CA1142673A - Thermoplastic elastomeric composition - Google Patents
Thermoplastic elastomeric compositionInfo
- Publication number
- CA1142673A CA1142673A CA000349157A CA349157A CA1142673A CA 1142673 A CA1142673 A CA 1142673A CA 000349157 A CA000349157 A CA 000349157A CA 349157 A CA349157 A CA 349157A CA 1142673 A CA1142673 A CA 1142673A
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Abstract
Abstract of the Disclosure A non-tacky thermoplastic elastomeric composition which is an optically clear blend of (A) a copolymer of ethyl or butyl acrylate or mixtures thereof with from 2 to 10% by weight of a copolymerizable ethylenic monomer containing an acid group and (B) a water-soluble polymer of a vinyl lactam having the structure
Description
This invention relates to a thermoplast:ic elastomeric composition comprising a blend of (~) a high molecular weight copolymer of ethyl or butyl acrylate or rnixtures thereof with an ethylenic monomer containing an acid group and (s) a water-S soluble polyvinyl lactam.
It has previously been proposed to provide thermoplastic elastomeric compositions in the form of oil extended hydrogenated block copolymers of styrene and conjugated dienes as described, for example, in Haefele et al. 3,485,787. Such compositions are unlike ordinary elastomers in that they possess the necessary ` strength without vulcanization or cross-linking and, therefore, they permanently retain their thermoplasticity. Acrylic elas-tomers have been made by chemically cross-linking polymers of acrylic esters such as polymers of ethyl or butyl acrylate, which polymers wi-thout cross-linking have inadequate tensile strcngth for most purposes, but such cross-linking destroys or greatly decreases the original thermoplasticity of the polymers.
It has also been proposed to react water-soluble poly (N~vinyl lactams) with polymeric carboxylic acids (including copolymers) to form water-insoluble compositions useful for a variety of purposes as described ln Stoner et al. U.S. Patent 2,901,457;
and in Ono et al. U.S. Patent 3,975,570, in which it was proposed to improve the moisture permeability of conventional pressure-sensitive adhesives which are copolymers of alkyl acryla-tes with acrylic or methacrylic acid by blending with them hydroxy-ethyl cellulose, it was stated tha-t blends of such adhesives with poly (vinyl pyrrolidone~ did not exhibit improved moisture `~
It has previously been proposed to provide thermoplastic elastomeric compositions in the form of oil extended hydrogenated block copolymers of styrene and conjugated dienes as described, for example, in Haefele et al. 3,485,787. Such compositions are unlike ordinary elastomers in that they possess the necessary ` strength without vulcanization or cross-linking and, therefore, they permanently retain their thermoplasticity. Acrylic elas-tomers have been made by chemically cross-linking polymers of acrylic esters such as polymers of ethyl or butyl acrylate, which polymers wi-thout cross-linking have inadequate tensile strcngth for most purposes, but such cross-linking destroys or greatly decreases the original thermoplasticity of the polymers.
It has also been proposed to react water-soluble poly (N~vinyl lactams) with polymeric carboxylic acids (including copolymers) to form water-insoluble compositions useful for a variety of purposes as described ln Stoner et al. U.S. Patent 2,901,457;
and in Ono et al. U.S. Patent 3,975,570, in which it was proposed to improve the moisture permeability of conventional pressure-sensitive adhesives which are copolymers of alkyl acryla-tes with acrylic or methacrylic acid by blending with them hydroxy-ethyl cellulose, it was stated tha-t blends of such adhesives with poly (vinyl pyrrolidone~ did not exhibit improved moisture `~
- 2 :
permeabilityO It has also been proposed to react water-soluble poly (N-vinyl lactams) with polymeric carboxylic acids (including copolymers) to form water-insoluble compositions useful for a variety of purposes, as described in Stoner et al. U.S. Patent 2,901,457. As pointed out by Stoner et al. at column 4, lines 56-73, the reaction product there described always has sub-; stantially the same properties and contains the two polymeric components in the same proportions regardless of the proportions of the two used to make the product. The compositions of the ; 10 present invention, on the other hand, vary in properties and inproportions of components depending upon proportions of starting materials.
A pressure-sensitive adhesive composition is known which is a blend of a poly (N-vinyl lactam) with certain acrylic ester copolymers of relatively low molecular weight. There are also described and claimed in U.S. Patent 4,300,820 of Shah, a highly water-sorptive composition which is a blend of large proportion of a poly (N-vinyl lactam) with certain copolymers.
It has now been found that high molecular weight ~0 copolymers of ethyl or butyl acrylate or mixtures thereof with acidic ethylenic monomers in which the acidic group is sulfonic, phosphonic or carboxylic, which copolymers are thermoplastic, can be converted into non-tacky, non-adhesive, strong and tough elastomeric compositions without loss of thermoplasticity by `: ~
- blending with the copolymers of poly (N-vinyl lactam), the -total blend containing from 2 to 15% of poly (N-vinyl lactam) b~
weight.
According to the present invention, therefore, there is provided a thermoplastic elastomeric composition comprising an optically clear blend of (A) a high molecular weight copolymer of ethyl or butyl acrylate or mixtures thereof with from 2 to 10 by weight, based on the weight of the copolymer, of a copoly-merizable ethylenic monomer containing an acid group and (s) a water-soluble polymer of a vinyl lactam having the structure ~X~
C=o N
in which X represents an alkylene bridge having three to five carbon atoms, said copolymer having a molecular weight of at least 600,000 and a glass transition temperature from -10C. to -50C., and said polymer being present in an amount of 2 to 15%
by weight of the blend and having a molecular weight of at least 10,000.
The copolymers employed in the present invention have high molecular weights, from about 600,000 to 1,000,000 or more, have glass transition temperatures from about -10 to about -50C., and are copolymers of ethyl or butyl acrylate or mixtures thereof with ethylenic monomers containing an acid group which is carboxy-lic, sulfonic or phosphonic, such as acrylic or methacrylic acid, crotonic acid, maleic acid, 2-sulfoethylmethacrylate, and l-phenylvinylphosphonic acid. Preferably, the acid group in the ethylenic monomer is carboxylic, acrylic acid being the acidic monomer of choice. The amount of copolymerizable ethylenic acid-containing monomer in the copolymer may vary from 2 to 10~ by - 4 _ ": ~
26~3 - .~
weight of the copolymer, the balance being ethvl or butyl acrylate.
The N-vinyl lactams, polymers of which can be used in the present invention include those having the structure ~ X~
/
; ~N
C~l=CH2 in which X represents an alkylene bridge having 3 to 5 carbon atoms, such as l-vinyl-2-pyrrolidone, 1-vinyl-5-methyl-2-pyrrolidone, l-vinyl-2-piperidone, and N-vinyl-epsilon-caprolactam; the polymers may have molecular weights from 10,000 to 1,000,000 or more. Polymers of l-vinyl-2-pyrrolidone, i.e., those in which X represents -CH2CH2CH2- are preferred.
The amount of polymeric - 4a -` :
N-vinyl lactam in the blend can vary Erom 2 to 15~ by weight of the total blend. Preferably the welght percent oE poly (N-vinyl lactam) based on the total weight of polymer and copolymer Y should total from 5 to 15.
- 5 The copolymers employed in the composition of the present invention can be prepared by conventional polymerization processes in emulsion, in solu-tion, or in bulk; they may range from about 600,000 to 1,000,000 or more in molecular weight, preferably from 750,000 to 1,000,000 or more. The poly (N-vinyl lactams) which are blended with the copolymers can also be pre-pared by conventional procedures and are widely available commercially.
The blended compositions can be made by mixing together solutions oE the copolymers and of the polymeric N-vinyl lactams in any desired vehicles or solvents which are miscible with each other, then removing the vehicle or solvent, as by evaporation.
It is also possible to blend the copolymer with the polymer on conventional mixing equipment such as a two-roll mill or in an extruder.
Although different polymers and copolymers are normally considered to be incompatible with one another when mixed, and incapable of forming a homogeneous blend having properties different from either of the components, the blends of the present invention are optically clear and transparent in the absence of any fillers or similar additives, indicating that the blends are homogeneous at least to the extent that no discre-te particles of `~ either component grea-ter than 4,000 A in diameter are present.
.
; 5 . Because of the thermoplas-ticity of the blended compositions of the present invention, they can be repea-tedly formed or shaped simply by heating to elevated temperatures, e.g., - 170--200C. and subjecting them to pressure, as for example in a S mold or in an extruder nozzle. When cooled to room temperature, the shaped articles made from the blended composition are transparent, extremely tough, and elastic in nature. They can be stretched to at leas-t 500~ of their original length, from which they rapidly regain their original length when tension is released.
The blended compositions exhibit considerably enhanced tensile strength and modulus of elasticity, and somewhat decreased elongation as contrasted to the non-blended acrylate copolymers.
The magnitude of these properties of the blended compositions depends upon the amount of acidic comonomer, molecular weight of the copolymer, the relative proportion of poly (N-vinyl lactam) to copolymer, and the molecular weight of the poly (N-vinyl lactam).
In general, an increase in the magnitude of the above variables results in increase of tensile strength of the blended composi-tion.
In order to achieve desirable properties and servicelife of the blended compositions, it may be desirable to include in the composition in addition to the polymeric N-vinyl lactam and the copolymer, conventional stabilizers, pigments, fillers and other compounding agents.
These blended compositions are especially suited for acceptable performance in an environment where there is exposure . . .
to sulfur-modified oils at elevated temperatures, under which conditions the unsaturated rubbers of commerce fail. The ~crylic ~lastomers , as a class, are not recommended for use in water, steam, or water soluble materials, such as methanol or ethylene glycol. An important application of these blended compositions is as seals and gaskets for auto enyines and other machines.
The following specific examples are intended to illustrate more fully the nature of -the present invention without acting as a limitation upon its scope.
Examples 1-6 Copolymers of ethyl acrylate with three different proportions of acrylic acid were prepared by conventional solution polymerization procedures by dissolving the desired proportions (40% solids) of monomers in ethyl acetate ; 15 and by employing as the initiator of polymerization a small amount (0.1% by weight of the monomers) of a free radical genera-tor such as benzoyl peroxide or 2-t-butylazo-2-cyano propane. Polymerization was carried out at 80-90C. to a high degree of conversion. The peak molecular weight as determined by gel permea'ion chroma-tography and stress strain properties as determined by ASTM procedure D~412 were as follows:
Ethyl Acrylate Copolymers Tensile Strenth, Wt% _ 3 PSI at Ultimate No. Acrylic Acid I Mp x 10 100% 300% jBreak Elongation, %
permeabilityO It has also been proposed to react water-soluble poly (N-vinyl lactams) with polymeric carboxylic acids (including copolymers) to form water-insoluble compositions useful for a variety of purposes, as described in Stoner et al. U.S. Patent 2,901,457. As pointed out by Stoner et al. at column 4, lines 56-73, the reaction product there described always has sub-; stantially the same properties and contains the two polymeric components in the same proportions regardless of the proportions of the two used to make the product. The compositions of the ; 10 present invention, on the other hand, vary in properties and inproportions of components depending upon proportions of starting materials.
A pressure-sensitive adhesive composition is known which is a blend of a poly (N-vinyl lactam) with certain acrylic ester copolymers of relatively low molecular weight. There are also described and claimed in U.S. Patent 4,300,820 of Shah, a highly water-sorptive composition which is a blend of large proportion of a poly (N-vinyl lactam) with certain copolymers.
It has now been found that high molecular weight ~0 copolymers of ethyl or butyl acrylate or mixtures thereof with acidic ethylenic monomers in which the acidic group is sulfonic, phosphonic or carboxylic, which copolymers are thermoplastic, can be converted into non-tacky, non-adhesive, strong and tough elastomeric compositions without loss of thermoplasticity by `: ~
- blending with the copolymers of poly (N-vinyl lactam), the -total blend containing from 2 to 15% of poly (N-vinyl lactam) b~
weight.
According to the present invention, therefore, there is provided a thermoplastic elastomeric composition comprising an optically clear blend of (A) a high molecular weight copolymer of ethyl or butyl acrylate or mixtures thereof with from 2 to 10 by weight, based on the weight of the copolymer, of a copoly-merizable ethylenic monomer containing an acid group and (s) a water-soluble polymer of a vinyl lactam having the structure ~X~
C=o N
in which X represents an alkylene bridge having three to five carbon atoms, said copolymer having a molecular weight of at least 600,000 and a glass transition temperature from -10C. to -50C., and said polymer being present in an amount of 2 to 15%
by weight of the blend and having a molecular weight of at least 10,000.
The copolymers employed in the present invention have high molecular weights, from about 600,000 to 1,000,000 or more, have glass transition temperatures from about -10 to about -50C., and are copolymers of ethyl or butyl acrylate or mixtures thereof with ethylenic monomers containing an acid group which is carboxy-lic, sulfonic or phosphonic, such as acrylic or methacrylic acid, crotonic acid, maleic acid, 2-sulfoethylmethacrylate, and l-phenylvinylphosphonic acid. Preferably, the acid group in the ethylenic monomer is carboxylic, acrylic acid being the acidic monomer of choice. The amount of copolymerizable ethylenic acid-containing monomer in the copolymer may vary from 2 to 10~ by - 4 _ ": ~
26~3 - .~
weight of the copolymer, the balance being ethvl or butyl acrylate.
The N-vinyl lactams, polymers of which can be used in the present invention include those having the structure ~ X~
/
; ~N
C~l=CH2 in which X represents an alkylene bridge having 3 to 5 carbon atoms, such as l-vinyl-2-pyrrolidone, 1-vinyl-5-methyl-2-pyrrolidone, l-vinyl-2-piperidone, and N-vinyl-epsilon-caprolactam; the polymers may have molecular weights from 10,000 to 1,000,000 or more. Polymers of l-vinyl-2-pyrrolidone, i.e., those in which X represents -CH2CH2CH2- are preferred.
The amount of polymeric - 4a -` :
N-vinyl lactam in the blend can vary Erom 2 to 15~ by weight of the total blend. Preferably the welght percent oE poly (N-vinyl lactam) based on the total weight of polymer and copolymer Y should total from 5 to 15.
- 5 The copolymers employed in the composition of the present invention can be prepared by conventional polymerization processes in emulsion, in solu-tion, or in bulk; they may range from about 600,000 to 1,000,000 or more in molecular weight, preferably from 750,000 to 1,000,000 or more. The poly (N-vinyl lactams) which are blended with the copolymers can also be pre-pared by conventional procedures and are widely available commercially.
The blended compositions can be made by mixing together solutions oE the copolymers and of the polymeric N-vinyl lactams in any desired vehicles or solvents which are miscible with each other, then removing the vehicle or solvent, as by evaporation.
It is also possible to blend the copolymer with the polymer on conventional mixing equipment such as a two-roll mill or in an extruder.
Although different polymers and copolymers are normally considered to be incompatible with one another when mixed, and incapable of forming a homogeneous blend having properties different from either of the components, the blends of the present invention are optically clear and transparent in the absence of any fillers or similar additives, indicating that the blends are homogeneous at least to the extent that no discre-te particles of `~ either component grea-ter than 4,000 A in diameter are present.
.
; 5 . Because of the thermoplas-ticity of the blended compositions of the present invention, they can be repea-tedly formed or shaped simply by heating to elevated temperatures, e.g., - 170--200C. and subjecting them to pressure, as for example in a S mold or in an extruder nozzle. When cooled to room temperature, the shaped articles made from the blended composition are transparent, extremely tough, and elastic in nature. They can be stretched to at leas-t 500~ of their original length, from which they rapidly regain their original length when tension is released.
The blended compositions exhibit considerably enhanced tensile strength and modulus of elasticity, and somewhat decreased elongation as contrasted to the non-blended acrylate copolymers.
The magnitude of these properties of the blended compositions depends upon the amount of acidic comonomer, molecular weight of the copolymer, the relative proportion of poly (N-vinyl lactam) to copolymer, and the molecular weight of the poly (N-vinyl lactam).
In general, an increase in the magnitude of the above variables results in increase of tensile strength of the blended composi-tion.
In order to achieve desirable properties and servicelife of the blended compositions, it may be desirable to include in the composition in addition to the polymeric N-vinyl lactam and the copolymer, conventional stabilizers, pigments, fillers and other compounding agents.
These blended compositions are especially suited for acceptable performance in an environment where there is exposure . . .
to sulfur-modified oils at elevated temperatures, under which conditions the unsaturated rubbers of commerce fail. The ~crylic ~lastomers , as a class, are not recommended for use in water, steam, or water soluble materials, such as methanol or ethylene glycol. An important application of these blended compositions is as seals and gaskets for auto enyines and other machines.
The following specific examples are intended to illustrate more fully the nature of -the present invention without acting as a limitation upon its scope.
Examples 1-6 Copolymers of ethyl acrylate with three different proportions of acrylic acid were prepared by conventional solution polymerization procedures by dissolving the desired proportions (40% solids) of monomers in ethyl acetate ; 15 and by employing as the initiator of polymerization a small amount (0.1% by weight of the monomers) of a free radical genera-tor such as benzoyl peroxide or 2-t-butylazo-2-cyano propane. Polymerization was carried out at 80-90C. to a high degree of conversion. The peak molecular weight as determined by gel permea'ion chroma-tography and stress strain properties as determined by ASTM procedure D~412 were as follows:
Ethyl Acrylate Copolymers Tensile Strenth, Wt% _ 3 PSI at Ultimate No. Acrylic Acid I Mp x 10 100% 300% jBreak Elongation, %
3 5 1076 _ _ 202 670 `:
Blends of the copolymers with poly (vinyl pyrrolidone), grade K-90 (M.w. 360,000), were prepared by dissolving appropriate amounts of the respective copolymer and the polymer in chloroform and then heating the resulting solution at 120C. under reduced pressure to evaporate the solvent and leave a transparent solid polymeric residue. The dry polymeric blends were then formed into sheets 2-3 mm in thickness in a press heated at 170C. and their stress-strain characteristics determined by the same ASTM
procedure as above. The results were as follows:
Blend of Copolymer with Poly(Vinyl pyrrolidone) Copolymer Wt% of Poly(vinyl Tensile Strength, PSI at Ultima-te ~o.~vrrolidone) 100% 300% BreakElongation, %
~ ............................. _ :- 1 10 76 156 508 778 ; 2 10 90 200 705 738 3 5 106 229 557 ~53 Example 7 A copolymer of 97.5% by weight of butyl acrylate and 2.5% by weight of acrylic acid was prepared by polymerizing the monomers in solution (50% solids) in refluxing ethyl acetate using the same inltiator as in -the preceding Examples. The , resulting copolymer was isolated by heating the solution at 120~C.
under vacuum to evaporate volatile materials. A mixture of 8.57 grams of the dry copo].ymer and 0.95 grams of poly (N-vinyl-2-, , .. . . .. . ...
-' , Z~73 pyrro].idone) having a molecular weight of 360,000 was dissolved in 50 ml of chloroform and the solution was heated at 120C. in vacùum to evaporate the solvent, leaving the solid transparent blended polymer composition. The blended composition was formed into a sheet as in the preceding Examples. The formed sheet was transparent, tough and elastic but more compliant than any of the blends of Examples 1-6.
B
.
Blends of the copolymers with poly (vinyl pyrrolidone), grade K-90 (M.w. 360,000), were prepared by dissolving appropriate amounts of the respective copolymer and the polymer in chloroform and then heating the resulting solution at 120C. under reduced pressure to evaporate the solvent and leave a transparent solid polymeric residue. The dry polymeric blends were then formed into sheets 2-3 mm in thickness in a press heated at 170C. and their stress-strain characteristics determined by the same ASTM
procedure as above. The results were as follows:
Blend of Copolymer with Poly(Vinyl pyrrolidone) Copolymer Wt% of Poly(vinyl Tensile Strength, PSI at Ultima-te ~o.~vrrolidone) 100% 300% BreakElongation, %
~ ............................. _ :- 1 10 76 156 508 778 ; 2 10 90 200 705 738 3 5 106 229 557 ~53 Example 7 A copolymer of 97.5% by weight of butyl acrylate and 2.5% by weight of acrylic acid was prepared by polymerizing the monomers in solution (50% solids) in refluxing ethyl acetate using the same inltiator as in -the preceding Examples. The , resulting copolymer was isolated by heating the solution at 120~C.
under vacuum to evaporate volatile materials. A mixture of 8.57 grams of the dry copo].ymer and 0.95 grams of poly (N-vinyl-2-, , .. . . .. . ...
-' , Z~73 pyrro].idone) having a molecular weight of 360,000 was dissolved in 50 ml of chloroform and the solution was heated at 120C. in vacùum to evaporate the solvent, leaving the solid transparent blended polymer composition. The blended composition was formed into a sheet as in the preceding Examples. The formed sheet was transparent, tough and elastic but more compliant than any of the blends of Examples 1-6.
B
.
Claims (7)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A thermoplastic elastomeric: composition comprising an optically clear blend of (A) a high molecular weight copolymer of ethyl or butyl acrylate or mixtures thereof with from 2 to 10% by weight, based on the weight of the copolymer, of a copolymerizable ethylenic monomer containing an acid group and (B) a water-soluble polymer of a vinyl lactam having the structure in which X represents an alkylene bridge having three to five carbon atoms, said copolymer having a molecular weight of at least 600,000 and a glass transition temperature from -10°C. to -50°C., and said polymer being present in an amount of 2 to 15%
by weight of the blend and having a molecular weight of at least 10, 000. - 2. A composition as claimed in claim 1 in which X
represents -CH2-CH2-CH2. - 3. A composition as claimed in claim 2 in which the copolymer is a copolymer of ethyl acrylate with a copolymerizable ethylenic monomer containing a carboxylic group.
- 4. A composition as claimed in claim 3 in which the ethylenic monomer is acrylic acid.
- 5. A composition as claimed in claim 2 in which the copolymer is a copolymer of butyl. acrylate with a copolymerizable ethylenic monomer containing a carboxylic group.
- 6. A composition as claimed in claim 5 in which the ethlylenic monomer is acrylic acid.
- 7. A composition as claimed in claim 2 in which the copolymer has a molecular weight of at least 750,000 and the amount of said polymer in the blend is from 5 to 15% by weight of the blend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000349157A CA1142673A (en) | 1980-04-03 | 1980-04-03 | Thermoplastic elastomeric composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000349157A CA1142673A (en) | 1980-04-03 | 1980-04-03 | Thermoplastic elastomeric composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142673A true CA1142673A (en) | 1983-03-08 |
Family
ID=4116630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000349157A Expired CA1142673A (en) | 1980-04-03 | 1980-04-03 | Thermoplastic elastomeric composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1142673A (en) |
-
1980
- 1980-04-03 CA CA000349157A patent/CA1142673A/en not_active Expired
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