US3254043A - Treatment of polybutadiene - Google Patents

Treatment of polybutadiene Download PDF

Info

Publication number
US3254043A
US3254043A US111162A US11116261A US3254043A US 3254043 A US3254043 A US 3254043A US 111162 A US111162 A US 111162A US 11116261 A US11116261 A US 11116261A US 3254043 A US3254043 A US 3254043A
Authority
US
United States
Prior art keywords
amine
polybutadiene
mooney viscosity
percent
cis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US111162A
Inventor
Gene F Trott
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
American Rubber and Chemical Co
Original Assignee
American Rubber and Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by American Rubber and Chemical Co filed Critical American Rubber and Chemical Co
Priority to US111162A priority Critical patent/US3254043A/en
Application granted granted Critical
Publication of US3254043A publication Critical patent/US3254043A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • the present invention is useful in the treatment of stereospecific polybutadiene containing at least about twenty-five percent (25%) cis-1,4 con-figuration.
  • the plasticity of a polymer is a function of several factors, among which may be mentioned molecular weight, molecular weight distribution, and various interand intramolecular forces.
  • the amine additives of the present invention are believed to exert their influence by modifying the molecular forces, characteristic of cis-1,4 polybutadiene in the solid state, due to packing of the molecular chains.
  • plasticity is defined in the American Society for Testing Materials Special Technical Publication No. 184 as being:
  • the plasticity of a polymer may be measured in several ways, the most common method in the United States being the use of a Mooney viscometer. The use of this instrument is described in the A.S.T.M. Standards of 1958, part 9, A.S.T.M. designation D92757T. The measure of plasticity obtained by using the Mooney viscometer is referred to as the Mooney viscosity.
  • the present invention solves this problem by providing a method for lowering the Mooney viscosity of (sis-1,4 polybutadiene. Furthermore, material treated according to the present invention emerges from a Garvey die with a much better rating than untreated material. (The Garvey die extrusion test is also described in A.S.T.M. Special Technical Publication No. 184.) The treated material emerges from the Garvey die test with improved surface, edges, corners and contours.
  • the additives employed in the present invention are primary or secondary amines containing at least six carbon atoms.
  • the amines may be aliphatic, aromatic, cyclic, saturated or unsaturated. Both mono and diamines may .be used. Best results have been obtained with unsaturated compounds.
  • primary amines are more effective than secondary amines. Particularly good results have been obtained using l-aminooctadecene- 9.
  • This last named amine is representative of a class of N-alkyl trimethylene diamines. Amines of this class give particularly good results, especially when the alkyl group contains from 12 to 18 carbon atoms.
  • the amine is mixed with the cis-l,4 polybutadiene at some stage after the desired degree of polymerization has taken place. This may be conveniently accomplished while the polymer is in the reaction solution in which it has been made.
  • the treated polymer is then recovered by conventional procedures.
  • an additional advantage of the invention may be obtained by using an unsaturated amine as a shortstop to the polymerization reaction which forms the polybutadiene. This would result in eliminating the need to use a conventional shortstop w-hich does not improve processibility.
  • the amount of amine to be added varies considerably. Some amines are more effective than others, and some samples of polybutadiene require more amine than others. In general, it may be said that where the polybutadiene has a relatively low Mooney viscosity to start with, less amine will be required to bring about a noticeable reduction in the Mooney viscosity. For example, as little as 0.2 of a percent may give an appreciable result. On the other hand, polybutadiene samples which initially have a high Mooney viscosity require more amine to bring about an appreciable lowering of the Mooney viscosity. As much as 1% amine may be required in some cases. Percentages are stated by weight based on the amount of polybutadiene.
  • the optimum amount of amine to be added can be stated as being from, roughly, two or three percent up to several percent. In the case of samples having'a very high initial Mooney viscosity as much as ten percent may be used.
  • Example 1 200 grams of polybutadiene, containing approximately cis-l,4 configuration, and having a Mooney viscosity at 212 F. of 42, was dissolved in approximately 3% liters of toluene. 6 grams of oleyl amine was then added to the polymer solution. The solution was stirred by hand. Steam was then injected into the mixture until nearly all of the toluene had been stream distilled, after which the polymer-amine mixture was dried on a hot 3 roll mill at approximately 200 to 220 F. The Mooney viscosity at 212 F. of the treated polymer was 28.
  • Example 2 200 grams of polybutadiene, containing approximately 95% cis-1,4 configuration, and having a Mooney viscosity at 212 F. of 46, was dissolved in approximately 3 /2 liters of toluene. 6 grams of dehydroabietyl amine was then added to the polymer solution. The solution was mixed thoroughly by hand stirring. Steam was then injected into the mixture until nearly all of the toluene had been removed, after which the polymer-amine mixture was dried on a hot roll mill at approximately 200 to 220 F. The Mooney viscosity at 212 F. of the treated polymer was 33%.
  • Garvey die data at 180 F. were obtained on the untreated raw polymer containing 50 parts high abrasion furnace carbon black (HAP), and on the treated raw polymer containing three percent (3%) dehydroabietyl amine and fifty (50) parts HAF carbon black.
  • HAP high abrasion furnace carbon black
  • the Garvey die readings are reported in the following table:
  • Example 3 Using the procedures of the foregoing examples, tests were run on many samples of polybutadiene, using various amines as additives.
  • the tested polybutadienes included materials varying from about twenty-five percent (25%) to iniety-eight percent (98%) in their content of cis-1,4 configuration. In all cases it was found that, when a primary or secondary amine containing at least six carbon atoms was added in an amount from few tenths of a percent to several percent, the Mooney viscosity was lowered and the Garvey extrusion index was increased.
  • a process for lowering the plasticity of polybutadiene containing at least twenty-five percent cis-1,4 configuration consisting essentially of incorporating in a solution of the polybutadiene a small but eifective amount of dehydroabietyl amine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

United States Patent 3,254,043 TREATMENT OF POLYBUTADEENE Gene F. Trott, Clarksville, Ind, assignor to American Rubber and Chemical Company, New York, N.Y., a corporation of Delaware No Drawing. Filed May 19, 1961, Ser. No. 111,162 1 Claim. (Cl. 260-27) This invention is concerned with a process for treating polybutadiene to improve its processibility. In particular, it is concerned with adding certain amines to polybutadiene having at least about twenty-five percent (25%) cis-1,4 configuration so that the plasticity of the material is reduced and it may be processed more readily. It should be emphasized that, by means of the present invention, the plasticity is reduced while other physical properties are not impaired, but are in some cases improved.
The present invention is useful in the treatment of stereospecific polybutadiene containing at least about twenty-five percent (25%) cis-1,4 con-figuration. The plasticity of a polymer is a function of several factors, among which may be mentioned molecular weight, molecular weight distribution, and various interand intramolecular forces. The amine additives of the present invention are believed to exert their influence by modifying the molecular forces, characteristic of cis-1,4 polybutadiene in the solid state, due to packing of the molecular chains.
The term plasticity is defined in the American Society for Testing Materials Special Technical Publication No. 184 as being:
The property possessed by certain solid materials of keeping the shape or form imparted to them by a deforming force. It is characterized by a complete lack of elasticity and may be regarded as a state of matter in which internal friction and tendency to flow balance each other.
The plasticity of a polymer may be measured in several ways, the most common method in the United States being the use of a Mooney viscometer. The use of this instrument is described in the A.S.T.M. Standards of 1958, part 9, A.S.T.M. designation D92757T. The measure of plasticity obtained by using the Mooney viscometer is referred to as the Mooney viscosity.
When a material has a high Mooney viscosity, it is difiicult to process. In particular, it is difficult to mill it or to extrude it. The present invention solves this problem by providing a method for lowering the Mooney viscosity of (sis-1,4 polybutadiene. Furthermore, material treated according to the present invention emerges from a Garvey die with a much better rating than untreated material. (The Garvey die extrusion test is also described in A.S.T.M. Special Technical Publication No. 184.) The treated material emerges from the Garvey die test with improved surface, edges, corners and contours.
Prior to the present invention it was often necessary to incorporate natural rubber with cis-1,4 polybutadiene in order to obtain material which could be readily proc essed. It is one of the very important advantages of the present invention that the use of natural rubber is no longer required for this purpose.
Conventional cis-1,4 polybutadiene can not be milled on a roll mill at high temperatures without great difiiculty. By the use of the present invention there are obtained materials which can be successfully and easily milled at much higher temperatures. The invention therefore makes is possible to manufacture cis-l,4 polybutadiene having a Mooney viscosity low enough to be consistent with easy processing, but having wear resistance and other desirable properties in no way impaired.
The additives employed in the present invention are primary or secondary amines containing at least six carbon atoms. The amines may be aliphatic, aromatic, cyclic, saturated or unsaturated. Both mono and diamines may .be used. Best results have been obtained with unsaturated compounds. In general, primary amines are more effective than secondary amines. Particularly good results have been obtained using l-aminooctadecene- 9. As examples of other amines which are useful in the present invention, there may be mentioned l-aminooctadecane, dehydroabietyl amine, dodecyl amine, ctyl amine, hexyl amine, distearyl amine, dipalmetyl amine, dihexyl amine, and oleic-1,3-propylenediamine (which may also be used in the form of its monoand di-oleates). This last named amine is representative of a class of N-alkyl trimethylene diamines. Amines of this class give particularly good results, especially when the alkyl group contains from 12 to 18 carbon atoms.
In carrying out the process of the present invention, the amine is mixed with the cis-l,4 polybutadiene at some stage after the desired degree of polymerization has taken place. This may be conveniently accomplished while the polymer is in the reaction solution in which it has been made. The treated polymer is then recovered by conventional procedures. Although experimental evidence is not yet conclusive, in some cases an additional advantage of the invention may be obtained by using an unsaturated amine as a shortstop to the polymerization reaction which forms the polybutadiene. This would result in eliminating the need to use a conventional shortstop w-hich does not improve processibility.
The amount of amine to be added varies considerably. Some amines are more effective than others, and some samples of polybutadiene require more amine than others. In general, it may be said that where the polybutadiene has a relatively low Mooney viscosity to start with, less amine will be required to bring about a noticeable reduction in the Mooney viscosity. For example, as little as 0.2 of a percent may give an appreciable result. On the other hand, polybutadiene samples which initially have a high Mooney viscosity require more amine to bring about an appreciable lowering of the Mooney viscosity. As much as 1% amine may be required in some cases. Percentages are stated by weight based on the amount of polybutadiene.
It has been observed that in general the lowering of the Mooney viscosity reaches a maximum when a particular amount of amine has been added, and the subsequent addition of still more amine causes no more lowering of the Mooney viscosity. For most purposes, the optimum amount of amine to be added can be stated as being from, roughly, two or three percent up to several percent. In the case of samples having'a very high initial Mooney viscosity as much as ten percent may be used.
The following examples are given solely for purposes of illustration and are not to be deemed as limitation of the present invention, many variations of which well occur to those skilled in the art without departing from the spirit or scope thereof.
Example 1 200 grams of polybutadiene, containing approximately cis-l,4 configuration, and having a Mooney viscosity at 212 F. of 42, was dissolved in approximately 3% liters of toluene. 6 grams of oleyl amine was then added to the polymer solution. The solution was stirred by hand. Steam was then injected into the mixture until nearly all of the toluene had been stream distilled, after which the polymer-amine mixture was dried on a hot 3 roll mill at approximately 200 to 220 F. The Mooney viscosity at 212 F. of the treated polymer was 28.
It is thus seen that the Mooney viscosity was lowered from 42 in the untreated material to 28 in the treated material. All Mooney viscosities are base on large rotor readings.
Example 2 200 grams of polybutadiene, containing approximately 95% cis-1,4 configuration, and having a Mooney viscosity at 212 F. of 46, was dissolved in approximately 3 /2 liters of toluene. 6 grams of dehydroabietyl amine was then added to the polymer solution. The solution was mixed thoroughly by hand stirring. Steam was then injected into the mixture until nearly all of the toluene had been removed, after which the polymer-amine mixture was dried on a hot roll mill at approximately 200 to 220 F. The Mooney viscosity at 212 F. of the treated polymer was 33%.
In order to show further the effect. of dehydroabietyl amine on the polybutadiene sample treated above, Garvey die data at 180 F. were obtained on the untreated raw polymer containing 50 parts high abrasion furnace carbon black (HAP), and on the treated raw polymer containing three percent (3%) dehydroabietyl amine and fifty (50) parts HAF carbon black. The Garvey die readings are reported in the following table:
It thus is seen that the treated polybutadiene scored better than the untreated material in every part of the test.
4 Example 3 Using the procedures of the foregoing examples, tests were run on many samples of polybutadiene, using various amines as additives. The tested polybutadienes included materials varying from about twenty-five percent (25%) to iniety-eight percent (98%) in their content of cis-1,4 configuration. In all cases it was found that, when a primary or secondary amine containing at least six carbon atoms was added in an amount from few tenths of a percent to several percent, the Mooney viscosity was lowered and the Garvey extrusion index was increased.
What is claimed is:
A process for lowering the plasticity of polybutadiene containing at least twenty-five percent cis-1,4 configuration, said process consisting essentially of incorporating in a solution of the polybutadiene a small but eifective amount of dehydroabietyl amine.
References Cited by the Examiner UNITED STATES PATENTS 2,234,204 3/1941 Starkweather et a1. 260-32.6 2,592,708 4/1952 Kelly 26032.6 2,643,981 6/1953 Kelly 26032.6 2,686,163 8/1954 Smith et al. 260-32.6 2,989,513 6/1961 Hendry et a1. 260-5 .OTHER REFERENCES Marchionna: Butalastic Polymers, Reinhold Publishing Corp., New York, 1946, page 423.
Railback et al.: Rubber and Plastics Age, October 1958, pages 867874.
Wilson: British Compounding Ingredients for Rubber, W. Heifer and Sons, Ltd., Cambridge, 1958, page 287.
MORRIS LIEBMAN, Primary Examiner.
LEON J. BERCOVITZ, Examiner.
L. G. KASTRINER, D. W. ERICKSON, B. A.
AMERNICK, Assistant Examiners.
US111162A 1961-05-19 1961-05-19 Treatment of polybutadiene Expired - Lifetime US3254043A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US111162A US3254043A (en) 1961-05-19 1961-05-19 Treatment of polybutadiene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US111162A US3254043A (en) 1961-05-19 1961-05-19 Treatment of polybutadiene

Publications (1)

Publication Number Publication Date
US3254043A true US3254043A (en) 1966-05-31

Family

ID=22336936

Family Applications (1)

Application Number Title Priority Date Filing Date
US111162A Expired - Lifetime US3254043A (en) 1961-05-19 1961-05-19 Treatment of polybutadiene

Country Status (1)

Country Link
US (1) US3254043A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3476599A (en) * 1966-09-12 1969-11-04 Gen Tire & Rubber Co Metal cleaning composition and method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2234204A (en) * 1939-03-28 1941-03-11 Du Pont Plastic polymer of butadiene and process of producing same
US2592708A (en) * 1947-09-18 1952-04-15 Gen Tire & Rubber Co Method of making cellular rubber using amines
US2643981A (en) * 1947-05-15 1953-06-30 Gen Tire & Rubber Co Method of making sponge rubber with the aid of amines
US2686163A (en) * 1952-04-02 1954-08-10 Firestone Tire & Rubber Co Reclaiming rubbers
US2989513A (en) * 1958-12-15 1961-06-20 Goodrich Co B F Curing of rubber with a sulfur-olefinic hydrocarbon interpolymer, and product obtained thereby

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2234204A (en) * 1939-03-28 1941-03-11 Du Pont Plastic polymer of butadiene and process of producing same
US2643981A (en) * 1947-05-15 1953-06-30 Gen Tire & Rubber Co Method of making sponge rubber with the aid of amines
US2592708A (en) * 1947-09-18 1952-04-15 Gen Tire & Rubber Co Method of making cellular rubber using amines
US2686163A (en) * 1952-04-02 1954-08-10 Firestone Tire & Rubber Co Reclaiming rubbers
US2989513A (en) * 1958-12-15 1961-06-20 Goodrich Co B F Curing of rubber with a sulfur-olefinic hydrocarbon interpolymer, and product obtained thereby

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3476599A (en) * 1966-09-12 1969-11-04 Gen Tire & Rubber Co Metal cleaning composition and method

Similar Documents

Publication Publication Date Title
US3706708A (en) Uniformly dispersible insoluble sulfur vulcanizing compositions
DE1495837A1 (en) Process for the production of thermoplastic-elastic molding compounds
Okieimen et al. Processing characteristics and physicomechanical properties of natural rubber and liquid natural rubber blends
US3254043A (en) Treatment of polybutadiene
US2540596A (en) Chloroprene polymer vulcanizates and method for preparing same
US2543844A (en) Plasticizing synthetic rubber with a reaction product of an alkyl mercaptan and a rubbery diolefin polymer
US2784165A (en) Synthetic rubber and rosin
US3449290A (en) Silicone elastomer compositions containing powdered polytetrafluoroethylene
US2819256A (en) Composition of rubber and a di(arylalkyl) peroxide
US2316949A (en) Method of plasticizing synthetic rubber
US2550363A (en) Lactam plasticizer for rubbers
US2413857A (en) Vulcanizable products and their manufacture
US3804801A (en) Fluorohydrocarbon elastomers
US2350007A (en) Process of heat-treating polymerization products
US2356955A (en) Compositions
US2480296A (en) Ethylene polymer compositions
US2975151A (en) Vulcanization of latex with organic hydroperoxide
US2235149A (en) Processing of mixed polymers of conjugated dienes and unsaturated nitriles
US2676944A (en) Rubber processing in the presence of carbon black and an organic peroxide
US2315849A (en) Manufacture of rubber
US3451459A (en) Rubber blends comprising natural rubber,cis-polybutadiene and a tertiary amine
US2199099A (en) Method of compounding rubber
US2389489A (en) Plasticized compositions
US2647879A (en) Improving the flex resistance of butadiene-1, 3 type polymers
US2423032A (en) Reclaiming synthetic rubber with an amine