CA1085084A - Resinous linear block copolymer of a monovinyl- substituted aromatic compound and a conjugated diene - Google Patents
Resinous linear block copolymer of a monovinyl- substituted aromatic compound and a conjugated dieneInfo
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- CA1085084A CA1085084A CA258,971A CA258971A CA1085084A CA 1085084 A CA1085084 A CA 1085084A CA 258971 A CA258971 A CA 258971A CA 1085084 A CA1085084 A CA 1085084A
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- monovinyl
- aromatic compound
- substituted aromatic
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Abstract
A RESINOUS LINEAR BLOCK COPOLYMER OF A MONOVINYL-SUBSTITUTED AROMATIC COMPOUND AND A CONJUGATED DIENE Abstract of the Disclosure A resinous linear block copolymer of a monovinyl-substituted aromatic compound and a conjugated diene wherein the polymerized monovinyl-substituted aromatic compound blocks have a heterogeneity index within the range of about 2.3 to 4.5. The heterogeneity index is the ratio of weight average to number average molecular weight. Such compositions exhibit high impact strength and can be made either by bending two linear block copolymers made under different conditions so as to give different lengths of the polymerized monovinyl-substi-tuted aromatic compound blocks, or by adding the monovinyl-substituted aromatic compound and a polymerization initiator in two or more increments prior to adding the conjugated diene. These compositions are particularly useful in applications such as injection molded articles where high impact strength is desirable.
Description
1085~8~
. .
~, - Back~ound of the lnvention This invention relates to high impact resinous linear copolymers of a monovinyl-substituted aromatic compound and a conjugated diene. In another aspect this invention relates to high impact blends of monovinyl-substituted aromatic compound/conjugated diene block copolymers.
It is well known to produce impact polystyrene by blending a rubber with the polystyrene. This results in improvement in the impact of the poly-styrene with a substantial sacrifice with respect to other properties~ It is also known that some but not all radial block copolymers exhibit high impact strength, see for instance Kitchen et al U.S, 3,639?517.
It would be desirable to achieve a linear polymer having high impact , strength without the disadvantages associated with rubber reinforced poly-~; ~
styrene.
^ Summary of the Invention ~ It is an object of this invention to provide high impact linear '~ block copolymers of a monovinyl-substituted aromatic compound and a conjugated diene.
It is a further object of this invention to provide high impact block , copolymer without the necessity of multiple addition of initiator and monovinyl-'~` 20 substituted aromatic compound; and ~ it is yet a further object of this invention to provide an improved ,.~
blend of monovinyl-substituted aromatic compound/conjugated diene copolymers.
In accordance with this invention there is provided a linear mono-. . .
vinyl substituted aromatic compound/conjugated diene block copolymer composi-tion characterized by a heterogeneity index of blocks of polymerized mono-vinyl-substituted aromatic compound within the range of about 2.3 to 4.5, preferably 2.4 to 4.5. In another aspect of this invention, there is pro-vided a blend of two resinous radial copolymers of monovinyl-substituted aromatic compound/conjugated diene which blend has a heterogeneity index for the monovinyl-substituted aromatic compound blocks of at least about 2.8, preferably within the range of about 2.8 to 3.5.
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85~84 Description of ehe P~eferred Embodiments It has been found that the high lmpact strength of resinous radialblock copolymers made with incremental addition of the monovinyl-substituted ; aromatic compound and initiator is related to the morphology. Specifically, with a very low heterogeneity index for the monovinyl-substituted aromatic compound block, i.e., less than about 2.8, the morphology is characterized by spheres of the diene component in the monovinyl-substituted aromatic compound componect. At a heterogeneity index above about 3.5 the morphology exhibits an inverted structure having spheres or ellipsoids of the monovinyl-substitu-ted aromatic component in a continuum of the diene component. This structure gives a cheesy (weak and crumbly~ product. This change in property above a heterogeneity index of about 3.5 may also be affected by incompatibility due to great differences in the molecular weights of the block. However, within the desired range of heterogeneity index of about 2.8 to 3.5 for the mono- -vinyl-substituted aromatic compound block of the radial polymer blends, there is present an alternating lamellar structure comprising alternate layers of con~ugated diene block~ and layers of monovinyl-substituted aromatic compound blocks.
; With linear polymers, samples having a heterogeneity index of the monovinyl substituted aromatic compound block of less than 2.3 tend to have the morphology characterized by spheres of the polymerized diene embedded in a continuum of polystyrene. On impact the polystyrene phase takes most of the load and hence low impact values are obtained whereas with the lamellar con-figuration there are alternating layers of polymerized styrene blocks and polymerized diene blocks which act in a reinforcing manner. With a heterogen-eity index of greater than about 4.5 the morphology for linear block copolymer is inverted with spheres or ellipsoids of polymerized monovinyl substituted aromatic compound being found in a continuum of polymerized diene. This structure gives a cheesy (weak and crumbly) product. This change in proper-ties above a heterogeneity index of 4.5 may also be affected by incompati-~ bility due to great variations in the molecular weights of the blocks.
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. .
~, - Back~ound of the lnvention This invention relates to high impact resinous linear copolymers of a monovinyl-substituted aromatic compound and a conjugated diene. In another aspect this invention relates to high impact blends of monovinyl-substituted aromatic compound/conjugated diene block copolymers.
It is well known to produce impact polystyrene by blending a rubber with the polystyrene. This results in improvement in the impact of the poly-styrene with a substantial sacrifice with respect to other properties~ It is also known that some but not all radial block copolymers exhibit high impact strength, see for instance Kitchen et al U.S, 3,639?517.
It would be desirable to achieve a linear polymer having high impact , strength without the disadvantages associated with rubber reinforced poly-~; ~
styrene.
^ Summary of the Invention ~ It is an object of this invention to provide high impact linear '~ block copolymers of a monovinyl-substituted aromatic compound and a conjugated diene.
It is a further object of this invention to provide high impact block , copolymer without the necessity of multiple addition of initiator and monovinyl-'~` 20 substituted aromatic compound; and ~ it is yet a further object of this invention to provide an improved ,.~
blend of monovinyl-substituted aromatic compound/conjugated diene copolymers.
In accordance with this invention there is provided a linear mono-. . .
vinyl substituted aromatic compound/conjugated diene block copolymer composi-tion characterized by a heterogeneity index of blocks of polymerized mono-vinyl-substituted aromatic compound within the range of about 2.3 to 4.5, preferably 2.4 to 4.5. In another aspect of this invention, there is pro-vided a blend of two resinous radial copolymers of monovinyl-substituted aromatic compound/conjugated diene which blend has a heterogeneity index for the monovinyl-substituted aromatic compound blocks of at least about 2.8, preferably within the range of about 2.8 to 3.5.
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85~84 Description of ehe P~eferred Embodiments It has been found that the high lmpact strength of resinous radialblock copolymers made with incremental addition of the monovinyl-substituted ; aromatic compound and initiator is related to the morphology. Specifically, with a very low heterogeneity index for the monovinyl-substituted aromatic compound block, i.e., less than about 2.8, the morphology is characterized by spheres of the diene component in the monovinyl-substituted aromatic compound componect. At a heterogeneity index above about 3.5 the morphology exhibits an inverted structure having spheres or ellipsoids of the monovinyl-substitu-ted aromatic component in a continuum of the diene component. This structure gives a cheesy (weak and crumbly~ product. This change in property above a heterogeneity index of about 3.5 may also be affected by incompatibility due to great differences in the molecular weights of the block. However, within the desired range of heterogeneity index of about 2.8 to 3.5 for the mono- -vinyl-substituted aromatic compound block of the radial polymer blends, there is present an alternating lamellar structure comprising alternate layers of con~ugated diene block~ and layers of monovinyl-substituted aromatic compound blocks.
; With linear polymers, samples having a heterogeneity index of the monovinyl substituted aromatic compound block of less than 2.3 tend to have the morphology characterized by spheres of the polymerized diene embedded in a continuum of polystyrene. On impact the polystyrene phase takes most of the load and hence low impact values are obtained whereas with the lamellar con-figuration there are alternating layers of polymerized styrene blocks and polymerized diene blocks which act in a reinforcing manner. With a heterogen-eity index of greater than about 4.5 the morphology for linear block copolymer is inverted with spheres or ellipsoids of polymerized monovinyl substituted aromatic compound being found in a continuum of polymerized diene. This structure gives a cheesy (weak and crumbly) product. This change in proper-ties above a heterogeneity index of 4.5 may also be affected by incompati-~ bility due to great variations in the molecular weights of the blocks.
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- 1085~84 Thus in accordance with the invention there is provided linear ; block copolymer compositions having a heterogeneity index within the range of about 2.3 to 4.5 for the polymerized monovinyl-substituted aromatic component blocks. In accordance with another aspect of this instant invention, there i8 provided blends of two block copolymers each of which has a heterogeneity index for the monovinyl-substituted aromatic compound blocks outside the range of about 2,8 to 3.5, the blend being within this range.
' The heterogeneity index is the ratio of weight average to number average molecular weight and is expressed by the formula ( 1 1 Sl 2 2 S2 ) 1 1 2 2 ~
,~ ~ NlMSl + N2M
Nl + N2 `~ where:
' W is weight of fraction (1 = Major, 2 = minor) ,;'. S i8 styrene content of the fraction N is moles styrene blocks in the fraction MS is molecular weight of styrene block in the fraction.
`, 20 The weight average and number average molecular weights used in the : above formula are calculated assuming monodispersity, which is a reasonable ` approximation since the molecular weight distribution of each polymer pro-duced is extremely narrow. Then the number of moles of initiator is divided into the number of grams of monomer to give grams of polymer per mole or the number average molecular weight which is essentially the same as the weight average molecular weight.
,~ Past experience based on actually digesting a copolymer in peroxide -.. ~
' to leave only the polymerized styrene block which was then analyzed using gel permeation chromatography has shown the calculated values to agree closely ` 30 with the measured values.
As an example of the calculations the following is a calculation of , the HI for Run 1 of Table II B:
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, ~ `~ - 1085~34 MSl = 75 x 103 MS2 = 17 x 10 , Wl = 0-58 -W2 = 0.42 , S = 75 x 103 = 0.862 1 87 x 103 S2 = ~ = 0.586 ;, Nl = 75 lOx~
N = 0.586 x 42 = 1.45 x 10-3 2 17 x 1o3 58 x .862 x 75 x 103 + .42 x .586 x 17 x 103 .58 x .862 + .42 x .586 HI = __ 667 x 75 x 103 + 1.45_x 17 x 103 .667 + 1.45 = (37.50 + 4.18) x 103 = 41.68 x 103 .50 + .246 .746 55.87 x 103 = 1.58 35.36 x 10~
"
s~l (50.02 + 24.65) x 103 - 7-4.67 x 103 2.112 2.112 Although the fo Dula is directed to the combination of two polymers either blended together or produced in situ, it should be noted that three or more polymers can be used. The expression as well as the following prepara-~? .
tive methods encompass such expansion. The block copolymers of this inven-tion are produced from a monovinyl-substituted aromatic compound and a con-.-. jugated diene.
~ The term resinous is used in the conventional sense to mean a normal-,r'~ ly solid material not having rubbery properties. Generally, such materials ~', will have a Shore D hardness (ASTM D-1706-61) of greater than 62, generally greater than 65. These final compositions of the invention and the constit-~, uent components will have from 50 to 95 weight percent polymerized monovinyl-,,, ~ .
substituted arom~tic component.
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-10~ 84 Suitable monovinyl-substituted aromatic compounds are those con-taining 8 to 18 carbon atoms per molecule. Examples of suitable compounds include styrene, 3-methylstyrene, 4-n-propylstyrene, 4-cyclohexylstyrene, 4-decylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenyl-n-butyl)-styrene, l-vinylnaphthalene, 2-vinylnaphthalene, and the ~ike and mixtures thereof. Styrene is the preferred monovinyl-substituted aromatic compound and for the sake of simplicity the invention hereinafter will be described in terms of utilizing styrene, it being understood that the invention is not limited to the use of styrene as the monovinyl-substituted aromatic compound.
Suitable conjugated dienes or mixtures thereof that can be used in this invention include those having 4 to 12 carbon atoms per molecule, those containing 4 to 8 carbon atoms being preferred. Exemplary of suitable com-pounds are 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene,
. -.
- 1085~84 Thus in accordance with the invention there is provided linear ; block copolymer compositions having a heterogeneity index within the range of about 2.3 to 4.5 for the polymerized monovinyl-substituted aromatic component blocks. In accordance with another aspect of this instant invention, there i8 provided blends of two block copolymers each of which has a heterogeneity index for the monovinyl-substituted aromatic compound blocks outside the range of about 2,8 to 3.5, the blend being within this range.
' The heterogeneity index is the ratio of weight average to number average molecular weight and is expressed by the formula ( 1 1 Sl 2 2 S2 ) 1 1 2 2 ~
,~ ~ NlMSl + N2M
Nl + N2 `~ where:
' W is weight of fraction (1 = Major, 2 = minor) ,;'. S i8 styrene content of the fraction N is moles styrene blocks in the fraction MS is molecular weight of styrene block in the fraction.
`, 20 The weight average and number average molecular weights used in the : above formula are calculated assuming monodispersity, which is a reasonable ` approximation since the molecular weight distribution of each polymer pro-duced is extremely narrow. Then the number of moles of initiator is divided into the number of grams of monomer to give grams of polymer per mole or the number average molecular weight which is essentially the same as the weight average molecular weight.
,~ Past experience based on actually digesting a copolymer in peroxide -.. ~
' to leave only the polymerized styrene block which was then analyzed using gel permeation chromatography has shown the calculated values to agree closely ` 30 with the measured values.
As an example of the calculations the following is a calculation of , the HI for Run 1 of Table II B:
~ .
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.' : ' ~, : ' ' ' .: '' . ' . . :
, ~ `~ - 1085~34 MSl = 75 x 103 MS2 = 17 x 10 , Wl = 0-58 -W2 = 0.42 , S = 75 x 103 = 0.862 1 87 x 103 S2 = ~ = 0.586 ;, Nl = 75 lOx~
N = 0.586 x 42 = 1.45 x 10-3 2 17 x 1o3 58 x .862 x 75 x 103 + .42 x .586 x 17 x 103 .58 x .862 + .42 x .586 HI = __ 667 x 75 x 103 + 1.45_x 17 x 103 .667 + 1.45 = (37.50 + 4.18) x 103 = 41.68 x 103 .50 + .246 .746 55.87 x 103 = 1.58 35.36 x 10~
"
s~l (50.02 + 24.65) x 103 - 7-4.67 x 103 2.112 2.112 Although the fo Dula is directed to the combination of two polymers either blended together or produced in situ, it should be noted that three or more polymers can be used. The expression as well as the following prepara-~? .
tive methods encompass such expansion. The block copolymers of this inven-tion are produced from a monovinyl-substituted aromatic compound and a con-.-. jugated diene.
~ The term resinous is used in the conventional sense to mean a normal-,r'~ ly solid material not having rubbery properties. Generally, such materials ~', will have a Shore D hardness (ASTM D-1706-61) of greater than 62, generally greater than 65. These final compositions of the invention and the constit-~, uent components will have from 50 to 95 weight percent polymerized monovinyl-,,, ~ .
substituted arom~tic component.
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-10~ 84 Suitable monovinyl-substituted aromatic compounds are those con-taining 8 to 18 carbon atoms per molecule. Examples of suitable compounds include styrene, 3-methylstyrene, 4-n-propylstyrene, 4-cyclohexylstyrene, 4-decylstyrene, 2-ethyl-4-benzylstyrene, 4-p-tolylstyrene, 4-(4-phenyl-n-butyl)-styrene, l-vinylnaphthalene, 2-vinylnaphthalene, and the ~ike and mixtures thereof. Styrene is the preferred monovinyl-substituted aromatic compound and for the sake of simplicity the invention hereinafter will be described in terms of utilizing styrene, it being understood that the invention is not limited to the use of styrene as the monovinyl-substituted aromatic compound.
Suitable conjugated dienes or mixtures thereof that can be used in this invention include those having 4 to 12 carbon atoms per molecule, those containing 4 to 8 carbon atoms being preferred. Exemplary of suitable com-pounds are 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, piperylene,
3-butyl-1,3-octadiene, and the like. The preferred diene is 1,3-butadiene and the invention hereinaftPr will be described in terms of butadiene, it being understood that butadiene hereinafter is referred to as exemplary only and the invention is not intended to be limited thereto.
, The polymerization initiators employed according to this invention are well known in the art and can be broadly depicted as organolithium in-20 itiators. Those preferred are hydrocarbyl monolithium compounds and can be represented by the formula RLi where R is a hydrocarbon radical selected from aliphatic, cycloaliphatic, or aromatic radicals containing from about l to 20 carbon atoms per molecule. Exemplary initiators suitable for use according to this invention include: n-butyllithium, sec-butyllithium, methyllithium, ' phenyllithium, naphthyllithium, p-tolyllithium, cyclohexyllithium, eicosyl-lithium, and the like. Because it is particularly effective, n-butyllithium is presently preferred.
. , Polymerization of the linear copolymers is carried out by initially ; adding styrene and initiator which results in the formation of polymerized styrene blocks having a terminal lithium atom. Thereafter if additional styrene and initiator are added new polymerized styrene blocks are begun utilizing part of the newly added styrene with the remainder serving to .. . .
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... . .. .. ' : : ' :' ~085~34 increase the length of the existing polymerized styrene blocks. Thereafter butadiene is added which forms a block of polymerized butadiene between the polymerized styrene block and the terminal lithium atom. At this point addi-tional styrene can be added to complete the polymer by forming a polymerized styrene block between the polymerized butadiene and the terminal lithium atom to give styrene-butadiene-styrene. Alternatively a difunctional coupling agent can be added so as to couple two of the styrene-butadiene blocks to give styrene-butadiene-butadiene-styrene. Difunctional coupling agents are known in the art and any of these known coupling agents can be utilized.
:-Suitable difunctional coupling agents include the diisocyanates, diimines (dia-:
ziridinyl), dialdehydes, dihalides, and the like. Exemplary compounds are:
; benzene-1,4-diisocyanate; naphthalene-2,6-diisocyanate; naphthalene-1,3-diisocyanate; di(l-aziridinyl)ethyl phosphine oxlde; di(2-phenyl-1-aziri-~,i dinyl)propyl phosphine oxide; di(2,3-dimethyl-aziridinyl)hexyl phosphine ~,, sulfide; 1,4-naphthalene dicarboxyaldehyde; 1,9-anthracene dicarboxyaldehyde;
,.~:1 .
5i' 2,4-hexanedione; 1,10-anthracenedione; dichlorodiethylsilane; dibro dibutyl-~il; silane; difluorodicyclohexylsilane; di-n-hexyldifluorotin; diphenyldibromo-tin; diethyldiallyltin; dicyclohexyldichlorotin; didodecylchlorobromotin;
di(3-methylphenyl)chloroallyltin; and the like.
., ~ 20 Another suitable difunctional treating agent is carbon dioxide.
,; The preferred difunctional coupling agents are esters of the formula ;~ RC - OR' ~ which are believed ~ react as follows:
~ ,.
., P
` 2P - Li ~ RC - OR' ~ R - C - P ~ R~OLi 0 OLi R and R' are preferably 1 to 6 carbon alkyl radicals. Most preferred is ethyl acetate.
The final linear block copolymer compositions of this invention con-tain 50 to 95 weight percent polymerized monovinyl-substituted aromatic , ,:
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10~35~84 ..
component and exhibit a falling dart impact strength of greater than 20 in.-lbs. (2.2 joules~, preferably greater than 25 in.-lbs. (2.8 joules). The separate constituents of the final composition also individually contain 50 to 95 weight percent polymerized monovinyl-substituted aromatic component but have a lower impact strength. The term resinous is used in a conventional sense to mean a normally solid material not having rubbery properties. Gen-erally such materials will have a Shore D hardness of greater than 62, gen-erally greater than 65.
The linear compositions of the invention can be produced by three techniques. In each instance sufficient time is allowed after the introduc-tion of each monomer for the substantially complete polymerization thereof before the addition of the next monomer.
Technique one encompasses multiple sequential addition of monomers and catalyst and no coupling is involved. The order of addition of components is styrene, initiator; initiator, styrene; butadiene; styrene (neglecting charging of solvent, modifier, etc.). Linear, block copolymers are prepared.
By regulating the quantity of styrene (S) charged in each increment as well ,...................................................................... . :
as quantity of butadiene (B) charged, a mixture of polymers is formed in situ -~ of Sl-S2-B-S3 and S2-B-S3, which in combination satisfy the required HI index.
Each subscript refers to a separately charged styrene increment.
Technique two encompasses multiple sequential addition of monomers -and initiator and coupling of the resulting products with a difunctional coupling agent (X) to obtain a mixture of linear polymers represented as Sl-S2-B-X-B-S2-Sl, Sl-S2-B-X-B-S2 and S2-B-X-B-S2 which taken together satis-fies the required HI index. The order of addition, neglecting solvent and modifier, is styrene, initiator; initiator, styrene; butadiene; coupling agent.
Technique three encompasses in the first instance mixing two or more difunctionally coupled styrene-butadiene diblock copolymers, each coupled polymer separately prepared, to obtain a final blend which satisfies the re-quired HI index or in the second instance mixing two or more separately ,, :
85~84 prepared block copolymers prepared by multiple addition of styrene and initiator.
The blend, using previous terminology, can be represented as a mixture of Sl-Bl-X-Bl-Sl and S2-B2-X-B2-S2 in the first instance, or Sl-S2-Bl-S3 plus S2-Bl-S3 and S4-S5-B2-S6 plus S5-B2-S6 in the second instance, where Bl and B2 represent , butadiene blocks of different molecular weights. However, the difference in number average molecular weights of the butadiene blocks preferably should not exceed about 10,000 in order to obtain the proper morphology. The order of addition in each reactor in the first instance, neglecting solvent and modifier,is styrene, initiator; butadiene; coupling agent. In the second instance, it is styrene, initiator; initiator, styrene; butadiene; styrene. The polymer solutions are then combined and mixed before recovering the final product.
Alternately, polymers previously recovered can be blended together by suitable means (roll mills, etc.).
It is also within the scope of this invention to mix a polymer pre-pared by means of technique one with one prepared by technique two or technique three and a polymer prepared by technique two with one of technique three to obtain a final blend which satisfies the required HI index range.
A general method of preparation of the various linear polymers, sub-ject to the limitations of this invention, is described in U. S. Patent 3,639,517 in which sequential polymerization of styrene or other monovinyl-substituted ;;;, -:
~ aromatic hydrocarbon and butadiene or other conjugated diene is employed.
r~'' The radial polymers of this invention are individually prepared accord-~?
ing to the method described in Kitchen et al, U. S. 3,639,517 except that multi-` ple addition of the monovinyl-substituted aromatic compound is not necessary.
Briefly, in accordance with the procedure outlined therein, sequential polymer-s ization of styrene or other monovinyl-substituted aromatic hydrocarbon and buta-diene or other conjugated diene is carried out and thereafter the resulting lithium-terminated polymer is coupled with a polyfunctional treating agent. As noted hereinabove, only a single charge of monovinyl-:i , .
: E~
.
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~ 1085~84 substituted aromatic compound and initiator is required for each individual polymer used to prepare the radial copolymer blends of this invention. Sty-rene and 1,3-butadiene are the presently preferred monomers in this aspect of the invention also.
In this aspect of the invention also, the polymer solutions result-ing from two separate polymerizations as described above are combined and mixed to form an intimate mixture of the polymer solutions. Subsequently, the mixture is recovered following the procedures described in said Kitchen et al patent.
It is within the scope of this aspect of the invention to form mixtures of separately recovered polymers by intensive mixing in Banbury mixers, extrusion compounding, roll milling, solution blending, and the like.
.~ The general method of preparing the high impact polymers of this invention is summarized by giving the charge order for forming two polymers, each polymer having different block lengths, followed by mixing as follows:
Reactor one Reactor two ; a) cyclohexane cyclohexane b) styrene styrene ;
c) tetrahydrofuram tetrahydrofuran ;
d) n-butyllithium n-butyllithium e) polymerize at 50-60C polymerize at 50-60C
.. . .
f) butadiene butadiene g) polymerize at 50-60C polymerize at 50-60C
h) polyfunctional treating agent polyfunctional treating agent i) combine solutions j) add stabilizer system k) devolatilize 1) finish (form granules or pellets) The sequence given above in each reactor is for making diblocks which are coupled by the polyfunctional treating agent to form a polymer which can ` 30 be expressed as: (styrene-butadiene~nY where Y is the polyfunctional treating - agent and n is an integer of 3-7 or more. It is within the scope of this .~ _9_ :.
.
.
' invention to employ as one or more components of the blend one or more poly-mers made by multiple addition of monovinyl-substituted aromatic hydrocarbon and initiator wherein for some reason the resulting polymer is off specifica-tion, i.e., has a heterogeneity index outside the range of about 2.8 to 3.5.
Broadly then this aspect of the invention involving radial polymer resides in the blending of two radial block copolymers of a monovinyl-substituted aro-matic compound and a coniugated diene each having a heterogeneity index out-., . side the range of about 2.8 to 3.5 with at least one less than 2.8 to give a blend having a heterogeneity index within the range of 2.8 to 3.5.
Exemplary polyfunctional treating agents that can be used in accord-ance with this aspect of the invention in the preparation of the branched block (xadial) copolymers are the polyepoxides such as epoxidized linseed oil, epoxidized soybean oil, and 1,2,5,6,9,10-triepoxydecane; polyimines such as tri~l~aziridinyl)phosphine oxide; polyisocyanates such as benzene-1,2,4-tri-isocyanate; polyaldehydes such as 1,4,7-naphthalenetricarboxyaldehyde; poly-halides such as silicon tetrachloride or polyketones such as 1~4~9~lo-anthra cenetetrone and polyalkoxysilanes such as methyltrimethoxysilane.
The compositions of this invention can, of course, contain conven-tional additives such as antioxidants, W stabilizers, fillers, pigments, and the like.
In the following Examples, Examples I to III relate to the first aspect of this invention (linear copolymer blends) and Example IV to the ` second aspect (radial copolymer blends).
EXAMPLE I
Polymers made according to technique one, previously described, were prepared by conducting each polymerization in 32 ounce (0.95 liter) glass beverage bottles. In each run, the following materials were added to the bottle, while under nitrogen, in the order shown:
; (1) cyclohexane (CyC6), then first increment of styrene (S) (2) purge 5 minutes with nitrogen, cap and fill with nitrogen (3) tetrahydrofuran (THF) ~ -10-' - - 1085~84
, The polymerization initiators employed according to this invention are well known in the art and can be broadly depicted as organolithium in-20 itiators. Those preferred are hydrocarbyl monolithium compounds and can be represented by the formula RLi where R is a hydrocarbon radical selected from aliphatic, cycloaliphatic, or aromatic radicals containing from about l to 20 carbon atoms per molecule. Exemplary initiators suitable for use according to this invention include: n-butyllithium, sec-butyllithium, methyllithium, ' phenyllithium, naphthyllithium, p-tolyllithium, cyclohexyllithium, eicosyl-lithium, and the like. Because it is particularly effective, n-butyllithium is presently preferred.
. , Polymerization of the linear copolymers is carried out by initially ; adding styrene and initiator which results in the formation of polymerized styrene blocks having a terminal lithium atom. Thereafter if additional styrene and initiator are added new polymerized styrene blocks are begun utilizing part of the newly added styrene with the remainder serving to .. . .
' ' ~ : : ' ' ., . '' . :' . .:. : .
~. . . . .
... . .. .. ' : : ' :' ~085~34 increase the length of the existing polymerized styrene blocks. Thereafter butadiene is added which forms a block of polymerized butadiene between the polymerized styrene block and the terminal lithium atom. At this point addi-tional styrene can be added to complete the polymer by forming a polymerized styrene block between the polymerized butadiene and the terminal lithium atom to give styrene-butadiene-styrene. Alternatively a difunctional coupling agent can be added so as to couple two of the styrene-butadiene blocks to give styrene-butadiene-butadiene-styrene. Difunctional coupling agents are known in the art and any of these known coupling agents can be utilized.
:-Suitable difunctional coupling agents include the diisocyanates, diimines (dia-:
ziridinyl), dialdehydes, dihalides, and the like. Exemplary compounds are:
; benzene-1,4-diisocyanate; naphthalene-2,6-diisocyanate; naphthalene-1,3-diisocyanate; di(l-aziridinyl)ethyl phosphine oxlde; di(2-phenyl-1-aziri-~,i dinyl)propyl phosphine oxide; di(2,3-dimethyl-aziridinyl)hexyl phosphine ~,, sulfide; 1,4-naphthalene dicarboxyaldehyde; 1,9-anthracene dicarboxyaldehyde;
,.~:1 .
5i' 2,4-hexanedione; 1,10-anthracenedione; dichlorodiethylsilane; dibro dibutyl-~il; silane; difluorodicyclohexylsilane; di-n-hexyldifluorotin; diphenyldibromo-tin; diethyldiallyltin; dicyclohexyldichlorotin; didodecylchlorobromotin;
di(3-methylphenyl)chloroallyltin; and the like.
., ~ 20 Another suitable difunctional treating agent is carbon dioxide.
,; The preferred difunctional coupling agents are esters of the formula ;~ RC - OR' ~ which are believed ~ react as follows:
~ ,.
., P
` 2P - Li ~ RC - OR' ~ R - C - P ~ R~OLi 0 OLi R and R' are preferably 1 to 6 carbon alkyl radicals. Most preferred is ethyl acetate.
The final linear block copolymer compositions of this invention con-tain 50 to 95 weight percent polymerized monovinyl-substituted aromatic , ,:
~-- \
10~35~84 ..
component and exhibit a falling dart impact strength of greater than 20 in.-lbs. (2.2 joules~, preferably greater than 25 in.-lbs. (2.8 joules). The separate constituents of the final composition also individually contain 50 to 95 weight percent polymerized monovinyl-substituted aromatic component but have a lower impact strength. The term resinous is used in a conventional sense to mean a normally solid material not having rubbery properties. Gen-erally such materials will have a Shore D hardness of greater than 62, gen-erally greater than 65.
The linear compositions of the invention can be produced by three techniques. In each instance sufficient time is allowed after the introduc-tion of each monomer for the substantially complete polymerization thereof before the addition of the next monomer.
Technique one encompasses multiple sequential addition of monomers and catalyst and no coupling is involved. The order of addition of components is styrene, initiator; initiator, styrene; butadiene; styrene (neglecting charging of solvent, modifier, etc.). Linear, block copolymers are prepared.
By regulating the quantity of styrene (S) charged in each increment as well ,...................................................................... . :
as quantity of butadiene (B) charged, a mixture of polymers is formed in situ -~ of Sl-S2-B-S3 and S2-B-S3, which in combination satisfy the required HI index.
Each subscript refers to a separately charged styrene increment.
Technique two encompasses multiple sequential addition of monomers -and initiator and coupling of the resulting products with a difunctional coupling agent (X) to obtain a mixture of linear polymers represented as Sl-S2-B-X-B-S2-Sl, Sl-S2-B-X-B-S2 and S2-B-X-B-S2 which taken together satis-fies the required HI index. The order of addition, neglecting solvent and modifier, is styrene, initiator; initiator, styrene; butadiene; coupling agent.
Technique three encompasses in the first instance mixing two or more difunctionally coupled styrene-butadiene diblock copolymers, each coupled polymer separately prepared, to obtain a final blend which satisfies the re-quired HI index or in the second instance mixing two or more separately ,, :
85~84 prepared block copolymers prepared by multiple addition of styrene and initiator.
The blend, using previous terminology, can be represented as a mixture of Sl-Bl-X-Bl-Sl and S2-B2-X-B2-S2 in the first instance, or Sl-S2-Bl-S3 plus S2-Bl-S3 and S4-S5-B2-S6 plus S5-B2-S6 in the second instance, where Bl and B2 represent , butadiene blocks of different molecular weights. However, the difference in number average molecular weights of the butadiene blocks preferably should not exceed about 10,000 in order to obtain the proper morphology. The order of addition in each reactor in the first instance, neglecting solvent and modifier,is styrene, initiator; butadiene; coupling agent. In the second instance, it is styrene, initiator; initiator, styrene; butadiene; styrene. The polymer solutions are then combined and mixed before recovering the final product.
Alternately, polymers previously recovered can be blended together by suitable means (roll mills, etc.).
It is also within the scope of this invention to mix a polymer pre-pared by means of technique one with one prepared by technique two or technique three and a polymer prepared by technique two with one of technique three to obtain a final blend which satisfies the required HI index range.
A general method of preparation of the various linear polymers, sub-ject to the limitations of this invention, is described in U. S. Patent 3,639,517 in which sequential polymerization of styrene or other monovinyl-substituted ;;;, -:
~ aromatic hydrocarbon and butadiene or other conjugated diene is employed.
r~'' The radial polymers of this invention are individually prepared accord-~?
ing to the method described in Kitchen et al, U. S. 3,639,517 except that multi-` ple addition of the monovinyl-substituted aromatic compound is not necessary.
Briefly, in accordance with the procedure outlined therein, sequential polymer-s ization of styrene or other monovinyl-substituted aromatic hydrocarbon and buta-diene or other conjugated diene is carried out and thereafter the resulting lithium-terminated polymer is coupled with a polyfunctional treating agent. As noted hereinabove, only a single charge of monovinyl-:i , .
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~ 1085~84 substituted aromatic compound and initiator is required for each individual polymer used to prepare the radial copolymer blends of this invention. Sty-rene and 1,3-butadiene are the presently preferred monomers in this aspect of the invention also.
In this aspect of the invention also, the polymer solutions result-ing from two separate polymerizations as described above are combined and mixed to form an intimate mixture of the polymer solutions. Subsequently, the mixture is recovered following the procedures described in said Kitchen et al patent.
It is within the scope of this aspect of the invention to form mixtures of separately recovered polymers by intensive mixing in Banbury mixers, extrusion compounding, roll milling, solution blending, and the like.
.~ The general method of preparing the high impact polymers of this invention is summarized by giving the charge order for forming two polymers, each polymer having different block lengths, followed by mixing as follows:
Reactor one Reactor two ; a) cyclohexane cyclohexane b) styrene styrene ;
c) tetrahydrofuram tetrahydrofuran ;
d) n-butyllithium n-butyllithium e) polymerize at 50-60C polymerize at 50-60C
.. . .
f) butadiene butadiene g) polymerize at 50-60C polymerize at 50-60C
h) polyfunctional treating agent polyfunctional treating agent i) combine solutions j) add stabilizer system k) devolatilize 1) finish (form granules or pellets) The sequence given above in each reactor is for making diblocks which are coupled by the polyfunctional treating agent to form a polymer which can ` 30 be expressed as: (styrene-butadiene~nY where Y is the polyfunctional treating - agent and n is an integer of 3-7 or more. It is within the scope of this .~ _9_ :.
.
.
' invention to employ as one or more components of the blend one or more poly-mers made by multiple addition of monovinyl-substituted aromatic hydrocarbon and initiator wherein for some reason the resulting polymer is off specifica-tion, i.e., has a heterogeneity index outside the range of about 2.8 to 3.5.
Broadly then this aspect of the invention involving radial polymer resides in the blending of two radial block copolymers of a monovinyl-substituted aro-matic compound and a coniugated diene each having a heterogeneity index out-., . side the range of about 2.8 to 3.5 with at least one less than 2.8 to give a blend having a heterogeneity index within the range of 2.8 to 3.5.
Exemplary polyfunctional treating agents that can be used in accord-ance with this aspect of the invention in the preparation of the branched block (xadial) copolymers are the polyepoxides such as epoxidized linseed oil, epoxidized soybean oil, and 1,2,5,6,9,10-triepoxydecane; polyimines such as tri~l~aziridinyl)phosphine oxide; polyisocyanates such as benzene-1,2,4-tri-isocyanate; polyaldehydes such as 1,4,7-naphthalenetricarboxyaldehyde; poly-halides such as silicon tetrachloride or polyketones such as 1~4~9~lo-anthra cenetetrone and polyalkoxysilanes such as methyltrimethoxysilane.
The compositions of this invention can, of course, contain conven-tional additives such as antioxidants, W stabilizers, fillers, pigments, and the like.
In the following Examples, Examples I to III relate to the first aspect of this invention (linear copolymer blends) and Example IV to the ` second aspect (radial copolymer blends).
EXAMPLE I
Polymers made according to technique one, previously described, were prepared by conducting each polymerization in 32 ounce (0.95 liter) glass beverage bottles. In each run, the following materials were added to the bottle, while under nitrogen, in the order shown:
; (1) cyclohexane (CyC6), then first increment of styrene (S) (2) purge 5 minutes with nitrogen, cap and fill with nitrogen (3) tetrahydrofuran (THF) ~ -10-' - - 1085~84
(4) first initiator charge, n-butyllithium (BuLi), 0.023 g/cm in cyclohexane ~: (5~ react at 60C for 30 minutes (60 minutes in run 2) (6) second initiator charge (7) second increment of styrene (8) react at 60C. for 15 minutes (60 minutes in run 2) (9) butadiene (B) (10) react at 60C for 30 minutes (60 minutes in run 2) ., .
(11) third increment of styrene 10(12) react at 60C. for 30 minutes (60 minutes in run 2) :~
(13) stabilizer system, 2 parts by weight per 100 parts by weight . monomer (phm) ';' The quantities of each component used in the polymerizations are given in the following Table IA.
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'~ 8S~84 After the stabilizer system was mixed with the polymer solution, each solution was devolatilized in a vacuum oven at 100C and the resulting drled product was milled on a roll mill at 285F (140C) for 3 minutes, after banding commenced, to further homogenize and densify the sample.
; The melt flow, glass transition temperature (Tg) (by differential thermal analysis, DTA), falling dart impact strength, elongation, dynamic modulus and loss was determined, when applicable, for each sample. The melt flow was determined in accordance with ASTM D1238-62T at 200C and a 5 kg load.
r' Tg was determined by DTA using a DuPont Thermal Analyzer, Model 900, equipped with a DSC cell. Dart impact strength was ascertained by noting the height in inches at which a free falling bullet-shaped brass dart weighing 1.123 lbs (0.509 kg) impacting a test sample broke 2 out of 4 samples tested at that height. The samples were made by injection molding slabs having the dimensions ~ 1 1/4" x 1 3/4" x 0.100" (3.2 cm x 4.4 cm x 0.25 cm). Each slab was positioned `' so that it was supported around its perimeter during the impact test and each ' sample was tested only once. The dynamic modulus and loss values were deter-mined by means of a Vibron Direct Reading Viscoelastometer, Model DW -II
~ (Vibron is a trademark of Toyo Instruments Co., Tokyo, Japan). The direct .~
reading viscoelastometer experiments were made on test samples cut from com-, . . .
pression molded film having dimensions about 1/8" wide (0.05 cm), 1.2" long (3 cm) and about 10 mils (0.025 cm) in thickness. Each test sample was measured at 35 Hz at temperatures ranging from about -100C to about 20C. The physical properties of each polymer sample and the test results are given in the follow-ing Table I B.
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(11) third increment of styrene 10(12) react at 60C. for 30 minutes (60 minutes in run 2) :~
(13) stabilizer system, 2 parts by weight per 100 parts by weight . monomer (phm) ';' The quantities of each component used in the polymerizations are given in the following Table IA.
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'~ 8S~84 After the stabilizer system was mixed with the polymer solution, each solution was devolatilized in a vacuum oven at 100C and the resulting drled product was milled on a roll mill at 285F (140C) for 3 minutes, after banding commenced, to further homogenize and densify the sample.
; The melt flow, glass transition temperature (Tg) (by differential thermal analysis, DTA), falling dart impact strength, elongation, dynamic modulus and loss was determined, when applicable, for each sample. The melt flow was determined in accordance with ASTM D1238-62T at 200C and a 5 kg load.
r' Tg was determined by DTA using a DuPont Thermal Analyzer, Model 900, equipped with a DSC cell. Dart impact strength was ascertained by noting the height in inches at which a free falling bullet-shaped brass dart weighing 1.123 lbs (0.509 kg) impacting a test sample broke 2 out of 4 samples tested at that height. The samples were made by injection molding slabs having the dimensions ~ 1 1/4" x 1 3/4" x 0.100" (3.2 cm x 4.4 cm x 0.25 cm). Each slab was positioned `' so that it was supported around its perimeter during the impact test and each ' sample was tested only once. The dynamic modulus and loss values were deter-mined by means of a Vibron Direct Reading Viscoelastometer, Model DW -II
~ (Vibron is a trademark of Toyo Instruments Co., Tokyo, Japan). The direct .~
reading viscoelastometer experiments were made on test samples cut from com-, . . .
pression molded film having dimensions about 1/8" wide (0.05 cm), 1.2" long (3 cm) and about 10 mils (0.025 cm) in thickness. Each test sample was measured at 35 Hz at temperatures ranging from about -100C to about 20C. The physical properties of each polymer sample and the test results are given in the follow-ing Table I B.
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1085~84 .
As can be seen, invention Run 2 representing the invention had a high impact strength similar to that of the best of the radial polymers as exemplified by control Run 4, and much better than that of ordinary radial polymer as exemplified by control Run 3. Impact was not determined on inven-tion Run 1, however, the temperature of tangent O~max was -80C., which is a value associated with good impact as will be discussed in more detail in the discussion following Table III C. Thus these data show surprisingly that linear polymer produced by multiple addition of initiator and styrene, having a heterogeneity index of the polymerized styrene blocks within the range of about 2.3 to 4.5 has an impact strength as good as or better than the best - radial polymer. Runs 3 and 4 contained 76 percent polymerized styrene and ;~
Runs 1 and 2 75 percent, i.e., they were essentially equal.
EXAMPLE II
~ Polymers made according to technique two, previously described, were ; prepared by conducting a series of individual polymerizations with variable quantities of monomers and coupling the resulting polymers with ethyl acetate as an example of a difunctional coupling agent. Each polymerization of the first 9 runs was conducted in a 32 ounce (0.95 liter) glass beverage bottle.
Each component used was added to the bottle in a nitrogen atmosphere. Prep-aration details are given in Table II A.
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~ 1085084 . Two runs were conducted in a 5 gallon (0,02 m3) stainless steel reactor. The following quantities of reactants and conditions were employed:
Run 10 Run 11 First charge:
cyclohexane 14,7 lbs (6.7 kg) 14.7 lbs (6.7 kg) ,' tetrahydrofuran 0.84 cm3 0.84 cm3 i styrene 1,59 kg 1,59 kg n-butyllithium (as solution cyclohexane) 0.90 g 0.87 g initial temperature 107F (42C~ 110F (43C) polymerization time, minutes 37 44 Second charge:
cyclohexane 0.3 lb (0.14 kg) 0.3 lb (0.14 kg) n-butyllithium 3.6 g 3.1 g styrene 0,69 kg 0.69 kg initial temperature 156F (69C) 166F (74C) polymerization time, minutes 24 21 Third charge:
cyclohe~ane 0.1 lb (0.045 kg) 0.1 lb (0.045 kg) butadiene 0.72 kg 0.72 kg initial temperature 161F (72C) 166F (74C) polymerization time, minutes 21 20 Fourth charge:
cyclohexane 0.2 lb (0.09 kg) 0.2 lb (0.09kg) ethyl acetate in CyC6 (0.19 g/cm3) 31 cm3 28 cm3 initial temperature 216F (102C) 218F (103C) reaction time, minutes 20 20 ~, Each polymer solution was treated with 6 cm water and the reactor pressured up to 110 psig (758 kPa gage) with carbon dioxide to improve the color of the polymer. Run 10 was C02 treated 20 minutes at 216F. (102C.) and run 11 was C02 treated 30 minutes at 216F. also. A 50 wt. % stabilizer : solution containing trils (nonylphenyl)phosphite and 2~6-di-t-butyl-4-methyl-~ -17-.
- : .
1~85~84 :
.: phenol dissolved in cyclohexane was then added to each polymer solution such ' that 1,5 parts by weight phosphite per 100 parts by weight total monomers (phm) and 0.5 phm phenol was present. Each polymer solution was flashed at 332F. (167C.) to remove solvent.
The physical properties of the polymers are presented in Table II B.
A general discussion of the test results is given following Table III C.
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This example shows surprisingly that high impact linear compositions can be obtained by multiple addition of the styrene monomer and catalyst followed by coupling to give a product with about a 2.3 to 4,5 heterogeneity index for the polymerized styrene blocks. The impact values of 48.3 to ~80 - for the linear polymer of invention Runs 7, 9~ lO and 11 compares favorably i with the best of the radial polymers as exemplified by control Run 4 of ; Example I and represents a dramatic improvement compared with linear polymer having a heterogeneity index below 2.4 as by control Runs 1-3 as well as a dramatic improvement compared with ordinary radial polymer as exemplified by control Run 3 of Example I. While impact was not determined on Runs 6 and 8, ;~ these runs exhibited a temperature of tangent ~ maximum and tangent ~ maximum associated with high impact strength as discussed in connection with Example III hereinbelow.
EXAMPLE III
Polymers made according to technique three, previously described ., .
wherein the order of addition was styrene, initiator, butadiene, coupling agent, were prepared by conducting a series of individual polymerizations to form diblock polymers each of which was coupled with ethyl acetate as the difunctional coupling agent. The resulting solutions were mixed as shown in Tables III A and III Bto form a mixture. Each mixture was treated with stabilizer solution as previously described, recovered by devolatilization in vacuo at 100C. for the bottle samples or by flashing at 332F. (167C.) to remove solvent for the larger preparations.
The preparation details are presented in Tables III A and B.
:
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-` ~085084 Table Ill A
Preparation of Individual Diblock, Difunctidnally Cou~led Copolymers Effective Ethyl Run CyC6 S ComPOnent THF BuLi B Component Acetate No. (cm3)-(~) (cmJ) (g) (cm3) (~) (cm3) (g~ Comments 1 325 3437.70.023 0.63 11 18.2 1.0 2 220 22.5 24.9 .015 4.47 7.5 12.3 6.6 ; 3 325 3437.70.023 0.63 11 18.2 1.0 Run 1 duplicate 4 220 22.5 24.9 .015 4.47 7.5 12.3 6.6 Run 2 duplicate 325 3437.70.023 0.94 11 1~.2 1.5
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1085~84 .
As can be seen, invention Run 2 representing the invention had a high impact strength similar to that of the best of the radial polymers as exemplified by control Run 4, and much better than that of ordinary radial polymer as exemplified by control Run 3. Impact was not determined on inven-tion Run 1, however, the temperature of tangent O~max was -80C., which is a value associated with good impact as will be discussed in more detail in the discussion following Table III C. Thus these data show surprisingly that linear polymer produced by multiple addition of initiator and styrene, having a heterogeneity index of the polymerized styrene blocks within the range of about 2.3 to 4.5 has an impact strength as good as or better than the best - radial polymer. Runs 3 and 4 contained 76 percent polymerized styrene and ;~
Runs 1 and 2 75 percent, i.e., they were essentially equal.
EXAMPLE II
~ Polymers made according to technique two, previously described, were ; prepared by conducting a series of individual polymerizations with variable quantities of monomers and coupling the resulting polymers with ethyl acetate as an example of a difunctional coupling agent. Each polymerization of the first 9 runs was conducted in a 32 ounce (0.95 liter) glass beverage bottle.
Each component used was added to the bottle in a nitrogen atmosphere. Prep-aration details are given in Table II A.
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~ 1085084 . Two runs were conducted in a 5 gallon (0,02 m3) stainless steel reactor. The following quantities of reactants and conditions were employed:
Run 10 Run 11 First charge:
cyclohexane 14,7 lbs (6.7 kg) 14.7 lbs (6.7 kg) ,' tetrahydrofuran 0.84 cm3 0.84 cm3 i styrene 1,59 kg 1,59 kg n-butyllithium (as solution cyclohexane) 0.90 g 0.87 g initial temperature 107F (42C~ 110F (43C) polymerization time, minutes 37 44 Second charge:
cyclohexane 0.3 lb (0.14 kg) 0.3 lb (0.14 kg) n-butyllithium 3.6 g 3.1 g styrene 0,69 kg 0.69 kg initial temperature 156F (69C) 166F (74C) polymerization time, minutes 24 21 Third charge:
cyclohe~ane 0.1 lb (0.045 kg) 0.1 lb (0.045 kg) butadiene 0.72 kg 0.72 kg initial temperature 161F (72C) 166F (74C) polymerization time, minutes 21 20 Fourth charge:
cyclohexane 0.2 lb (0.09 kg) 0.2 lb (0.09kg) ethyl acetate in CyC6 (0.19 g/cm3) 31 cm3 28 cm3 initial temperature 216F (102C) 218F (103C) reaction time, minutes 20 20 ~, Each polymer solution was treated with 6 cm water and the reactor pressured up to 110 psig (758 kPa gage) with carbon dioxide to improve the color of the polymer. Run 10 was C02 treated 20 minutes at 216F. (102C.) and run 11 was C02 treated 30 minutes at 216F. also. A 50 wt. % stabilizer : solution containing trils (nonylphenyl)phosphite and 2~6-di-t-butyl-4-methyl-~ -17-.
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1~85~84 :
.: phenol dissolved in cyclohexane was then added to each polymer solution such ' that 1,5 parts by weight phosphite per 100 parts by weight total monomers (phm) and 0.5 phm phenol was present. Each polymer solution was flashed at 332F. (167C.) to remove solvent.
The physical properties of the polymers are presented in Table II B.
A general discussion of the test results is given following Table III C.
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This example shows surprisingly that high impact linear compositions can be obtained by multiple addition of the styrene monomer and catalyst followed by coupling to give a product with about a 2.3 to 4,5 heterogeneity index for the polymerized styrene blocks. The impact values of 48.3 to ~80 - for the linear polymer of invention Runs 7, 9~ lO and 11 compares favorably i with the best of the radial polymers as exemplified by control Run 4 of ; Example I and represents a dramatic improvement compared with linear polymer having a heterogeneity index below 2.4 as by control Runs 1-3 as well as a dramatic improvement compared with ordinary radial polymer as exemplified by control Run 3 of Example I. While impact was not determined on Runs 6 and 8, ;~ these runs exhibited a temperature of tangent ~ maximum and tangent ~ maximum associated with high impact strength as discussed in connection with Example III hereinbelow.
EXAMPLE III
Polymers made according to technique three, previously described ., .
wherein the order of addition was styrene, initiator, butadiene, coupling agent, were prepared by conducting a series of individual polymerizations to form diblock polymers each of which was coupled with ethyl acetate as the difunctional coupling agent. The resulting solutions were mixed as shown in Tables III A and III Bto form a mixture. Each mixture was treated with stabilizer solution as previously described, recovered by devolatilization in vacuo at 100C. for the bottle samples or by flashing at 332F. (167C.) to remove solvent for the larger preparations.
The preparation details are presented in Tables III A and B.
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-` ~085084 Table Ill A
Preparation of Individual Diblock, Difunctidnally Cou~led Copolymers Effective Ethyl Run CyC6 S ComPOnent THF BuLi B Component Acetate No. (cm3)-(~) (cmJ) (g) (cm3) (~) (cm3) (g~ Comments 1 325 3437.70.023 0.63 11 18.2 1.0 2 220 22.5 24.9 .015 4.47 7.5 12.3 6.6 ; 3 325 3437.70.023 0.63 11 18.2 1.0 Run 1 duplicate 4 220 22.5 24.9 .015 4.47 7.5 12.3 6.6 Run 2 duplicate 325 3437.70.023 0.94 11 1~.2 1.5
6 220 22.5 24.9 .015 4.47 7.5 12.3 6.6
7 325 36.3 39.9 .023 0.49 8.7 14.3 0.29
8 220 19.9 21.9 .015 1.83 10.1 16.6 1.33
9 325 37.5 41.2 .023 0.30 7.5 12.3 0.30 ~...................................................................... .
220 18.8 20.7 .015 1.75 11.2 18.5 1.25 11 325 38.8 42.6 .023 0.31 6.2 10.2 0.31 , 12 220 17.5 19.2 .015 1.67 12.5 20.6 1.17 ,''l 13 325 40.9 45.0 .023 0.33 4.1 6.8 0.33 i 14 220 15.4 16.9 .015 1.53 14.6 24.0 1.03 ;~ 20 15 295 37.4 41.5 .020 0.79 3.2 5.3 0.25 16 250 18.9 21.0 .017 3.70 15.6 25.9 1.26 17 295 37.0 41.0 .020 0.60 2.8 4.7 0.22 ~I 18 250 19.3 21.4 .018 3.75 16.0 26.5 1.28 .~ 19 295 40.9 45.0 .023 0.91 4.1 6.8 0.33 ~, 20 250 15.4 16.9 .015 3.06 14.6 24.0 1.03 .
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Preparation of Indlvidual Diblockj Difu_ctionally Coupled Copolymers in ~ S~irred Reactor Effective Ethyl Run _ CyC~,~ S Component THF BuLi B Component Acetate No.(Pounds)(kg) (kg) (cm3) (g) (kg) (cm3) 21 9.4 4.3 1.254 0.40 0.93 0.171 6.4 22 7.1 3.2 0.624 0.31 2.97 0.451 20.0 23 8.9 4.0 1.161 0.38 0.63 0.189 4.4 ~ 10 24 7.6 3,4 0.725 0.32 3.10 0.425 21.0 - 25 9.4 4,3 1.254 0.41 0.67 0.171 4.6 26 7.1 3.2 0.624 0.31 2.66 0.451 18.0 27 9.9 4.5 1.335 0.42 0.92 0.165 6.9 28 6.6 3.0 0.550 0.28 2.33 0.450 16.0 .. ~ .
298.9 4.0 1.242 0.380.52 0.1084.1 , 30 7.6 3.4 0.621 0.32 2.68 0.529 18.4 .' ,' .
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la~s~4 'The magnitude and temperature of the tan O~ maxihum corresponding to the glass transition temperature of the polybutadiene blocks are used as criteria of polymer morphology. Samples exhibiting high tan 0~ max values, ; i.e., from about 0.045 up to about 0.200 or more along with T(tanO~ max) values ranging from about -87 to about -75C. are shown inthe tables to have good impact properties as determined by the falling dart tests. Such samples have impact values in the dart test ranging from about 20in-lbs to greater than 80 in-lbs (the limit of the test). Micrographs taken of several radial polymers made using multiple styrene and initiator addition as is exemplified in control Run 4, Table I B, having a tan cfmax of 0.149, T(tan ~ max) of -78C., dart impact of 53.0 in-lbs and HI of 3.0 are shown to possess lamellar : morphology. Such polymers have alternating layers of polybutadiene and poly-styrene. Since the invention samples have high test values for the criteria described above it is reasoned that they all exhibit lamellar morphology.
On the other hand ordinary radial polymers are illustrative of co-polymers exhibiting good but not outstanding impact values; control Run 3, Table I B i8 an example. This sample has a tan o'max of 0.027, a T(tanc~max) of -93C., a dart impact of ~ 10 in-lbs and a HI of 1Ø Micrographs taken of ;1l similar ordinary radial polymers show them to possess a spherical morphology in which spheres of polybutadiene are embedded in a continuum of polystyrene.
On impact, the polystyrene phase takes most of the load, hence relatively low impact values are to be expected which correlate with the ~ibron results.
Inspection of the data presented in Table III C, shows that some polymer mixtures exhibiting a styrene block HI index in the desired range of about 2.3 to about 3.9 do not appear to have lamellar morphology based on low impact values, and/or low tan ~ max values. The polymers of Runs 1, 2, and 4-8 illustrate this. It should be noted that the polymer mixture of Run 6 also possesses a T(tan ~ max) of -87C. which is in the desired range. This is because in mixtures of polymers another requirement is also needed, namely, that the butadiene blocks of each polymer in the mixture have similar enough molecular weights to be compatible. In Runs 1, 2, and 4-8, the difference lass~s4 between the molecular weights of the butadiene block ranges from about 19,000 to about 128,000, The incompatibility apparently influences the morphology of the mixed polymers, thus the desired lamellar morphology is not realized and -relatlvely low impact values are found in molded articles made from these pol~mer blends. It is thought that these polymer blends may exhibit cylin-drlcal morphology, i,e., cylinders of butadiene blocks in a continuum of styrene blocks.
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Invention ~uns 10, 11, 12 and 15 of Table III-C meet all the desired criteria including compatibility of butadiene blocks. Run 14 is on the border-line between those blends that have the greatly improved impact strength andthose that do not. The difference in molecular weights of the butadiene blocks in these blends ranges from about 0 to about 9,000. Thus, for a final criterion, the molecular weight difference between butadiene blocks of mixed linear polymers (blends) should be less than about 10,000.
EXAMPLE IV - PART I
., A series of diblock polymers containing polymerized styrene and polymerized butadiene was prepared in 32 ounce (0.95 litre) glass beverage i bottles and coupled with epoxidized soybean oil containing an average of 4 ~1 epoxide groups per molecule. In each run, the following materials were added 20 to the bottle, while under nitrogen, in the order shown:
1) cyclohexane (C C6) then first increment of styrene (S) 2) purge 5 minutes with nitrogen, cap and fill with nitrogen 3) tetrahydrofuran (THF) 4) n-butyllithium (0.023 g/cm3 in cyclohexane) BuLi 5) react at 60C for 30 minutes 6) second increment of styrene (if used) and react 60C for 30 minutes - note that no additional initiator is added so this is not a multiple addition of styrene in the sense contemplated by said Kitchen et al patent, 7) butadiene (B), react at 60C for 30 minutes 8) epoxidized soybean oil (ES0) and react at 60C for 30 minutes .~
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-- ` 1085~84 , . .. .
9~ stabilizer system 2 pa~ts by weight per lOO parts by weight monomer (phm).
f. The quantities of each component used are given in the following table:
Table I
Individual Radial Block Copol~mer Fdrmation Effective(a) Run C~C6 First S THF BuLi Second SA B ES0 No. (cm~) (g) Ccm3? (g) (cm3) (g) (cmJ~ (~) (cm~) (g) ' 1 400 26.5 29.1 0.073 2.0 0 0 27.5 45.4 0.27 , 10 2 400 50.0 55.0 0.023 3.2 28.731.5 7.3 12.0 0.433 400 31.9 35.0 0.013 2.0 0 0 23.1 38.1 0.27 4 400 50.0 55.0 0.023 3.2 23.125.4 11.9 19.6 0.43 "'"J 5 400 36.? 39.8 0.013 2.0 0 0 17.8 29.4 0.27 s, 6 400 50.0 35.0 0.023 3.2 18.820.6 17.2 28.4 0.43 7 220 27.7 30.5 0.013 6.7 0 0 23.0 28.0 0.25 8 400 50.0 55.0 0.023 1.7 28.030.8 12.2 20.0 0.45 :' 9 220 32.4 35.6 0.013 6.7 0 0 18.4 30.4 0.25 600 50.0 55.0 0.023 1.7 23.025.3 16.9 27.7 0.45 11 220 38.4 42.1 0.013 6.7 0 0 12.7 21.0 0.25 `i( 20 12 600 50.0 55.0 0.023 1.7 17.519.2 22.5 37.1 0.45 ,~ 13 220 24.0 26.4 0.013 6.7 0 0 26.0 43.0 0.25 . 14 400 50.0 55.0 0.023 1.7 32.335.5 7.7 12.7 0.45400 40.5 44.5 0.013 2.0 0 0 15.5 22.3 0.27 ^` 16 400 50.0 55.0 0.023 3.2 14.515.9 21.5 35.5 0.43 17 175 11.6 12.8 0.006 3.2 0 0 12.5 20.6 0.27 18 310 39.0 42.9 0.011 0.8 0 0 3.9 6.4 0.07 19 175 15.4 16.9 0.006 3.2 0 0 8.7 14.3 0.27 , 20 310 35.2 38.7 0.011 0.8 0 0 7.7 12.7 0,07,;', (a) Slightly more than this was used depending on the measured catalyst , 30 poisons. The effective a unt is the cc of the solution used in ; addition to a small amount needed ~ scavenge poisons.
,. . .
;,i Notes: The styrene in each even numbered run was added in two portions ,, because of safety considerations. After the first portion polymerized, the remainder was charged and allowed to polymerize. Thus, a single polystyrene block was formed from two styrene portions, i.e., it was not multiple addi-, tions as defined hereinbefore because no additional initiator was added.
The THF and ES0 were each added as a solution in cyclohexane, having ` 0.034 gram of compound per cm3 solvent.
The stabilizer system consisted of 1.5 phm tr~(mixed mono- and dinonyl-phenyl~ phosphite (Wytox 312), and 0.5 phm 2,6-di-t-butyl-4-methylphenol con-tained in cyclohexane.
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1085~)84 . . .
EXAMPLE IV - P~RT II
; The polymer cements made in Part I of the Example were combined in :' .
pairs, i.e.~ runs 1 and 27 3 and 4, 5 and 6, etc., to obtain a cement, in each instance~ except for two control runs~ containing a mixture of polymers of differing polystyrene block molecular weights. Each cement mixture was thor-oughly blended together, devolatilized in a vacuum oven at 210F (99C), and the dried material was milled on a roll mill at 280F (I38C) for 3 minutes after banding commenced to further homogenize and densify the sample. Film samples for the dynamic viscoelastic measurements were prepared by compression molding 1 g samples at 500Q psig (34,47 MPa g) for 4 minutes and then for 1 minute at 30,000 psig (206,8 MPa g), The samples were cooled in about 10-15 minutes to about 190F (88C) under the 30,000 psig initial pressure by passing cooling water through the press and then removed. The measurements of dynamic :~ modulus and 1055 angle were carried out by means of a Vibron Direct Reading Viscoelastometer, Model DW -II (Toyo Instruments Co., Tokyo, ~apan). All experiments were made on test samples cut from the compression molded film which were about 1/8~' wide (0.05 cm), 1.21' long (3 cm) and about 10 mils (0,025 cm) in thickness. The samples were tested at 35 H at temperatures ranging from about -100C to about 20C.
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: ~ ~085~84 -In discussing the test results, especially the Vibron results, it is to be noted that the magnitude of the maximum loss tangent (tan ofmax) and the temperature at which the tanc~ max occurs for the polybutadiene blocks are used as criteria of polymer morphology. From work on other polymers it is observed that test samples exhibiting high tanc' max values, i.e., from about 0,045 to about 0.200 or more along with T(tan Gf max~ ranging from about -87 to about -75C have dart impact values ranging from about 20 to greater than the test limit of 80 in-lbs. Micrographs taken of multiple addition polymers of the type described in said Kitchen et al patent as exemplified in control run 12, having a tan dr max o 0.149, T(tan cf max) of -78C, dart ; impact of 53.0 in-lbs. and a HI of 3,0 are shown to possess lamellar morph-ology. Since the invention polymers of runs 8, 9 and 10 possess the requisite HI values ~2,8 to 3,1~, the requisite tano~ max values (0.0625 to 0.1050) and requisite T~tanor max) values of (-87 to -81) it is reasoned that these poly-:!
mers would exhibit lamellar morphology and that therefore their dart impact values, if run, would fall between 20 and 80 in-lbs.
Control run 11 illustrates properties of a typical single styrene and initiator addition polymer which exhibits relatively low impact strength ~; compared to the multiple addition polymers of said Kitchen et al patent and the blends of this invention. Micrographs taken of single addition polymers show them to possess a spherical morphology in which spheres of polybutadiene are embedded in a continuum of polystyrene. On impact, the polystyrene phase takes most of the load, hence these polymers exhibit relatively low impact ~' values. Control runs 1 to 7 are illustrative of polymers also possessing the spherical morphology of the polymer of control run 11, by analogy, since the HI values of each polymer are less than 2,8. The Vibron test results, i,e "
tan o~ max of less than about 0.045 along with T(tan of max) values of less thanabout -88C for control runs 1 to 7 are typical ~f polymers exhibiting the spherical morphology.
While this invention has been described in,detail for the purpose of illustration it is not to be construed as limited t~ereby but is intended to cover all changes and modifications within the spirit and scope thereof.
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220 18.8 20.7 .015 1.75 11.2 18.5 1.25 11 325 38.8 42.6 .023 0.31 6.2 10.2 0.31 , 12 220 17.5 19.2 .015 1.67 12.5 20.6 1.17 ,''l 13 325 40.9 45.0 .023 0.33 4.1 6.8 0.33 i 14 220 15.4 16.9 .015 1.53 14.6 24.0 1.03 ;~ 20 15 295 37.4 41.5 .020 0.79 3.2 5.3 0.25 16 250 18.9 21.0 .017 3.70 15.6 25.9 1.26 17 295 37.0 41.0 .020 0.60 2.8 4.7 0.22 ~I 18 250 19.3 21.4 .018 3.75 16.0 26.5 1.28 .~ 19 295 40.9 45.0 .023 0.91 4.1 6.8 0.33 ~, 20 250 15.4 16.9 .015 3.06 14.6 24.0 1.03 .
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., -~ ~able III B
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Preparation of Indlvidual Diblockj Difu_ctionally Coupled Copolymers in ~ S~irred Reactor Effective Ethyl Run _ CyC~,~ S Component THF BuLi B Component Acetate No.(Pounds)(kg) (kg) (cm3) (g) (kg) (cm3) 21 9.4 4.3 1.254 0.40 0.93 0.171 6.4 22 7.1 3.2 0.624 0.31 2.97 0.451 20.0 23 8.9 4.0 1.161 0.38 0.63 0.189 4.4 ~ 10 24 7.6 3,4 0.725 0.32 3.10 0.425 21.0 - 25 9.4 4,3 1.254 0.41 0.67 0.171 4.6 26 7.1 3.2 0.624 0.31 2.66 0.451 18.0 27 9.9 4.5 1.335 0.42 0.92 0.165 6.9 28 6.6 3.0 0.550 0.28 2.33 0.450 16.0 .. ~ .
298.9 4.0 1.242 0.380.52 0.1084.1 , 30 7.6 3.4 0.621 0.32 2.68 0.529 18.4 .' ,' .
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la~s~4 'The magnitude and temperature of the tan O~ maxihum corresponding to the glass transition temperature of the polybutadiene blocks are used as criteria of polymer morphology. Samples exhibiting high tan 0~ max values, ; i.e., from about 0.045 up to about 0.200 or more along with T(tanO~ max) values ranging from about -87 to about -75C. are shown inthe tables to have good impact properties as determined by the falling dart tests. Such samples have impact values in the dart test ranging from about 20in-lbs to greater than 80 in-lbs (the limit of the test). Micrographs taken of several radial polymers made using multiple styrene and initiator addition as is exemplified in control Run 4, Table I B, having a tan cfmax of 0.149, T(tan ~ max) of -78C., dart impact of 53.0 in-lbs and HI of 3.0 are shown to possess lamellar : morphology. Such polymers have alternating layers of polybutadiene and poly-styrene. Since the invention samples have high test values for the criteria described above it is reasoned that they all exhibit lamellar morphology.
On the other hand ordinary radial polymers are illustrative of co-polymers exhibiting good but not outstanding impact values; control Run 3, Table I B i8 an example. This sample has a tan o'max of 0.027, a T(tanc~max) of -93C., a dart impact of ~ 10 in-lbs and a HI of 1Ø Micrographs taken of ;1l similar ordinary radial polymers show them to possess a spherical morphology in which spheres of polybutadiene are embedded in a continuum of polystyrene.
On impact, the polystyrene phase takes most of the load, hence relatively low impact values are to be expected which correlate with the ~ibron results.
Inspection of the data presented in Table III C, shows that some polymer mixtures exhibiting a styrene block HI index in the desired range of about 2.3 to about 3.9 do not appear to have lamellar morphology based on low impact values, and/or low tan ~ max values. The polymers of Runs 1, 2, and 4-8 illustrate this. It should be noted that the polymer mixture of Run 6 also possesses a T(tan ~ max) of -87C. which is in the desired range. This is because in mixtures of polymers another requirement is also needed, namely, that the butadiene blocks of each polymer in the mixture have similar enough molecular weights to be compatible. In Runs 1, 2, and 4-8, the difference lass~s4 between the molecular weights of the butadiene block ranges from about 19,000 to about 128,000, The incompatibility apparently influences the morphology of the mixed polymers, thus the desired lamellar morphology is not realized and -relatlvely low impact values are found in molded articles made from these pol~mer blends. It is thought that these polymer blends may exhibit cylin-drlcal morphology, i,e., cylinders of butadiene blocks in a continuum of styrene blocks.
', .
Invention ~uns 10, 11, 12 and 15 of Table III-C meet all the desired criteria including compatibility of butadiene blocks. Run 14 is on the border-line between those blends that have the greatly improved impact strength andthose that do not. The difference in molecular weights of the butadiene blocks in these blends ranges from about 0 to about 9,000. Thus, for a final criterion, the molecular weight difference between butadiene blocks of mixed linear polymers (blends) should be less than about 10,000.
EXAMPLE IV - PART I
., A series of diblock polymers containing polymerized styrene and polymerized butadiene was prepared in 32 ounce (0.95 litre) glass beverage i bottles and coupled with epoxidized soybean oil containing an average of 4 ~1 epoxide groups per molecule. In each run, the following materials were added 20 to the bottle, while under nitrogen, in the order shown:
1) cyclohexane (C C6) then first increment of styrene (S) 2) purge 5 minutes with nitrogen, cap and fill with nitrogen 3) tetrahydrofuran (THF) 4) n-butyllithium (0.023 g/cm3 in cyclohexane) BuLi 5) react at 60C for 30 minutes 6) second increment of styrene (if used) and react 60C for 30 minutes - note that no additional initiator is added so this is not a multiple addition of styrene in the sense contemplated by said Kitchen et al patent, 7) butadiene (B), react at 60C for 30 minutes 8) epoxidized soybean oil (ES0) and react at 60C for 30 minutes .~
;'' ~ , . ..
-- ` 1085~84 , . .. .
9~ stabilizer system 2 pa~ts by weight per lOO parts by weight monomer (phm).
f. The quantities of each component used are given in the following table:
Table I
Individual Radial Block Copol~mer Fdrmation Effective(a) Run C~C6 First S THF BuLi Second SA B ES0 No. (cm~) (g) Ccm3? (g) (cm3) (g) (cmJ~ (~) (cm~) (g) ' 1 400 26.5 29.1 0.073 2.0 0 0 27.5 45.4 0.27 , 10 2 400 50.0 55.0 0.023 3.2 28.731.5 7.3 12.0 0.433 400 31.9 35.0 0.013 2.0 0 0 23.1 38.1 0.27 4 400 50.0 55.0 0.023 3.2 23.125.4 11.9 19.6 0.43 "'"J 5 400 36.? 39.8 0.013 2.0 0 0 17.8 29.4 0.27 s, 6 400 50.0 35.0 0.023 3.2 18.820.6 17.2 28.4 0.43 7 220 27.7 30.5 0.013 6.7 0 0 23.0 28.0 0.25 8 400 50.0 55.0 0.023 1.7 28.030.8 12.2 20.0 0.45 :' 9 220 32.4 35.6 0.013 6.7 0 0 18.4 30.4 0.25 600 50.0 55.0 0.023 1.7 23.025.3 16.9 27.7 0.45 11 220 38.4 42.1 0.013 6.7 0 0 12.7 21.0 0.25 `i( 20 12 600 50.0 55.0 0.023 1.7 17.519.2 22.5 37.1 0.45 ,~ 13 220 24.0 26.4 0.013 6.7 0 0 26.0 43.0 0.25 . 14 400 50.0 55.0 0.023 1.7 32.335.5 7.7 12.7 0.45400 40.5 44.5 0.013 2.0 0 0 15.5 22.3 0.27 ^` 16 400 50.0 55.0 0.023 3.2 14.515.9 21.5 35.5 0.43 17 175 11.6 12.8 0.006 3.2 0 0 12.5 20.6 0.27 18 310 39.0 42.9 0.011 0.8 0 0 3.9 6.4 0.07 19 175 15.4 16.9 0.006 3.2 0 0 8.7 14.3 0.27 , 20 310 35.2 38.7 0.011 0.8 0 0 7.7 12.7 0,07,;', (a) Slightly more than this was used depending on the measured catalyst , 30 poisons. The effective a unt is the cc of the solution used in ; addition to a small amount needed ~ scavenge poisons.
,. . .
;,i Notes: The styrene in each even numbered run was added in two portions ,, because of safety considerations. After the first portion polymerized, the remainder was charged and allowed to polymerize. Thus, a single polystyrene block was formed from two styrene portions, i.e., it was not multiple addi-, tions as defined hereinbefore because no additional initiator was added.
The THF and ES0 were each added as a solution in cyclohexane, having ` 0.034 gram of compound per cm3 solvent.
The stabilizer system consisted of 1.5 phm tr~(mixed mono- and dinonyl-phenyl~ phosphite (Wytox 312), and 0.5 phm 2,6-di-t-butyl-4-methylphenol con-tained in cyclohexane.
'`
:
1085~)84 . . .
EXAMPLE IV - P~RT II
; The polymer cements made in Part I of the Example were combined in :' .
pairs, i.e.~ runs 1 and 27 3 and 4, 5 and 6, etc., to obtain a cement, in each instance~ except for two control runs~ containing a mixture of polymers of differing polystyrene block molecular weights. Each cement mixture was thor-oughly blended together, devolatilized in a vacuum oven at 210F (99C), and the dried material was milled on a roll mill at 280F (I38C) for 3 minutes after banding commenced to further homogenize and densify the sample. Film samples for the dynamic viscoelastic measurements were prepared by compression molding 1 g samples at 500Q psig (34,47 MPa g) for 4 minutes and then for 1 minute at 30,000 psig (206,8 MPa g), The samples were cooled in about 10-15 minutes to about 190F (88C) under the 30,000 psig initial pressure by passing cooling water through the press and then removed. The measurements of dynamic :~ modulus and 1055 angle were carried out by means of a Vibron Direct Reading Viscoelastometer, Model DW -II (Toyo Instruments Co., Tokyo, ~apan). All experiments were made on test samples cut from the compression molded film which were about 1/8~' wide (0.05 cm), 1.21' long (3 cm) and about 10 mils (0,025 cm) in thickness. The samples were tested at 35 H at temperatures ranging from about -100C to about 20C.
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: ~ ~085~84 -In discussing the test results, especially the Vibron results, it is to be noted that the magnitude of the maximum loss tangent (tan ofmax) and the temperature at which the tanc~ max occurs for the polybutadiene blocks are used as criteria of polymer morphology. From work on other polymers it is observed that test samples exhibiting high tanc' max values, i.e., from about 0,045 to about 0.200 or more along with T(tan Gf max~ ranging from about -87 to about -75C have dart impact values ranging from about 20 to greater than the test limit of 80 in-lbs. Micrographs taken of multiple addition polymers of the type described in said Kitchen et al patent as exemplified in control run 12, having a tan dr max o 0.149, T(tan cf max) of -78C, dart ; impact of 53.0 in-lbs. and a HI of 3,0 are shown to possess lamellar morph-ology. Since the invention polymers of runs 8, 9 and 10 possess the requisite HI values ~2,8 to 3,1~, the requisite tano~ max values (0.0625 to 0.1050) and requisite T~tanor max) values of (-87 to -81) it is reasoned that these poly-:!
mers would exhibit lamellar morphology and that therefore their dart impact values, if run, would fall between 20 and 80 in-lbs.
Control run 11 illustrates properties of a typical single styrene and initiator addition polymer which exhibits relatively low impact strength ~; compared to the multiple addition polymers of said Kitchen et al patent and the blends of this invention. Micrographs taken of single addition polymers show them to possess a spherical morphology in which spheres of polybutadiene are embedded in a continuum of polystyrene. On impact, the polystyrene phase takes most of the load, hence these polymers exhibit relatively low impact ~' values. Control runs 1 to 7 are illustrative of polymers also possessing the spherical morphology of the polymer of control run 11, by analogy, since the HI values of each polymer are less than 2,8. The Vibron test results, i,e "
tan o~ max of less than about 0.045 along with T(tan of max) values of less thanabout -88C for control runs 1 to 7 are typical ~f polymers exhibiting the spherical morphology.
While this invention has been described in,detail for the purpose of illustration it is not to be construed as limited t~ereby but is intended to cover all changes and modifications within the spirit and scope thereof.
.: :
' ' ' ~ . :
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. A linear resinous monovinyl-substituted aromatic compound/con-jugated diene block copolymer composition characterized by having polymerized monovinyl-substituted aromatic compound blocks with a heterogeneity index within the range of 2.3 to 4.5.
2. A composition according to claim 1 wherein said monovinyl-sub-stituted aromatic compound is styrene and said conjugated diene is butadiene and said heterogeneity index is within the range of 2.4 to 4.5.
3. A composition according to claim 2 wherein said block copolymer is produced by introducing initiator and said styrene in at least two incre-ments prior to introduction of said butadiene.
4. A composition according to claim 2 wherein said block copolymer is produced by introducing initiator and said styrene in at least two incre-ments prior to introducing said butadiene and thereafter coupling the result-ing polymerized styrene-polymerized butadiene blocks with a difunctional coupling agent.
5. A composition according to claim 2 produced by blending two linear block copolymers wherein a polymerized butadiene block of each of the components constituting said blend has a molecular weight such that a dif-ference between the number average molecular weights of said polymerized butadiene blocks is less than 10,000.
6. A composition according to claim 2 having a falling dart impact strength of greater than 20 in-lbs.
7. A resinous composition produced by introducing a monovinyl-substituted aromatic compound and an initiator into a polymerization zone, thereafter introducing at least one additional increment of said monovinyl-substituted aromatic compound and said initiator, thereafter introducing a conjugated diene, and thereafter introducing additional monovinyl-substituted aromatic compound, said resulting composition having a heterogeneity index of polymerized monovinyl-substituted aromatic compound blocks within the range of 2.3 to 4.5.
8. A composition according to claim 7 wherein said monovinyl-substituted aromatic compound is styrene, said conjugated diene is butadiene, and said initiator is an organolithium compound.
9. A resinous composition prepared by introducing into a polymeri-zation zone a monovinyl-substituted aromatic compound and an initiator; after said monovinyl-substituted aromatic compound has been substantially all poly-merized introducing at least one additional increment of monovinyl-substituted aromatic compound and initiator; after said additional monovinyl-substituted aromatic compound has been essentially all polymerized introducing a conjugated diene monomer; after said conjugated diene monomer has been essentially all polymerized introducing a difunctional coupling agent; said composition being characterized by polymerized monovinyl-substituted aromatic compound blocks having a heterogeneity index within the range of 2,3 to 4.5.
10. A composition according to claim 9 wherein said monovinyl-substituted aromatic compound is styrene, said conjugated diene is butadiene, and said initiator is an organolithium compound.
11. A resinous composition prepared by blending two copolymers each of which is produced by introducing a monovinyl-substituted aromatic compound and an initiator into a polymerization zone; after said monovinyl-substituted aromatic compound is essentially all polymerized introducing at least one additional increment of said monovinyl-substituted aromatic compound and said initiator; after said additional monovinyl-substituted aromatic compound is essentially all polymerized introducing a conjugated diene; after said con-jugated diene is essentially all polymerized introducing a difunctional coupling agent, said composition being characterized by polymerized monovinyl-substituted aromatic compound blocks having a heterogeneity index within the range of 2.3 to 4.5.
12. A composition according to claim 11 wherein said monovinyl-substituted aromatic compound is styrene, said conjugated diene is butadiene, said initiator is an organolithium compound, and polymerized blocks of said butadiene in each of the components constituting said blend have a molecular weight such that the difference between the number average molecular weights of said polymerized butadiene blocks in said components is less than 10,000.
13, A resinous composition prepared by blending two polymers each of which is produced by introducing a monovinyl-substituted aromatic compound and an initiator into a polymerization zone; after said polymerization is essentially complete introducing at least one additional increment of said monovinyl-substituted aromatic compound and said initiator; after the poly-merization of said second increment of monovinyl-substituted aromatic compound is essentially complete introducing a conjugated diene; after the polymeriza-tion of said conjugated diene is essentially complete introducing another increment of said monovinyl-substituted aromatic compound, the resulting blend being characterized by polymerized monovinyl-substituted aromatic compound blocks having a heterogeneity index within the range of 2.3 to 4.5.
14. A composition according to claim 13 wherein said monovinyl-substituted aromatic compound is styrene, said conjugated diene is butadiene, said initiator is an organolithium compound and blocks of polymerized diene in each of the components constituting said blend have a molecular weight such that the difference between the number average molecular weight of said poly-merized butadiene blocks in each of said components is less than 10,000.
15. A resinous composition comprising a blend of two polymers each produced by introducing a monovinyl-substituted aromatic compound and an initiator into a polymerization zone; after the polymerization of said mono-vinyl-substituted aromatic compound is essentially complete introducing a conjugated diene into said polymerization zone; after the polymerization of said conjugated diene is essentially complete introducing another increment of said monovinyl-substituted aromatic compound, the resulting blend being characterized by polymerized monovinyl-substituted aromatic compound blocks having a heterogeneity index within the range of 2 3 to 4.5.
16. A composition according to claim 15 wherein said monovinyl-substituted aromatic compound is styrene, said conjugated diene is butadiene, said initiator is an organolithium compound, and blocks of polymerized buta-diene in each of said components constituting said blend have a molecular weight such that the difference between the number average molecular weight of said butadiene blocks in each of said components constituting said blend differ from each other by less than 10,000,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA344,752A CA1090034A (en) | 1975-11-10 | 1980-01-30 | Blend of resinous radial copolymers of a monovinyl- substituted aromatic compound and a conjugated diene |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/630,608 US4080407A (en) | 1975-11-10 | 1975-11-10 | Resinous linear copolymers having blocks with a heterogeneity index of 2.3 to 4.5 |
| US05/630,607 US4051197A (en) | 1975-11-10 | 1975-11-10 | Blend of radial block copolymers having high impact strength |
| US630,607 | 1975-11-10 | ||
| AU53713/79A AU520851B2 (en) | 1975-11-10 | 1979-12-11 | Block copolymers |
| US630,608 | 1984-07-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1085084A true CA1085084A (en) | 1980-09-02 |
Family
ID=27154885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,971A Expired CA1085084A (en) | 1975-11-10 | 1976-08-12 | Resinous linear block copolymer of a monovinyl- substituted aromatic compound and a conjugated diene |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5278260A (en) |
| AU (1) | AU507780B2 (en) |
| CA (1) | CA1085084A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787407A (en) * | 1980-11-21 | 1982-05-31 | Japan Synthetic Rubber Co Ltd | Preparation of styrene-butadiene copolymer |
| JPS61291610A (en) * | 1985-06-18 | 1986-12-22 | Japan Synthetic Rubber Co Ltd | Block copolymer and its composition |
| EP1605003B1 (en) * | 2003-03-19 | 2009-06-17 | Denki Kagaku Kogyo Kabushiki Kaisha | Block copolymer mixture containing star-branched block copolymer |
| WO2005010096A1 (en) | 2003-07-28 | 2005-02-03 | Denki Kagaku Kogyo Kabushiki Kaisha | Block copolymer composition |
| KR20090052767A (en) * | 2007-11-21 | 2009-05-26 | 금호석유화학 주식회사 | Method for preparing complex styrenic block copolymer and asphalt composition containing it |
-
1976
- 1976-08-12 CA CA258,971A patent/CA1085084A/en not_active Expired
- 1976-11-05 AU AU19337/76A patent/AU507780B2/en not_active Ceased
- 1976-11-10 JP JP51135124A patent/JPS5278260A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU1933776A (en) | 1978-05-11 |
| JPS5278260A (en) | 1977-07-01 |
| AU507780B2 (en) | 1980-02-28 |
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