-4-methyl-1-pentene or a copolymer of an ~-olefin such as an ethylene/pro-1~41893 pylene copol~ er, an ethylelle/l-butene copol~er, an ethylene/4-methyl-1-pentene copolymer, an ethylene/bu-tadiene copolymer, an ethyleile~propylene/diene copolymer, a propylene/l-butene copolymer, a propylene/4-methyl-1-pentene copol~ er c~nd an ethylene/vinyl acetate copolymer;olefinic copolymer portions containing a moiety derived from the aforesaid comonomers and resulting from the block copolymerization of the polymers or copolymers exemplified above and polymers or copo3.ymers derived from the above-exemplified comonomers; and random copolymers havi~g amoiety derived from the above-exemplified comonomers such as an ethylene/acrylic acid copolyTner, an ethylene/methyl acryl?Ate copolymer, an ethylene,~ethyl methacrylate co-polymer, an ethylene/methyl methacrylate copolymer, a propylene/N N-diethylaminopropyl methacrylate copolymer, and a styrene/N,N-dimethylaminoethyl methacrylate copoly-merO
~ he sulfobetaine-mo~lified olefinic copolymers of this invention has a sulfobetaine group of the formula -~-Rl- N~-R2-Y-S03 ~
chemically bound to the moiety derived from the aforesaid comonomer of -the olefinic copolymer.
In the formula, Rl represents an a3kylene group containing 1 to 12 c~rbon atoms, preferably an alkylene 2~ group containing 1 to 6 carbon atoms; R2, an alkylene group containing 1 to 3 carbon atoms; each of R3 an~ R4, 1~41893 a member sel~cted from the class consisting of ai hydrogen atom, alkyl groups containin~ ]. to 10 c~rbon atoms, pre-ferably 1 to 4 carbon atoms, ~olyoxyalkylene groups con-t~ining 2 to 6 carbon ~toms, hydroxyalkyl groups contain-in~ 1 to 6 carbon atoms, carboxyalkyl groups (-RCCOH in which R represents a Cl-C10, preferably Cl-C4, alkyl group) and C2-C4 carboxylate alkyl groups (-RCC'OM in which R is as defined and ~ represents ~ metal atom such as Na, K, Zn, Ca, ~a, Sr. Pb, Mg or Al), preferably ex-clu~in~ hy~rogen; X, an o~ygen atom, a carbonyl group,an ester bond, an amide bond or a methylene group, pre-ferably an oxygen ato~, ~n ~ster bond or a methylene group; and Y, an oxygen atom, or a methylene group, pre-ferably the latter.
~referably, R2 and Y in the above formula of the sulfobetaine group are both methylene groups, Specific ex~mples of the sulfobetaine ~roups are listed belowO
-CcH2cH2 ~ CH -CC`OCE2CH2 N 3 ~ N ~ 3 I ` CH3 C~ '~ CH
As antistatic compounds which most resemble the sulfobetaine-modified olefinic copolymers of this inven-tion, Japanese Laid-Open Patent Publication No. 31027j77 (laid open on March 9, 1977) discloses compounds formed 11~1893 by reacting a tertiary ~mine-containing vinyl monomer of the formula (cH2)n-l F~ Rlo I. CH2=C-CO-Y_A-N-R
(~12in-l R2 II. C~2=C-Z-CII2-N-R3 ( CH2 ~n-l III. CH2=C ~ ~
wherein Y represents -O- or -~I-, A re~resents an alkylene group containing 2 to 6 carbon atoms, Z represents -O-, an alkylene group containing 1 to 6 carhon atoms or ~ phenylene o~ Rl, R2, and R~ represents an alkyl group containing 1 to 4 carbon atoms, n is an integer of 1 to 4, and m is an integer of 2 to 4, with the reaction product formed between a mono-, di-, or 1~ trihalogenated acetate and a sultone of the following formula IV. 4CH2)m~o3 wherein m is as de~ined above.
It is stated in this Publication that portion of the final compound which contains a moiety derived from the sultone and bonded to the auaternary nitrogen atom has 1~4~893 any one of the following structuresO
~ CH2COO(CI~2~n~C~Me.
-N-cH-coo(cH2)n5 ~ c-coo(cH2)n5o3~Ie (Me represents a metal atom constituting the acetate).
~he sulfobetain~-modified oléfinic copolymers of this invention are distin~uished from these suggested compounds in that the corresponding portion of these copolymers has the following structures.
-N_(cl-C3 alkYlene)~CH2 S3 C~' (Cl-C~; alk91ene)_o_so3 ~
Furthermore, as will be shown in Comparative Example 11, the compounds suggested in the above-cited Publication do not show the excellent antistatic properties possessed by the sulfobetaine-modi~ied olefinic copolymers of this invention.
The sulfobetaine-modified olefinic copolymer of this invention has a sulfobetsine group of the above formula which is bonded chemically to the moiety derived from the comonomer of an olefinic copolymer having a number average molecular weight, measured by a vapor-11~1893 pressure osmometer, of about ~00 to about 100,000. Thecopolymer preferably has a number average molecular weight of about 800 to about 25,000. If the number average molecular weight is less than about 500, it will bleed out or become sticky on the surface of a shaped article prepared from a composition composed of a syn-thetic polymeric material and the sulfobetaine-modified olefinic copolymer. Or the sulfobetaine-modified olefinic copolymer tends to be dissolved easily when such a shaped article comes into contact with water or solvents. Hence, the durability of the antistatic effect is aggravated. Gn the other hand, when the number average molecular weight is higher than about 100,~00, it is difficult to disperse the sulfobetaine-modified olefinic copolymer uniformly in a synthetic polymeric material, or it does not easily impart a sufficient antistatic effect. Or the appearance of a shaped article containing it becomes poor.
Examples of the ~-olefin containing 2 to 6 carbon atoms from which the olefin copolymer having a number average molecular 1~eight of about 500 to about 100,000~ preferably about 800 to about 25,000, is derived are ethylene, propylene, l-butene, and 4-methyl-1-pentene.
~he~ can be used either singly or as a mixture of two or more D ~he comonomer includes, for example, unsaturated carboxylic ~cids containing 3 to 12 carbon atoms such as acrylic acid, methacrylic acid, ~-ethylacrylic acid, atropic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, undecylenic acid and 5-norbornene-2,3-dicarboxylic acid; and their functional derivatives. Examples of such functional derivatives include the anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; the mono- or di-alkyl esters (preferably C4-C18 alkyl esters) such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, dimethyl fumarate, monoethyl fumarate, diethyl itaconate, monomethyl itaconate, dimethyl citraconate, and 5-norbornene-2,3-dimethylcarboxylate; and aminoethyl esters, aminopropyl esters, mono- or di-alkyl aminoethyl esters and dihydroxyalkylamino ethyl esters of the aforesaid unsaturated carboxylic acids such as aminoethyl meth-acrylate, N-methylaminoethyl methacrylate, N,N-diethyl-aminoethyl methacrylate, N,N-dihydroxyethylaminoethyl methacrylate, aminoethyl acrylate, N-ethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dihydroxy-ethylaminoethyl acrylate, diaminoethyl maleate, di-N-ethylaminoethyl maleate, and di-N,N-diethylamino-ethyl maleate. The alkyl group of the alkylaminoethyl esters or hydroxyalkylaminoethyl esters preferably con-tains 1 to 6 carbon atoms.
Other examples of the comonomer include unsat-urated esters of carboxylic acids containing 3 to 12 carbon atoms such as vinyl aceta~e, allyl acetate and undecenyl acetate; and C3-Cg unsaturated amines selected from alkenylamines, N-alkylalkenylamines, N,N-dialkyl-il4~893 g alkenylamines, N-hy~roxyalkylalkenylamines ~nd N,N-dihydroxyall~ylalkenylamines, typified by allylamine, I~,N-dimethylallylamine, N,N-~iethylallylamine, I~-hydroxy-ethylallylamine, and N,N-dihydroxypropylallylamine.
Preferably, the hydroxyal~yl group contains 2 to 6 carbon atoms and the alkenyl group contains 3 to 9 carbon atoms.
Preferred comonomers are acrylic acid, its derivatives, methacrylic acid, its derivatives, and N,N-diethylallylamine.
These comonomers can be used either singly or as a mixture of two or more.
~ he olefinic copolymer which cor.stitutes the basic part of the sulfobetaine-modified olefinic copoly-mer of this invention may be any of random, block, and 1~ graft copolymers. Conveniently, a ma~or proportion of the basic part is a moiety derived fron an a-olefin con-taining 2 to 6 carbon atoms as exemplified hereinabove.
Preferably, for this purpose, the olefinic copolymer which constitutes the basic part comprises about 30 to about 99 mole~', more preferably about 40 to about 95 mole~, of a moiety derived from the a-olefin~ and the remainder consisting of a moiety derived from the comonomer.
~xamples of the basic part are olefinic copoly-mer portions havin~ a moiety resulting ~rom the graft-copolymerizing of the aforesaid comonomer with a homopoly-mer of an a_olefinc such as polyethylene, polypropylene7 polystyrene, poly-l-butene and poly-4-methyl-1-pentene or a copolymer of an ~-olefin such as an ethylene/pro-1~41893 pylene copol~ er, an ethylelle/l-butene copol~er, an ethylene/4-methyl-1-pentene copolymer, an ethylene/bu-tadiene copolymer, an ethyleile~propylene/diene copolymer, a propylene/l-butene copolymer, a propylene/4-methyl-1-pentene copol~ er c~nd an ethylene/vinyl acetate copolymer;olefinic copolymer portions containing a moiety derived from the aforesaid comonomers and resulting from the block copolymerization of the polymers or copolymers exemplified above and polymers or copo3.ymers derived from the above-exemplified comonomers; and random copolymers havi~g amoiety derived from the above-exemplified comonomers such as an ethylene/acrylic acid copolyTner, an ethylene/methyl acryl?Ate copolymer, an ethylene,~ethyl methacrylate co-polymer, an ethylene/methyl methacrylate copolymer, a propylene/N N-diethylaminopropyl methacrylate copolymer, and a styrene/N,N-dimethylaminoethyl methacrylate copoly-merO
~ he sulfobetaine-mo~lified olefinic copolymers of this invention has a sulfobetaine group of the formula -~-Rl- N~-R2-Y-S03 ~
chemically bound to the moiety derived from the aforesaid comonomer of -the olefinic copolymer.
In the formula, Rl represents an a3kylene group containing 1 to 12 c~rbon atoms, preferably an alkylene 2~ group containing 1 to 6 carbon atoms; R2, an alkylene group containing 1 to 3 carbon atoms; each of R3 an~ R4, 1~41893 a member sel~cted from the class consisting of ai hydrogen atom, alkyl groups containin~ ]. to 10 c~rbon atoms, pre-ferably 1 to 4 carbon atoms, ~olyoxyalkylene groups con-t~ining 2 to 6 carbon ~toms, hydroxyalkyl groups contain-in~ 1 to 6 carbon atoms, carboxyalkyl groups (-RCCOH in which R represents a Cl-C10, preferably Cl-C4, alkyl group) and C2-C4 carboxylate alkyl groups (-RCC'OM in which R is as defined and ~ represents ~ metal atom such as Na, K, Zn, Ca, ~a, Sr. Pb, Mg or Al), preferably ex-clu~in~ hy~rogen; X, an o~ygen atom, a carbonyl group,an ester bond, an amide bond or a methylene group, pre-ferably an oxygen ato~, ~n ~ster bond or a methylene group; and Y, an oxygen atom, or a methylene group, pre-ferably the latter.
~referably, R2 and Y in the above formula of the sulfobetaine group are both methylene groups, Specific ex~mples of the sulfobetaine ~roups are listed belowO
-CcH2cH2 ~ CH -CC`OCE2CH2 N 3 ~ N ~ 3 I ` CH3 C~ '~ CH
3~ ~ SO3 / CH2 C~I2-CH2 , CH2 N / 3 ~ ~ / 3 I `CH ~ I CH3 CH2 3 ~ I
S03 / C~2 O - CH2 114189;~
-COOC}I2CH2 CH -COOCH2CH2 CH
~? N ' 3 ~ N ~ 3 CH ~ CH
:3 ' ~ I
SC 3 CH2 S~3 / CH2 P-CH2 . n-CH2 C~,H ~ C H OH
~;~ N/ ' 5 ~3 N' 2 4 C-3 ' C2H C-) ' C2H40H
SO 3CH2 5 SO 3~C, H2 CH2-CH2 , CH2-CH2 X2CX2(:))2H CH2COCTI
N' ~)N' ( CH2CH2C) ) 2H ~? ~ CH2COOH
SO3~ C,H2 SO3~ C,H2 CH
C H OH ~ CH
~)N~ 2 4 (~N' 3 C~ I ` C2H4H ~? ' C2H40H
SO 3 ~ ,C 2 SO 3 C, H2 CH2-CH2 ' CH2-CH2 1~ 4~893 - ~ocH2cEI, -COCH2CH
N ~ ~ M ' 3 I C,,II40H i3 ' CH2COOH
SO- 31CH2 3 C, ~I2 ` CH2-CH2 CH2-C'I2 -COCH2CH2 -CCH2C~'~2 ~N~ 2 5 ' CHz ~? l ~C2H
SO 3CH2 ' S~) 3 CH2 5 C~12-C~I2 , CH2-CH2 ~3 N~C 22 2~ ~(CH2cH2c')2H
CH;?COOH ~ I ( C~I2CH2C ) 2H
SO c~2 -SO 3~ C, TI2 CH C H C~2-C~2 -CH2CH2CH2-CH2C~2C~2 ~ N'~ N ' 2 5 (~ I CH ~! ' ` C H
CH2-CH2 ~ CH2-CII2 ,C2 402 2 2` (CH2cH2)2H
C2H40H 3 1 ( CH2CH2C ) 2H
SG C T'[ SO C, H2 CH2-C~2 C~2-C~I2 1~1893 -C~2CH2CH2 CCl~-I(CH ) CH COCH ~ ,Ch3 ~ N~ 2 ~ N~
9CHCH2 SC3 ' CH~
-CONH(CH2~6 -CG~I(CH~)~
/(C~I2C~2C)2H'- \ CH COOH
(~ I (CH2CH20~2H ~ I CE~2COOH
S03 CIH2 S03~ C,~12 CH2-CH2 CEI2-C~2 ~!~.N ~+`N~(CH2cl~2)2H
CEI~ ~ I (C~2CH2C~)2H
` CH2-C~I2 CH2-CH2 -COI~(CH2)12 ~CH2COO~a N
~_) I CH2COCNa S03 ClH2 In preferred examples of the sulfobetaine-modified olefinic copolymer of this invention, the ~mount of the sulfobetaine group is generally about 0.01 to about 6 millimoles, preferably about Ool to ~bout 5 mil-limoles, per @ram of the sulfobetaine-modified olefinic copo lymer .
~he sulfobetaine-modified olefinic copolymer " ~1418~3 of this invention can be prepared easily by the following methods, for example.
(a) A sulfobetaine-modified olefinic copolymer in which X in the formula represents an ester bond can be prepared by reacting a copolymer of an -olefin having 2 to 6 carbon atoms and a C3-C12 unsaturated carboxylic acid or its functional derivative, or a graft copolymer resulting from the graft copolymerization of a homo- or copolymer of the a-olefin with a C3-C12 unsaturated carboxylic acid or its functional derivative, with an alkanolamine containing 4 to 9 carbon atoms such as N,N-dimethylethanolamine, and reacting the reaction product further with a C2-C4 sultone such as 1,2-ethanesultone, 1,3-propanesultone or 1,4-butanesultone or a C2-C4 cyclic alkylene sulfate such as ethylene sulfate l-methyl-ethylene sulfate or 1,3-propylene sulfate.
(b) A sulfobetaine-modified olefinic copolymer in which X in the formula represents an oxygen atom can be produced by reacting a copolymer of an a-olefin having 2 to 6 carbon atoms and a C4-C12 carboxylic acid unsaturated ester, or a graft copolymer resulting from the graft-co-polymerization of a homo- or copoIymer of the olefin with a C4-C12 carboxylic acid unsaturated ester, with a C4-Cg alkanolamine, and reacting the reaction product further with a C2-C4 sultone or a C2-C4 cyclic alkylene sulfate.
(c) A sulfobetain-modified olefinic copolymer in which X in the formula represents a methylene group can be prepared by reacting a copolymer of an a-olefin having i~4~893 - ~6 -to 6 carbon ~toms and an N,I~-dialkylalkenylamine, or a ~raft copol~er re~sulting frori the graft-copolymerization o~ a homo- or copolymer of the Q-olefin with the I~,N-di-alkylalXenylamine, with a C2-C4- sultone or a C2-C4 cyclic alkylene sulfate.
(~) A sulfobetaine-modified olefinic copolymer in which X in the formul3 represents an amide bond can be prepared by reacting a copolymer of an ~-olefin having 2 to 6 carbon atoms and a C3-C12 unsatur?ted carboxylic acid or its acid anhydride, or a graft copolymer resulting from the graft-copolymerization of a homo- or copolymer of the a-olefin with the uns~turated carboxylic acid or its acid anhydride, with an N,N-dialkylalkylenediamine or an N,N-dihydroxyalkylalkylenediamine, followed optionally by addition-reaction of an alkylene oxide containing 2 to 4 carbon atoms; and reacting the reaction product with a C2-C4 sultone or a C2-C4 cyclic alkylene sulfateO
~ he base polymers used in processes (a) to (d) are produced by, for example, radical polymerization in the presence or absence of a solvent under atmospheric or elevated pressures~ The reaction with the alksnol~mine or alkylenediamine is ef~ected by dissolving the base polymer in a hydrocarbon solvent such as p-xylene, and heating the mixture in the presence or absence of an esterification, ester-interchange or dehydrating catalyst.
~he reaction with the sultone or cyclic sulfate proceeds by gradually ad~ing the sultone or cyclic sulfate to the aforesaid reaction product at an elevated temperature.
According to this invention, there can also be provided a method for static prevention of a synthetic polymeric material by incorporating an antistatically effective amount of the sulfobetaine-modified olefinic copolymer of the invention into the polymeric material;
and an antistatic composition of a synthetic polymeric material containing an antistatically effective amount of the sulfobetaine-modified olefinic copolymer.
Examples of synthetic polymeric materials which are to be rendered antistatic in accordance with this invention include olefin polymers or copolymers such as polyethylene, polypropylene, poly-l-butene, poly-4-methyl-l-pentene, polystyrene, an ethylene~propylene copolymer, an ethylene/l-butene copolymer, an ethylene/4-methyl-1-pentene copolymer and an ethylene/vinyl acetate copolymer;
polyamides and copolyamides; polyesters and copolyesters;
polyvinyl chloride; polycarbonates; and ABS resin, AS
resin, acrylic resins and acrylonitrile resins. Especially favorable results can be obtained when the sulfobetaine-modified olefinic copolymers of this invention are in-corporated into homo- or copolymers of a-olefins contain-ing 2 to 6 carbon atoms.
The antistatic agent of this invention may be added to these synthetic polymeric materials by any desired methods. For example, a method can be employed by which the antistatic agent and other optional additives are added in specified concentrations uniformly to a powder or pellets of the polymeric material. Or a master batch of a synthetic polymeric material containing the antistatic agent in a high concentration is prepared in advance, and added to the polymeric material. In some case, the antistatic agent may be added during the poly-merization of the olefinic monomers. Any known means of addition can be used, and for example, mixing can be performed by using rolls, mixersJ or extruders. If desired, the antistatic agent may be added as a solution in a solvent, and the solvent is removed afterward by distillation.
The proportion of the antistatic agent used in this invention differs according to the type of the anti-static agent, the content of the sulfobetaine group, and the type and end use of the synthetic polymeric mate-rial. It is generally about 0.01 to about 300 millimoles, preferably about 0.05 to about 100 millimoles, as the sulfobetaine group per 100 g of the synthetic polymeric material.
The antistatic synthetic polymeric composition comprising a synthetic polymeric material and an anti-statically effective amount of the sulfobetaine-modified olefinic copolymer of this invention may further include at least one additive selected from antioxidants, ultra-violet light absorbers, lubricants, plasticizers, mold releasing agents, fire retardants, fillers, coloring agents and other antistatic agents.
The antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, tetrakis[methylene-3-(3',5'-di-tert-~141893 butyl-4'-hydroxyphenyl)propionate]methane, and dilauryl thiodipropionate, and are added in an amount of up to about 2% by weight, for example, about 0.01 to about 2%
by weight, based on the weight of the synthetic polymeric material.
The lubricants include, for example, calcium stearate, butyl stearate and polyethylene wax, and are added in an amount of up to about 5% by weight, for example about 0.01 to about 5% by weight, based on the weight of the synthetic polymeric material.
The plasticizers include, for example, dibutyl phthalate and dioctyl phthalate, and are added in an amount of up to about 150% by weight, for example about 10 to about 150% by weight, based on the weight of the synthetic polymeric material.
The mold releasing agents include, for example, silicones, and are added in an a unt of up to about 5~
by weight, for example, about 0.01 to about 5% by weight, based on the weight of the synthetic polymeric material.
Examples of the fire retardants are diphenyloctyl phosphate, tetrabromobenzene, antimonous trioxide, and tris(2,3-dibromopropyl) phosphate. They are added in an amount of up to about 50% by weight, for example about 0.1 to about 50% by weight, based on the weight of the syn-thetic polymeric material.
Examples of the other antistatic agents which may be used together with the antistatic agent in ac-cordance with this invention include N,N-bis(2-hydroxy-~ 41893 ethyl)dodecylamine, N,N-bis~2-hydroxyethyl nostearate) octadecylamine, and N-hydroxyethyl-N-sodiocarboxymethyl-octadecyl betaine. They are added in an amount of up to about 3% by weight, for example about 0.01 to about 3% by weight, based on the weight of the synthetic polymeric material.
The ultraviolet absorbers are, for example, nickel dibutyl dithiocarbamate, 2-hydroxy-4-methoxy-benzophenone, and bis(2,2,6,6-tetramethyl-piperidinyl-4) sebacate, and are added in an amount of up to about 1%
by weight, for example about 0.01 to 1% by weight, based on the weight of the synthetic polymeric material.
The fillers include, for example, mica, silicates, and diatomite-kiesel-guhr, and are added in an amount of up to about 100% by weight, for example about 1 to about 100% by weight, based on the weight of the synthetic polymeric material.
The coloring agents are, for example, titanium dioxide and ferric oxide, and are added in an amount of up to about 5% by weight, for example, about 0.1 to about 5% by weight, based on the weight of the synthetic poly-meric material.
The synthetic polymeric composition containing the antistatic agent in accordance with this invention can be shaped into articles of various configurations.
~or example, it can be formed into films, stretched films, tapes, stretched tapes, sheets, fibers, and other solid shaped articles. Preferably, the polymeric composition '~^
~41893 containing the antistatic agent of the invention is shaped into fibers or stretched or unstretched films or sheets.
These shaped articles are characterized by the fact that they show an excellent antistatic effect without being subjected to a special surface treatment such as corona discharge treatment, and the antistatic effect is long-lasting because the antistatic agent does not dis-solve when such shaped articles come into contact with water or solvents. They further have the advantage that the incorporation of the antistatic agent of the inven-tion does not degrade the properties of the base polymer such as its antiblocking property, surface printability or surface gloss, nor does it cause the surfaces of the shaped articles to become tacky.
The following Examples taken in conjunction with Comparative Examples more specifically illustrate the production of the sulfobetaine-modified olefinic copoly-mers of the invention and their utilization as antistatic agents.
Example 1 Ninety (90) grams of a random copolymer ~a number average molecular weight (Mn) = 8,000~ of ethylene and N,N-dimethylaminoethyl methacrylate was dissolved in 1,000 g of p-xylene, and then 40 g of 1,3-propanesultone was added. They were reacted at 135 C for 2 hours. The reaction mix~ure was put into methanol to precipitate the product, followed by purification to afford a sulfobetane-modified olefinic copolymer (designated "antistatic agent 114~893 A"~ which was found to have a sulfobetaine group content of 1.5 millimoles/g, a number average molecular weight of 9,300, a density of 1.04 g/cc and a melting point of 109C. The number average molecular weight ~Mn) was measured by a vapor pressure osmometer; the density, by a density gradient method; and the melting point, by a differential scanning calorimeter made by Perkin-Elmer Company. The same methods of measurements were used in the following examples.
The sulfobetaine-modified olefinic copolymer contained the following units.
~CH2 -CH
CooCH2CH2N(CH3)2 m CoocH2cH2 N(CH3)2-(CH2)3S3 J
Q
(n:m:Q=17:0.6:1.4) Example 2 The procedure of Example 1 was repeated except that a copolymer (Mn=5,000) of ethylene and N,N-diethyl-aminoethyl methacrylate was used as the base polymer.
1~41893 ~ sulfobetaine-modified clefinic copol~er was obtained which had a sul~obet~in group content of 0.8 millimole/g, a number aver~ge molecul~r weight of 5,~00, a density of 1-03 g/cc and ~ melting point of 10~C (designated "antistatic agent B").
The sulfobetaine-modified olefinic copolymer contained the following units.
CH2-C~2~--~ CH3 - ! CH2-C _ COOCH2CH2N(C2H5)2 m - -CH -~ t CoocH2cH2N(c2H5)2-(cH2)3so3 J
(n:m:~=12:0.1:0O4) ExamPle 3 Twenty grams of a copolymer (~n=25,000) of ethylene and ethyl acrylate was dissolved in 200 g of p-xylene. ~he solution was heated to ~C, and 0.1 g o~
sodium methylate and 13.6 g of N,N-dimethyl ethanolamine were added dropwiseO After the addition, they were re~ct-ed for 4 hoursO The unreacted eth~nolamine was removed, and then 3.4 g of 1,3-propanesultone was added and reacted ` ~141893 _ ~4 -at 135C for 2 hours. The product was purified to afford a sulfobetaine-modified olefinic ccpolymer (designated "~ntistatic agent C") which w~s found to have ~ sulfo-betaine group content of 0.5 millimole/g, a number average molecular weight of 29,000, a density of 1~04 g/cc and a melting point of ~4C.
The sulfobetaine-modified olefinic copolymer contained the following units.
~ CH2-CH
10t C~2 Cl ~
COOCH2C~2N(CH3)2 J
m ~ CH2-~H , I
¦ CC0CH2CH ~(cH3)2-(C~2~3$3 (n:m:~=17:0.1:0.3) Example 4 ~hree hundred grams of polyethylene wax (~n-2,500) was melted at 140C, and with strong stirring, 156.6 g of N,N-diethyl allylamine and 6 g of di-tert-butyl peroxide were ~dded. They were re~cted for 6 hours, c~nd the reaction product was dissolved in 4,000 g of p-xylene, and 122g of 1,3-propanesultone w~s added and reacted at 135C for 2 hoursO ~he product was purified to form a sulfobetaine-modified olefinic co-~4~893 - 2~ -pol~er in which -CH2(CH2)2~(C2H5)2 ( 2 ? 3 3 cally bound to the moiety of polyethylene. The modified copolymer was found to have a sulfobetaine group content of 0.7 millimole/g, a number average molecular weight of 3,100, a density of 1003 g/cc and a melting point of 128C. ~he modified copolymer is desi~nated "antistatic agent D".
ExamPles 5 to 8 and Comparative Example 1 ~o 100 parts by weight of polypropylene powder (having a density of 0.91 g/cc, a melt index of 1.0 g/lQ
min., and a melting point of 165C was ad~ed each of an-tistatic agent A (Example 5), antistatic agent B (Example 6), antistatic agent C (Example 7) or c~ntistatic agent (Example 8~ in an amount of 1.5, 1, 2, or 3 parts by weight respectively, and they were mixed by a Henschel mixer. The mixture was pelletized t~ form polypropylene pellets containing the antistatic agent.
~ he pellets were molded into films by an in-flation molding machine to form film I ~containing 1.5 parts by weight of antistatic agent ~ (Example 5)~, film II ~containing 1 part by weight of antistatic agent B
(Example 6)~, film III ~containing 2 parts by weight of antistatic agent C ~Example 7)~, and film IV tcontaining 3 parts by weight o~ antistatic agent D (Example 8)~.
In the same way as above, polypropylene pellets containing no antistatic agent were molded into a film tdesignated film V (Comparative Example 1)~
~hese films were allowed to stand for a week in - ~6 -a constant temperature-constant humidity cha~lber at 25C
and 60:~ RH, and then their surface resistivities were measured by using a surface resistivity measuring device (TR-42, made by Taked~ Riken Co., ~td~)o The results are shown in Table 1.
Table 1 ExampleSample Antistatic agent Surface resistivity Type Amount (ohms) wèight)_ ~ilm I A 1.5 1.0 x 101 6 Film II B 1 1.0 x 1012 7 Film III C 1 5.0 x 1011 8 Film IV D 3 5O0 x 101 _ Comparative 17 Example 1 ~ilm V Not added above loO x 10 Examples 9 and 10 and Comparative ~xample 1 Gne hundred parts by weight of polypropylene pellets having a density of 0.91 g/cc, a melt index of 1.0 g/10 min. and a melting point of 165C were uniformly mixed with 1 part by weight of c~ntistatic agent A by a Henschel mixer, and then pelletized to form polypropylene pellets containing the antistatic agent (Example 9).
In the same way as above, 100 parts of poly-ethylene pellets having a density of 00954 g/cc, a melt index of 0O9 g/10 min. and a melting point of 131C were mixed uniformly with 2 parts by weight of antistatic agent B~ and pelletized to form polyethylene pell.ets containing ~14i893 -- ~7 -the antist~tic agent (h~xample 10).
~hese pellets were molded into films by using an inflation molding machine to obt~in film VI (~xample 9) and film VII (~xP~ple 10).
In the same way as above, the same polyethylene pellets as used in Ex~mple 10 were molded into a film without adding any antistatic agent to form film VIII
(Comparative Example 2)o These films were allowed to stand for 2 days in a constant temperature-constant humidity chamber at 25C
and 60/v RH, and their surface resistivities were measuredO
The results ~re shown in T~ble 20 _able 2 Example Sample Base Antistatic agent ~ur~ace re-polymer l~I~e Amount sistivity (parts by (ohms) 9 Film VI Poly- 11 propylene A 1 5.0 x 10 Film VII Poly- 10 ethylene 2 5.0 x 10 Compa- Poly- above rative Film VIII ethylene Not added 1.0 x 10 7 Example 2 i Example 11 and Comp~rative Examples 3 to 6 One hundred parts by weight of polypropylene powder having a density of OD91 gicc, a melting point of 165C and a melt index of 1.0 g/10 minO was mixed uni-fo~mly with 1 part by weight each of antistatic a~ent A
~Example 11) ~nd the four commercially available antistatic 1~41893 2 ,C~, agents indicated in Table 3 (Comparative Examples 3 to 6 by a Henschel mixer, and then pelletized to form pellets.
~ he pellets were folw~ed into sheets by an ex-truder fitted with a sheet-forming die, and then stretched to 5 times their original dimension both in the machine and transverse ~irections. ~hese biaxially oriented films, either as such or ~fter having been subjected to corona discharge treatment, were allowed to stand for 2 dc~ys in a constant temperature-constant humidity cha~mber at 25C and 60' RH, and then their surface resistivities were measured.
The results are shown in Table 3.
Table 3 Surface resistivity Antistatic agent (ohms) Corona Corona disch~rge discharge performed not _ _ _ performed Example 11 Antis.~atic ageht A 2.0 x 1011 4~0 x 1011 __ _ ._ .
Comparative 11 above Exa~ple 3 lauryl betaine 1.0 x 10 1.0 x 10 7 _.
Comparative hydroxyethyl-Example 4 sodiocarboxymethylalkyl 500 x 101 above 17 Compar~tive alkyl betaine above Example 5 2.0 x 1011 1.0 x 1017 _ . .. ~
Ccmparative dimethyl alkyl betaine 12 above 17 ~xc~mple 6 ._.......................... 1~0 x 10 1.0 x 10 Example 12 and Comparative Examples 7 to 10 ~he corona discharge-treated films obtained in Example 1 and Comparative Exa~ples 3 to 6 were e.~ch -` 1141893 extracted for ? hours with water, heptane an~ ethanol at their boiling points, and then dried under reduced pres-sure. ~he dried films were allowed to stand for 2 days in a constant temperature-constant hu~lidity chamber at 25 C and 6~' RH, and their surface resistivities were measured~ The results are shown in Table 40 _ _ ,, ~o , ~o, ~o ~o ~o i x j~xl ~ x, ~x l~x ~ 1~1 O I G O O O ¦ O O O O
~ ~ OJ ~ I ~ r O rt~ ~
~0 ~ _ I
~ ~n ~ C~ ~ r~ c~
~ ~ ~0 ~3 ~0 ~0 ~0 5 ~ h ~! ~ ~ ~1 ~1 rl ~ ~3 X I ~X I ~ X ~X ~,X
u~ ~S 3 O 00 1 o 5 oO oO
~1 h u~ ~ ~ ¦ ,~ o 0 ~1 0 ~
h 1~ _ ¦ _ __ J Q) ~J C~ C' C' C~ ~) ~1 i ~1vl ~1 ~1 Q~ ¢ ~ O ~ O O O O
~ h ~, ~J I ~1 r 1 ~i ~
E~ ,~ ~ X I ~ X ~ X ~ X ~ X
~ O 00 O O 00 oO
_ _ ~I ~ ~ ~_ ~ ~
~ I ~ .~
I I.,0, ~ ~
,o ~ 0~ .~ $~ ~
~ C) ~ j0 0
S03 / C~2 O - CH2 114189;~
-COOC}I2CH2 CH -COOCH2CH2 CH
~? N ' 3 ~ N ~ 3 CH ~ CH
:3 ' ~ I
SC 3 CH2 S~3 / CH2 P-CH2 . n-CH2 C~,H ~ C H OH
~;~ N/ ' 5 ~3 N' 2 4 C-3 ' C2H C-) ' C2H40H
SO 3CH2 5 SO 3~C, H2 CH2-CH2 , CH2-CH2 X2CX2(:))2H CH2COCTI
N' ~)N' ( CH2CH2C) ) 2H ~? ~ CH2COOH
SO3~ C,H2 SO3~ C,H2 CH
C H OH ~ CH
~)N~ 2 4 (~N' 3 C~ I ` C2H4H ~? ' C2H40H
SO 3 ~ ,C 2 SO 3 C, H2 CH2-CH2 ' CH2-CH2 1~ 4~893 - ~ocH2cEI, -COCH2CH
N ~ ~ M ' 3 I C,,II40H i3 ' CH2COOH
SO- 31CH2 3 C, ~I2 ` CH2-CH2 CH2-C'I2 -COCH2CH2 -CCH2C~'~2 ~N~ 2 5 ' CHz ~? l ~C2H
SO 3CH2 ' S~) 3 CH2 5 C~12-C~I2 , CH2-CH2 ~3 N~C 22 2~ ~(CH2cH2c')2H
CH;?COOH ~ I ( C~I2CH2C ) 2H
SO c~2 -SO 3~ C, TI2 CH C H C~2-C~2 -CH2CH2CH2-CH2C~2C~2 ~ N'~ N ' 2 5 (~ I CH ~! ' ` C H
CH2-CH2 ~ CH2-CII2 ,C2 402 2 2` (CH2cH2)2H
C2H40H 3 1 ( CH2CH2C ) 2H
SG C T'[ SO C, H2 CH2-C~2 C~2-C~I2 1~1893 -C~2CH2CH2 CCl~-I(CH ) CH COCH ~ ,Ch3 ~ N~ 2 ~ N~
9CHCH2 SC3 ' CH~
-CONH(CH2~6 -CG~I(CH~)~
/(C~I2C~2C)2H'- \ CH COOH
(~ I (CH2CH20~2H ~ I CE~2COOH
S03 CIH2 S03~ C,~12 CH2-CH2 CEI2-C~2 ~!~.N ~+`N~(CH2cl~2)2H
CEI~ ~ I (C~2CH2C~)2H
` CH2-C~I2 CH2-CH2 -COI~(CH2)12 ~CH2COO~a N
~_) I CH2COCNa S03 ClH2 In preferred examples of the sulfobetaine-modified olefinic copolymer of this invention, the ~mount of the sulfobetaine group is generally about 0.01 to about 6 millimoles, preferably about Ool to ~bout 5 mil-limoles, per @ram of the sulfobetaine-modified olefinic copo lymer .
~he sulfobetaine-modified olefinic copolymer " ~1418~3 of this invention can be prepared easily by the following methods, for example.
(a) A sulfobetaine-modified olefinic copolymer in which X in the formula represents an ester bond can be prepared by reacting a copolymer of an -olefin having 2 to 6 carbon atoms and a C3-C12 unsaturated carboxylic acid or its functional derivative, or a graft copolymer resulting from the graft copolymerization of a homo- or copolymer of the a-olefin with a C3-C12 unsaturated carboxylic acid or its functional derivative, with an alkanolamine containing 4 to 9 carbon atoms such as N,N-dimethylethanolamine, and reacting the reaction product further with a C2-C4 sultone such as 1,2-ethanesultone, 1,3-propanesultone or 1,4-butanesultone or a C2-C4 cyclic alkylene sulfate such as ethylene sulfate l-methyl-ethylene sulfate or 1,3-propylene sulfate.
(b) A sulfobetaine-modified olefinic copolymer in which X in the formula represents an oxygen atom can be produced by reacting a copolymer of an a-olefin having 2 to 6 carbon atoms and a C4-C12 carboxylic acid unsaturated ester, or a graft copolymer resulting from the graft-co-polymerization of a homo- or copoIymer of the olefin with a C4-C12 carboxylic acid unsaturated ester, with a C4-Cg alkanolamine, and reacting the reaction product further with a C2-C4 sultone or a C2-C4 cyclic alkylene sulfate.
(c) A sulfobetain-modified olefinic copolymer in which X in the formula represents a methylene group can be prepared by reacting a copolymer of an a-olefin having i~4~893 - ~6 -to 6 carbon ~toms and an N,I~-dialkylalkenylamine, or a ~raft copol~er re~sulting frori the graft-copolymerization o~ a homo- or copolymer of the Q-olefin with the I~,N-di-alkylalXenylamine, with a C2-C4- sultone or a C2-C4 cyclic alkylene sulfate.
(~) A sulfobetaine-modified olefinic copolymer in which X in the formul3 represents an amide bond can be prepared by reacting a copolymer of an ~-olefin having 2 to 6 carbon atoms and a C3-C12 unsatur?ted carboxylic acid or its acid anhydride, or a graft copolymer resulting from the graft-copolymerization of a homo- or copolymer of the a-olefin with the uns~turated carboxylic acid or its acid anhydride, with an N,N-dialkylalkylenediamine or an N,N-dihydroxyalkylalkylenediamine, followed optionally by addition-reaction of an alkylene oxide containing 2 to 4 carbon atoms; and reacting the reaction product with a C2-C4 sultone or a C2-C4 cyclic alkylene sulfateO
~ he base polymers used in processes (a) to (d) are produced by, for example, radical polymerization in the presence or absence of a solvent under atmospheric or elevated pressures~ The reaction with the alksnol~mine or alkylenediamine is ef~ected by dissolving the base polymer in a hydrocarbon solvent such as p-xylene, and heating the mixture in the presence or absence of an esterification, ester-interchange or dehydrating catalyst.
~he reaction with the sultone or cyclic sulfate proceeds by gradually ad~ing the sultone or cyclic sulfate to the aforesaid reaction product at an elevated temperature.
According to this invention, there can also be provided a method for static prevention of a synthetic polymeric material by incorporating an antistatically effective amount of the sulfobetaine-modified olefinic copolymer of the invention into the polymeric material;
and an antistatic composition of a synthetic polymeric material containing an antistatically effective amount of the sulfobetaine-modified olefinic copolymer.
Examples of synthetic polymeric materials which are to be rendered antistatic in accordance with this invention include olefin polymers or copolymers such as polyethylene, polypropylene, poly-l-butene, poly-4-methyl-l-pentene, polystyrene, an ethylene~propylene copolymer, an ethylene/l-butene copolymer, an ethylene/4-methyl-1-pentene copolymer and an ethylene/vinyl acetate copolymer;
polyamides and copolyamides; polyesters and copolyesters;
polyvinyl chloride; polycarbonates; and ABS resin, AS
resin, acrylic resins and acrylonitrile resins. Especially favorable results can be obtained when the sulfobetaine-modified olefinic copolymers of this invention are in-corporated into homo- or copolymers of a-olefins contain-ing 2 to 6 carbon atoms.
The antistatic agent of this invention may be added to these synthetic polymeric materials by any desired methods. For example, a method can be employed by which the antistatic agent and other optional additives are added in specified concentrations uniformly to a powder or pellets of the polymeric material. Or a master batch of a synthetic polymeric material containing the antistatic agent in a high concentration is prepared in advance, and added to the polymeric material. In some case, the antistatic agent may be added during the poly-merization of the olefinic monomers. Any known means of addition can be used, and for example, mixing can be performed by using rolls, mixersJ or extruders. If desired, the antistatic agent may be added as a solution in a solvent, and the solvent is removed afterward by distillation.
The proportion of the antistatic agent used in this invention differs according to the type of the anti-static agent, the content of the sulfobetaine group, and the type and end use of the synthetic polymeric mate-rial. It is generally about 0.01 to about 300 millimoles, preferably about 0.05 to about 100 millimoles, as the sulfobetaine group per 100 g of the synthetic polymeric material.
The antistatic synthetic polymeric composition comprising a synthetic polymeric material and an anti-statically effective amount of the sulfobetaine-modified olefinic copolymer of this invention may further include at least one additive selected from antioxidants, ultra-violet light absorbers, lubricants, plasticizers, mold releasing agents, fire retardants, fillers, coloring agents and other antistatic agents.
The antioxidants include, for example, 2,6-di-tert-butyl-p-cresol, tetrakis[methylene-3-(3',5'-di-tert-~141893 butyl-4'-hydroxyphenyl)propionate]methane, and dilauryl thiodipropionate, and are added in an amount of up to about 2% by weight, for example, about 0.01 to about 2%
by weight, based on the weight of the synthetic polymeric material.
The lubricants include, for example, calcium stearate, butyl stearate and polyethylene wax, and are added in an amount of up to about 5% by weight, for example about 0.01 to about 5% by weight, based on the weight of the synthetic polymeric material.
The plasticizers include, for example, dibutyl phthalate and dioctyl phthalate, and are added in an amount of up to about 150% by weight, for example about 10 to about 150% by weight, based on the weight of the synthetic polymeric material.
The mold releasing agents include, for example, silicones, and are added in an a unt of up to about 5~
by weight, for example, about 0.01 to about 5% by weight, based on the weight of the synthetic polymeric material.
Examples of the fire retardants are diphenyloctyl phosphate, tetrabromobenzene, antimonous trioxide, and tris(2,3-dibromopropyl) phosphate. They are added in an amount of up to about 50% by weight, for example about 0.1 to about 50% by weight, based on the weight of the syn-thetic polymeric material.
Examples of the other antistatic agents which may be used together with the antistatic agent in ac-cordance with this invention include N,N-bis(2-hydroxy-~ 41893 ethyl)dodecylamine, N,N-bis~2-hydroxyethyl nostearate) octadecylamine, and N-hydroxyethyl-N-sodiocarboxymethyl-octadecyl betaine. They are added in an amount of up to about 3% by weight, for example about 0.01 to about 3% by weight, based on the weight of the synthetic polymeric material.
The ultraviolet absorbers are, for example, nickel dibutyl dithiocarbamate, 2-hydroxy-4-methoxy-benzophenone, and bis(2,2,6,6-tetramethyl-piperidinyl-4) sebacate, and are added in an amount of up to about 1%
by weight, for example about 0.01 to 1% by weight, based on the weight of the synthetic polymeric material.
The fillers include, for example, mica, silicates, and diatomite-kiesel-guhr, and are added in an amount of up to about 100% by weight, for example about 1 to about 100% by weight, based on the weight of the synthetic polymeric material.
The coloring agents are, for example, titanium dioxide and ferric oxide, and are added in an amount of up to about 5% by weight, for example, about 0.1 to about 5% by weight, based on the weight of the synthetic poly-meric material.
The synthetic polymeric composition containing the antistatic agent in accordance with this invention can be shaped into articles of various configurations.
~or example, it can be formed into films, stretched films, tapes, stretched tapes, sheets, fibers, and other solid shaped articles. Preferably, the polymeric composition '~^
~41893 containing the antistatic agent of the invention is shaped into fibers or stretched or unstretched films or sheets.
These shaped articles are characterized by the fact that they show an excellent antistatic effect without being subjected to a special surface treatment such as corona discharge treatment, and the antistatic effect is long-lasting because the antistatic agent does not dis-solve when such shaped articles come into contact with water or solvents. They further have the advantage that the incorporation of the antistatic agent of the inven-tion does not degrade the properties of the base polymer such as its antiblocking property, surface printability or surface gloss, nor does it cause the surfaces of the shaped articles to become tacky.
The following Examples taken in conjunction with Comparative Examples more specifically illustrate the production of the sulfobetaine-modified olefinic copoly-mers of the invention and their utilization as antistatic agents.
Example 1 Ninety (90) grams of a random copolymer ~a number average molecular weight (Mn) = 8,000~ of ethylene and N,N-dimethylaminoethyl methacrylate was dissolved in 1,000 g of p-xylene, and then 40 g of 1,3-propanesultone was added. They were reacted at 135 C for 2 hours. The reaction mix~ure was put into methanol to precipitate the product, followed by purification to afford a sulfobetane-modified olefinic copolymer (designated "antistatic agent 114~893 A"~ which was found to have a sulfobetaine group content of 1.5 millimoles/g, a number average molecular weight of 9,300, a density of 1.04 g/cc and a melting point of 109C. The number average molecular weight ~Mn) was measured by a vapor pressure osmometer; the density, by a density gradient method; and the melting point, by a differential scanning calorimeter made by Perkin-Elmer Company. The same methods of measurements were used in the following examples.
The sulfobetaine-modified olefinic copolymer contained the following units.
~CH2 -CH
CooCH2CH2N(CH3)2 m CoocH2cH2 N(CH3)2-(CH2)3S3 J
Q
(n:m:Q=17:0.6:1.4) Example 2 The procedure of Example 1 was repeated except that a copolymer (Mn=5,000) of ethylene and N,N-diethyl-aminoethyl methacrylate was used as the base polymer.
1~41893 ~ sulfobetaine-modified clefinic copol~er was obtained which had a sul~obet~in group content of 0.8 millimole/g, a number aver~ge molecul~r weight of 5,~00, a density of 1-03 g/cc and ~ melting point of 10~C (designated "antistatic agent B").
The sulfobetaine-modified olefinic copolymer contained the following units.
CH2-C~2~--~ CH3 - ! CH2-C _ COOCH2CH2N(C2H5)2 m - -CH -~ t CoocH2cH2N(c2H5)2-(cH2)3so3 J
(n:m:~=12:0.1:0O4) ExamPle 3 Twenty grams of a copolymer (~n=25,000) of ethylene and ethyl acrylate was dissolved in 200 g of p-xylene. ~he solution was heated to ~C, and 0.1 g o~
sodium methylate and 13.6 g of N,N-dimethyl ethanolamine were added dropwiseO After the addition, they were re~ct-ed for 4 hoursO The unreacted eth~nolamine was removed, and then 3.4 g of 1,3-propanesultone was added and reacted ` ~141893 _ ~4 -at 135C for 2 hours. The product was purified to afford a sulfobetaine-modified olefinic ccpolymer (designated "~ntistatic agent C") which w~s found to have ~ sulfo-betaine group content of 0.5 millimole/g, a number average molecular weight of 29,000, a density of 1~04 g/cc and a melting point of ~4C.
The sulfobetaine-modified olefinic copolymer contained the following units.
~ CH2-CH
10t C~2 Cl ~
COOCH2C~2N(CH3)2 J
m ~ CH2-~H , I
¦ CC0CH2CH ~(cH3)2-(C~2~3$3 (n:m:~=17:0.1:0.3) Example 4 ~hree hundred grams of polyethylene wax (~n-2,500) was melted at 140C, and with strong stirring, 156.6 g of N,N-diethyl allylamine and 6 g of di-tert-butyl peroxide were ~dded. They were re~cted for 6 hours, c~nd the reaction product was dissolved in 4,000 g of p-xylene, and 122g of 1,3-propanesultone w~s added and reacted at 135C for 2 hoursO ~he product was purified to form a sulfobetaine-modified olefinic co-~4~893 - 2~ -pol~er in which -CH2(CH2)2~(C2H5)2 ( 2 ? 3 3 cally bound to the moiety of polyethylene. The modified copolymer was found to have a sulfobetaine group content of 0.7 millimole/g, a number average molecular weight of 3,100, a density of 1003 g/cc and a melting point of 128C. ~he modified copolymer is desi~nated "antistatic agent D".
ExamPles 5 to 8 and Comparative Example 1 ~o 100 parts by weight of polypropylene powder (having a density of 0.91 g/cc, a melt index of 1.0 g/lQ
min., and a melting point of 165C was ad~ed each of an-tistatic agent A (Example 5), antistatic agent B (Example 6), antistatic agent C (Example 7) or c~ntistatic agent (Example 8~ in an amount of 1.5, 1, 2, or 3 parts by weight respectively, and they were mixed by a Henschel mixer. The mixture was pelletized t~ form polypropylene pellets containing the antistatic agent.
~ he pellets were molded into films by an in-flation molding machine to form film I ~containing 1.5 parts by weight of antistatic agent ~ (Example 5)~, film II ~containing 1 part by weight of antistatic agent B
(Example 6)~, film III ~containing 2 parts by weight of antistatic agent C ~Example 7)~, and film IV tcontaining 3 parts by weight o~ antistatic agent D (Example 8)~.
In the same way as above, polypropylene pellets containing no antistatic agent were molded into a film tdesignated film V (Comparative Example 1)~
~hese films were allowed to stand for a week in - ~6 -a constant temperature-constant humidity cha~lber at 25C
and 60:~ RH, and then their surface resistivities were measured by using a surface resistivity measuring device (TR-42, made by Taked~ Riken Co., ~td~)o The results are shown in Table 1.
Table 1 ExampleSample Antistatic agent Surface resistivity Type Amount (ohms) wèight)_ ~ilm I A 1.5 1.0 x 101 6 Film II B 1 1.0 x 1012 7 Film III C 1 5.0 x 1011 8 Film IV D 3 5O0 x 101 _ Comparative 17 Example 1 ~ilm V Not added above loO x 10 Examples 9 and 10 and Comparative ~xample 1 Gne hundred parts by weight of polypropylene pellets having a density of 0.91 g/cc, a melt index of 1.0 g/10 min. and a melting point of 165C were uniformly mixed with 1 part by weight of c~ntistatic agent A by a Henschel mixer, and then pelletized to form polypropylene pellets containing the antistatic agent (Example 9).
In the same way as above, 100 parts of poly-ethylene pellets having a density of 00954 g/cc, a melt index of 0O9 g/10 min. and a melting point of 131C were mixed uniformly with 2 parts by weight of antistatic agent B~ and pelletized to form polyethylene pell.ets containing ~14i893 -- ~7 -the antist~tic agent (h~xample 10).
~hese pellets were molded into films by using an inflation molding machine to obt~in film VI (~xample 9) and film VII (~xP~ple 10).
In the same way as above, the same polyethylene pellets as used in Ex~mple 10 were molded into a film without adding any antistatic agent to form film VIII
(Comparative Example 2)o These films were allowed to stand for 2 days in a constant temperature-constant humidity chamber at 25C
and 60/v RH, and their surface resistivities were measuredO
The results ~re shown in T~ble 20 _able 2 Example Sample Base Antistatic agent ~ur~ace re-polymer l~I~e Amount sistivity (parts by (ohms) 9 Film VI Poly- 11 propylene A 1 5.0 x 10 Film VII Poly- 10 ethylene 2 5.0 x 10 Compa- Poly- above rative Film VIII ethylene Not added 1.0 x 10 7 Example 2 i Example 11 and Comp~rative Examples 3 to 6 One hundred parts by weight of polypropylene powder having a density of OD91 gicc, a melting point of 165C and a melt index of 1.0 g/10 minO was mixed uni-fo~mly with 1 part by weight each of antistatic a~ent A
~Example 11) ~nd the four commercially available antistatic 1~41893 2 ,C~, agents indicated in Table 3 (Comparative Examples 3 to 6 by a Henschel mixer, and then pelletized to form pellets.
~ he pellets were folw~ed into sheets by an ex-truder fitted with a sheet-forming die, and then stretched to 5 times their original dimension both in the machine and transverse ~irections. ~hese biaxially oriented films, either as such or ~fter having been subjected to corona discharge treatment, were allowed to stand for 2 dc~ys in a constant temperature-constant humidity cha~mber at 25C and 60' RH, and then their surface resistivities were measured.
The results are shown in Table 3.
Table 3 Surface resistivity Antistatic agent (ohms) Corona Corona disch~rge discharge performed not _ _ _ performed Example 11 Antis.~atic ageht A 2.0 x 1011 4~0 x 1011 __ _ ._ .
Comparative 11 above Exa~ple 3 lauryl betaine 1.0 x 10 1.0 x 10 7 _.
Comparative hydroxyethyl-Example 4 sodiocarboxymethylalkyl 500 x 101 above 17 Compar~tive alkyl betaine above Example 5 2.0 x 1011 1.0 x 1017 _ . .. ~
Ccmparative dimethyl alkyl betaine 12 above 17 ~xc~mple 6 ._.......................... 1~0 x 10 1.0 x 10 Example 12 and Comparative Examples 7 to 10 ~he corona discharge-treated films obtained in Example 1 and Comparative Exa~ples 3 to 6 were e.~ch -` 1141893 extracted for ? hours with water, heptane an~ ethanol at their boiling points, and then dried under reduced pres-sure. ~he dried films were allowed to stand for 2 days in a constant temperature-constant hu~lidity chamber at 25 C and 6~' RH, and their surface resistivities were measured~ The results are shown in Table 40 _ _ ,, ~o , ~o, ~o ~o ~o i x j~xl ~ x, ~x l~x ~ 1~1 O I G O O O ¦ O O O O
~ ~ OJ ~ I ~ r O rt~ ~
~0 ~ _ I
~ ~n ~ C~ ~ r~ c~
~ ~ ~0 ~3 ~0 ~0 ~0 5 ~ h ~! ~ ~ ~1 ~1 rl ~ ~3 X I ~X I ~ X ~X ~,X
u~ ~S 3 O 00 1 o 5 oO oO
~1 h u~ ~ ~ ¦ ,~ o 0 ~1 0 ~
h 1~ _ ¦ _ __ J Q) ~J C~ C' C' C~ ~) ~1 i ~1vl ~1 ~1 Q~ ¢ ~ O ~ O O O O
~ h ~, ~J I ~1 r 1 ~i ~
E~ ,~ ~ X I ~ X ~ X ~ X ~ X
~ O 00 O O 00 oO
_ _ ~I ~ ~ ~_ ~ ~
~ I ~ .~
I I.,0, ~ ~
,o ~ 0~ .~ $~ ~
~ C) ~ j0 0
4 rl c~ ! ~ a) ~ l ~ 0 r~l ¦ X X J~ I S
~ 'q P~ , O O r~ ~1 ~
cl; t~i ¦ h 0 a~ r~l r~/
r-l ,!;~ C),O Ll~ ~
o I ~ I . co ~, ~ ! r
~ 'q P~ , O O r~ ~1 ~
cl; t~i ¦ h 0 a~ r~l r~/
r-l ,!;~ C),O Ll~ ~
o I ~ I . co ~, ~ ! r
5 a) CG
~1 h~ hrl I hr~ h~l C;, ~ , ~'V ~, ~
~ r7j ~ ~
X c~ X ! G X I O X O ~ i ~1 1 V ~ I V ~1 ! v ~ ~
Example 13 A copolymer of ethylene and N,N-dimethylamino-ethyl methacrylate (Mn=8J000; N content 1.7 millimoles/g) was dissolved in p-xylene, and 1,3-propanesultone was added and reacted at 130C for 3 hours. The reaction product had a sulfur content of 2.9% by weight and a sulfobetaine group content of 0.91 millimoles/g, and contained the following units.
~CH2 -CH2)n lCH C \ / (CH ) SO oJ
~n:m=20:1) One hundred parts by weight of polypropylene having a density of 0.91 g/cc, a melt index of l.S g/10 min., and a melting point of 165C was mixed with 2 parts by weight of the reaction product obtained, 0.1 part of tetrakis (methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate~ methane, 0.1 part of 2,6-di-tert-butyl-4-methyl phenol and 0.1 part of calcium stearate. The mix-ture was pelletized by using an extruder with an inner cylinder diameter of 15 mm. The pellets were then molded into a film by an extruder fitted with a T-die, and the film was stretched to 5 times its original dimension both ~ - 31 -in the machine and transverse directions at 143C to form a biaxially oriented film having a thickness of 20 micronsO
The film was subaected to corona discharge treatment, and its surface resistivity was measuredO The results are shown in Table ~.
Comparative Exam~le 11 The same copolymer of ethylene and N,M-dimethyl-aminoethyl meth~crylate as used in Ex~ple 13 was reacted with ClCH2CO~(CH2)3SC3Na (with an S content of 13~/o by weig~ht and an Na content of 10.4' by weight) in p-xylene at 130C for 9 hours to afford a reaction product which was found to have an S content of 2~78,~ by weight, ~
betaine content of 0O87 milliequivalent/g, an Na content of 2.6 x 10 4 milliequivalent/g, and a Cl content of 0.02 milliequivalent/g. The product contained the following units r t CH2-CH
---CH2-C ~ - I--l CH3 CH3 CCOCH2CH2-N-CH2COO(CX2)3S03 . m (n:m=20:1) A biaxially oriented ~ilm sub~ected to corona discharge treatment was prepared in the s~me w-ay ~s in Example 13 using the reaction product, and its surface - ~4~893 -- 3~ --: resistivity.was~e~sured. The results are-shown in Table 5.
~able 5 ~urface resistivity (eh~s 5xample 13 1.0 x 1ol2 to 1ol3 Ccmparative 16 Example 11 1.0 x 10
~1 h~ hrl I hr~ h~l C;, ~ , ~'V ~, ~
~ r7j ~ ~
X c~ X ! G X I O X O ~ i ~1 1 V ~ I V ~1 ! v ~ ~
Example 13 A copolymer of ethylene and N,N-dimethylamino-ethyl methacrylate (Mn=8J000; N content 1.7 millimoles/g) was dissolved in p-xylene, and 1,3-propanesultone was added and reacted at 130C for 3 hours. The reaction product had a sulfur content of 2.9% by weight and a sulfobetaine group content of 0.91 millimoles/g, and contained the following units.
~CH2 -CH2)n lCH C \ / (CH ) SO oJ
~n:m=20:1) One hundred parts by weight of polypropylene having a density of 0.91 g/cc, a melt index of l.S g/10 min., and a melting point of 165C was mixed with 2 parts by weight of the reaction product obtained, 0.1 part of tetrakis (methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate~ methane, 0.1 part of 2,6-di-tert-butyl-4-methyl phenol and 0.1 part of calcium stearate. The mix-ture was pelletized by using an extruder with an inner cylinder diameter of 15 mm. The pellets were then molded into a film by an extruder fitted with a T-die, and the film was stretched to 5 times its original dimension both ~ - 31 -in the machine and transverse directions at 143C to form a biaxially oriented film having a thickness of 20 micronsO
The film was subaected to corona discharge treatment, and its surface resistivity was measuredO The results are shown in Table ~.
Comparative Exam~le 11 The same copolymer of ethylene and N,M-dimethyl-aminoethyl meth~crylate as used in Ex~ple 13 was reacted with ClCH2CO~(CH2)3SC3Na (with an S content of 13~/o by weig~ht and an Na content of 10.4' by weight) in p-xylene at 130C for 9 hours to afford a reaction product which was found to have an S content of 2~78,~ by weight, ~
betaine content of 0O87 milliequivalent/g, an Na content of 2.6 x 10 4 milliequivalent/g, and a Cl content of 0.02 milliequivalent/g. The product contained the following units r t CH2-CH
---CH2-C ~ - I--l CH3 CH3 CCOCH2CH2-N-CH2COO(CX2)3S03 . m (n:m=20:1) A biaxially oriented ~ilm sub~ected to corona discharge treatment was prepared in the s~me w-ay ~s in Example 13 using the reaction product, and its surface - ~4~893 -- 3~ --: resistivity.was~e~sured. The results are-shown in Table 5.
~able 5 ~urface resistivity (eh~s 5xample 13 1.0 x 1ol2 to 1ol3 Ccmparative 16 Example 11 1.0 x 10
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A sulfobetaine-modified olefinic copolymer comprising an olefinic copolymer having a number average molecular weight of about 500 to about 100,000 derived from a major proportion of an .alpha.-olefin having 2 to 6 carbon atoms and a minor proportion of a comonomer selected from the group consisting of unsatur-ated carboxylic acids containing 3 to 12 carbon atoms, functional derivatives of said unsaturated carboxylic acids, unsaturated esters of carboxylic acids con-taining 4 to 12 carbon atoms and unsaturated amines containing 3 to 9 carbon atoms, and chemically bound to the comonomer-derived moiety of said olefinic co-polymer, a sulfobetaine group of the formula wherein R1 represents an alkylene group containing 1 to 12 carbon atoms, R2 rep-resents an alkylene group containing 1 to 3 carbon atoms, R3 and R4 each repre-sent a member selected from the class consisting of a hydrogen atom, alkyl groups containing 1 to 10 carbon atoms, polyoxyalkylene groups containing 2 to 6 carbon atoms, hydroxyalkyl groups containing 1 to 6 carbon atoms, carboxyalkyl groups containing 2 to 4 carbon atoms and carboxylate alkyl groups containing 2 to 4 carbon atoms, X represents an oxygen atom, a carbonyl group, an ester bond, an amide bond or a methylene group, and Y represents an oxygen atom or a methyl-ene group.
2. The sulfobetaine-modified olefinic copolymer of claim 1 wherein the comonomer is selected from the group consisting of acrylic acid, the functional derivatives thereof, methacrylic acid and the functional derivatives thereof.
3. The sulfobetaine-modified olefinic copolymer of claim 1 wherein the comonomer is selected from the group consisting of N,N-diethyl allylamine and N,N-dimethyl allylamine.
4. The sulfobetaine-modified olefinic copolymer of claim 1 wherein in the formula of the sulfobetaine group, X represents an oxygen atom, an ester bond or a methylene group.
5. The sulfobetaine-modified olefinic copolymer of claim 1 wherein in the formula of the sulfobetaine group, R2 and Y both represent a methylene group.
6. The sulfobetaine-modified olefinic copolymer of claim 1 wherein the amount of the sulfobetaine group is about 0.1 to about 5 millimoles per gram of the sulfobetaine-modified olefinic copolymer.
7. A process for producing the sulfobetaine-modified olefinic copolymer of claim 1, which comprises either (a) reacting a copolymer of an a-olefin containing 2 to 6 carbon atoms and a C3-C12 unsaturated carboxylic acid or its functional derivative, or a graft copolymer resulting from the graft copolymerization of a homo- or co-polymer of said .alpha.-olefin with said unsaturated carboxylic acid or its functional derivative, with an alkanolamine containing 4 to 9 carbon atoms, and further re-acting the reaction product with a sultone containing 2 to 4 carbon atoms or a cyclic alkylene sulfate containing 2 to 4 carbon atoms; or (b) reacting a copolymer of an a-olefin containing 2 to 6 carbon atoms and an unsaturated ester of a carboxylic acid containing 4 to 12 carbon atoms, or a graft copolymer resulting from the graft copolymerization of a homo-or copolymer of said a-olefin with said unsaturated ester of carboxylic acid, with an alkanolamine containing 4 to 9 carbon atoms, and reacting the reaction product with a sultone containing 2 to 4 carbon atoms or a cyclic alkylene sul-fate containing 2 to 4 carbon atoms; or (c) reacting a copolymer of an -olefin containing 2 to 6 carbon atoms and an N,N-dialkyl-alkenylamine or a graft copolymer resulting from the graft copolymerization of a homo- or copolymer of said .alpha.-olefin with said N,N-dialkyl-alkenylamine, with a sultone containing 2 to 4 carbon atoms or a cyclic alkylene sulfate containing 2 to 4 carbon atoms; or (d) reacting a copolymer of an .alpha.-olefin containing 2 to 6 carbon atoms and a C3-C12 unsaturated carboxylic acid or its acid anhydride or a graft copolymer resulting from the graft copolymerization of a homo- or copolymer of said .alpha.-olefin with said unsaturated carboxylic acid or its acid anhydride, with an N,N-dialkyl or N,N-dihydroxyalkyl alkenediamine containing 4 to 16 carbon atoms, optionally reacting the reaction product with an alkylene oxide contain-ing 2 to 4 carbon atoms, and then reacting either of these reaction products with a sultone containing 2 to 4 carbon atoms or a cyclic alkylene sulfate con-taining 2 to 4 carbon atoms.
8. An antistatic synthetic polymer composition comprising (1) a syn-thetic polymeric material and (2) an antistatically effective amount of a sulfo-betaine-modified olefinic copolymer, said sulfobetaine-modified copolymer com-prising an olefinic copolymer having a number average molecular weight of about 500 to about 100,000 derived from a major proportion of an .alpha.-olefin having 2 to 6 carbon atoms and a minor proportion of a comonomer selected from the group consisting of unsaturated carboxylic acids containing 3 to 12 carbon atoms, functional derivatives of said unsaturated carboxylic acid, unsaturated esters of carboxylic acids containing 4 to 12 carbon atoms and unsaturated amines con-taining 3 to 9 carbon atoms, and chemically bound to the comonomer-derived moiety of said olefinic copolymer, a sulfobetaine group of the formula wherein R1 represents an alkylene group containing 1 to 12 carbon atoms, R2 rep-resents an alkylene group containing 1 to 3 carbon atoms, R3 and R4 each repre-sent a member selected from the class consisting of a hydrogen atom, alkyl groups containing 1 to 10 carbon atoms, polyoxyalkylene groups containing 2 to 6 carbon atoms, hydroxyalkyl groups containing 1 to 6 carbon atoms, carboxyalkyl groups containing 2 to 4 carbon atoms and carboxylate alkyl groups containing 2 to 4 carbon atoms, X represents an oxygen atom, a carbonyl group, an ester bond, an amide bond or a methylene group, and Y represents an oxygen atom or a methyl-ene group.
9. The composition of claim 8 wherein the synthetic polymeric material is selected from the group consisting of polyolefins, copolyolefins, polyamides, copolyamides, polyesters, copolyesters, polyvinyl chloride, polycarbonates, ABS
resin, AS resin, acrylic resins, and acrylonitrile resins.
resin, AS resin, acrylic resins, and acrylonitrile resins.
10. The composition of claim 8 wherein the amount of the sulfobetaine-modified olefinic copolymer is about 0.01 to about 300 millimoles as the amount of the sulfobetaine group per 100 g of the synthetic polymeric material.
11. The composition of claim 8 which further comprises at least one additive selected from the group consisting of antioxi-dants, ultraviolet light absorbers, lubricants, plasticizers, mold releasing agents, fire retardants, fillers, colouring agents and other antistatic agents.
12. A method for preventing static buildup on a synthetic polymeric material, which comprises incorporating an antistatically effective amount of the compound of any one of claims 1 to 3 into said synthetic polymeric material.
13. A method for preventing static buildup on a synthetic polymeric material, which comprises incorporating an antistatically effective amount of the compound of any one of claims 4 to 6 into said synthetic polymeric material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP133,116/77 | 1977-11-08 | ||
| JP52133116A JPS5923350B2 (en) | 1977-11-08 | 1977-11-08 | antistatic agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1141893A true CA1141893A (en) | 1983-02-22 |
Family
ID=15097162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000315997A Expired CA1141893A (en) | 1977-11-08 | 1978-11-08 | Sulfobetaine-modified olefinic copolymer, process for preparation thereof, and use thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5923350B2 (en) |
| CA (1) | CA1141893A (en) |
| DE (1) | DE2848517A1 (en) |
| FR (1) | FR2407942A1 (en) |
| GB (1) | GB2010283B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1257046A (en) * | 1985-06-27 | 1989-07-04 | John R.B. Boocock | Polyolefins modified with sulphur trioxide/trimethylamine |
| CA2008537A1 (en) * | 1989-05-12 | 1990-11-12 | Marvin R. Havens | Permanently antistatic polymeric rigid containers |
| US5064699A (en) * | 1989-05-19 | 1991-11-12 | W. R. Grace & Co.-Conn. | Semi-rigid heat-sealable laminates with permanent antistatic characteristics |
| JPH0327747U (en) * | 1989-07-28 | 1991-03-20 |
-
1977
- 1977-11-08 JP JP52133116A patent/JPS5923350B2/en not_active Expired
-
1978
- 1978-11-08 FR FR7831535A patent/FR2407942A1/en active Granted
- 1978-11-08 GB GB7843648A patent/GB2010283B/en not_active Expired
- 1978-11-08 DE DE19782848517 patent/DE2848517A1/en not_active Ceased
- 1978-11-08 CA CA000315997A patent/CA1141893A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2010283B (en) | 1982-06-16 |
| FR2407942B1 (en) | 1980-10-03 |
| JPS5466386A (en) | 1979-05-28 |
| FR2407942A1 (en) | 1979-06-01 |
| DE2848517A1 (en) | 1979-05-10 |
| JPS5923350B2 (en) | 1984-06-01 |
| GB2010283A (en) | 1979-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1164135A (en) | Film-forming thermoplastic elastomeric polymer compositions | |
| US3355319A (en) | Self-supporting film with a heat-sealable coating of an ionic copolymer of an olefin and carboxylic acid with metal ions distributed throughout | |
| US2938879A (en) | Non-blocking polyethylene compositions | |
| US3425981A (en) | Olefin polymer compositions containing ethylene oxide polymers having a molecular weight of from 100,000 to 10 million | |
| US3338739A (en) | Ionic copolymer coated with vinylidene chloride copolymer | |
| KR940009407A (en) | Electretized nonwoven fabric and method of manufacturing the same | |
| EP0124347A1 (en) | Method for modifying the surface of polymer materials | |
| US3470122A (en) | Compositions comprising ethylene-vinyl acetate copolymer,fatty acid salt,fatty acid amide and particulate material | |
| US3165492A (en) | Solid poly-alpha-mono-olefin containing n, n'-alkylene bis amides | |
| CA1141893A (en) | Sulfobetaine-modified olefinic copolymer, process for preparation thereof, and use thereof | |
| ATE3643T1 (en) | COPOLYMER OF CORE-BROMATED STYRENE AND ACRYLIC NITRILE AND METHOD OF MAKING SUCH COPOLYMER. | |
| US3396137A (en) | Composition comprising an ethylene polymer and an nu-substituted unsaturated carboxylic amide | |
| DE2023154A1 (en) | Polyolefin/maleic anhydride graft copoly- - mers for film production | |
| US3376275A (en) | Urethanes in films to improve sliding properties | |
| US5543451A (en) | Polyolefins/alkenyllactamide composition | |
| US3709957A (en) | Polyethylene blends of ethylenemethacrylic acid copolymer and polyethylene | |
| GB2031449A (en) | Antistatic resin composition | |
| US5286525A (en) | Method of improving the printing of polyolefins with water-based inks | |
| US5393814A (en) | Polyolefin composition | |
| US3216825A (en) | Photographic film element comprising butadiene polymeric coatings on polyethylene and other polymeric hydrocarbons | |
| US5232966A (en) | Method of improving the printing of polyolefins with water-based inks | |
| AU733489B2 (en) | Polyolefins having greater than 5 percent 2-hydroxyethyl methacrylate grafted thereto | |
| US3846391A (en) | Oxy-bis-(n-alkylamides) and their use as slip additives | |
| US3232791A (en) | Regenerated cellulose film having a moistureproof coating | |
| US3548036A (en) | Polymonoolefins containing an amine antistatic additive dispersed therein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |