CA1331411C - High impact, styrenic polymer/thermoplastic polymer grafted blends - Google Patents
High impact, styrenic polymer/thermoplastic polymer grafted blendsInfo
- Publication number
- CA1331411C CA1331411C CA000574718A CA574718A CA1331411C CA 1331411 C CA1331411 C CA 1331411C CA 000574718 A CA000574718 A CA 000574718A CA 574718 A CA574718 A CA 574718A CA 1331411 C CA1331411 C CA 1331411C
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- Prior art keywords
- polymer
- styrenic polymer
- modified styrenic
- moieties
- reactive groups
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyamides (AREA)
Abstract
ABSTRACT
HIGH IMPACT SYTRENIC POLYMER/THERMOPLASTIC
POLYMER GRAFTED BLENDS
A modified styrenic polymer is described, which comprises the reaction product of said polymer with an ethylenically unsaturated grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from carboxylic acid, acid anhydride, acid amide, imido, carboxylic ester, amino, hydroxyl, epoxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, pyridyl, 1,3-oxazoline, 1,3 oxazine, oxazolone, oxazinones, and any derivatives, combinations and mixtures thereof:
and wherein the remaining one to three of R1, R2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; said modified styrenic polymer containing said reactive groups as pendant reactive functionalities.
The present invention also includes a melt blended composition comprising the reaction product as recited above and a thermoplastic polymer which is reactive with pendant reactive functionalities of the reaction product.
HIGH IMPACT SYTRENIC POLYMER/THERMOPLASTIC
POLYMER GRAFTED BLENDS
A modified styrenic polymer is described, which comprises the reaction product of said polymer with an ethylenically unsaturated grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from carboxylic acid, acid anhydride, acid amide, imido, carboxylic ester, amino, hydroxyl, epoxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, pyridyl, 1,3-oxazoline, 1,3 oxazine, oxazolone, oxazinones, and any derivatives, combinations and mixtures thereof:
and wherein the remaining one to three of R1, R2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; said modified styrenic polymer containing said reactive groups as pendant reactive functionalities.
The present invention also includes a melt blended composition comprising the reaction product as recited above and a thermoplastic polymer which is reactive with pendant reactive functionalities of the reaction product.
Description
, . . - . . .
.. ..
HIG~ .MP~G-I~ ~lYRENIC pOLYMER/~!E.RMOPLgSTlC -.' POLYMER 'RQFTED BLEND J ';~
FieLd of the In~e. tion :
7'his in~enti.on relates to styrenic polyrners rnod.ified with ethlye.nical'ly unsaturatecl graf't linking agents, the rnethods to achieve such modification, and '~
cor!lpositions containing the rnoclif'iecl styrenic polymers, '~
especially styrenic polymer/thermoplastiG graft~d 10 blends. .'~
~. . .
B kqrQ~n~ 5~ In~e.nt on Styrenic polymers such as n~s are known to be irnrniscible with polyarnides, particularly in the blend ;; ratios of interest ranging from 1:9 to 9.l (see e~g. .'.: ;~
' Y.U. Le~ede~, et al, J. ~pplied Polymer Science 25, '.';'~' 24g3, 1g80). `~-~ue to this mutual incompatibility, simple ~;
,. , ... ~ .
mechanica'l blends of ~BS and ny'lon 6 tend to be brittle and readil-v delaminate when the molded parts are flexed ,''~
or twisted. US Pat. 4,496,6~0 discloses connpositions ' of modified ~BS and nylon blends -in which the ~BS
25 portion was significant'ly rnodified through -~`;:' ' copolymerization with as much as 10% acrylamide monomer units to obtain useful le~els of cornpatibility and propertles.
; I European Patent ~pplication ~202214 (1986) ! i~
-: teaches the use of styrene--acrylonitrile-maleic anhydride terpolymers as cornpatibilizers ~or ~BS--nylon 1~
blends. ~ .~
~: 35 ~....
~`~
- ~ 1 3 3 ~
.
~!rt!-m-a~r.~- o-:f -~t-t~e- l,n,,~,,,n,,t,"-,~,.,o,,n .,,,',' "rhe present in~entlon pro~-lcles a modif'ied styrenic polyrner cornprising the reaction procluct of ' ~'~
saitd polyrnRr with an ethylenica'l'ly unsaturat~!cl grafting ,,~
agent ha~ing the forrnula~
~':':, :
~, C = C ~ Q~
''';'''''' whRrein one to three of R1, R2, R~ and ,;,',.
~4 are rnoieties containing reacti~e growps selected from carboxylic acid, acid anhydride, acicl amide, '~"~
irnido, carboxylic ester, arnino, hydroxyl, epoxy, .~
15 isocyanate, carbamate, carbamoyl la~tam, acyl lactam, .. .
pyridyl, 1,3-oxazoline, 1,3 oxazine, oxazolone, oxazinones, and any deri~atittJes, combinations and rnixtures thereof; ''i; "!'' and wherein the. remaining onR to three of R~
R2, R3 and R4 are H or a hydrocarbon radical of ~.
from about 1 to abowt 2n carbon atoms; said modifiRd .,.:.. i.,' styrenic polymer containing said reactittJe groups as ~`,':.:::i,.,' pendant reacti~e functionalities. ~.... `~', :.
The present in~ention also includes a rnelt ,~-~
blended composition compri.sing the reaction product as recited abo~e and a therrnoplastic polymer which is ~Y;~
`: reactivR with pendant reactittJR functionalities of the '~
30 reaction product. t The composition of the modified styrenic . ~' polymers and the thernnoplastic polyrner optionally and '~
preftRrably contains frorn about 5 to 50 percent by ,,~
: 35 weight of an elastorneric polymer. "~
j ~
,''.','.'~`.;~`.~
;`~`~
` -`` 133~
.. ,. ,3,~"
-rhe present inventi.on also inclucles rnetho~s of - :. ~
making the reaction procluct and compc)sitions contai.ning :: :
the reac-tion product. lhe compositiorls of the present ..
inventj.on c~n be prepared by conventional polymer melt blending techniques. lhis rnethocl is typically conducted at a temperature above the rnelting ternperature of the polyrneric additives in a closed ,~
mixing device such as an extrucler. The rnethod preferahly first comprises rnelt blending the styrenlc polyrners and the grafting agent to form a reaction ~' product. The reaction product is then melt blended with the therrnoplasti.c polyrner which i5 reactive with ; the reactive groups of the reaction product. '.. ~
It has ~een found that in the preferred .:~.
ernbodirnents, the first method results :in a reaction~
~: product which can also be called a modifiecl or functionalized styrenic polyrner. l~he second rnethod or second step is a method to make a composition of this reaction product or rnodif'ied styre.nic polymer and a thermoplastic polymer. This two--step method produces a ~: cornposition with irnpro~ed tensile elongation properties. , .
ET~ILED DESCRIPTION OF THE _ _ENTION .-~
Styrenic polyrners suitable for modification according to the present invention are those having at least about 25% by weight of the polymer units derived ';,~
~` from a vinyl aromatic compound o~ the formula~
30 1 ~ R~ - ~H~L
;,~. .
~ Z(P) ~' ; '''",' , ' ''.'.~
~. . ..
r ~ 3 3 3. 4 ~ ~
oherRi.n R i.s hyc~rogelt, (I.oo~r) alky:L or halog~!n, Z i.s ~inyl, halog~!n or ('lower) alkyl, arl~ p -ls O or an integQr of Frorn 1 to the nurnber o-f replaceable hydrogen atoms on the benzene nwc].Rus. ~lerein, the terrr `'(lower) alkyl" is intended to rnean alkyl of From about 1 to 6 carbon atorns.
The terrrl "styr~nic polyrners" as wsed broadly ' ' throughout this discloswre ancd the ~ppertded clairns includes, homopolymers and copolyrners oF styrene and 10 inclwdes both rigicl resirts and those comrnon'ly reFerred .
to as high impact styrenic resins. l'he latter refers to resins such as those preparecl by graf't ;' polymerizcltion of styren~ and optionally onR or more of copolyrnerizable ~in!/'l monomers in the presence of an ..
15 e'lastorrleric polymer swbstrate, as well as resins ' ' prepared by blendiny a rigid styrenic matrix polyrner with a graFted rwbb~ry substrate. Examples inclwde polystyrene, polychlorostyrene and polybrornostyrene, as : `.
well as high impact polystyrenes, which ha~e been .~
20 rnodiFied by a natural or synthetlc rwbber, e.g. ''' polyhutadiene, polyisoprene, butyl rwbber, ethylene-propylene diene copolyrners-(EPDM rubber), '''' ethylene-propylene copolymers, natwral rwbbers, .:. :
acrylate rubbers, polysulfide rubbers, polyurethane ~:;'.'' 25 rubbers, styrene-butadiene rwbbers (SBR), and the .' like. Examples of styrene copolymers inclwde both .:.'"
rigid and rwbber rnodified copolymers of styrene with cornonomers se'lected froln alpha-rnethyl styrene, "~
halostyrenes, ~inyl alkyl benzenes, acrylonitrile, :~
methacrylonitri'le, acry'lates and methacry:late esters of lower alcohols etc. The rwbber rT~odified copolymers .~' include po'lybwtadiene rnodified styrene-acrylorlitrile resins (~RS), acry'late elastomRr modified 5hN ~hS~ EP ~ ::
or EP~M rwbber yra~ted S~N copolyrner, ~Sh such as ... " ~'~
RO~R1~ , ~ow) styrene-butadiene, chlorinated polyethylene, modified, styrene-acryloni-trile ~;
copolym~r ~h~S), styrene--isoprene block copolymers ;~
and hydroyenated prodwcts thereof ~e.g. Kraton~
: .:
r~ rrloclification of tht! styr~!ni.c F)olyrllc!rs of th~?
in~ent-.i.on is accornplishecl by attaching an unsaturated grafti.llg agellt to the styrenic polymel^ backbone, reswlting in a penclant functi.onality l-he grafting agellt has a first turlctiorlal group, the ethylenically unsatwrated doub].e bond, which is react-i~? with the styrenic polymer, and one or rnore second functi.onal group, designated Rl - R~, that will be reactive with a polymer ha~ing reacti~e groups such as hydroxy, amine, and the like, particularly when such groups are encl groups, The grafti.ng agent rrlay be represented by the general formula: -. . . ~., .
~ ~C = C~ 3 wherein one or more of the second twnctional groups are ~
20 rnoieties containing reacti~e groups s~?lectecl from .:
carboxy:Lic aci.d, acicl anhydride, acid arnide, irnido, carboxylic ester, amirle, hyclroxyl, epoxy growps, isocyanates, carbamates, acyl lactams, pyridyl, 1,3 ;~
oxazoli.ne, 1,3 oxazines, oxazolones, oxazinones, and ~.
cornb-lnations, rnixtures and deri~ati~es thereof.
. ~
Grafting agents comprising an ethylenically unsaturated double bond and the second functional group may be reacted with the styrenic polymer by themsel~es, or in a mixture with a readily a~ailable rnonorner to act as a cliluent. ~inyl monomers such as styrene, methyl ~:
methacrylates, and the like are particularly suited for ::
this last-mentioned purpose. ~clclitionally, the grafting agent may be attached to a carrier rnolecwle swch as an oligorrler that is cornpatible with all or a -;
~ 3 ~
. -h porti.on oF th(! styr~ulic pol.yrrler i.t .-is cles-irecl-to '' moclify. Particu].arly suitclblc-! oli.gomers are li.qui.cl '~.
polybutadiene., hyclrogenated polybutadiene, po~ystyrene-polybut~cli.ene block copolymers,polyethers, ~nd the like ~ p " '.
Illustrative of graf-ting agents switablc! f'or use~, '.'.
w-.ith:in the context of the present lnventi.on are maleic'~' anhyclricle, hlrrlaric aGicl, monoalkyl, esters of maleic ':-acid, rnonoa:Lkyl esters uf f'umalrlc acicl, acry'.lic acid, ,'' 10 methacry'li.c acid ancl corresponding esters, ntethacry'loyl '~
or acry:loyL capro.Lactam, rnethacry'loy'l or acryloyl '.,'.. '' lauroll.lctam, isopropenyl oxa~oline, vinyl oxazolc)ne, '' vinyl pyridine, glycidyl acrylate, glyciclyl ' :.
me~thacrylatc!, diglycidyl fumarate and the like, whether 15 alone or in any combination -~
'~', ' Preferred among these grafting agents are malei.c':~-'.
anhydride, furnaric acid, acrylic acids ancl ::;
corresponcling esters, acryloyl and methacryloyl '~
lactarns, glycidyl acrylate and rnethacrylates, 2-isopropenyl, 1,3 oxazoline, vinyl pyridine and the ~.:
like In some preferred embodirnents, rubbery high mo'lecu'lar weiyht rnateria'ls are added to the styrenic polyrners to irnprove the overall impact resistance.'''~.'.:-' l'his may take the forrrl o~' conventional rubber :~
dispersions, added prior to or during blending with other po:lyrners. However, the present inventors have '~
. 30 fownd that it is preferable to have the rubbery ,`
rnaterials prefurlctionalized. ~ddition of such rubbers .~
to the modifi~d styrenic polymers serves to impro~e .' .
properties obtained when the modifiecl styrenic polymers-~
are then graft blended with one or more second polymers: :' having terrninal reactive end groups or pendant groups.
.., ;, .:
"'" i~ _7_ ~ 33~
- This is particularly e~id~nt when the styr~nic polym~rs are blended with polyamides. For example, the present inuentors haue discouered that the notched Izod of th~
final blends could b0 substantially impro~ed, while retaining a high elongation to break. The present inuentors do not wish to be bound by theory, howeu0r, it is postulated that the inclusion of the functionalized olefins may actually toughen the styrenic thermoplastic polymer/second polymer interface.
Suitable rubbery polymers within the context of those described above are defined las having an ~l'M
D-638 tensile modulus of less than about 40,000, typically less than ~5,~00, and pre~erably less than 20,000. They can be homopolymers,random, block or gratt copo'lymers. Useful rubbery po'lymers can be made from reactiue monomers which can be part of the polymer chains or branches, or grafted on to the polymer.
These reactiue monomers can include dienes, and carboxylic acids and deri~ati~es thereof such as esters and anhydrides. Such rubbery polymers include butadiene polymers, butadiene~styrene copolymers, isoprene, chloroprene, acrylonitrile~butadiene copolymers, isobutylene, isobutylene/butadiene copolymers, ehtylene/propylene copolymers, ethylene/propylene/diene copolymers. Useful rubbery polymers can include aromatic ~inyl monomers, olefins, acrylic acid and methacrylic acid and their :
deriuati~es, ethylene-propylene diene monomers and meta'l salts thereot-. Usetul rubbery polymers are ~' disclosed in U.S. Patent 4,315,08~ and 4,174,358. ! ' The preferred rubber in the context of the present inuention includes a gra~t copolymer which is a copolymer of ethylene and an alpha-olefin other than ethylene, ha~ing a t'unctionality such as carboxyl or ~`~
' ', r r ~ 3 3 ~
~nhyclri.de graf~ecl tc~ th-~ e~-hy~l~c!rle copolyrrler . -r~l(:,! :, "
~thy'lenf~ and ~-Olefill iS pr~?,''erclbly a copo'l.ymer of '( '.
ethylene and an f'olf!fin seleçted ~rorn at least one C3-C~, preferabl!/ G3--C6 ~olefin, Propylene is a preff!rrf!d monomfer selected as the C3--C~a O~--olefin -.
in the copolyrner. Other C~-C6o~olefins, such as 1--butene, l--pentene, ~ncl 1--hexane can be used ln place of or in adclition to propylene in the copo].yrners.
The carboxyl or carboxyla-te func-tionallty, can 10 be supplied by reacting the ethyleneJC3--C6 d-olefin ~' copolyrrler with an unsaturated graft moiety taken frorn ' ' the class consisting of ~-,B-ethylen:ically unsaturatf!d ~' '-clicarboxy'lic acids ha~ing trom 4 to 8 carhon atoms, or .: :
deri~ati~es thereof. Such cleri~ati~es i.ncl~lde ~' .
anhydrides of the di.carboxy'lic acicls, or the met~l salts of the acids, or the monoestc!r of the dicarboxy:Lic acid ha~ing frorn O to lOO percent of the carboxylic acid groups ionized by neutralizat-ion with ~ -metal basic salt, and the 'like. ~l:lustrati~e of such !
acids and cleri~ati~es are rnaleic acid, maleic anhydri.de, maleic acid rnonoethyl ester, rnetal sal~s of ~' rmaleic aci.d rnonoethyl ester, fumaric acid, furnaric acid ;~
monoethyl ester, itaconic acid, ~inyl benzoic acid, ~ ' ~inyl phthalic acid, metal salts of furnaric acid 25 rnonoethyl ester, rnonoesters and rnaleic or furnaric acid '.~;;
or itaconlc acids where the alcohol i5 methyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, '.
2-ethyl h~xyl, decyl, stearyl, methoxy ethyl, ethoxy '~
ethyl, hydroxy or ethyl, and the like. The graft ~`
. 30 moiety can be grafted to the ethylene copolyrner by any well-krlowrl graftirlg process. i.~'.' ~ useful cnpolymer of ethy'lene and an alpha~olefirl contains from 30 to ~O and prefc!rably ~O ' to 4S weight percent of the a'lpha--olefin based on the ethy'lene. rhe copo'lyrner a'lso contains from O.l to ~
~ ~:
. ~
.''~
.. ..
HIG~ .MP~G-I~ ~lYRENIC pOLYMER/~!E.RMOPLgSTlC -.' POLYMER 'RQFTED BLEND J ';~
FieLd of the In~e. tion :
7'his in~enti.on relates to styrenic polyrners rnod.ified with ethlye.nical'ly unsaturatecl graf't linking agents, the rnethods to achieve such modification, and '~
cor!lpositions containing the rnoclif'iecl styrenic polymers, '~
especially styrenic polymer/thermoplastiG graft~d 10 blends. .'~
~. . .
B kqrQ~n~ 5~ In~e.nt on Styrenic polymers such as n~s are known to be irnrniscible with polyarnides, particularly in the blend ;; ratios of interest ranging from 1:9 to 9.l (see e~g. .'.: ;~
' Y.U. Le~ede~, et al, J. ~pplied Polymer Science 25, '.';'~' 24g3, 1g80). `~-~ue to this mutual incompatibility, simple ~;
,. , ... ~ .
mechanica'l blends of ~BS and ny'lon 6 tend to be brittle and readil-v delaminate when the molded parts are flexed ,''~
or twisted. US Pat. 4,496,6~0 discloses connpositions ' of modified ~BS and nylon blends -in which the ~BS
25 portion was significant'ly rnodified through -~`;:' ' copolymerization with as much as 10% acrylamide monomer units to obtain useful le~els of cornpatibility and propertles.
; I European Patent ~pplication ~202214 (1986) ! i~
-: teaches the use of styrene--acrylonitrile-maleic anhydride terpolymers as cornpatibilizers ~or ~BS--nylon 1~
blends. ~ .~
~: 35 ~....
~`~
- ~ 1 3 3 ~
.
~!rt!-m-a~r.~- o-:f -~t-t~e- l,n,,~,,,n,,t,"-,~,.,o,,n .,,,',' "rhe present in~entlon pro~-lcles a modif'ied styrenic polyrner cornprising the reaction procluct of ' ~'~
saitd polyrnRr with an ethylenica'l'ly unsaturat~!cl grafting ,,~
agent ha~ing the forrnula~
~':':, :
~, C = C ~ Q~
''';'''''' whRrein one to three of R1, R2, R~ and ,;,',.
~4 are rnoieties containing reacti~e growps selected from carboxylic acid, acid anhydride, acicl amide, '~"~
irnido, carboxylic ester, arnino, hydroxyl, epoxy, .~
15 isocyanate, carbamate, carbamoyl la~tam, acyl lactam, .. .
pyridyl, 1,3-oxazoline, 1,3 oxazine, oxazolone, oxazinones, and any deri~atittJes, combinations and rnixtures thereof; ''i; "!'' and wherein the. remaining onR to three of R~
R2, R3 and R4 are H or a hydrocarbon radical of ~.
from about 1 to abowt 2n carbon atoms; said modifiRd .,.:.. i.,' styrenic polymer containing said reactittJe groups as ~`,':.:::i,.,' pendant reacti~e functionalities. ~.... `~', :.
The present in~ention also includes a rnelt ,~-~
blended composition compri.sing the reaction product as recited abo~e and a therrnoplastic polymer which is ~Y;~
`: reactivR with pendant reactittJR functionalities of the '~
30 reaction product. t The composition of the modified styrenic . ~' polymers and the thernnoplastic polyrner optionally and '~
preftRrably contains frorn about 5 to 50 percent by ,,~
: 35 weight of an elastorneric polymer. "~
j ~
,''.','.'~`.;~`.~
;`~`~
` -`` 133~
.. ,. ,3,~"
-rhe present inventi.on also inclucles rnetho~s of - :. ~
making the reaction procluct and compc)sitions contai.ning :: :
the reac-tion product. lhe compositiorls of the present ..
inventj.on c~n be prepared by conventional polymer melt blending techniques. lhis rnethocl is typically conducted at a temperature above the rnelting ternperature of the polyrneric additives in a closed ,~
mixing device such as an extrucler. The rnethod preferahly first comprises rnelt blending the styrenlc polyrners and the grafting agent to form a reaction ~' product. The reaction product is then melt blended with the therrnoplasti.c polyrner which i5 reactive with ; the reactive groups of the reaction product. '.. ~
It has ~een found that in the preferred .:~.
ernbodirnents, the first method results :in a reaction~
~: product which can also be called a modifiecl or functionalized styrenic polyrner. l~he second rnethod or second step is a method to make a composition of this reaction product or rnodif'ied styre.nic polymer and a thermoplastic polymer. This two--step method produces a ~: cornposition with irnpro~ed tensile elongation properties. , .
ET~ILED DESCRIPTION OF THE _ _ENTION .-~
Styrenic polyrners suitable for modification according to the present invention are those having at least about 25% by weight of the polymer units derived ';,~
~` from a vinyl aromatic compound o~ the formula~
30 1 ~ R~ - ~H~L
;,~. .
~ Z(P) ~' ; '''",' , ' ''.'.~
~. . ..
r ~ 3 3 3. 4 ~ ~
oherRi.n R i.s hyc~rogelt, (I.oo~r) alky:L or halog~!n, Z i.s ~inyl, halog~!n or ('lower) alkyl, arl~ p -ls O or an integQr of Frorn 1 to the nurnber o-f replaceable hydrogen atoms on the benzene nwc].Rus. ~lerein, the terrr `'(lower) alkyl" is intended to rnean alkyl of From about 1 to 6 carbon atorns.
The terrrl "styr~nic polyrners" as wsed broadly ' ' throughout this discloswre ancd the ~ppertded clairns includes, homopolymers and copolyrners oF styrene and 10 inclwdes both rigicl resirts and those comrnon'ly reFerred .
to as high impact styrenic resins. l'he latter refers to resins such as those preparecl by graf't ;' polymerizcltion of styren~ and optionally onR or more of copolyrnerizable ~in!/'l monomers in the presence of an ..
15 e'lastorrleric polymer swbstrate, as well as resins ' ' prepared by blendiny a rigid styrenic matrix polyrner with a graFted rwbb~ry substrate. Examples inclwde polystyrene, polychlorostyrene and polybrornostyrene, as : `.
well as high impact polystyrenes, which ha~e been .~
20 rnodiFied by a natural or synthetlc rwbber, e.g. ''' polyhutadiene, polyisoprene, butyl rwbber, ethylene-propylene diene copolyrners-(EPDM rubber), '''' ethylene-propylene copolymers, natwral rwbbers, .:. :
acrylate rubbers, polysulfide rubbers, polyurethane ~:;'.'' 25 rubbers, styrene-butadiene rwbbers (SBR), and the .' like. Examples of styrene copolymers inclwde both .:.'"
rigid and rwbber rnodified copolymers of styrene with cornonomers se'lected froln alpha-rnethyl styrene, "~
halostyrenes, ~inyl alkyl benzenes, acrylonitrile, :~
methacrylonitri'le, acry'lates and methacry:late esters of lower alcohols etc. The rwbber rT~odified copolymers .~' include po'lybwtadiene rnodified styrene-acrylorlitrile resins (~RS), acry'late elastomRr modified 5hN ~hS~ EP ~ ::
or EP~M rwbber yra~ted S~N copolyrner, ~Sh such as ... " ~'~
RO~R1~ , ~ow) styrene-butadiene, chlorinated polyethylene, modified, styrene-acryloni-trile ~;
copolym~r ~h~S), styrene--isoprene block copolymers ;~
and hydroyenated prodwcts thereof ~e.g. Kraton~
: .:
r~ rrloclification of tht! styr~!ni.c F)olyrllc!rs of th~?
in~ent-.i.on is accornplishecl by attaching an unsaturated grafti.llg agellt to the styrenic polymel^ backbone, reswlting in a penclant functi.onality l-he grafting agellt has a first turlctiorlal group, the ethylenically unsatwrated doub].e bond, which is react-i~? with the styrenic polymer, and one or rnore second functi.onal group, designated Rl - R~, that will be reactive with a polymer ha~ing reacti~e groups such as hydroxy, amine, and the like, particularly when such groups are encl groups, The grafti.ng agent rrlay be represented by the general formula: -. . . ~., .
~ ~C = C~ 3 wherein one or more of the second twnctional groups are ~
20 rnoieties containing reacti~e groups s~?lectecl from .:
carboxy:Lic aci.d, acicl anhydride, acid arnide, irnido, carboxylic ester, amirle, hyclroxyl, epoxy growps, isocyanates, carbamates, acyl lactams, pyridyl, 1,3 ;~
oxazoli.ne, 1,3 oxazines, oxazolones, oxazinones, and ~.
cornb-lnations, rnixtures and deri~ati~es thereof.
. ~
Grafting agents comprising an ethylenically unsaturated double bond and the second functional group may be reacted with the styrenic polymer by themsel~es, or in a mixture with a readily a~ailable rnonorner to act as a cliluent. ~inyl monomers such as styrene, methyl ~:
methacrylates, and the like are particularly suited for ::
this last-mentioned purpose. ~clclitionally, the grafting agent may be attached to a carrier rnolecwle swch as an oligorrler that is cornpatible with all or a -;
~ 3 ~
. -h porti.on oF th(! styr~ulic pol.yrrler i.t .-is cles-irecl-to '' moclify. Particu].arly suitclblc-! oli.gomers are li.qui.cl '~.
polybutadiene., hyclrogenated polybutadiene, po~ystyrene-polybut~cli.ene block copolymers,polyethers, ~nd the like ~ p " '.
Illustrative of graf-ting agents switablc! f'or use~, '.'.
w-.ith:in the context of the present lnventi.on are maleic'~' anhyclricle, hlrrlaric aGicl, monoalkyl, esters of maleic ':-acid, rnonoa:Lkyl esters uf f'umalrlc acicl, acry'.lic acid, ,'' 10 methacry'li.c acid ancl corresponding esters, ntethacry'loyl '~
or acry:loyL capro.Lactam, rnethacry'loy'l or acryloyl '.,'.. '' lauroll.lctam, isopropenyl oxa~oline, vinyl oxazolc)ne, '' vinyl pyridine, glycidyl acrylate, glyciclyl ' :.
me~thacrylatc!, diglycidyl fumarate and the like, whether 15 alone or in any combination -~
'~', ' Preferred among these grafting agents are malei.c':~-'.
anhydride, furnaric acid, acrylic acids ancl ::;
corresponcling esters, acryloyl and methacryloyl '~
lactarns, glycidyl acrylate and rnethacrylates, 2-isopropenyl, 1,3 oxazoline, vinyl pyridine and the ~.:
like In some preferred embodirnents, rubbery high mo'lecu'lar weiyht rnateria'ls are added to the styrenic polyrners to irnprove the overall impact resistance.'''~.'.:-' l'his may take the forrrl o~' conventional rubber :~
dispersions, added prior to or during blending with other po:lyrners. However, the present inventors have '~
. 30 fownd that it is preferable to have the rubbery ,`
rnaterials prefurlctionalized. ~ddition of such rubbers .~
to the modifi~d styrenic polymers serves to impro~e .' .
properties obtained when the modifiecl styrenic polymers-~
are then graft blended with one or more second polymers: :' having terrninal reactive end groups or pendant groups.
.., ;, .:
"'" i~ _7_ ~ 33~
- This is particularly e~id~nt when the styr~nic polym~rs are blended with polyamides. For example, the present inuentors haue discouered that the notched Izod of th~
final blends could b0 substantially impro~ed, while retaining a high elongation to break. The present inuentors do not wish to be bound by theory, howeu0r, it is postulated that the inclusion of the functionalized olefins may actually toughen the styrenic thermoplastic polymer/second polymer interface.
Suitable rubbery polymers within the context of those described above are defined las having an ~l'M
D-638 tensile modulus of less than about 40,000, typically less than ~5,~00, and pre~erably less than 20,000. They can be homopolymers,random, block or gratt copo'lymers. Useful rubbery po'lymers can be made from reactiue monomers which can be part of the polymer chains or branches, or grafted on to the polymer.
These reactiue monomers can include dienes, and carboxylic acids and deri~ati~es thereof such as esters and anhydrides. Such rubbery polymers include butadiene polymers, butadiene~styrene copolymers, isoprene, chloroprene, acrylonitrile~butadiene copolymers, isobutylene, isobutylene/butadiene copolymers, ehtylene/propylene copolymers, ethylene/propylene/diene copolymers. Useful rubbery polymers can include aromatic ~inyl monomers, olefins, acrylic acid and methacrylic acid and their :
deriuati~es, ethylene-propylene diene monomers and meta'l salts thereot-. Usetul rubbery polymers are ~' disclosed in U.S. Patent 4,315,08~ and 4,174,358. ! ' The preferred rubber in the context of the present inuention includes a gra~t copolymer which is a copolymer of ethylene and an alpha-olefin other than ethylene, ha~ing a t'unctionality such as carboxyl or ~`~
' ', r r ~ 3 3 ~
~nhyclri.de graf~ecl tc~ th-~ e~-hy~l~c!rle copolyrrler . -r~l(:,! :, "
~thy'lenf~ and ~-Olefill iS pr~?,''erclbly a copo'l.ymer of '( '.
ethylene and an f'olf!fin seleçted ~rorn at least one C3-C~, preferabl!/ G3--C6 ~olefin, Propylene is a preff!rrf!d monomfer selected as the C3--C~a O~--olefin -.
in the copolyrner. Other C~-C6o~olefins, such as 1--butene, l--pentene, ~ncl 1--hexane can be used ln place of or in adclition to propylene in the copo].yrners.
The carboxyl or carboxyla-te func-tionallty, can 10 be supplied by reacting the ethyleneJC3--C6 d-olefin ~' copolyrrler with an unsaturated graft moiety taken frorn ' ' the class consisting of ~-,B-ethylen:ically unsaturatf!d ~' '-clicarboxy'lic acids ha~ing trom 4 to 8 carhon atoms, or .: :
deri~ati~es thereof. Such cleri~ati~es i.ncl~lde ~' .
anhydrides of the di.carboxy'lic acicls, or the met~l salts of the acids, or the monoestc!r of the dicarboxy:Lic acid ha~ing frorn O to lOO percent of the carboxylic acid groups ionized by neutralizat-ion with ~ -metal basic salt, and the 'like. ~l:lustrati~e of such !
acids and cleri~ati~es are rnaleic acid, maleic anhydri.de, maleic acid rnonoethyl ester, rnetal sal~s of ~' rmaleic aci.d rnonoethyl ester, fumaric acid, furnaric acid ;~
monoethyl ester, itaconic acid, ~inyl benzoic acid, ~ ' ~inyl phthalic acid, metal salts of furnaric acid 25 rnonoethyl ester, rnonoesters and rnaleic or furnaric acid '.~;;
or itaconlc acids where the alcohol i5 methyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, '.
2-ethyl h~xyl, decyl, stearyl, methoxy ethyl, ethoxy '~
ethyl, hydroxy or ethyl, and the like. The graft ~`
. 30 moiety can be grafted to the ethylene copolyrner by any well-krlowrl graftirlg process. i.~'.' ~ useful cnpolymer of ethy'lene and an alpha~olefirl contains from 30 to ~O and prefc!rably ~O ' to 4S weight percent of the a'lpha--olefin based on the ethy'lene. rhe copo'lyrner a'lso contains from O.l to ~
~ ~:
. ~
.''~
3 3 ~
percent, and preferably 0.1 to 4 percen~, and more preferably 0.3 to 2.0 percent by weight of the graft moiety. The graft copolymer has a number average molecular weight of from 2,000 to lOo,OoO, preferably 2,000 to 65,000, more p~eferably 5,000 to 35,000, and most preferably 5,000 to 20,000. Typical values of reduced solution viscosity (RSV) are from 0.5 to 3.5.
A RSV of 2.8 corresponds to a number average molecular weight of about B0,000 and a RS~ of 10 corresponds to a number average molecular weight of 12,000.
The modified styrenic polymers of the invention are especially suitable for blending with second polymers that have reactive groups such as amine, hyd~oxyl, and carboxyl groups, as end groups or groups that are ~endant to the polymer backbone. The present inventors do not wish to be bound by theory, however, they have found that the ethylenically unsaturated ~;
grafting agents of the present inventions can be used -~
as effective graft linking agents, due to their dual 20 reactivity. This is by way of a reaction mechanism of ~-attachment of the functionality to the styrenic polymer backbone through the ethylenically unsaturated double bond. The grafting agents are ~hen also highly effective in reacting with reactive groups of the second polymer through their second functional moiety.
It is believed that the resulting modified styrenic ~olymer contains the functionalities attached as pendant units, as opposed to the introduction of such ~ ~-units in the eolymer backbone through copolymerization 30 techniques which results in copolymers such as ;~ ;
exemplified by various conventional styrene-maleic anhydride copolymers (e.g. Dylark~ , Arco ). It is believed that such pendant units offer more rotational freedom, and consequently better reactivity, as ~ ;
35 compared to the more restricted functionalized , coeolymers. 5urerisingly, the result is a grafted link that is stable, especially thermally, to permit extruder processing.
"'';', '' ~ "', ..
~ 3 ~
-lC~
Of the po'l.ymers hav1ng reacti.~e groups, an~ ar~ -sultabl.c? for blencliny wi.th the rnodifiecl styrenic po1yrn~!rs, may be merl-tioned fullct.10rla'.Lized po:Lyolef-i.rls, po1yesters~ polyarrlicles, and the like, whether a'l.or)e or "
in any comb-lnatiorl, inc:Lucl-lng mixtures thereof.
Particu'.l.arly preferred For blencling w.ith the f'unctional~ized styrenic polyrners of the -.invent1on are the po'.l.yami.des ancl po'l.yesters.
Polyarnides suitable for ~se herein -lnclucle the . ~' 10 long chain po1ymeric ami.des ha~i.ng recurring amide : "~
groups as part ofthe polyrner backbone ancl preferably having a nwmber a~erage rno1ecu'le weight, as measurecl by end group titration of abo~t 15,000 to 40,000. The '.
polyarnicles su-.itable for use herein can be procluced by any con~elltional process known in the art.
.
Non-limiting examples of such polyarnides are: ''' (a) those prepared by the po'lymerization of lactarns, preferably epsilon~caprolactam (nylon ~); (b) those 20 prepared by the condensation of a diarrline with a '-~
cli~asic acid, preferably the condensation of hexarrlethylerle diarnine with adipic acid (ny'lon 6,6) and '.'''~
the condensation of hexamethylene diamine with scbacic acid (nylon 6,10), the condensation of hexarnethylene diamine with terephthalic and isophthali.c acids, tetramethy1ene-diamine w-.ith adipic acid ~nylon 4,6), and the condensation of metaxylylene diamine with adipic acid and/or terephthalic/isophthalic acid and/or ~ i epsilon caprolactam; and those prepared by -~
. I 30 self--condensation of amino acids, preFerably self-condensation of 11--amino-~nclecanoic acid .:'. !' (nylon-11); or randorn, block, or graft interpolymers ';~
consisting of two or more of these polyamides. :.:'~
Preferred are those obtained by the polyrnerization of epsilon-caprolactam.
F~o:l.yarnicles such a nylon--6 or nylc,n 6 6 can conta.in a ~ariety of terminal functionaliti.es including (aj a carboxyl group attafhed to both ends of the polyarmicle ch~i.n: (b) a carboxyl group attached to one encl ancl an amide group attached to thc! other encl of the po:Lyamide chain (the "cappecd" encl) (only polylactarrls); (c) ~n arnino group attached to both rncls of the polyarrlide chai.n; (d) a carboxyl group attached t:o one end and an arrline group attachecl to the other end : . :
of the polyamicde chaln (only polylactarns); ancl rni.xtwres t h e r e o f Polyamides ha~i.ng "excess" amine terminati.on are polyarnides ha~ing rnolecules with rnore than 50 rnole pr,rcent ancl preferably 60 to 97 mole present of its end groups as arnino end groups. ~rnine end group termination is typically produced by inclucling an excess of diamines during polymerization. ~ preferred diamine is hexarnethylene diamine. :
Other exarnples of diarnines suitable for use herein includQ tetramethylene diamine pentarr1ethylene .
diamine octamethlene diarnine decamethyl.ene diarnine and 1 12 diamines dodecane. The amount of diamine needed to produce the excess arnino terrninated polyamides of the present in~enti.on ~aries depending on the amount ot amine desired and the rnolecule weight of the resùlti.ng polymer and can be easily determined by one skilled in the art. For examp.le about 0.25 rnole .~: :
percent of hexamethylene diamine is required to produce ..
a polyepsiloncaprolactam of about 21 000 nurnb~r a~erage molecular weight ha~ing about 80 equivalents/10 g :`: c~
arnino end groups and about 17 equi~alents/106g acid ., ~ ..
end groups.
;'`.' :~ .
, ~ -:
`' ~ ;. '~. ~
~l33~
Si.rrl:ilrlr].y, polyamicles having more than 50 molepc,rcent of' t.h~ end t3roup5 as acid end grollps can be formed by ha~ing an excess of diac-lds such as sebacic acid present o~er cliamines during polymerization. Such .-polyarnides are considered acid terrninatc!d polyarnides.
Useful diacids inclucle but are not lirnited to oxalic acicl, mal.onic acid, succirlic acid, glutaric acid, adipic acid, pirnelic ac-ld, suberic acid, azeli.c aci.d, and sebacic acid as nott!d. ' .' Polyesters useful for bl~nding with the mcclified ' styrenic po'lyrners of the in~entlon inclucle linear, saturated polyesters of aromatic dicarboxylic acids. :'~
'I'he pref'erred 'linear saturated po'lyesters inc'lude polyethylerle terephthalate, poly(butylene terephtha'late), arld po'ly~l,4-cyc'lohexarle dimethylene terephthalate), with poly(ethylene terephthalate? being moxt preferred due to the low molding ternperatures . ::
possible. The poly(ethylene terephthalate) for use with the preserlt in~ention has an intrinsic ~iscosity .
range between about 0.4 and about 1.20, with a preferred intrinsic ~iscosity range between about 0.45 . ~
and 0.6. Intrinsic viscosity is obtained by : ~ ' extrapolation of ~iscosity ~alues to zero concentratio of solutions of poly(ethylene terephthalate) in 60 to 25 40 weight~olume ratio of phenol and ' '::.
tetrach-loroethane. The measurements are normalized to '.`~.
25~C. lhe poly (ethylene terephthalate) melts between about 250~C and 2Y5~. The poly~ethylene .::
terephtha'late~ can con~airlrninor arnounts, up to 5/0, of .
30 other comonomers such as 1,4 cyclohexanedirnethanol, ':~
burylenedio`l, neopenty'lendiol, diethylerle g'lyco'l, or :~;
glutaric acid. ,~;
.. ~
~::
, ; ~13- ~33~
Functionaliæed polyolefins useful in the pLesent invention are carboxylated polypro~ylene (Polybond~
from BP chemicals), maleated polypropylene, (Plexar~
Chemplex) ethylene-acrylic acid copolymer, e~hylene-methacrylic acid copolymer and ethylene vinyl alcohol copolymer and the like.
Preferred compositions o~ the present invention contain from about S to 50 percent of the modified styrenic polymer, more preferably from about 5 to 30 percent - ~ ', "'' '.
The styrenic polymer/thermoplastic polymer ~
blends of this invention may also contain one or more ~ -conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation, lubricants and mold release agents, colorants, including dyes and pigments, flame retardants, fibrous and particulate fillers and reinforcements, plasticizers, and the like. These additives are preferably added during the blending of the modified styrenic polymer with the second thermoplastic polymer.
Representat1ve oxidative and thermal stabilizers `
which may be present in blends of the present invention include Group I metal halides, such as sodium, eotassium, lithium, cuprous halides, such as chloride, bromide, iodide; hindered phenols, hydroquinones, and varieties of substituted members of those groups and combinations thereof.
~ epresentative lubricants and mold release agents include stearic ~cid, stearyl alcohol, and stearamides. Representative organic dyes include nigrosine. while representative pigments, include ~- . .' ~ '. ' . . ~ , .:
~ 3 ~
-~14-ti tani.urrl r,lic)xi.de, cadrrliurn sulFiclc?, caclmiurrl seJ.enide, phtha'l.ocyanines, ultrarnarinc! blue, carbon black, ancl the like. Represc3ntat:ive fillers lnclucde carbon fibers, glass f'ibers, amorphous sili.ca, asbestos, .' calcium silicate, a.Lurrlirlurn si:Licate, magrlesiurn carbonate, kaolin, chalk, powdered quartz, mica, feldspar, and the 'like.
Representative flame-retardants include organic .: .
halogenated compourlds such as clecabromodiphenyl e-ther, bronninated polystyrene, and the like.
Representative plasticizers include lactarns such as caprolactam and lauryl lactam, sulfonarnides such as o,p toluenesulfonarnicle and N-ethyl, 15 o,p-toluenesulfonarrlicde ancl other plastici.zers known in ; ~:
the art. ~:
In the methocl cf the present invention, a reaction product is forrnecl by contactirlg the styrenic polymer wlth the grafting agent, usiny conventional techniques such as heatiMg in a solvent rnedium, ;~
melt~blending, and the like. Particularly preferred .
are rne'lt-blending techniques such as high shear rnixing in a Farrel]. conti.nuous mixer, mixing either in a .
rubbery state or mo'lten state usiny extruder processing. The present in~entors have discovered that the graft 'linking of the preserlt invelntion is particularly suited for extruder processing, and thus, :~
extruder processing techniques ancl the like are . 30 particularly preferred.
When conventional rnelt-blencling techniques are utilized, it is preferable that they be performed in a :' closecl rnixing de~ice, such as an extruder, for a time.::~
35 sufficieMt to allow a reaction to occur between the ; ~.
- ~ 3 ~
,.. lr,~,................ i . , graf'ti.ng ager1t ancl the polyrner. Tf.!rrlF)eratllrf!s that m~y ~ ~ :"be uti.l.i.zf.~d ~ary accorcl.i.ng to the prUpf!rti~!s of the ' -.:
componellts ernployc!d, hw-t ~re typ:Lca'Lly at abo~e the melt-lng terrlperatwrc! of the polymer components, bt,lt below temperaturc!s that lead to degradat1on of the cornponents. Typ-ical extrucler processing temperatllres rallge frorn about 150~, -to about ~OO~C, particularly .~.:
preferred, howe~er, are tempf3ratwrf1s of abowt 180~C to ilbo~t ~70~C. .
~n effecti~e amount of grafting agent usehll to :.
fur1ct-lon~ ize the styrer1ic resirlrr1ay ~ary wlcle.'ly depencli.ng on tbt3 parti.cular styrenic polymer and gri1ft:ing ager1t uti1i.zecl as we'l'l as the des-lrecl characteristics of the resulting reacti.on product. In .
sorne preferred emhoclirnents, the arnount of graftirlg agent can range f'rom abot,lt O.l ~ 20% by wt., based on the weight of the polyrner to be modified, and ' :~
preferak~ly ~rom about 0.2 to about 10% by wt.
In sorne ernbodiments of the rnethod of the present i.nvention, the styrenic polymer may be melt--blended with the graft.ing agent using conditions which are -"
Se~Rre enough for a satisfactory reaction to occur without the necessity oF adding a Free rad-ical ~'--.;.:.
25 catalyst. The restllt-lng reaction product neecl not be .
the cornp'lete reaction of the styrenic po'lyrner with the grafting agent. It is necessary only that a sufficient amount of reaction occur between the polymer and the grafting agent so that the reactive growps, a~tachecl in '.
, , 30 a pendar1t rnanner to the styren:ic po'lyrrler backbone, can further react with a therrrloplastic po'lyme.r to forrrl :.~
graft type linkages. ~'.. ' .'~ ', ,: ' "', The reaction prodt~tct can also be forrned using ', ''`.:
35 the styren-ic polymer and the grafting agent as recitecl '~
abo~e in the presence of a f'ree radical catalyst. i'~ '' ~rnounts employed are con~entional arnounts of the -.. -;'~'.
'' ;"` '",.
.",.,,,", ~ ,", " ,~- ,-catalyst ~ b-l~ t~ nswrc! generati.orl of:' f'rec! radicals on the stylnerlic po-lyrner backbone that react wi.th the ethylenica'lly uns~tur~-ted clouble borld of the graft:ing agent. Usefu]. f'ree raclical catalysts -include peroxicles such as dialkyl, di, and diacyl peroxide.s. Other useful free raclical. cata'lysts inclusle N-bromoirrlicles dialkylazos ar~d the like.
The reaction product itselF is useful as a struct~lral resln. Howe.~er, it also dernonstrates aclhesive prc)p~rties usehl3. For larrlination to other polyrners, coe~trusion with other polyrners, metal bonding, and the li.ke. . -The reacticin product is also a stable procluct ;~
15 that may be stored for further b.Lendirl~3 with a second -~ :
polyrner. ~lternatively, blending of the f'unctionalized styrenic polymer with the second therrnop.lastic po'lyrner may take place irnmediately after its f'ormation to form a blended composite as described herein. Formation of ~ :~
20 a styrenic polymer/thermoplastic polyrner blended ~:
composite is achieued by blending the second polyrner as ~- '-described herein oith the styrenic polymer, gra~ting ~'' agent, and any other desired additional cornponents. ~:
The components may be added together at the same time, 25 or added together in any cornbination or in any ~'~
sequential fashion of indi~idual or combined com~
ponents. Howe~er, in the pre~erred embodirnents, the :'.. "~' styrenic polymer/grafting agent reaction is first '~
carried out, and the resulting rnodified styrenic ,,, 30 polymer is then cornbined with the second polymer component to forrn the styren:ic polymer~thermoplastic polymer blend. ~esired amounts of rubbery materials rnay be ~dded at any time to impro~e the irnpact resis~
tance. Howe~er, it is preferred that these rubbery 35 rnaterials are o~' the. ~'urlctionalized type and it is ~ ;
. :.
~ , .. .: . .
~; ~
3 ~
-^:L7-z~-lso pre''errecl tha-t ttle rubbers be preblendec1 wi.th the mocdi.fi.ecl styreni.c polymer pri.or to b].endi.ng Wit.t1 any :~
seconcl polyrner.
' ' Thermoplastic compositio1)s of the in~ention 5 demonstrate improvf!d toughness and delan1-lnation ~ ~ ;
resistance. It should thus be appreciated that they can be rnade lnto a wide range of useful article~s by conventional rnolding methods employed i.n the fabricatior1 of thermoplastic articles i.e. as molded lO parts extrucled shapes e.g. tubinfg films sheets : -.
fibers and oriented fibers laminates ancl wire coating. "Molcling" means forming an article by deforming the blend in the heatecl plastic state.
The cornpositi.ons of this in~enti.on are characterizecl by an outstarlding combinatlon of '~`.'-~' properties foremost of which is outstanding toughness in ~iew of the quantity of functiona:Lized styrenic '~
polymer pres~nt with the second polyrr1er such as a 20 po'lyam:ide. 1he unusua'lly high toughness pro~ides '~';
greater dwcti.lity less sensitiuity to scratch~s and .~
rnolded in notches and ~astly reduced susceptibility to :'.'` '.
catastrophic failure when compared with previously known compositions in rnolded parts. Injection molded '~
25 parts of'ten are of ~arying thicknesses and may ha~e ''";.'.` ~
scratches molded-win notches of ~arying radii and ; . :.
molded in stresses. In addition orientation effects '~
may cause ~aried ductility throughout a rnolded part.
the maintenance of high uniform ~alues of notched Izocl '';.. ;.. ':~.
30 toughness throughout such rnolded parts characterizes ~ :p'~
the irnprovecd compositi.ons resistance to brittle .''~'`.
breaks. l'he compositions are of sufficient toughness '~
that the effect of minor changes in processing ';~' conditions will not cause significant ~ariations in 35 tou~hness from lot to lot quantities of compositi.on. ~:
~''"; , Z~ ~
~33~
fX~MPL.ES
Th~ fol].ow-lrlg exarnples are by way oF
il1us tration O~ certa-.in embodiments o-F the invent-lor and are not to be construed a5 limi.tati.ve thereoF, Exan~le_1 ~ mixtwre of ~Y parts of cornrnerclal h~S powcler (Blendex 201, ~org--Warner), 3 parts of maleic anhydride 10 was extrucled on a corotating, twin--screw extrwder (28 :
mm, Leistritz; LtD - ~0~ with all ten zones of the barrel set at 180C, ~t a screw speed of 150 rpm the die pressure was 2,S00 psi. l~he extrudate of maleic anhydride rnodifiecl ~RS was cooled and pelletizecl ; ' .
.
~3.3 parts of the rnodified ~S pellets were '''.'' mixed w-i.th 26.7 parts of the ~irgin hRS (Rlendex~201) arld 60 parts of amine terminated nylon 6 (formic acid ~iscos-ity 58; Camine'~ /2 rneq g 1) land the blerld 20 was re-extrucled on the twin-screw extruder at 230G and ':m :
a throughput rate of' 2~ 'lbsJhr. 'I~he blend extr~date was cooled, pellet-lzecl and dri~d. :~;
I~ellets o~ the ~US-nylon blend were injection molded -into standard tensile and flexural ~ars at 22V-240UC. .
'~
h control exarrlple was done under similar : `
conditions with ~BS and nylon mechanical blend with no ;"~.' , 30 grafting agent present.
~','~'', .:~ :
: ' ,"
For th~ graftc!cl bl(-)ncl (60/40 ~RS N6) the propert:-l.es were~
Flexura.l.rrlodul.~ls: 345 000 psi -rensil~ strength: 9 700 psi Elongatic~n to break: 80% : ~:
Irnp~ct energy to break: (~ 12 ft./sec. -~ :
impact speed) 56.4 ft. lbs.
(uyrlatup instrurnentecl impact) ,~ .
Notched Izod: ~ 3/16" th-ickness 2.1 ft lbs/in.
1 0 '"' '' '" "
For the control blerlcl ...
Flexura].rncdulus:342 000 psi lenslle strerl~th: 9 700 psi lS Elongati.on: 25%
Nothced Izod: @ 3~16" thickncss 1.& ft. lbs/in.
Impact energy to break (@ 12 ft./sec.
irnpact speed) (r)ynatup) 2.8 ft. ::
lbs./in.
.'.''''' ,`'` '."';
Ex~ e 2 This experiment was done with a one--pass :~:
operation in the twi~screw extruder with downstream caddition of nylon ~ to the rnodified ~BS rnelt.
49.~ parts ~BS powder (~lendex 201? was rnixed :~
with 0.5 parts of maleic anhydride and extruded on a corotating twin screw extruder (2~ nrrl leistritz? wi.th Zone 1 at 1~0C Zone 2 at l90G Zone 3 at 220C. ~t ~one 4 set at 2~0UC 50 parts oF arrline te.rrrlinated ~.-nylon 6 ~Fn~ - ~3; Larnine~ - /2 rneq g ) was added. .;;
Zones 6-10 were set at 230G. The extrusion of the .;.~:.
rnelt blend was carried out at ~ rate of 15.3 lbs/hr arld ~ 2(~) ~ 3~ J~ ~
250 rpm screlA~ speecl. rh~? bl.~.!ncl extru(late was coo~l.ecl, pel].etizecl arlcl clri~cl, ~~rhe clri.e~ f)~ rlylc~n fi blend pellets were Lnjf3ct-lon moldecl .into starlclard -tenslle arld flexural test bars. ~ control exarrlple WclS 5irrli.larly cvnducted -in the absence of grAfting ay~ t.
Ex. 2 _~rafted2Contr~1 (ungraft~?cl) Flex. modulus 337,000 psi 356,000 ~.. :.
Tensile strencJth9,400 ~,000 Elongation at break 245 28 ' ' (%) Notched Izod l.6 l.3 (ft lbs/in ~ 3/l6" th.i.ckness) Exarnple ~
percent, and preferably 0.1 to 4 percen~, and more preferably 0.3 to 2.0 percent by weight of the graft moiety. The graft copolymer has a number average molecular weight of from 2,000 to lOo,OoO, preferably 2,000 to 65,000, more p~eferably 5,000 to 35,000, and most preferably 5,000 to 20,000. Typical values of reduced solution viscosity (RSV) are from 0.5 to 3.5.
A RSV of 2.8 corresponds to a number average molecular weight of about B0,000 and a RS~ of 10 corresponds to a number average molecular weight of 12,000.
The modified styrenic polymers of the invention are especially suitable for blending with second polymers that have reactive groups such as amine, hyd~oxyl, and carboxyl groups, as end groups or groups that are ~endant to the polymer backbone. The present inventors do not wish to be bound by theory, however, they have found that the ethylenically unsaturated ~;
grafting agents of the present inventions can be used -~
as effective graft linking agents, due to their dual 20 reactivity. This is by way of a reaction mechanism of ~-attachment of the functionality to the styrenic polymer backbone through the ethylenically unsaturated double bond. The grafting agents are ~hen also highly effective in reacting with reactive groups of the second polymer through their second functional moiety.
It is believed that the resulting modified styrenic ~olymer contains the functionalities attached as pendant units, as opposed to the introduction of such ~ ~-units in the eolymer backbone through copolymerization 30 techniques which results in copolymers such as ;~ ;
exemplified by various conventional styrene-maleic anhydride copolymers (e.g. Dylark~ , Arco ). It is believed that such pendant units offer more rotational freedom, and consequently better reactivity, as ~ ;
35 compared to the more restricted functionalized , coeolymers. 5urerisingly, the result is a grafted link that is stable, especially thermally, to permit extruder processing.
"'';', '' ~ "', ..
~ 3 ~
-lC~
Of the po'l.ymers hav1ng reacti.~e groups, an~ ar~ -sultabl.c? for blencliny wi.th the rnodifiecl styrenic po1yrn~!rs, may be merl-tioned fullct.10rla'.Lized po:Lyolef-i.rls, po1yesters~ polyarrlicles, and the like, whether a'l.or)e or "
in any comb-lnatiorl, inc:Lucl-lng mixtures thereof.
Particu'.l.arly preferred For blencling w.ith the f'unctional~ized styrenic polyrners of the -.invent1on are the po'.l.yami.des ancl po'l.yesters.
Polyarnides suitable for ~se herein -lnclucle the . ~' 10 long chain po1ymeric ami.des ha~i.ng recurring amide : "~
groups as part ofthe polyrner backbone ancl preferably having a nwmber a~erage rno1ecu'le weight, as measurecl by end group titration of abo~t 15,000 to 40,000. The '.
polyarnicles su-.itable for use herein can be procluced by any con~elltional process known in the art.
.
Non-limiting examples of such polyarnides are: ''' (a) those prepared by the po'lymerization of lactarns, preferably epsilon~caprolactam (nylon ~); (b) those 20 prepared by the condensation of a diarrline with a '-~
cli~asic acid, preferably the condensation of hexarrlethylerle diarnine with adipic acid (ny'lon 6,6) and '.'''~
the condensation of hexamethylene diamine with scbacic acid (nylon 6,10), the condensation of hexarnethylene diamine with terephthalic and isophthali.c acids, tetramethy1ene-diamine w-.ith adipic acid ~nylon 4,6), and the condensation of metaxylylene diamine with adipic acid and/or terephthalic/isophthalic acid and/or ~ i epsilon caprolactam; and those prepared by -~
. I 30 self--condensation of amino acids, preFerably self-condensation of 11--amino-~nclecanoic acid .:'. !' (nylon-11); or randorn, block, or graft interpolymers ';~
consisting of two or more of these polyamides. :.:'~
Preferred are those obtained by the polyrnerization of epsilon-caprolactam.
F~o:l.yarnicles such a nylon--6 or nylc,n 6 6 can conta.in a ~ariety of terminal functionaliti.es including (aj a carboxyl group attafhed to both ends of the polyarmicle ch~i.n: (b) a carboxyl group attached to one encl ancl an amide group attached to thc! other encl of the po:Lyamide chain (the "cappecd" encl) (only polylactarrls); (c) ~n arnino group attached to both rncls of the polyarrlide chai.n; (d) a carboxyl group attached t:o one end and an arrline group attachecl to the other end : . :
of the polyamicde chaln (only polylactarns); ancl rni.xtwres t h e r e o f Polyamides ha~i.ng "excess" amine terminati.on are polyarnides ha~ing rnolecules with rnore than 50 rnole pr,rcent ancl preferably 60 to 97 mole present of its end groups as arnino end groups. ~rnine end group termination is typically produced by inclucling an excess of diamines during polymerization. ~ preferred diamine is hexarnethylene diamine. :
Other exarnples of diarnines suitable for use herein includQ tetramethylene diamine pentarr1ethylene .
diamine octamethlene diarnine decamethyl.ene diarnine and 1 12 diamines dodecane. The amount of diamine needed to produce the excess arnino terrninated polyamides of the present in~enti.on ~aries depending on the amount ot amine desired and the rnolecule weight of the resùlti.ng polymer and can be easily determined by one skilled in the art. For examp.le about 0.25 rnole .~: :
percent of hexamethylene diamine is required to produce ..
a polyepsiloncaprolactam of about 21 000 nurnb~r a~erage molecular weight ha~ing about 80 equivalents/10 g :`: c~
arnino end groups and about 17 equi~alents/106g acid ., ~ ..
end groups.
;'`.' :~ .
, ~ -:
`' ~ ;. '~. ~
~l33~
Si.rrl:ilrlr].y, polyamicles having more than 50 molepc,rcent of' t.h~ end t3roup5 as acid end grollps can be formed by ha~ing an excess of diac-lds such as sebacic acid present o~er cliamines during polymerization. Such .-polyarnides are considered acid terrninatc!d polyarnides.
Useful diacids inclucle but are not lirnited to oxalic acicl, mal.onic acid, succirlic acid, glutaric acid, adipic acid, pirnelic ac-ld, suberic acid, azeli.c aci.d, and sebacic acid as nott!d. ' .' Polyesters useful for bl~nding with the mcclified ' styrenic po'lyrners of the in~entlon inclucle linear, saturated polyesters of aromatic dicarboxylic acids. :'~
'I'he pref'erred 'linear saturated po'lyesters inc'lude polyethylerle terephthalate, poly(butylene terephtha'late), arld po'ly~l,4-cyc'lohexarle dimethylene terephthalate), with poly(ethylene terephthalate? being moxt preferred due to the low molding ternperatures . ::
possible. The poly(ethylene terephthalate) for use with the preserlt in~ention has an intrinsic ~iscosity .
range between about 0.4 and about 1.20, with a preferred intrinsic ~iscosity range between about 0.45 . ~
and 0.6. Intrinsic viscosity is obtained by : ~ ' extrapolation of ~iscosity ~alues to zero concentratio of solutions of poly(ethylene terephthalate) in 60 to 25 40 weight~olume ratio of phenol and ' '::.
tetrach-loroethane. The measurements are normalized to '.`~.
25~C. lhe poly (ethylene terephthalate) melts between about 250~C and 2Y5~. The poly~ethylene .::
terephtha'late~ can con~airlrninor arnounts, up to 5/0, of .
30 other comonomers such as 1,4 cyclohexanedirnethanol, ':~
burylenedio`l, neopenty'lendiol, diethylerle g'lyco'l, or :~;
glutaric acid. ,~;
.. ~
~::
, ; ~13- ~33~
Functionaliæed polyolefins useful in the pLesent invention are carboxylated polypro~ylene (Polybond~
from BP chemicals), maleated polypropylene, (Plexar~
Chemplex) ethylene-acrylic acid copolymer, e~hylene-methacrylic acid copolymer and ethylene vinyl alcohol copolymer and the like.
Preferred compositions o~ the present invention contain from about S to 50 percent of the modified styrenic polymer, more preferably from about 5 to 30 percent - ~ ', "'' '.
The styrenic polymer/thermoplastic polymer ~
blends of this invention may also contain one or more ~ -conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation, lubricants and mold release agents, colorants, including dyes and pigments, flame retardants, fibrous and particulate fillers and reinforcements, plasticizers, and the like. These additives are preferably added during the blending of the modified styrenic polymer with the second thermoplastic polymer.
Representat1ve oxidative and thermal stabilizers `
which may be present in blends of the present invention include Group I metal halides, such as sodium, eotassium, lithium, cuprous halides, such as chloride, bromide, iodide; hindered phenols, hydroquinones, and varieties of substituted members of those groups and combinations thereof.
~ epresentative lubricants and mold release agents include stearic ~cid, stearyl alcohol, and stearamides. Representative organic dyes include nigrosine. while representative pigments, include ~- . .' ~ '. ' . . ~ , .:
~ 3 ~
-~14-ti tani.urrl r,lic)xi.de, cadrrliurn sulFiclc?, caclmiurrl seJ.enide, phtha'l.ocyanines, ultrarnarinc! blue, carbon black, ancl the like. Represc3ntat:ive fillers lnclucde carbon fibers, glass f'ibers, amorphous sili.ca, asbestos, .' calcium silicate, a.Lurrlirlurn si:Licate, magrlesiurn carbonate, kaolin, chalk, powdered quartz, mica, feldspar, and the 'like.
Representative flame-retardants include organic .: .
halogenated compourlds such as clecabromodiphenyl e-ther, bronninated polystyrene, and the like.
Representative plasticizers include lactarns such as caprolactam and lauryl lactam, sulfonarnides such as o,p toluenesulfonarnicle and N-ethyl, 15 o,p-toluenesulfonarrlicde ancl other plastici.zers known in ; ~:
the art. ~:
In the methocl cf the present invention, a reaction product is forrnecl by contactirlg the styrenic polymer wlth the grafting agent, usiny conventional techniques such as heatiMg in a solvent rnedium, ;~
melt~blending, and the like. Particularly preferred .
are rne'lt-blending techniques such as high shear rnixing in a Farrel]. conti.nuous mixer, mixing either in a .
rubbery state or mo'lten state usiny extruder processing. The present in~entors have discovered that the graft 'linking of the preserlt invelntion is particularly suited for extruder processing, and thus, :~
extruder processing techniques ancl the like are . 30 particularly preferred.
When conventional rnelt-blencling techniques are utilized, it is preferable that they be performed in a :' closecl rnixing de~ice, such as an extruder, for a time.::~
35 sufficieMt to allow a reaction to occur between the ; ~.
- ~ 3 ~
,.. lr,~,................ i . , graf'ti.ng ager1t ancl the polyrner. Tf.!rrlF)eratllrf!s that m~y ~ ~ :"be uti.l.i.zf.~d ~ary accorcl.i.ng to the prUpf!rti~!s of the ' -.:
componellts ernployc!d, hw-t ~re typ:Lca'Lly at abo~e the melt-lng terrlperatwrc! of the polymer components, bt,lt below temperaturc!s that lead to degradat1on of the cornponents. Typ-ical extrucler processing temperatllres rallge frorn about 150~, -to about ~OO~C, particularly .~.:
preferred, howe~er, are tempf3ratwrf1s of abowt 180~C to ilbo~t ~70~C. .
~n effecti~e amount of grafting agent usehll to :.
fur1ct-lon~ ize the styrer1ic resirlrr1ay ~ary wlcle.'ly depencli.ng on tbt3 parti.cular styrenic polymer and gri1ft:ing ager1t uti1i.zecl as we'l'l as the des-lrecl characteristics of the resulting reacti.on product. In .
sorne preferred emhoclirnents, the arnount of graftirlg agent can range f'rom abot,lt O.l ~ 20% by wt., based on the weight of the polyrner to be modified, and ' :~
preferak~ly ~rom about 0.2 to about 10% by wt.
In sorne ernbodiments of the rnethod of the present i.nvention, the styrenic polymer may be melt--blended with the graft.ing agent using conditions which are -"
Se~Rre enough for a satisfactory reaction to occur without the necessity oF adding a Free rad-ical ~'--.;.:.
25 catalyst. The restllt-lng reaction product neecl not be .
the cornp'lete reaction of the styrenic po'lyrner with the grafting agent. It is necessary only that a sufficient amount of reaction occur between the polymer and the grafting agent so that the reactive growps, a~tachecl in '.
, , 30 a pendar1t rnanner to the styren:ic po'lyrrler backbone, can further react with a therrrloplastic po'lyme.r to forrrl :.~
graft type linkages. ~'.. ' .'~ ', ,: ' "', The reaction prodt~tct can also be forrned using ', ''`.:
35 the styren-ic polymer and the grafting agent as recitecl '~
abo~e in the presence of a f'ree radical catalyst. i'~ '' ~rnounts employed are con~entional arnounts of the -.. -;'~'.
'' ;"` '",.
.",.,,,", ~ ,", " ,~- ,-catalyst ~ b-l~ t~ nswrc! generati.orl of:' f'rec! radicals on the stylnerlic po-lyrner backbone that react wi.th the ethylenica'lly uns~tur~-ted clouble borld of the graft:ing agent. Usefu]. f'ree raclical catalysts -include peroxicles such as dialkyl, di, and diacyl peroxide.s. Other useful free raclical. cata'lysts inclusle N-bromoirrlicles dialkylazos ar~d the like.
The reaction product itselF is useful as a struct~lral resln. Howe.~er, it also dernonstrates aclhesive prc)p~rties usehl3. For larrlination to other polyrners, coe~trusion with other polyrners, metal bonding, and the li.ke. . -The reacticin product is also a stable procluct ;~
15 that may be stored for further b.Lendirl~3 with a second -~ :
polyrner. ~lternatively, blending of the f'unctionalized styrenic polymer with the second therrnop.lastic po'lyrner may take place irnmediately after its f'ormation to form a blended composite as described herein. Formation of ~ :~
20 a styrenic polymer/thermoplastic polyrner blended ~:
composite is achieued by blending the second polyrner as ~- '-described herein oith the styrenic polymer, gra~ting ~'' agent, and any other desired additional cornponents. ~:
The components may be added together at the same time, 25 or added together in any cornbination or in any ~'~
sequential fashion of indi~idual or combined com~
ponents. Howe~er, in the pre~erred embodirnents, the :'.. "~' styrenic polymer/grafting agent reaction is first '~
carried out, and the resulting rnodified styrenic ,,, 30 polymer is then cornbined with the second polymer component to forrn the styren:ic polymer~thermoplastic polymer blend. ~esired amounts of rubbery materials rnay be ~dded at any time to impro~e the irnpact resis~
tance. Howe~er, it is preferred that these rubbery 35 rnaterials are o~' the. ~'urlctionalized type and it is ~ ;
. :.
~ , .. .: . .
~; ~
3 ~
-^:L7-z~-lso pre''errecl tha-t ttle rubbers be preblendec1 wi.th the mocdi.fi.ecl styreni.c polymer pri.or to b].endi.ng Wit.t1 any :~
seconcl polyrner.
' ' Thermoplastic compositio1)s of the in~ention 5 demonstrate improvf!d toughness and delan1-lnation ~ ~ ;
resistance. It should thus be appreciated that they can be rnade lnto a wide range of useful article~s by conventional rnolding methods employed i.n the fabricatior1 of thermoplastic articles i.e. as molded lO parts extrucled shapes e.g. tubinfg films sheets : -.
fibers and oriented fibers laminates ancl wire coating. "Molcling" means forming an article by deforming the blend in the heatecl plastic state.
The cornpositi.ons of this in~enti.on are characterizecl by an outstarlding combinatlon of '~`.'-~' properties foremost of which is outstanding toughness in ~iew of the quantity of functiona:Lized styrenic '~
polymer pres~nt with the second polyrr1er such as a 20 po'lyam:ide. 1he unusua'lly high toughness pro~ides '~';
greater dwcti.lity less sensitiuity to scratch~s and .~
rnolded in notches and ~astly reduced susceptibility to :'.'` '.
catastrophic failure when compared with previously known compositions in rnolded parts. Injection molded '~
25 parts of'ten are of ~arying thicknesses and may ha~e ''";.'.` ~
scratches molded-win notches of ~arying radii and ; . :.
molded in stresses. In addition orientation effects '~
may cause ~aried ductility throughout a rnolded part.
the maintenance of high uniform ~alues of notched Izocl '';.. ;.. ':~.
30 toughness throughout such rnolded parts characterizes ~ :p'~
the irnprovecd compositi.ons resistance to brittle .''~'`.
breaks. l'he compositions are of sufficient toughness '~
that the effect of minor changes in processing ';~' conditions will not cause significant ~ariations in 35 tou~hness from lot to lot quantities of compositi.on. ~:
~''"; , Z~ ~
~33~
fX~MPL.ES
Th~ fol].ow-lrlg exarnples are by way oF
il1us tration O~ certa-.in embodiments o-F the invent-lor and are not to be construed a5 limi.tati.ve thereoF, Exan~le_1 ~ mixtwre of ~Y parts of cornrnerclal h~S powcler (Blendex 201, ~org--Warner), 3 parts of maleic anhydride 10 was extrucled on a corotating, twin--screw extrwder (28 :
mm, Leistritz; LtD - ~0~ with all ten zones of the barrel set at 180C, ~t a screw speed of 150 rpm the die pressure was 2,S00 psi. l~he extrudate of maleic anhydride rnodifiecl ~RS was cooled and pelletizecl ; ' .
.
~3.3 parts of the rnodified ~S pellets were '''.'' mixed w-i.th 26.7 parts of the ~irgin hRS (Rlendex~201) arld 60 parts of amine terminated nylon 6 (formic acid ~iscos-ity 58; Camine'~ /2 rneq g 1) land the blerld 20 was re-extrucled on the twin-screw extruder at 230G and ':m :
a throughput rate of' 2~ 'lbsJhr. 'I~he blend extr~date was cooled, pellet-lzecl and dri~d. :~;
I~ellets o~ the ~US-nylon blend were injection molded -into standard tensile and flexural ~ars at 22V-240UC. .
'~
h control exarrlple was done under similar : `
conditions with ~BS and nylon mechanical blend with no ;"~.' , 30 grafting agent present.
~','~'', .:~ :
: ' ,"
For th~ graftc!cl bl(-)ncl (60/40 ~RS N6) the propert:-l.es were~
Flexura.l.rrlodul.~ls: 345 000 psi -rensil~ strength: 9 700 psi Elongatic~n to break: 80% : ~:
Irnp~ct energy to break: (~ 12 ft./sec. -~ :
impact speed) 56.4 ft. lbs.
(uyrlatup instrurnentecl impact) ,~ .
Notched Izod: ~ 3/16" th-ickness 2.1 ft lbs/in.
1 0 '"' '' '" "
For the control blerlcl ...
Flexura].rncdulus:342 000 psi lenslle strerl~th: 9 700 psi lS Elongati.on: 25%
Nothced Izod: @ 3~16" thickncss 1.& ft. lbs/in.
Impact energy to break (@ 12 ft./sec.
irnpact speed) (r)ynatup) 2.8 ft. ::
lbs./in.
.'.''''' ,`'` '."';
Ex~ e 2 This experiment was done with a one--pass :~:
operation in the twi~screw extruder with downstream caddition of nylon ~ to the rnodified ~BS rnelt.
49.~ parts ~BS powder (~lendex 201? was rnixed :~
with 0.5 parts of maleic anhydride and extruded on a corotating twin screw extruder (2~ nrrl leistritz? wi.th Zone 1 at 1~0C Zone 2 at l90G Zone 3 at 220C. ~t ~one 4 set at 2~0UC 50 parts oF arrline te.rrrlinated ~.-nylon 6 ~Fn~ - ~3; Larnine~ - /2 rneq g ) was added. .;;
Zones 6-10 were set at 230G. The extrusion of the .;.~:.
rnelt blend was carried out at ~ rate of 15.3 lbs/hr arld ~ 2(~) ~ 3~ J~ ~
250 rpm screlA~ speecl. rh~? bl.~.!ncl extru(late was coo~l.ecl, pel].etizecl arlcl clri~cl, ~~rhe clri.e~ f)~ rlylc~n fi blend pellets were Lnjf3ct-lon moldecl .into starlclard -tenslle arld flexural test bars. ~ control exarrlple WclS 5irrli.larly cvnducted -in the absence of grAfting ay~ t.
Ex. 2 _~rafted2Contr~1 (ungraft~?cl) Flex. modulus 337,000 psi 356,000 ~.. :.
Tensile strencJth9,400 ~,000 Elongation at break 245 28 ' ' (%) Notched Izod l.6 l.3 (ft lbs/in ~ 3/l6" th.i.ckness) Exarnple ~
4~.~ parts of ~BS powcler, 0.5 parts of maleic Anhydride and 0.05 parts ot dicumyl peroxide were rnixed and extruded on a 2~ mm, corotating Leistritz, twinscrew extruder with Zone l set at 2V0U. 20ne 2 at : :.
2lOC, Zone 3 set at 240C. ~t .Zone 4 which was j ''.
maintained at 235C, 5 parts of rnaleated ethylene--propylen~ rubber (Exxon's MD~ 746, ethylene~propylene ratio 47/53; 0.4% rnaleic anhydride, Mooney viscosity , 25) was charged and the blen~ was extruded with the rernaining zones (Zone 5-lO set at 250~C) at a screw speed of 150 rpm and throughput of 15.6 lbs/hr. This EP rubber blended, maleic anhydride , 30 yrafted ~BS (50 parts) was n~ixed with 50 parts of amine `'.
terminated ny'lon 6 (F~ 5~; Lamine~ r- '7~ rneq 9 and extruded on a l" singlR screw extrwder (Killion, ~D
_ 30) equippe.d with Maddox mixirly screw at 50U~E 50 rprn and fi.~ lbs~hr. throuyhput rate. The blended ~xtrudate '~
was coo'led, pel:Letized arld dr^ied~ 'I~he blend pe'l'lets i,. ~, "';.,''~'.'.','.
~'",', 133~
2~
were inject:i.on mol.decl into stan(:larcl t:en~.i.le and :' f'].exural test bars The notched Izocl of this ~BS--nylon , '-~ .
b:lend was 14.1 ft.'lbs~in. (:3/l6" th-lck test bars).
..:'~,' ' ~
Flexural rrlodu].us:288,000 psi - .'~.. -.;' 5 'I'ensile strength:8,10U psi Elongation to breal<: 231% i-:~
'. ~ ~. '' E~xample This experiment was performed on a 28 rnm "'. .::~
co-rotatirlg twin screw extruder (Leistritz, LtD = 40) equippecl with an intensi~e mixing screw ancl a ' .'~
downstrearn feed port in the 4th zone. ~a ~.
89 parts of ~BS powder (Borg~Warner ~lendex~201) '~
was dry blended with 1 part of rnaleic anhydride (M~
then extruded on the twin screw extruder with 10 parts rna`leated ethylene-propy:lerle rubber (Exxon MD~ r/46, E/P
ratio 47/53, 0.4% M~, Mooney ~is~osity _. 25~ added via 20 the downstrearn feed port. -Ihis rnixture was extruded at '~
250 rprrl with a temp profile of 180, 1~0, 220, 220, 220, .-~
230, 23~, 23~, 230, 230~C (~ones l-lOj at a rate of .;
17.5 lb~hr. The resulting maleated ~BS/EPR blend was .
water coo'led and pelletized. ;p~
50 parts of dried maleated ~S--EPR blend pellets was extruded on the twin screw ex~ruder with 50 par~s . :
of amine terminated nylon 6 (F~U = 58, arnine .
equi~alents ~ 72 meq~g) added ~ia the downstrearn feed '~
, 30 port. This grafted blend was extruded at 200 rpm with ;~
a temp profile of 215, 250, 230, 250, 250, 250, 250, 250, 250, 250C {Zones 1--10~ at a rate of 22 lb~hr.
l'he resulting ~BS~EPR~N6 grafted blend was water cooled and pelletized.
~'-"'' ' '' ':' ' .:.~ .',:`
~`' ~ 3 3 ~
~ otchecl ]:zocl (f't. I.h/in) ~1 23~C = ~.3' flex rnodulus (10 ps.i) = 28r/; f1eX strength llO psi) ,-9.~; tensile rnodulus ~103 psi) - 38r/; -tens.ile strength (10 psi.) _ 8.5; elongation at break 122%.
Com~arati~e Exarrlp'le.
. __, ___ .. _.. _ . ___ ~ , 90 parts ~S powcler (Borg~Warner Blend~x 201) was extrucled on a 28rnrrl co rotati.rly -twin scrtJw extruder (Leistriz, LJL) . 40~ at 250 RPM with a terrlp. profi.le of lU~ 0, 2l~ 3~ 3~, 230, ~30, ~0, ~0, 220C j.
(zones 1-10) at 1~ LB~HR with 10 parts maleated ,'~
ethy'lene-propylene rubber (~xxon MO'v r/l~ ~ E/P ratio -47/53, 0.4% M~, MoonRy viscosity _. 25) addRd at the 5th';~
zone. This ~ rubber blencl was cooled and '~
pelletizecl.
50 parts of the ~MSJEP rubber blended pellets ~', was dry blended with 50 parts arnine terrninated nylon 6 (F~ = 58, aminR eqwivalents = 72 meg/g) and extruded '~
or a 1" single screw extruder (killion KL~-100, L/D ~
30) equipped with a maddox mixing scr~w. The kl~nd was extruded at 50 RPM, heated at 400, ~00, 510, ~00F
(zones 1-4), with a throughpwt rate of 52g/min. The resu'lting ~S/N6 EP rubber mixture was cooled and ,.
25 pelletized. ~fter drying the pellets WerR injection ,~
molded irlto standard flexural and tensi'le test bars.
.- .. . :
RT NotchRd Izod = 3.8 FT-L~/IN
1~ensi'1e Strength = 8,~00 psi ~';,''''', 3Q E].ongation - 14%
This comparati~e ExamplR illustrates the neecl for maleation of the ~S to get a mylon blend product ,.,'~
with a high elongation. Maleated EPR in unmaleated ~BS
does not result in a product with high elongation.
''~' :',','.,'.''', ~'.~ '`'.'~'"
..", .:: ' .
.; ~;.. .
Exarr~le 5 :' .
........... ....... ......... .
~ 8 parts of comnle~rcial nB5 pel.lets (Borg-Warn~r, Çycolac LlOOo) were rnixed with 2 parts of rnaleic anhydricle ~ncl the mixtwre was extruclecl on a on~-~inch single screw extruder (Wayrle L/D -. 25 to l) a-t 225Ç
and about 5 lbs/hr throughput rate. The extruclate was -~ ~, water coc;led and pelle-tizeci. lhe pellets were clried at 80O0 under ~acuurrl for 15 hrs. The moclifiecl nB~s (50 :
parts) was mixecl with ~o parts of arrline terrrlirlated ' . ~, ny'lon 6 ( r n~J ~ J~3, amirle eql,liva'lents ~ meq ~
and ext.ruclecl on the sarrle extruder at 250C, The ~h:.
resu1ting ~BS-ny'lon gra~'ted blend was pel.letize~d and dri~d, rhe properties of the inject-lon moldecl blend were: Flex~lral rnod~l1us ~ ,000 ps-i; Flexural ::
strength _ ~,'300 psi; tensile strength a ~ ~ ~00 psi;
tensi,le elongatior~ at break ._ 22 Exam~le 6 .
Th-i.s experiment was performed on a l" single screw extruder (Killion KL--100, L~D - 30) in three ,'~, steps, The extruder was eq~ippecl with a Maddox mixing screw for each step, ;,;.
99 parts of Blendex 201 nBs powder (Borg-Warner, ~: :
7.1 ft. lb~in notched :Lzod) was dry blended with 1 part ~ ' ' maleic anhydride (M~), then extruded at 40 rpm on the ' .'' 1" extruder heated to 300, 3S0, 400, 400"F ('~ones 1-4~
at a rate of 25 gJrnin, This grafted ~BS was water ~ :' , 30 c,ooled and pel^letized, ~;
~0 parts of maleated ~BS pel].ets were dry ,.
b'lended with lO parts ethylene--ethy'l acrylate--rna'leic anhydride terpolymer (Lotador ~040, CDF chimie) then 35 extruded at ~0 rprn on the l" extruder heated to ~U0, ''' '.
425, 4S0, 4S0F tZones 1-4) at a rate of 4~ g/min, The M~-g-~S~rubber blend was water cooled and pelletized, 50 parts of maleated ABS/rubber blend pellets were dry blended with 50 parts o~ amine terminated nylon 6 pellets (FAV = 58, amine equivalents - 72 meq/g) and extruded at 50 rpm on the 1" extruder heated to 400, 500, 500, 500F (Zones 1-4) at a rate of 49 g/min. The resulting ABS/rubber/N6 grafted blend (45/5/50) was water cooled and pelletized.
Dried pellets were injection molded into standard tensile and flexural test bars. The following - `~
results were obtained: Notched Izod (ft. lb/in) @ 23C
= 1.6: flex modulus tlO psi) = 298; flex strength -9.6; tensile modulus (103 psi) = 340; tensile strength = 8.3; elon~ation at brea~ = 11%.
Example 7 . ~., .
This experimen~ was performed on a 1" single ~ `
screw extruder (Killiion KL-100, L/D = 30) in two steps. The extruder was equipped with a Maddox mixing ~-~
20 screw for each step. ;
98.8 parts of ethylene-propylene rubber grafted SAN copolymer ~OSA, Rove ~701, Dow) lightly coated with mineral oil ( 1%) then dry blended with 1 part maleic ~;
anhydride (MA) and 0.2 parts dicumyl peroxide (DCP).
This mixture was extruded at 40 rpm on tha 1" extruder `
heated to 300, 350, 400, 400F (Zones 1-4) at a rate of ~
40 g/min. The resulting grafted Rovel strand was water ;~ -cooled and pelletized. ~ ~
' ` -`, 50 parts of the dried maleated OSA pellets were ~ `~
dry blended with 50 parts of amine terminated nylon 6 ,-~
pellets (FAV = 58, amine eguivalents = 72 meq~g) and extruded at 50 rpm on the 1" extruder heated to 450, -500, 500, 500F (Zones 1-4) at a rate of 45 g/min. The resulting OSA~nylon grafted blend was water cooled and pelletized (A~
~ ~31 ~ ~
~ h].encl wi.thol,lt the peroxlcle -ln:i.t:i.ator (~Ci)) was preparecl :i.n the sarrle fashion. Pellets of both blencls were cdried then lnjectiorl rnoldecl into starld~rcl tensi and flexural test barcls (B).
l-he following reslllts were ~Ibta.il7ecl:
7f! Y~
RT Notched Izod (ft. lb/in) 2.2 O.S ', l'ensile Strerlgth (103 psi) ;3.3 7.7 E],ongation at Break 107% l~% ., . ~' - ,' Ex_rlpl,,~e,~
This experirrlent was performecl on a :I" single screw extruder (Ki.. L'lion KL-lOV, liV 30~ in three ' ', steps. l'he extrucler was equippecl with a Maddox mixiny screw for each step.
98.9 parts of Mobil 5600 high impact polystyr~ne (H'IP~ was light'ly coated with rnineral oil ( 1%) then ,': ' clry blencled with 1 part maleic anhydride (M~) and 0.1 part dicurnyl peroxide (I~CP). -I'his rnixture was extruded at 50 rprn on the 1" extrwder, heated to 300, 330, ~00, .
210~ (Zones 1-4) at a rate of 23 g/min. l'he resulting grafted HIPS strand was water coolecl and pe].letized.
90 parts of the dried rnaleated HIPS pellets were dry blended with 10 parts maleated ethylene--propylene rubber (Exxon MUV 746, E/P ratio _ 47/53, 0.4% M~
Mooney ~iscosity - 25) then extruded at 4n rpm on the :' 1" extruder heated to ~00, 425, 4~0, ~60~ ones 1-4) at a rate of 42 g~min. The result-i.ng rnaleated HIPS/EP , ~
rubber blend was w~ter cooled arld pe'l.letized. : ~, :' 3 3. ~
50 parts of clr-.i.ecl ma].eatc-!cl ~IIPS/E.:PR bl.encl pel1ets was clry blerlclc!cl w-.it:h 50 parts of amine terrninated ny10n 6 pellets (f~ arrlirle equ-i~a1ellti = '~2 meq/g) ancl extrucled at S0 rprrl on the l" extrucler heated 400 ~0~ 5~ oo<~l (Z.orles 1-4) at ~ rate c)f : . .
5 50 g~mln. lhe resu1ting ~lIPSJEPRfN6 graftecl b].encl ~.' :.--. :
(45/S/~j~) was w~ter coo1ed arld pe1'1rtizecl (#8n)~
~ b1erld without the peroxide ini.t-.iator (D~P) was prepared in the same fashion (#~ el1r!ts of' both '~
10 blencls were clriecl then i.njection rno1clecl into stanclarcl tensile and flexural test barcls. 'I'he fo110wing results wer~ obtainecl~
8n 8B ' '`'~"
Notched Izocl (ft. lb./in) ~23~C 1.5 0 5 :-.~
Flex Modu1us (lO psi) 257 242 . .' `.
; Flex ~trength 8.0 6.l Terlsile Modu1us (lO psi) 289 267 ;~:~:';';'~;"
: 20 'I'ensi'le Strength 6.6 4 ~
E:longation at Rreak 18~ 2%
~x~rn~LQ~
~7.2 parts of ~BS powder (~1enclex 201 Borg-Warner~ was mixed with 0.1 parts of dicurrly1 ''``.. ';. ' peroxicle and extrwcled on a l" sing1e screw extruder '.. --(~i11ion) while sirnultaneously injec-ting into the rnolten ~BS 2.7 parts o~ l:l mixture oF styrene and ."''~-.
N-rnethacryloyl capro1actarrl via a liquid injec-tor assembly attached to the extruder at approximate1y the i'`~:`.' rniddle portion of the screw. 'l'he liquid injector .'`' consisted of a single piston a precision metering purn `~
(Model ~-30-~ ~lder 1aboratories San Car10s '~
35 Calfornia~ with r nominal flow rrte range of 0.05 -- 1.5 ~ ~
'-' .''~'. ..
''~'.~'.''~;;' ' ~33~
27- !
ml/min and a maximum pressure rating of 5000 psi. The temperatures of Zones 1 to 4 of the extruder were maintained at 177C, 205C, 230C and 230C
repsectively. The overall throughput rate of the extrudate was about 30 g/min. The extrudate consisting of Cunctionalized ABS was cooled, pelletized and dried.
50 parts of the functionalized ABS was mixed with 50 parts of amine terminated nylon 6 (FAV = 58) and extruded on the same extruder at 260C at a throughput rate of 42 g/min. The ABS-nylon blend ex~rudate was cooled, pelletizecl and dried. The dried blend product was injection molded into standard A5TM ~ ~
tensile and flexural bars. ;
RT Notched Izod = 2.1 FT-LB/IN
Tensile Strength = 8,600 PSI
Elongation - 15%
ExamPle 10 This experiment was carried out on a 28 mm co-ro~ating, twin screw extruder (Leistritz, 40 = 40) `~
equipped with a modified mixing screw and a downstream feed port in the 7th zone.
44.5 parts of eth ~ene-propylene rubber grafted ~;
SAN copolymer ~OSA, Rove 01, Dow) and 5 parts maleated ethylene-propylene rubber (Exxon MDV 746, E/P
ratio 47/53, 0.4% M~, Mooney viscosity = 25), lightly coated with mineral oil ( 1%), were dry blended with 0.4 parts maleic anhydride and 0.1 parts dicumyl peroxide. This mixture was extruded at 150 rpm with a `~
temp profile of 200, 235, 250, 220, 240C (Zones 1-5), '- ,' ' 2500C (Zon~?s 6-10) at a rate oE :l5 :L~/hr with so parts arni.ne ternli.natecl nylon 6 (F~U _ 58, amine equ~ alents =
72 rneqJg) aclcled ~ia the clownstrearn feed port. rhe reswlt-ing OS~/nylon 6 graftecl blencl Wc15 cool~cl ancl pelleti.zed. The blencl pellets were clried and injection molcled into nSTM standarcl test bars. The RT notchecl lzod (1/4" thick) was 14.4 ft. lb/irl; tensile strength .::
was 7,700 psi, elongcltiorl at break was 133%; fle~ural modulus was 2~1,0ljV psi. .:`
~xarrlple 11 ~ . This exarrlple i:l.lustrates the use of graft coup:Lirlg agerlts for ~ 'EI blencl.
{~ parts of po].yethylene terephthalate (I.~
0.68; Lcarboxyl~ = V.034 meq./g ) was rnixecl with l part of m--phenylene bisoxazoline (Takeda, Japan) ancl extrudecl at 2~0C~C on a co-rotating twin--screw extrucle.r ~28 mm, Leistrit~) at 21 lbs/hr throughput rate. The 20 resu1ting procluct was l'~T whose carboxyl groups were .
essentially capped with oxazoline rnoiety ( [carboxyl] =
0.004 meqg ) 50 parts of these 'moclifiecl' PET ~ ~
pellets were mixed with 50 parts maleated ~iS ~from :-;.. ~.
example l) and extruded on the same twin-screw extruder at 230(` at 12.~ lbs/hr throughput rate. The blend extrudate was pelleti.zed, driecl and injeGtion molded into standard tensile and f1ex~lral bars.
B. ~ control blend was rnade by melt blending a 30 Irtixture of ~o parts of urlmodifi.ed ~S arld unrnodifi~d .~
I~ET ~0.68 I.~.) and extruding urlder sirn-ilar conditions. :.
35 Notched Izod (ft lbs~In) 1.3 9 ~,;.:.
Tensi].e Modulus (lO psi) 317 321 Tensile Strength (lO psi) 8 Elongation at break (%) 36 20 ;~ ~.
. ~,,;.
,',;.,- ~,.
5~` 5~f~
L33:3 f~ll ... 2 txa¢!P:le l?
. ~ powdL!r--pell~!t rrllx-t~ oF too typL!s oF ~E3S
~lendex 201 and cycolac SM lO00 (3:l ratio) was fed into the throat of a l" Klllion extrucler eluippecl with 5 a liquid ir1jectior1 port. 2--isopropenyl oxazol.ine (r)ow) ~:
was inject~-cl into the rnelt oF ~E1S at a rate of l.759/rnin while the ~BS was ex-trud~d at a rate oF
25y/min. The mL~lt t~!mperatures w~re maintair)ecl b~tween 240C-260C whil~ di~ pressure of 3V0 psi was noted at ~ screw speed oF S0 rpm. The modifiecl nE~S was cooled ancd pellet-lzecl anci dr:ied. PET (I.U. _ o~r~) was rnel-t . ~.
blencled with 4 wt% of low molecular weight ethylene~-acrylic ac.id copolyrn~r neutrall2ed with sodiurn (hclyn Ionorner wax hllied) adcled as a preferrecl 15 nucleator for pEr~ lhis nucleated ~EI was prepared in ~:~
a single screw extruder pelletizecd and dried. 50 ; .
parts of nucleated ~ T was rnixed with 50 parts of the oxazoline-modified h5S and extruded on l" killi.on -~
extruder while nnaintaining melt ternperatures between 240C-260C. The extruded blend was cooled pcllctized and cdried. ;~
B. ~ control blencl was prepar~d with the same nucleated PET with unmodified ~BS under sirnilar ccnditions. The two hl~nds were injection molded at a melt ternperature of ~2SG and mold ternperature of 40C
into standard tensile and flexure bars. The samples were then annealed at 160C for 4 hours and the ~ ;M
followiny properties were obtained~
( C o n t r o 'l T~nsile Str~ngth (lO psi) 8.06 6.01 Tensile Modulus (lO psi) 352 333 .~.
35 Elongation (%~ 2.5 l.8 ~
Izod Impact (Unnotched~ 3.2 l.5 ~ ~.
Ift lbs~In) ' ~ .
2lOC, Zone 3 set at 240C. ~t .Zone 4 which was j ''.
maintained at 235C, 5 parts of rnaleated ethylene--propylen~ rubber (Exxon's MD~ 746, ethylene~propylene ratio 47/53; 0.4% rnaleic anhydride, Mooney viscosity , 25) was charged and the blen~ was extruded with the rernaining zones (Zone 5-lO set at 250~C) at a screw speed of 150 rpm and throughput of 15.6 lbs/hr. This EP rubber blended, maleic anhydride , 30 yrafted ~BS (50 parts) was n~ixed with 50 parts of amine `'.
terminated ny'lon 6 (F~ 5~; Lamine~ r- '7~ rneq 9 and extruded on a l" singlR screw extrwder (Killion, ~D
_ 30) equippe.d with Maddox mixirly screw at 50U~E 50 rprn and fi.~ lbs~hr. throuyhput rate. The blended ~xtrudate '~
was coo'led, pel:Letized arld dr^ied~ 'I~he blend pe'l'lets i,. ~, "';.,''~'.'.','.
~'",', 133~
2~
were inject:i.on mol.decl into stan(:larcl t:en~.i.le and :' f'].exural test bars The notched Izocl of this ~BS--nylon , '-~ .
b:lend was 14.1 ft.'lbs~in. (:3/l6" th-lck test bars).
..:'~,' ' ~
Flexural rrlodu].us:288,000 psi - .'~.. -.;' 5 'I'ensile strength:8,10U psi Elongation to breal<: 231% i-:~
'. ~ ~. '' E~xample This experiment was performed on a 28 rnm "'. .::~
co-rotatirlg twin screw extruder (Leistritz, LtD = 40) equippecl with an intensi~e mixing screw ancl a ' .'~
downstrearn feed port in the 4th zone. ~a ~.
89 parts of ~BS powder (Borg~Warner ~lendex~201) '~
was dry blended with 1 part of rnaleic anhydride (M~
then extruded on the twin screw extruder with 10 parts rna`leated ethylene-propy:lerle rubber (Exxon MD~ r/46, E/P
ratio 47/53, 0.4% M~, Mooney ~is~osity _. 25~ added via 20 the downstrearn feed port. -Ihis rnixture was extruded at '~
250 rprrl with a temp profile of 180, 1~0, 220, 220, 220, .-~
230, 23~, 23~, 230, 230~C (~ones l-lOj at a rate of .;
17.5 lb~hr. The resulting maleated ~BS/EPR blend was .
water coo'led and pelletized. ;p~
50 parts of dried maleated ~S--EPR blend pellets was extruded on the twin screw ex~ruder with 50 par~s . :
of amine terminated nylon 6 (F~U = 58, arnine .
equi~alents ~ 72 meq~g) added ~ia the downstrearn feed '~
, 30 port. This grafted blend was extruded at 200 rpm with ;~
a temp profile of 215, 250, 230, 250, 250, 250, 250, 250, 250, 250C {Zones 1--10~ at a rate of 22 lb~hr.
l'he resulting ~BS~EPR~N6 grafted blend was water cooled and pelletized.
~'-"'' ' '' ':' ' .:.~ .',:`
~`' ~ 3 3 ~
~ otchecl ]:zocl (f't. I.h/in) ~1 23~C = ~.3' flex rnodulus (10 ps.i) = 28r/; f1eX strength llO psi) ,-9.~; tensile rnodulus ~103 psi) - 38r/; -tens.ile strength (10 psi.) _ 8.5; elongation at break 122%.
Com~arati~e Exarrlp'le.
. __, ___ .. _.. _ . ___ ~ , 90 parts ~S powcler (Borg~Warner Blend~x 201) was extrucled on a 28rnrrl co rotati.rly -twin scrtJw extruder (Leistriz, LJL) . 40~ at 250 RPM with a terrlp. profi.le of lU~ 0, 2l~ 3~ 3~, 230, ~30, ~0, ~0, 220C j.
(zones 1-10) at 1~ LB~HR with 10 parts maleated ,'~
ethy'lene-propylene rubber (~xxon MO'v r/l~ ~ E/P ratio -47/53, 0.4% M~, MoonRy viscosity _. 25) addRd at the 5th';~
zone. This ~ rubber blencl was cooled and '~
pelletizecl.
50 parts of the ~MSJEP rubber blended pellets ~', was dry blended with 50 parts arnine terrninated nylon 6 (F~ = 58, aminR eqwivalents = 72 meg/g) and extruded '~
or a 1" single screw extruder (killion KL~-100, L/D ~
30) equipped with a maddox mixing scr~w. The kl~nd was extruded at 50 RPM, heated at 400, ~00, 510, ~00F
(zones 1-4), with a throughpwt rate of 52g/min. The resu'lting ~S/N6 EP rubber mixture was cooled and ,.
25 pelletized. ~fter drying the pellets WerR injection ,~
molded irlto standard flexural and tensi'le test bars.
.- .. . :
RT NotchRd Izod = 3.8 FT-L~/IN
1~ensi'1e Strength = 8,~00 psi ~';,''''', 3Q E].ongation - 14%
This comparati~e ExamplR illustrates the neecl for maleation of the ~S to get a mylon blend product ,.,'~
with a high elongation. Maleated EPR in unmaleated ~BS
does not result in a product with high elongation.
''~' :',','.,'.''', ~'.~ '`'.'~'"
..", .:: ' .
.; ~;.. .
Exarr~le 5 :' .
........... ....... ......... .
~ 8 parts of comnle~rcial nB5 pel.lets (Borg-Warn~r, Çycolac LlOOo) were rnixed with 2 parts of rnaleic anhydricle ~ncl the mixtwre was extruclecl on a on~-~inch single screw extruder (Wayrle L/D -. 25 to l) a-t 225Ç
and about 5 lbs/hr throughput rate. The extruclate was -~ ~, water coc;led and pelle-tizeci. lhe pellets were clried at 80O0 under ~acuurrl for 15 hrs. The moclifiecl nB~s (50 :
parts) was mixecl with ~o parts of arrline terrrlirlated ' . ~, ny'lon 6 ( r n~J ~ J~3, amirle eql,liva'lents ~ meq ~
and ext.ruclecl on the sarrle extruder at 250C, The ~h:.
resu1ting ~BS-ny'lon gra~'ted blend was pel.letize~d and dri~d, rhe properties of the inject-lon moldecl blend were: Flex~lral rnod~l1us ~ ,000 ps-i; Flexural ::
strength _ ~,'300 psi; tensile strength a ~ ~ ~00 psi;
tensi,le elongatior~ at break ._ 22 Exam~le 6 .
Th-i.s experiment was performed on a l" single screw extruder (Killion KL--100, L~D - 30) in three ,'~, steps, The extruder was eq~ippecl with a Maddox mixing screw for each step, ;,;.
99 parts of Blendex 201 nBs powder (Borg-Warner, ~: :
7.1 ft. lb~in notched :Lzod) was dry blended with 1 part ~ ' ' maleic anhydride (M~), then extruded at 40 rpm on the ' .'' 1" extruder heated to 300, 3S0, 400, 400"F ('~ones 1-4~
at a rate of 25 gJrnin, This grafted ~BS was water ~ :' , 30 c,ooled and pel^letized, ~;
~0 parts of maleated ~BS pel].ets were dry ,.
b'lended with lO parts ethylene--ethy'l acrylate--rna'leic anhydride terpolymer (Lotador ~040, CDF chimie) then 35 extruded at ~0 rprn on the l" extruder heated to ~U0, ''' '.
425, 4S0, 4S0F tZones 1-4) at a rate of 4~ g/min, The M~-g-~S~rubber blend was water cooled and pelletized, 50 parts of maleated ABS/rubber blend pellets were dry blended with 50 parts o~ amine terminated nylon 6 pellets (FAV = 58, amine equivalents - 72 meq/g) and extruded at 50 rpm on the 1" extruder heated to 400, 500, 500, 500F (Zones 1-4) at a rate of 49 g/min. The resulting ABS/rubber/N6 grafted blend (45/5/50) was water cooled and pelletized.
Dried pellets were injection molded into standard tensile and flexural test bars. The following - `~
results were obtained: Notched Izod (ft. lb/in) @ 23C
= 1.6: flex modulus tlO psi) = 298; flex strength -9.6; tensile modulus (103 psi) = 340; tensile strength = 8.3; elon~ation at brea~ = 11%.
Example 7 . ~., .
This experimen~ was performed on a 1" single ~ `
screw extruder (Killiion KL-100, L/D = 30) in two steps. The extruder was equipped with a Maddox mixing ~-~
20 screw for each step. ;
98.8 parts of ethylene-propylene rubber grafted SAN copolymer ~OSA, Rove ~701, Dow) lightly coated with mineral oil ( 1%) then dry blended with 1 part maleic ~;
anhydride (MA) and 0.2 parts dicumyl peroxide (DCP).
This mixture was extruded at 40 rpm on tha 1" extruder `
heated to 300, 350, 400, 400F (Zones 1-4) at a rate of ~
40 g/min. The resulting grafted Rovel strand was water ;~ -cooled and pelletized. ~ ~
' ` -`, 50 parts of the dried maleated OSA pellets were ~ `~
dry blended with 50 parts of amine terminated nylon 6 ,-~
pellets (FAV = 58, amine eguivalents = 72 meq~g) and extruded at 50 rpm on the 1" extruder heated to 450, -500, 500, 500F (Zones 1-4) at a rate of 45 g/min. The resulting OSA~nylon grafted blend was water cooled and pelletized (A~
~ ~31 ~ ~
~ h].encl wi.thol,lt the peroxlcle -ln:i.t:i.ator (~Ci)) was preparecl :i.n the sarrle fashion. Pellets of both blencls were cdried then lnjectiorl rnoldecl into starld~rcl tensi and flexural test barcls (B).
l-he following reslllts were ~Ibta.il7ecl:
7f! Y~
RT Notched Izod (ft. lb/in) 2.2 O.S ', l'ensile Strerlgth (103 psi) ;3.3 7.7 E],ongation at Break 107% l~% ., . ~' - ,' Ex_rlpl,,~e,~
This experirrlent was performecl on a :I" single screw extruder (Ki.. L'lion KL-lOV, liV 30~ in three ' ', steps. l'he extrucler was equippecl with a Maddox mixiny screw for each step.
98.9 parts of Mobil 5600 high impact polystyr~ne (H'IP~ was light'ly coated with rnineral oil ( 1%) then ,': ' clry blencled with 1 part maleic anhydride (M~) and 0.1 part dicurnyl peroxide (I~CP). -I'his rnixture was extruded at 50 rprn on the 1" extrwder, heated to 300, 330, ~00, .
210~ (Zones 1-4) at a rate of 23 g/min. l'he resulting grafted HIPS strand was water coolecl and pe].letized.
90 parts of the dried rnaleated HIPS pellets were dry blended with 10 parts maleated ethylene--propylene rubber (Exxon MUV 746, E/P ratio _ 47/53, 0.4% M~
Mooney ~iscosity - 25) then extruded at 4n rpm on the :' 1" extruder heated to ~00, 425, 4~0, ~60~ ones 1-4) at a rate of 42 g~min. The result-i.ng rnaleated HIPS/EP , ~
rubber blend was w~ter cooled arld pe'l.letized. : ~, :' 3 3. ~
50 parts of clr-.i.ecl ma].eatc-!cl ~IIPS/E.:PR bl.encl pel1ets was clry blerlclc!cl w-.it:h 50 parts of amine terrninated ny10n 6 pellets (f~ arrlirle equ-i~a1ellti = '~2 meq/g) ancl extrucled at S0 rprrl on the l" extrucler heated 400 ~0~ 5~ oo<~l (Z.orles 1-4) at ~ rate c)f : . .
5 50 g~mln. lhe resu1ting ~lIPSJEPRfN6 graftecl b].encl ~.' :.--. :
(45/S/~j~) was w~ter coo1ed arld pe1'1rtizecl (#8n)~
~ b1erld without the peroxide ini.t-.iator (D~P) was prepared in the same fashion (#~ el1r!ts of' both '~
10 blencls were clriecl then i.njection rno1clecl into stanclarcl tensile and flexural test barcls. 'I'he fo110wing results wer~ obtainecl~
8n 8B ' '`'~"
Notched Izocl (ft. lb./in) ~23~C 1.5 0 5 :-.~
Flex Modu1us (lO psi) 257 242 . .' `.
; Flex ~trength 8.0 6.l Terlsile Modu1us (lO psi) 289 267 ;~:~:';';'~;"
: 20 'I'ensi'le Strength 6.6 4 ~
E:longation at Rreak 18~ 2%
~x~rn~LQ~
~7.2 parts of ~BS powder (~1enclex 201 Borg-Warner~ was mixed with 0.1 parts of dicurrly1 ''``.. ';. ' peroxicle and extrwcled on a l" sing1e screw extruder '.. --(~i11ion) while sirnultaneously injec-ting into the rnolten ~BS 2.7 parts o~ l:l mixture oF styrene and ."''~-.
N-rnethacryloyl capro1actarrl via a liquid injec-tor assembly attached to the extruder at approximate1y the i'`~:`.' rniddle portion of the screw. 'l'he liquid injector .'`' consisted of a single piston a precision metering purn `~
(Model ~-30-~ ~lder 1aboratories San Car10s '~
35 Calfornia~ with r nominal flow rrte range of 0.05 -- 1.5 ~ ~
'-' .''~'. ..
''~'.~'.''~;;' ' ~33~
27- !
ml/min and a maximum pressure rating of 5000 psi. The temperatures of Zones 1 to 4 of the extruder were maintained at 177C, 205C, 230C and 230C
repsectively. The overall throughput rate of the extrudate was about 30 g/min. The extrudate consisting of Cunctionalized ABS was cooled, pelletized and dried.
50 parts of the functionalized ABS was mixed with 50 parts of amine terminated nylon 6 (FAV = 58) and extruded on the same extruder at 260C at a throughput rate of 42 g/min. The ABS-nylon blend ex~rudate was cooled, pelletizecl and dried. The dried blend product was injection molded into standard A5TM ~ ~
tensile and flexural bars. ;
RT Notched Izod = 2.1 FT-LB/IN
Tensile Strength = 8,600 PSI
Elongation - 15%
ExamPle 10 This experiment was carried out on a 28 mm co-ro~ating, twin screw extruder (Leistritz, 40 = 40) `~
equipped with a modified mixing screw and a downstream feed port in the 7th zone.
44.5 parts of eth ~ene-propylene rubber grafted ~;
SAN copolymer ~OSA, Rove 01, Dow) and 5 parts maleated ethylene-propylene rubber (Exxon MDV 746, E/P
ratio 47/53, 0.4% M~, Mooney viscosity = 25), lightly coated with mineral oil ( 1%), were dry blended with 0.4 parts maleic anhydride and 0.1 parts dicumyl peroxide. This mixture was extruded at 150 rpm with a `~
temp profile of 200, 235, 250, 220, 240C (Zones 1-5), '- ,' ' 2500C (Zon~?s 6-10) at a rate oE :l5 :L~/hr with so parts arni.ne ternli.natecl nylon 6 (F~U _ 58, amine equ~ alents =
72 rneqJg) aclcled ~ia the clownstrearn feed port. rhe reswlt-ing OS~/nylon 6 graftecl blencl Wc15 cool~cl ancl pelleti.zed. The blencl pellets were clried and injection molcled into nSTM standarcl test bars. The RT notchecl lzod (1/4" thick) was 14.4 ft. lb/irl; tensile strength .::
was 7,700 psi, elongcltiorl at break was 133%; fle~ural modulus was 2~1,0ljV psi. .:`
~xarrlple 11 ~ . This exarrlple i:l.lustrates the use of graft coup:Lirlg agerlts for ~ 'EI blencl.
{~ parts of po].yethylene terephthalate (I.~
0.68; Lcarboxyl~ = V.034 meq./g ) was rnixecl with l part of m--phenylene bisoxazoline (Takeda, Japan) ancl extrudecl at 2~0C~C on a co-rotating twin--screw extrucle.r ~28 mm, Leistrit~) at 21 lbs/hr throughput rate. The 20 resu1ting procluct was l'~T whose carboxyl groups were .
essentially capped with oxazoline rnoiety ( [carboxyl] =
0.004 meqg ) 50 parts of these 'moclifiecl' PET ~ ~
pellets were mixed with 50 parts maleated ~iS ~from :-;.. ~.
example l) and extruded on the same twin-screw extruder at 230(` at 12.~ lbs/hr throughput rate. The blend extrudate was pelleti.zed, driecl and injeGtion molded into standard tensile and f1ex~lral bars.
B. ~ control blend was rnade by melt blending a 30 Irtixture of ~o parts of urlmodifi.ed ~S arld unrnodifi~d .~
I~ET ~0.68 I.~.) and extruding urlder sirn-ilar conditions. :.
35 Notched Izod (ft lbs~In) 1.3 9 ~,;.:.
Tensi].e Modulus (lO psi) 317 321 Tensile Strength (lO psi) 8 Elongation at break (%) 36 20 ;~ ~.
. ~,,;.
,',;.,- ~,.
5~` 5~f~
L33:3 f~ll ... 2 txa¢!P:le l?
. ~ powdL!r--pell~!t rrllx-t~ oF too typL!s oF ~E3S
~lendex 201 and cycolac SM lO00 (3:l ratio) was fed into the throat of a l" Klllion extrucler eluippecl with 5 a liquid ir1jectior1 port. 2--isopropenyl oxazol.ine (r)ow) ~:
was inject~-cl into the rnelt oF ~E1S at a rate of l.759/rnin while the ~BS was ex-trud~d at a rate oF
25y/min. The mL~lt t~!mperatures w~re maintair)ecl b~tween 240C-260C whil~ di~ pressure of 3V0 psi was noted at ~ screw speed oF S0 rpm. The modifiecl nE~S was cooled ancd pellet-lzecl anci dr:ied. PET (I.U. _ o~r~) was rnel-t . ~.
blencled with 4 wt% of low molecular weight ethylene~-acrylic ac.id copolyrn~r neutrall2ed with sodiurn (hclyn Ionorner wax hllied) adcled as a preferrecl 15 nucleator for pEr~ lhis nucleated ~EI was prepared in ~:~
a single screw extruder pelletizecd and dried. 50 ; .
parts of nucleated ~ T was rnixed with 50 parts of the oxazoline-modified h5S and extruded on l" killi.on -~
extruder while nnaintaining melt ternperatures between 240C-260C. The extruded blend was cooled pcllctized and cdried. ;~
B. ~ control blencl was prepar~d with the same nucleated PET with unmodified ~BS under sirnilar ccnditions. The two hl~nds were injection molded at a melt ternperature of ~2SG and mold ternperature of 40C
into standard tensile and flexure bars. The samples were then annealed at 160C for 4 hours and the ~ ;M
followiny properties were obtained~
( C o n t r o 'l T~nsile Str~ngth (lO psi) 8.06 6.01 Tensile Modulus (lO psi) 352 333 .~.
35 Elongation (%~ 2.5 l.8 ~
Izod Impact (Unnotched~ 3.2 l.5 ~ ~.
Ift lbs~In) ' ~ .
Claims (22)
1. A modified styrenic polymer comprising the reaction product of said polymer with an ethylenically unsaturated grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from amino, hydroxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, 1,3 oxazoline, 1,3-oxazine, oxazolone, oxazinones and any derivatives, combinations, and mixtures thereof;
and wherein the remaining one to three of R1, R2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; said modified styrenic polymer containing said reactive groups as pendant reactive functionalities.
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from amino, hydroxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, 1,3 oxazoline, 1,3-oxazine, oxazolone, oxazinones and any derivatives, combinations, and mixtures thereof;
and wherein the remaining one to three of R1, R2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; said modified styrenic polymer containing said reactive groups as pendant reactive functionalities.
2. The modified styrenic polymer of claim 1 wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from amino, hydroxyl, and combinations thereof.
3. The modified styrenic polymer of claim 1 wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from isocyanate, carbamate, carbamoyl lactam, acyl lactam, and combinations thereof.
4. The modified styrenic polymer of claim 1 wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from 1,3-oxazoline, 1,3-oxazine, oxazolone, oxazinones, and combinations thereof.
5. The modified styrenic polymer of claim 1 wherein said ethylenically unsaturated grafting agent is selected from the group consisting of 2-isopropenyl, 1,3-oxazoline, and combinations thereof.
6. The modified styrenic polymer of claim 1 wherein the styrenic polymer is selected from the group consisting of conventional polystyrenes, styrene-containing copolymers, styrene-acrylonitrile-butadiene copolymers, and elastomer modified styrenic polymers.
7. The modified styrenic polymer of claim 6 wherein said styrenic polymer is selected from the group consisting of styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-acrylonitrile-butadiene terpolymers, high impact polystyrene, ABS, OSA, ASA, and ACS.
8. The modified styrenic polymer of claim 7 wherein said styrenic polymer is an elastomer modified styrene-acrylonitrile copolymer.
9. The modified styrenic polymer of claim 1 further comprising a rubbery material.
10. The modified styrenic polymer of claim 9 wherein said rubbery material is functionalized ethylene-propylene.
11. The modified styrenic polymer of claim 10 wherein said functionalized ethylene-propylene is functionalized with moieties selected from the group consisting of carboxyl and anhydride moieties.
12. A blended composition comprising the modified styrenic polymer of claim 1 and a second polymer having reactive moieties selected from the group consisting of amine, hydroxyl, and carboxyl; said reactive moieties present as end groups or groups pendant to the second polymer backbone.
13. The blended composition of claim 12 wherein said second polymer is selected from the group consisting of functionalized polyolefins, polyesters, and polyamides.
14. The blended composition of claim 13 wherein said second polymer is a polyester.
15. The blended composition of claim 13 wherein said second polymer is a polyamide.
16. A method for forming a blended polymer composition comprising the steps of:
a. contacting a styrenic polymer with an effective amount of grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from carboxylic acid, acid anhydride, acid amide, imido, carboxylic ester, amino, hydroxyl, epoxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, pyridyl, 1,3-oxazoline, 1,3-oxazine, oxazolone, oxazinones, and any derivatives, combinations, and mixtures thereof;
and wherein the remaining one to three of R1 2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; for a time sufficient for a reaction to occur between said styrenic polymer and said grafting agent to produce a modified styrenic polymer containing said reactive groups of said grafting agent as pendant reactive functionalities;
and b. contacting said modified styrenic polymer with a second polymer having nucleophilic reactive moieties selected from the group consisting of amine, hydroxyl, and carboxyl to form a blended composition.
a. contacting a styrenic polymer with an effective amount of grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from carboxylic acid, acid anhydride, acid amide, imido, carboxylic ester, amino, hydroxyl, epoxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, pyridyl, 1,3-oxazoline, 1,3-oxazine, oxazolone, oxazinones, and any derivatives, combinations, and mixtures thereof;
and wherein the remaining one to three of R1 2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; for a time sufficient for a reaction to occur between said styrenic polymer and said grafting agent to produce a modified styrenic polymer containing said reactive groups of said grafting agent as pendant reactive functionalities;
and b. contacting said modified styrenic polymer with a second polymer having nucleophilic reactive moieties selected from the group consisting of amine, hydroxyl, and carboxyl to form a blended composition.
17. The method of claim 16 wherein said contacting steps a and b take place in an extruder in a temperature range above the melting temperatures of the components and below temperatures leading to degradation of the components.
18. The method of claim 17 wherein the amount of grafting agent contacted with styrenic polymer in step a is about 0.1 - 20% by weight of styrenic polymer.
19. The method of claim 18 wherein step a is conducted in the presence of a free radical catalyst.
20. A composition comprising:
(a) a modified styrenic polymer comprising the reaction product of saidpolymer with an ethylenically unsaturated grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from carboxylic acid, acid anhydride, acid amide, imido, carboxylic ester, amino, hydroxyl, epoxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, pyridyl, 1,3-oxazoline, 1,3-oxazine, oxazolone, oxazinones and any derivatives, combinations, and mixtures thereof;
and wherein the remaining one to three of R1, R2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; said modified styrenic polymer containing said reactive groups as pendant reactive functionalities; and (b) a rubbery material.
(a) a modified styrenic polymer comprising the reaction product of saidpolymer with an ethylenically unsaturated grafting agent having the formula:
wherein one to three of R1, R2, R3 and R4 are moieties containing reactive groups selected from carboxylic acid, acid anhydride, acid amide, imido, carboxylic ester, amino, hydroxyl, epoxy, isocyanate, carbamate, carbamoyl lactam, acyl lactam, pyridyl, 1,3-oxazoline, 1,3-oxazine, oxazolone, oxazinones and any derivatives, combinations, and mixtures thereof;
and wherein the remaining one to three of R1, R2, R3 and R4 are H or a hydrocarbon radical of from about 1 to about 20 carbon atoms; said modified styrenic polymer containing said reactive groups as pendant reactive functionalities; and (b) a rubbery material.
21. The composition of claim 20 wherein said rubbery material is functionalized ethylene-propylene.
22. The composition of claim 21 wherein said functionalized ethylene-propylene is functionalized with moieties selected from the group consisting of carboxyl and anhydride moieties.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8873887A | 1987-08-24 | 1987-08-24 | |
| US088,738 | 1987-08-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1331411C true CA1331411C (en) | 1994-08-09 |
Family
ID=22213157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000574718A Expired - Fee Related CA1331411C (en) | 1987-08-24 | 1988-08-15 | High impact, styrenic polymer/thermoplastic polymer grafted blends |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4902749A (en) |
| EP (1) | EP0375728B1 (en) |
| JP (1) | JP2690989B2 (en) |
| KR (1) | KR960014557B1 (en) |
| AT (1) | ATE90367T1 (en) |
| CA (1) | CA1331411C (en) |
| DE (1) | DE3881700T2 (en) |
| WO (1) | WO1989001962A1 (en) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS638450A (en) * | 1986-06-27 | 1988-01-14 | Japan Synthetic Rubber Co Ltd | Thermoplastic elastomer composition |
| US5013795A (en) * | 1989-04-10 | 1991-05-07 | Minnesota Mining And Manufacturing Company | Azlactone graft copolymers |
| US5262484A (en) * | 1989-04-10 | 1993-11-16 | Minnesota Mining And Manufacturing Company | Azlactone graft copolymers |
| US5216074A (en) * | 1989-07-17 | 1993-06-01 | Japan Synthetic Rubber Co., Ltd. | Thermoplastic elastomer composition |
| JPH03199214A (en) * | 1989-12-27 | 1991-08-30 | Sumitomo Chem Co Ltd | Modified polymer rubber and production thereof |
| CA2041610A1 (en) * | 1990-05-04 | 1991-11-05 | Elisabeth S. Papazoglou | Process for the preparation of polyamide blends having improved low temperature properties |
| IT1241135B (en) * | 1990-05-15 | 1993-12-29 | Montedipe Srl | SHOCKPROOF IMPACT VINYLAROMATIC COPOLYMER TO IMPROVE MECHANICAL CHARACTERISTICS |
| DE69119688T2 (en) * | 1990-10-10 | 1997-01-16 | Minnesota Mining & Mfg | Graft copolymers and graft copolymer / protein compositions |
| US5132361A (en) * | 1991-01-24 | 1992-07-21 | General Electric Company | Copolymers prepared from polymers of ethylenically polymerizable cyclic ortho esters |
| IT1245603B (en) * | 1991-03-29 | 1994-09-29 | Montedipe Srl | THERMOPLASTIC COMPOSITIONS WITH IMPROVED MECHANICAL CHARACTERISTICS |
| IT1251665B (en) * | 1991-10-08 | 1995-05-19 | Himont Inc | THERMOPLASTIC POLYMERIC COMPOSITIONS |
| US5552480A (en) * | 1992-02-28 | 1996-09-03 | Idemitsu Petrochemical Co., Ltd. | Thermoplastic resin composition |
| US6146574A (en) * | 1993-07-13 | 2000-11-14 | Huntsman Petrochemical Corporation | Article manufacture using polyolefin containing polyetheramine modified functionalized polyolefin |
| US5783630A (en) * | 1993-07-13 | 1998-07-21 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| US6031048A (en) * | 1993-07-13 | 2000-02-29 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| DE69403398T2 (en) * | 1993-07-13 | 1997-09-25 | Huntsman Spec Chem Corp | Modification of polypropylene by polyether amines |
| US5985999A (en) * | 1993-07-13 | 1999-11-16 | Huntsman, Petrochemical Corporation | Dyeable polyolefin containing polyetheramine modified functionalized polyolefin |
| US5959032A (en) * | 1993-07-13 | 1999-09-28 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| US5408002A (en) * | 1993-09-09 | 1995-04-18 | Minnesota Mining And Manufacturing Company | Azlactone-functional polymer blends, articles produced therefrom and methods for preparing both |
| FR2717487B1 (en) * | 1994-03-16 | 1998-06-26 | Atochem Elf Sa | Coextrusion binder composition and coextruded multilayer complex in which said composition is used as an adhesive layer. |
| CA2196335A1 (en) * | 1994-10-17 | 1996-04-25 | Exxonmobil Chemical Patents, Inc. | Oleaginous compositions comprising grafted isomonoolefin alkylstyrene polymers |
| DE19501998A1 (en) * | 1995-01-24 | 1996-07-25 | Basf Ag | Thermoplastic polyamide molding compounds |
| US5668217A (en) * | 1996-05-16 | 1997-09-16 | Huntsman Petrochemical Corporation | Amidoamine modification of polypropylene |
| DE19739686A1 (en) * | 1997-09-10 | 1999-03-11 | Basf Ag | Thermoplastic molding compounds based on polyesters and polycarbonate |
| NL1007074C2 (en) * | 1997-09-19 | 1999-03-22 | Dsm Nv | Compatibilising copolymer |
| US6093496A (en) * | 1998-05-12 | 2000-07-25 | Huntsman Petrochemical Corporation | Polyolefin containing polyetheramine modified functionalized polyolefin |
| US6353054B1 (en) * | 2000-07-31 | 2002-03-05 | Bridgestone Corporation | Alkenyl-co-maleimide/diene rubber copolymers and applications |
| FR2821082B1 (en) * | 2001-02-16 | 2007-03-23 | Rhodia Eng Plastics Srl | THERMOPLASTIC POLYMER COMPOSITION BASED ON POLYAMIDE |
| DE10259266A1 (en) * | 2002-12-17 | 2004-07-01 | Basf Ag | Thermoplastic molding compounds |
| DE102005037329A1 (en) * | 2005-08-04 | 2007-02-08 | Basf Ag | Thermoplastic molding compounds based on polyesters and styrene copolymers |
| EP2035497A2 (en) * | 2006-06-07 | 2009-03-18 | Ineos ABS (Jersey) Limited | Soft touch, low gloss polymer resins |
| DE102007009921A1 (en) * | 2007-02-27 | 2008-08-28 | Evonik Degussa Gmbh | Continuous process for the preparation of a reactive polymer |
| US8658576B1 (en) | 2009-10-21 | 2014-02-25 | Encore Wire Corporation | System, composition and method of application of same for reducing the coefficient of friction and required pulling force during installation of wire or cable |
| WO2012163822A1 (en) | 2011-06-01 | 2012-12-06 | Basf Se | Polyester with styrene copolymers |
| US8889769B2 (en) | 2011-06-27 | 2014-11-18 | Basf Se | Weathering-resistant polyester molding compositions with styrene copolymers |
| JP5933708B2 (en) | 2011-06-27 | 2016-06-15 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Weather-resistant polyester molding compound with styrene copolymer |
| US9352371B1 (en) | 2012-02-13 | 2016-05-31 | Encore Wire Corporation | Method of manufacture of electrical wire and cable having a reduced coefficient of friction and required pulling force |
| JP5993236B2 (en) * | 2012-07-23 | 2016-09-14 | デンカ株式会社 | Multilayer sheet, solar cell backsheet, and solar cell module |
| US11328843B1 (en) * | 2012-09-10 | 2022-05-10 | Encore Wire Corporation | Method of manufacture of electrical wire and cable having a reduced coefficient of friction and required pulling force |
| US10056742B1 (en) | 2013-03-15 | 2018-08-21 | Encore Wire Corporation | System, method and apparatus for spray-on application of a wire pulling lubricant |
| DE102019118856A1 (en) * | 2019-07-11 | 2021-01-14 | Voss Automotive Gmbh | Ternary polymer blend, in particular for pipe extrusion, thermoplastic plastic pipe made from such a blend and its use |
| CN112812485B (en) * | 2020-12-28 | 2022-10-21 | 金发科技股份有限公司 | SMA composite material and preparation method and application thereof |
| CN113444326A (en) * | 2021-07-22 | 2021-09-28 | 广东粤化新材料技术开发有限公司 | High-toughness polystyrene resin and preparation method thereof |
Family Cites Families (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB778102A (en) * | 1955-02-25 | 1957-07-03 | Styrene Products Ltd | Improvements in and relating to adhesive compositions and polymeric products for usetherein |
| US3134746A (en) * | 1961-06-09 | 1964-05-26 | Borg Warner | Blends of epsilon caprolactam polymer and graft copolymer alkenyl cyanide and alkenyl substituted aromatic hydrocarbon on polybutadiene |
| US3386964A (en) * | 1963-12-19 | 1968-06-04 | Allied Chem | Terpolymers of epsilon-caprolactam, mu-xylylenediamine, and a dicarboxylic acid |
| US3435093A (en) * | 1965-12-17 | 1969-03-25 | Du Pont | Polymer blends of polyethylene terephthalate and alpha-olefin,alpha,beta-unsaturated carboxylic acid copolymers |
| GB1250877A (en) * | 1967-12-09 | 1971-10-20 | ||
| US3661866A (en) * | 1970-05-11 | 1972-05-09 | Kimberly Clark Co | High strength polystyrene |
| US3668274A (en) * | 1970-09-10 | 1972-06-06 | Rohm & Haas | Acrylic modifiers for polycarbonamides |
| US4013613A (en) * | 1971-10-01 | 1977-03-22 | General Electric Company | Reinforced intercrystalline thermoplastic polyester compositions |
| US3794625A (en) * | 1971-10-26 | 1974-02-26 | Custom Resins Inc | Transparent polyamides from caprolactam and a mixture of a methyldiamino cyclohexane and a dibasicorganic acid |
| US4018746A (en) * | 1972-04-05 | 1977-04-19 | Hoechst Aktiengesellschaft | Transparent copolyamides from m-xylylene diamine, an aliphatic diamine and terephthalic acid |
| JPS5061449A (en) * | 1973-10-02 | 1975-05-27 | ||
| DE2403889A1 (en) * | 1974-01-28 | 1975-08-07 | Hoechst Ag | THERMOPLASTIC MOLDING COMPOUNDS |
| US4133802A (en) * | 1974-03-26 | 1979-01-09 | Toyo Boseki Kabushiki Kaisha | Meta-xylylene diamine/aliphatic dicarboxylic acid polyamide film |
| US4174358A (en) * | 1975-05-23 | 1979-11-13 | E. I. Du Pont De Nemours And Company | Tough thermoplastic nylon compositions |
| US4098860A (en) * | 1975-10-11 | 1978-07-04 | Toyo Boseki Kabushiki Kaisha | Production of biaxially drawn film of polyamide blend |
| US3968071A (en) * | 1975-11-20 | 1976-07-06 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin molding composition |
| DE2906222A1 (en) * | 1979-02-17 | 1980-08-28 | Bayer Ag | POLYMER BLENDS |
| US4429076A (en) * | 1979-06-13 | 1984-01-31 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic polymer composition |
| DE2926778A1 (en) * | 1979-07-03 | 1981-01-15 | Bayer Ag | FIBER REINFORCED POLYAMIDE MOLDS |
| US4398642A (en) * | 1979-11-02 | 1983-08-16 | Toyo Boseki Kabushiki Kaisha | Multi-ply vessel and method for production thereof |
| US4404317A (en) * | 1981-07-09 | 1983-09-13 | E. I. Du Pont De Nemours & Co. | Polyamide blends |
| WO1983000492A1 (en) * | 1981-08-13 | 1983-02-17 | Shiraki, Toshinori | Modified block copolymer composition |
| US4427828A (en) * | 1981-09-01 | 1984-01-24 | The Firestone Tire & Rubber Company | Impact resistant polymeric compositions containing polyamides, maleic anhydride adducts of hydrogenated polymers and graft copolymers thereof |
| CA1196439A (en) * | 1981-11-30 | 1985-11-05 | Thomas S. Grant | Alloys of styrenic resins and polyamides |
| US4496690A (en) * | 1981-11-30 | 1985-01-29 | Borg-Warner Chemicals, Inc. | Alloys of styrenic resins and polyamides |
| JPS58198560A (en) * | 1982-05-17 | 1983-11-18 | Sumitomo Chem Co Ltd | Polyamide resin composition |
| JPS5956443A (en) * | 1982-09-24 | 1984-03-31 | Mitsubishi Gas Chem Co Inc | Resin composition for molding material |
| JPS60137961A (en) * | 1983-12-26 | 1985-07-22 | Ube Ind Ltd | Manufacture of polyamide composition |
| US4537929A (en) * | 1984-01-20 | 1985-08-27 | Plastic Specialties And Technologies, Inc. | High impact nylon composition |
| US4713415A (en) * | 1985-05-10 | 1987-12-15 | Monsanto Company | Rubber modified nylon composition |
| US4783503A (en) * | 1985-08-16 | 1988-11-08 | Shell Oil Company | Impact resistant blends of thermoplastic polyamides and modified block copolymers |
| JPS6281444A (en) * | 1985-10-04 | 1987-04-14 | Toyobo Co Ltd | Thermoplastic resin composition |
| US4740552A (en) * | 1986-02-14 | 1988-04-26 | Borg-Warner Chemicals, Inc. | Alloys of styrenic resins and polyamides |
| US4795782A (en) * | 1986-09-25 | 1989-01-03 | Shell Oil Company | Impact resistant blends of thermoplastic polyamides, functionalized polyolefins and functionalized elastomers |
-
1988
- 1988-07-29 AT AT88907954T patent/ATE90367T1/en not_active IP Right Cessation
- 1988-07-29 WO PCT/US1988/002580 patent/WO1989001962A1/en active IP Right Grant
- 1988-07-29 JP JP63507277A patent/JP2690989B2/en not_active Expired - Lifetime
- 1988-07-29 DE DE8888907954T patent/DE3881700T2/en not_active Expired - Fee Related
- 1988-07-29 KR KR1019890700701A patent/KR960014557B1/en not_active IP Right Cessation
- 1988-07-29 EP EP88907954A patent/EP0375728B1/en not_active Expired - Lifetime
- 1988-08-15 CA CA000574718A patent/CA1331411C/en not_active Expired - Fee Related
- 1988-10-19 US US07/262,196 patent/US4902749A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE90367T1 (en) | 1993-06-15 |
| EP0375728A1 (en) | 1990-07-04 |
| US4902749A (en) | 1990-02-20 |
| DE3881700T2 (en) | 1993-09-16 |
| KR890701698A (en) | 1989-12-21 |
| JPH03501133A (en) | 1991-03-14 |
| EP0375728B1 (en) | 1993-06-09 |
| KR960014557B1 (en) | 1996-10-16 |
| WO1989001962A1 (en) | 1989-03-09 |
| JP2690989B2 (en) | 1997-12-17 |
| DE3881700D1 (en) | 1993-07-15 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |