CA2479856A1 - Ethylene-alpha-olefin polymers, processes and uses - Google Patents
Ethylene-alpha-olefin polymers, processes and uses Download PDFInfo
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- CA2479856A1 CA2479856A1 CA002479856A CA2479856A CA2479856A1 CA 2479856 A1 CA2479856 A1 CA 2479856A1 CA 002479856 A CA002479856 A CA 002479856A CA 2479856 A CA2479856 A CA 2479856A CA 2479856 A1 CA2479856 A1 CA 2479856A1
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- olefin
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Abstract
A novel series of copolymers and terpolymers, useful as base oils for synthetic lubricants, are produced by polymerization of ethylene, an alpha-olefin, and optionally a third monomer comprising an alpha-olefin of 3 to 20 carbon atoms, in the presence of a combination catalyst comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane. The copolymer or terpolymer may be further processed by thermal cracking to yield novel cracked polymers, and the cracked polymers may be hydrogenated. The copolymers or terpolymers may also be hydroisomerized. All the polymers are useful as base oils for lubricating oils and consumer products.
Description
ETHYLENE-ALPI~iA-OLEFIN POLYMERS , PROCESSES AND USES
Field of the Invention This invention relates to ethylene-olefin polymers, processes for their production, and uses thereof.as low molecular weight liquid, solid or wax-like products.
Background of the Invention Increasing demand in the oil industry has created a need for a high performance synthetic base oils with low volatility and high oxidative stability. Currently, aoly-alpha-olefins (PAO) are used as synthetic base oils but costs are high. This has created a demand for a low cost alternative to PAO such as synthetic hydrocarbons with equivalent or better properties. The present invention is based, in part, on the surprising and unexpected discovery that synthetic base oils may be formulated directly into motor oils or fracticnated into different viscosity grade oils wit: properties equivalent to commercial PAO.
Various prior art publications are available relating tc poly-alpha-olefin polymers. Reference may be made to U.S.
=nts 4,668,834, 9,542,199, 5,446,221, 4,704,491, 4,377,720, 4,463,201, 4,769,510, 4,404,344, 5,321,107, 5,151,204, 4,922,046, 4,794,096, 4,668,834, 9,Sfl7,515, a:~d 5,24,c00. Many cf these prior art patents involve polymerization of et::yiene cr poly-alpha-olefins using a catalyst combination ccmprv_s~ng a transition metal compleX
and an aiumiroxane.
The ~=esen:. _~':~e:-:__.... rrcvces pcivmers of ~-~, .,_ Nv-:Jlefin5 w:llc:: r:aVe d .. y!': V::S~OSltl indeX, lOW pt:ur t.0-nt, low c;:lc cra:-::c:ne ,:~cc~:t,~, .. y:. :ire poi::t and excel;e: _ CX~Ccti:: ta..r.l--t'J.
Field of the Invention This invention relates to ethylene-olefin polymers, processes for their production, and uses thereof.as low molecular weight liquid, solid or wax-like products.
Background of the Invention Increasing demand in the oil industry has created a need for a high performance synthetic base oils with low volatility and high oxidative stability. Currently, aoly-alpha-olefins (PAO) are used as synthetic base oils but costs are high. This has created a demand for a low cost alternative to PAO such as synthetic hydrocarbons with equivalent or better properties. The present invention is based, in part, on the surprising and unexpected discovery that synthetic base oils may be formulated directly into motor oils or fracticnated into different viscosity grade oils wit: properties equivalent to commercial PAO.
Various prior art publications are available relating tc poly-alpha-olefin polymers. Reference may be made to U.S.
=nts 4,668,834, 9,542,199, 5,446,221, 4,704,491, 4,377,720, 4,463,201, 4,769,510, 4,404,344, 5,321,107, 5,151,204, 4,922,046, 4,794,096, 4,668,834, 9,Sfl7,515, a:~d 5,24,c00. Many cf these prior art patents involve polymerization of et::yiene cr poly-alpha-olefins using a catalyst combination ccmprv_s~ng a transition metal compleX
and an aiumiroxane.
The ~=esen:. _~':~e:-:__.... rrcvces pcivmers of ~-~, .,_ Nv-:Jlefin5 w:llc:: r:aVe d .. y!': V::S~OSltl indeX, lOW pt:ur t.0-nt, low c;:lc cra:-::c:ne ,:~cc~:t,~, .. y:. :ire poi::t and excel;e: _ CX~Ccti:: ta..r.l--t'J.
Summary of the Invention An obj ect of the present invention is to provide a novel polymer useful, for example, as a base oil for lubricating oils and consumer products.
According to one aspect of the invention there is provided a cracked liquid copolymer of ethylene and an olefin, said copolymer being characterized by:
(a) mol % of ethylene from 50 to 75~;
(b) number average molecular weight of < 2000;
(c) molecular weight distribution of < 2;
(d) random monomer distribution; and (e) a head-to-tail molecular structure.
According to another aspect of the invention there is provided a process for the production of a cracked copolymer, comprising the steps of:
(a) polymerizing ethylene and at least one olefin in the presence of a single-site catalyst comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane to produce a precursor copolymer; and (b) cracking at least a portion of the precursor copolymer to produce a cracked copolymer at a temperature above 300°C.
Also disclosed herein is a process for the production of an ethylene-olefin copolymer, comprising the steps of:
a) polymerizing ethylene and at least one olefin in the presence of a co-catalyst combination comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane to produce a copolymer;
and optionally, b) subjecting at least a portion of said copolymer to thermal cracking to produce a cracked hydrocarbon, or hydroisomerizing said copolymer to produce an isomerization hydrocarbon product.
The present description also includes novel copolymers obtained from the polymerization process and the novel thermally cracked product. Hydrogenation of the polymer obtained from the thermal cracking process may produce a hydrogenated copolymer.
A copolymer produced by the reaction of ethylene and an olefin may be characterized as follows:
(a) mole $ ethylene of from 50 to 75~;
(b) number average molecular weight of < 2000;
(c) molecular weight distribution of < 2.5;
(d) bromine number of < 53;
(e) a head to tail molecular structure; and (f) a pour point of below about 0°C.
Also disclosed herein is a process for the production of a terpolymer by reaction under polymerization conditions of ethylene, at least one olefin monomer different from ethylene, and at least one third monomer comprising an ethenically unsaturated hydrocarbon such as an olefin having a carbon chain length of greater than three, in the presence of a catalyst combination comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane. Also provided is the novel terpolymer produced as a result of this process. This novel terpolymer may also be thermally cracked and hydrogenated, or hydroisomerized.
A hydrogenated cracked terpolymer produced according to the invention may have a bromine number ranging from 0 to 1.5.
According to one aspect of the invention there is provided a cracked liquid copolymer of ethylene and an olefin, said copolymer being characterized by:
(a) mol % of ethylene from 50 to 75~;
(b) number average molecular weight of < 2000;
(c) molecular weight distribution of < 2;
(d) random monomer distribution; and (e) a head-to-tail molecular structure.
According to another aspect of the invention there is provided a process for the production of a cracked copolymer, comprising the steps of:
(a) polymerizing ethylene and at least one olefin in the presence of a single-site catalyst comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane to produce a precursor copolymer; and (b) cracking at least a portion of the precursor copolymer to produce a cracked copolymer at a temperature above 300°C.
Also disclosed herein is a process for the production of an ethylene-olefin copolymer, comprising the steps of:
a) polymerizing ethylene and at least one olefin in the presence of a co-catalyst combination comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane to produce a copolymer;
and optionally, b) subjecting at least a portion of said copolymer to thermal cracking to produce a cracked hydrocarbon, or hydroisomerizing said copolymer to produce an isomerization hydrocarbon product.
The present description also includes novel copolymers obtained from the polymerization process and the novel thermally cracked product. Hydrogenation of the polymer obtained from the thermal cracking process may produce a hydrogenated copolymer.
A copolymer produced by the reaction of ethylene and an olefin may be characterized as follows:
(a) mole $ ethylene of from 50 to 75~;
(b) number average molecular weight of < 2000;
(c) molecular weight distribution of < 2.5;
(d) bromine number of < 53;
(e) a head to tail molecular structure; and (f) a pour point of below about 0°C.
Also disclosed herein is a process for the production of a terpolymer by reaction under polymerization conditions of ethylene, at least one olefin monomer different from ethylene, and at least one third monomer comprising an ethenically unsaturated hydrocarbon such as an olefin having a carbon chain length of greater than three, in the presence of a catalyst combination comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane. Also provided is the novel terpolymer produced as a result of this process. This novel terpolymer may also be thermally cracked and hydrogenated, or hydroisomerized.
A hydrogenated cracked terpolymer produced according to the invention may have a bromine number ranging from 0 to 1.5.
nora~led Description of the Invention , The present invention relates in one embodiment to a process for producing copolymers of ethylene and an olefin polymer, comprising polymerizing ethylene and one or mode olefin monomers having 3 to 20 carbon atoms under polymerization conditions in the presence of a catalyst combination comprising a compound of a transition metal of Group IVb of the Periodic Table and. an aluminoxan~e. In a further embodiment, this obtained copolymer is subjected to thermal cracking or hydroisomerizatian, and optionally, the cracked polymer is subjected to hydrogenation.
This invention further concerns a process for producing an ethylene-olefin polymer, comprising the steps of: polymerizing ethylene and one or more olefin monomers having 3 to 20 carbon atoms in the presence of a catalyst combination comprising a compound of a transition metal o~
Group IVb of the Periodic Table, and an aluminoxane, and hydroisomerizing the obtained polymer.
Hy ethylene-olefin polymer;,, there is meant a copolymer obtained by reaction of an ethylene monomer and one or more additional olefin monomers of suitable reactivity.
The etr.~flene-olefin polymer may be, for example, a copolymer, a terpolymer, a tetrapolymer, etc., depending on the number of rro nomer s reacted in the process .
.r. one embodiment of the process of this invention, the starting material to be fed to t:-.e polymerization reaction system is a mixture of ethy?en~e (ethane) and ore cr more olefins having about 3 to 20 carbon atoms. The contEnt of ethylene in the star t=:.g material is preferably afloat 2 to 80 ~:ole~s, preferably about 4 to 55 moles, and the content of the clef-:1 is preferably about 2C to 98 mole%, preferably aboLt ~5 to 96 mole'.
Specific examp:~s o~ t::e one or more olefins having 3 to 2C carbon atoms ~:::.c:: :~~ay ~ce ~ssed as a starting mater=al := in tie process c~ ~::;s _.-:~,~er.t~c:: a:e i-propane (preDyienei , i-butane, _-hexane, ~-T~et:~.,,~::-_-penter.~e, i-octane, 1-dace.~.e, _. -dc~decere , _ to t r acece~:e , _ :-:exacecene , _ -oc tadacene , eicocene, styrene and «-methylstyrene, 2-methyl-1-butene, 2-methyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl-1-pentene, 2-methyl-1-propene.
In an important embodiment of the invention,, liquid 5 copolymers and terpolymers are provided. Generally, liquid copolymers and terpolymers are produced when the amount of ethylene used in the polymerization reaction is less than about 60 mole percent. However, liquid polymers may also be produced using higher amounts of ethylene if a comonomer is used which introduces longer side chains (e.g., C6 and up) into the polymer.
In a further embodiment, semi-solid (low melting solids) and solid polymers are also provided. Such polymers are usually produced when the ethylene content is more than about 75 mole percent. However, solid and semi-solid polymers can be produced when the ethylene content is higher than 75% depending on the other comonomers.
The catalyst combinations used in the polymerization processes of the present invention are well known as catalysts for such polymerization reactions. Such catalysts comprise preferably the combination of (a) metallocene ccmpounds which are compounds of a transition metal of Group IVb of the Periodic 'able and (b) ar. aiuminexane.
Suez metallocene compounds are preferably tri- and ~5 tetravalent metal= havinc one e. two f:aptc n'--ligancs selected from the group comprisi~:g cyclepentadienyl, indenyl, flucrenyi with the maximum :,u;n~er of hydrogen substituted With alkyl, alkenyl, aryl, alkylaryl, arylakyl er benzo radicals to none. when. t'.~.ere are two n5-ligands, they rnay be 3C t:-~e same or different which are eit::er connected by bricking groups, selected frem the group comprising, C:-C, alkylene, R~Si, R,Si:, R2Si-C-S-n;, ic,Ge, R;P, RAN with R being hydrogen:
alkyl or aryl radicals, . ;:: t'.~.e two y-ligands are et connected. The ne~ _ hapte _ canes are Eit:~er halogen c: R, __ there aZE tW0 C. C..~.e SI:C: _-CanCS f0= the t°traValenC'; C=
trivaienc:~ trap=~t;~.. ~et~;, ~e=pecti~.~ely. where there cnly ere :apt: , _; ;aids, __ cGr. ~e selected f:cm t~:e -=c;:~
This invention further concerns a process for producing an ethylene-olefin polymer, comprising the steps of: polymerizing ethylene and one or more olefin monomers having 3 to 20 carbon atoms in the presence of a catalyst combination comprising a compound of a transition metal o~
Group IVb of the Periodic Table, and an aluminoxane, and hydroisomerizing the obtained polymer.
Hy ethylene-olefin polymer;,, there is meant a copolymer obtained by reaction of an ethylene monomer and one or more additional olefin monomers of suitable reactivity.
The etr.~flene-olefin polymer may be, for example, a copolymer, a terpolymer, a tetrapolymer, etc., depending on the number of rro nomer s reacted in the process .
.r. one embodiment of the process of this invention, the starting material to be fed to t:-.e polymerization reaction system is a mixture of ethy?en~e (ethane) and ore cr more olefins having about 3 to 20 carbon atoms. The contEnt of ethylene in the star t=:.g material is preferably afloat 2 to 80 ~:ole~s, preferably about 4 to 55 moles, and the content of the clef-:1 is preferably about 2C to 98 mole%, preferably aboLt ~5 to 96 mole'.
Specific examp:~s o~ t::e one or more olefins having 3 to 2C carbon atoms ~:::.c:: :~~ay ~ce ~ssed as a starting mater=al := in tie process c~ ~::;s _.-:~,~er.t~c:: a:e i-propane (preDyienei , i-butane, _-hexane, ~-T~et:~.,,~::-_-penter.~e, i-octane, 1-dace.~.e, _. -dc~decere , _ to t r acece~:e , _ :-:exacecene , _ -oc tadacene , eicocene, styrene and «-methylstyrene, 2-methyl-1-butene, 2-methyl-1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl-1-pentene, 2-methyl-1-propene.
In an important embodiment of the invention,, liquid 5 copolymers and terpolymers are provided. Generally, liquid copolymers and terpolymers are produced when the amount of ethylene used in the polymerization reaction is less than about 60 mole percent. However, liquid polymers may also be produced using higher amounts of ethylene if a comonomer is used which introduces longer side chains (e.g., C6 and up) into the polymer.
In a further embodiment, semi-solid (low melting solids) and solid polymers are also provided. Such polymers are usually produced when the ethylene content is more than about 75 mole percent. However, solid and semi-solid polymers can be produced when the ethylene content is higher than 75% depending on the other comonomers.
The catalyst combinations used in the polymerization processes of the present invention are well known as catalysts for such polymerization reactions. Such catalysts comprise preferably the combination of (a) metallocene ccmpounds which are compounds of a transition metal of Group IVb of the Periodic 'able and (b) ar. aiuminexane.
Suez metallocene compounds are preferably tri- and ~5 tetravalent metal= havinc one e. two f:aptc n'--ligancs selected from the group comprisi~:g cyclepentadienyl, indenyl, flucrenyi with the maximum :,u;n~er of hydrogen substituted With alkyl, alkenyl, aryl, alkylaryl, arylakyl er benzo radicals to none. when. t'.~.ere are two n5-ligands, they rnay be 3C t:-~e same or different which are eit::er connected by bricking groups, selected frem the group comprising, C:-C, alkylene, R~Si, R,Si:, R2Si-C-S-n;, ic,Ge, R;P, RAN with R being hydrogen:
alkyl or aryl radicals, . ;:: t'.~.e two y-ligands are et connected. The ne~ _ hapte _ canes are Eit:~er halogen c: R, __ there aZE tW0 C. C..~.e SI:C: _-CanCS f0= the t°traValenC'; C=
trivaienc:~ trap=~t;~.. ~et~;, ~e=pecti~.~ely. where there cnly ere :apt: , _; ;aids, __ cGr. ~e selected f:cm t~:e -=c;:~
comprising cyclopentadienyl, indenyl, fluorenyl with from the maximum number of hydrogen substituted with R or benzo radicals or to none. The transition metal will have three or two non-hapto ligands in the +4 and +3 oxidation state, respectively. One hydrogen of the hapto ligand may be substituted with a heteratom moiety selected from the group NR, NRz, PR, PRs which are connected by C1-C, alklene, R=Si, R,Siz to the ns-ring. The appropriate number of non-hapto ligands is three for tetravalent metal in the case of coordinate bondings NRZ or PRA moiety and one less nan-hapto ligands for the trivalent metal. These numbers are decreased by one in the case of covalent bonding NR or PR moieties.
Illustrative but not limiting examples of titanium compounds comprise bis-(cyclopentadienyl) dimethyl-titanium, bis-(cyclopentadienyl) diisopropyltitanium, bis(cyclopentadienyl) dimethyltitanium, bis(cyclopenta-dienyl) methyltitanium monochloride, bis(cyclopenta-dienyl) ethyltitanium monochloride, bis(cyclopentadienyl) isopropyltitanium monochloride, ,bis(cyclopentadienyl) titanium dichloride, dimethylsilylene (1-n5-2,3,4,5-tetramethylpentadienyl) (t-butylamido) titanium dichloride, 2-dimethyl amincet:~yi-ns-cyclopentadienyl titanium di cnlcr ide .
Illustrative b~;t not limiting examples of zirccrium ccmpou.~.ds compr:.se as bis (isoprepyicyclopentadienyl) zircor.ium dichloriQe, bis(cyclopentadienyl)dimet~:yl zirccnium, bislcyclepentadienyl>-diet:~ylzircom um, bis (methylcyclopenta-dienyl) diisopropylzirconium, bis(cyclopentadienyl) methylzirconium mor.~chloride, bis (cyclopentadienyl)echylzirconium Tonochioride, bis(cycio-petadienyl)zirccnium dichloride, rac-ethylene bis-(1-~=-indery_) zirconium dichloride, rac-et:~ylene bis (1-r~'--irdenyl) zirccnium dichic:_de, rac-eti:ylene bis(1-n'--4,5,6,7-tetra:~ydrcmdenyl ) z;_ ~c.~.~um dichlor ide and iscprcpyl ice.~.e---r,'--cyclcrer.:ad~e~.,r . , S-r,--1 ~l::ca'v'Z:yl ) zirccniumdichlcr; ~e.
Specific exam:.le= cf ::af.~.iurn ccmpcuncs comp~r~=e ..: 1 S ( c V C ~ O - r; E .~. t a C ~ a !: Y ~ , .~r i m E t f'1 V i ~": n i : W '.: ,Ti , 7 , bis(cyclopentadienyl)methylhafnium monochloride, and bistcyclopentadienyl)hafnium dichloride.
The aluminoxane co-catalyst useful in the catalysts of the present invention are polymeric aluminum cocr~ound's which can be represented by the general formulae iR-Al-O)"
which is a cyclic compound and R tR-Al-O-) ~,AlRz, which is a linear compound. In the general formula R is a Cl-CS alkyl group such as, for example, methyl, ethyl, propyl, butyl and pentyl and n is an integer from 1 to about 20. Most preferably, R is methyl and n is about 4. Generally, in the preparation of alumoxanes from, for example, aluminum trimethyl and water, a mixture of the linear and cyclic compounds is obtained.
The proportion of the catalyst comprising a compound I5 of a transition metal of Group IVb of the Periodic Table may be, for example, 10'B tc 10'' gram-atom/liter, preferably 1fl'' to 10'' gram-atom/liter, as the concentration of the catalyst comprising a compound of a transition metal in ~he polymerization reaction. The proportion of the aluminoxane used may be, for example, 10'' to 10'1 gram-atom/liter, preferably 10~' to 5x10~~ gram-atom/lter, as the concentration of the aluminum atom in tine polymerization reaction. The ratio of the aluminu.~.: atom to the transition metal i:~ the po?vmer;zatic:. reaction system may be, fcr example, ir. ~he nonce cf 25 to 106, preferably 50 to 10'. The molecular weight of the polymer ;nay be controlled by using hydrogen, ardjor by adjusting the polymerization temperature, or by changing the monomer concentrations.
The ccpolymerizatiers arid te~olymerizations co~sld .0 also ee performed ~.:s_na other co-catalysts, without R,Al ( Jcurnay cf ro1 ymer ~ci once : Part A : Fol ymer C~:emi stry, Vol .
32. 2387-2393 (1994).x.
While the above descr~pti;..~. represents preferred ys=s f~- ~ .. ~ _ ~~~ ~ ,~. ,y ~ _ Catal ~_ u_e _ t..e ~ve.:~~cr., ecu~va_e. ~ ~aLa~ st_ 3r:c ~5 ccrr;Di::at~or.= may ;:isc be usec to effect the clefs~:
aciv-merizaticn.
Illustrative but not limiting examples of titanium compounds comprise bis-(cyclopentadienyl) dimethyl-titanium, bis-(cyclopentadienyl) diisopropyltitanium, bis(cyclopentadienyl) dimethyltitanium, bis(cyclopenta-dienyl) methyltitanium monochloride, bis(cyclopenta-dienyl) ethyltitanium monochloride, bis(cyclopentadienyl) isopropyltitanium monochloride, ,bis(cyclopentadienyl) titanium dichloride, dimethylsilylene (1-n5-2,3,4,5-tetramethylpentadienyl) (t-butylamido) titanium dichloride, 2-dimethyl amincet:~yi-ns-cyclopentadienyl titanium di cnlcr ide .
Illustrative b~;t not limiting examples of zirccrium ccmpou.~.ds compr:.se as bis (isoprepyicyclopentadienyl) zircor.ium dichloriQe, bis(cyclopentadienyl)dimet~:yl zirccnium, bislcyclepentadienyl>-diet:~ylzircom um, bis (methylcyclopenta-dienyl) diisopropylzirconium, bis(cyclopentadienyl) methylzirconium mor.~chloride, bis (cyclopentadienyl)echylzirconium Tonochioride, bis(cycio-petadienyl)zirccnium dichloride, rac-ethylene bis-(1-~=-indery_) zirconium dichloride, rac-et:~ylene bis (1-r~'--irdenyl) zirccnium dichic:_de, rac-eti:ylene bis(1-n'--4,5,6,7-tetra:~ydrcmdenyl ) z;_ ~c.~.~um dichlor ide and iscprcpyl ice.~.e---r,'--cyclcrer.:ad~e~.,r . , S-r,--1 ~l::ca'v'Z:yl ) zirccniumdichlcr; ~e.
Specific exam:.le= cf ::af.~.iurn ccmpcuncs comp~r~=e ..: 1 S ( c V C ~ O - r; E .~. t a C ~ a !: Y ~ , .~r i m E t f'1 V i ~": n i : W '.: ,Ti , 7 , bis(cyclopentadienyl)methylhafnium monochloride, and bistcyclopentadienyl)hafnium dichloride.
The aluminoxane co-catalyst useful in the catalysts of the present invention are polymeric aluminum cocr~ound's which can be represented by the general formulae iR-Al-O)"
which is a cyclic compound and R tR-Al-O-) ~,AlRz, which is a linear compound. In the general formula R is a Cl-CS alkyl group such as, for example, methyl, ethyl, propyl, butyl and pentyl and n is an integer from 1 to about 20. Most preferably, R is methyl and n is about 4. Generally, in the preparation of alumoxanes from, for example, aluminum trimethyl and water, a mixture of the linear and cyclic compounds is obtained.
The proportion of the catalyst comprising a compound I5 of a transition metal of Group IVb of the Periodic Table may be, for example, 10'B tc 10'' gram-atom/liter, preferably 1fl'' to 10'' gram-atom/liter, as the concentration of the catalyst comprising a compound of a transition metal in ~he polymerization reaction. The proportion of the aluminoxane used may be, for example, 10'' to 10'1 gram-atom/liter, preferably 10~' to 5x10~~ gram-atom/lter, as the concentration of the aluminum atom in tine polymerization reaction. The ratio of the aluminu.~.: atom to the transition metal i:~ the po?vmer;zatic:. reaction system may be, fcr example, ir. ~he nonce cf 25 to 106, preferably 50 to 10'. The molecular weight of the polymer ;nay be controlled by using hydrogen, ardjor by adjusting the polymerization temperature, or by changing the monomer concentrations.
The ccpolymerizatiers arid te~olymerizations co~sld .0 also ee performed ~.:s_na other co-catalysts, without R,Al ( Jcurnay cf ro1 ymer ~ci once : Part A : Fol ymer C~:emi stry, Vol .
32. 2387-2393 (1994).x.
While the above descr~pti;..~. represents preferred ys=s f~- ~ .. ~ _ ~~~ ~ ,~. ,y ~ _ Catal ~_ u_e _ t..e ~ve.:~~cr., ecu~va_e. ~ ~aLa~ st_ 3r:c ~5 ccrr;Di::at~or.= may ;:isc be usec to effect the clefs~:
aciv-merizaticn.
The polymerization reaction in the process of this invention may be carried out in absence of a solvent or in a hydrocarbon solvent. Examples of a hydrocarbon solvent suitable for this purpose are aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecene and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and petroleum fractions such as gasoline, kerosene, lubricant base stocks and light oils. The starting olefins may themselves serve as the hydrocarbon medium. Among these hydrocarbon media, the aromatic ' hydrocarbons and the starting olefins may be preferably used in the process of this invention.
The polymerization temperature in this first step of the process of the invention may range, for example, from about 0C to about 200C, preferably from about 40C to about 120C.
When the polymerization reaction in the process of this invention is carried out in the absence of hydrogen, a liguid copolymer having a high bromine value is obtained which contains unsaturation (double bonds). This copolymer is usually a high molecular weight copolymer. When the polymerization is carried out in the presence of hydrogen, a liquid polymer having a low bromine value or a bromine value of substantially zero may be obtained. Some unsaturation may be present. The hydrogen is used to control (lower) the molecular weight of the copolymer.
Excess solvent may be removed by evaporation and a light copolymer (boiling point below 371C (700F) in ASTM D-2887 Simulated Distillation) is recovered by distillation under vacuum.
The product resulting from this copolymerization reaction of ethylene monomer and an olefin monomer different from ethylene is a copolymer suitable as a base oil for synthetic lubricants. The polymer may be characterized as containing from 50 to 75 mole % ethylene, having a number average molecular weight in exc-es=_ of 1000, a molecular weight distribution in excess of 2, a bromine number in excess of 2, and'~a molecular structure which is head to tail with a random monomer distribution.
In a further aspect, the present invention provides vinylidene olefin polymers, copolymers, and terpolymers from vinylidene monomers alone or copolymerized with other non vinylidene monomers. Vinylidene monomers are characterized by the formula:
CHZ=CR1R2 wherein R, and RZ are independently selected from the group consisting of C,-C2o aliphatic groups, alicyclic groins and aromatic groups. Preferred vinylidene monomers are 2-methyl propene (isobutylene) and 4-methylpentene.
Homopolymers of vinylidene monomers may be produced or a vinlidene monomer may be reacted with one or more comot~ome rs which may be a second vinylidene monomer or an alpha-olefin.
Suitable alpha-olefin comonomers comprise ethEne, propene, styrene, ethylidene, norbornene, non-conjugated dienes, norbornene, and the like.
These vinylidene polymers are produced in generally the same manner and under the same conditions as the other polymers of the invention. however, it is preferred to use a tri-catalyst system comprising a catalytic amount of triisobutyl aluminum (TIBA) , a TeCl catalyst, ( (CSM.e~) Si~iez_ ~N(T-Bu)TiCl2" and a borate, triphenyl carbenium tetrakis (pentafluorophenyl) borate. The monomers are contacted with this catalyst system at a termperature ranging from a3~out 20°C to 40°C, a polymerization pressure of about x.34 to 1.7 atm (5 to 25 psig) and a residence time of .about 0.5 to 2 hour" and preferably in the presence of hydrogen. Preferred ratios of reactants comprise olefin to vinylidene olefin ranging from about 5-50 mole ~: olefins to 50-95 mole ~
vinylidene olefin, and optionally about 0-2 percent hydrogen.
In a preferred fur then embodiment of the invention, a third monomeric reactant different from ethylene and the Glefin polymer, :;;ay be included in the initial polymerization.
reaCtlGn t0 fCriCi c :.Cr''jJG!1~'~le~ ; rGW:Ct. i'hi5 tr:lrd ~O!ilpC::Erit must contain unsaturation so that polymerization can occur and is selected from the group consisting of olefins having 4 to 20 carbon atoms.
Preferred reactants are olefins of 4 to 12 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-hepter~e, 1- ., octene, 1-decene, 1-undecene and 1-dodecene, 2-methyl-1-pentene, styrene, «-methylstyrene, 2-methyl-1-butene, 3-methyl-1-butene, 9-methyl-1-pentene, 2-methyl-1-pentene, 2-methyl-1-propene.
In conducting the reaction with the third monomeric reactant, it is preferred to use about 0.1 up to ~40 mole percent, preferably about 1 to 20 mole percent of the third monomer, based on the total composition.
The terpolymer produced in this embodiment of the invention may be characterized as a liquid terpolymer of ethylene, a first olefin different from ethylene, and a second olefin different from ethylene and the first olefin, preferably having 4 to about 2;0 carbon atoms; and characterized by:
(a) mole ~ ethylene of from 10 to 80~;
(b) mole ~ of said first olefin of from 19 to 80~;
(c) mole ~ of said second olefin of from 1~ to 10$;
(d) number average molecular weight of 3D0-l0,fla0;
(e) molecular weight distribution of < 2.5; and a (f) bromine number in the range of 0 to 53.
The terpolymer resulting from reaction using the third monomer reactant is also useful as a synthetic base oil for synthetic lubricants and as a white oil for use in cosmetics and medicines. The third monomer provides a beneficial effect by lowering the pour point of the final base oil.
The presence of the third monomer during the polymerization reaction may reauire a change in catGlyst or polymerization reaction conditions. Obviously, ether and additional different r~~cnomers may be included in t~:e reaCt~On tQ ~:I'~vui7Ce ~e~:alr'..Oil~~.aer~~ etC.
In a further embodiment of the invention, the intermediate copolymer or terpolymer resulting from the polymerization reaction, is subjected to cracking, prefer-ably thermal cracking. As noted above, once tie polymerization reaction is completed, excess solvent is removed and those polymers having boiling points below about 371°C (700°F) in ASTM D-2887 Simulated Distillation are recovered by distillation. The catalyst may be washed from the copolymer or terpolymer with an aqueous base (e. g., 1M NaOH) or acid (e. g., 1M HC1). The resulting copolymer or terpolymer product is then subjected to . cracking, preferably under thermal conditions but catalytic cracking could be used as is known in the art. The thermal cracking process is carried at a temperature range of from about 250°C to about 550°C, preferably from about 350°C
to about 950°C.
The pressure in the cracking step of the invention may range, for example, from about 0.1 to 30 mm Hg vacuum pressure, preferably from about fl.2 to about 10 mm Hg vacuum pressure.
The cracked product in liquid form may optionally be washed with an aqueous base or aqueous acid, and water.
Preferably, the cracked feed is washed with aqueous 1M
NaOH, followed by large quantities of water.
r_ As a result of the thermal cracking process, there is produced a copolymer or terpolymer or segments thereof which contain unsaturation (double bonds). The thermally cracked polymeric product is Glso useful as a synthetic base oil for synthetic lubricants.
The cracked liquid copolymer may be described as a liquid Copolymer of ethylene and an olefin, said copolymer being characterized by:
(a) mole ~ ethylene of from 10 to 75~;
(b) nu~~iber average molecular weight of < 2000;
(c) molecular weic:l~ cistributior. of < 2;
~'rC.iTIIiZE rluJ~~r vl < .~.~.: ~ Gnd e) G ~:EG~ tJ tell mVleCL:~Gr eC..trlJVtur~.
The cracked liquid terpolymer may be described as a liquid terpolymer of ethylene, a first olefin, and a second olefin having 3 to about 20; carbon atoms: said terpolymer being characterized by:
(a) mole $ ethylene of from 10 to 80$;
(b) mole $ of said first olefin of from 14 to 80$:
(c) mole $ of said second olefin of from 1$ to 10~~
(d) number average molecular weight of 300-10,000;
(e) molecular weight distribution of < 2.5: and a (f) bromine number in the range of 0 to 53.
In the thermal cracking process, the polymer appears to crack or separate substantially in the center of the i ' polymer. These are narrow molecular weight range products particularly useful as 2, 4 and 6 centistoke oils. For I5 example, in a polymer having a number average molecular weight of about 1200, the resulting cracked products will have two segments of about 600 number average molecular weight each. Also, after cracking the segments will not exclusively exhibit vinylidene unsaturation but rather will have allyl unsaturates and some internal double bonds .
The bromine number of a preferred hydrogenated cracked hydrocarbon product will range from 0 up to 1.0, the kinematic viscosity at 100C will range from 2 to 16 cSt, the viscosity index will range from 140 to 160, and the .
pour point will be below 0C.
In a further embodiment, the cracked product is then hydrogenated by reaction with hydrogen gas in the presence of a catalytic amount (0.1 to 5 wt.~) of a catalyst.
Examples of suitable hydrogenating catalysts are metals of Group VIII of the Periodic Table such as iron, cobalt, nickel, rhodium, palladium and platinum. These catalysts are deposited on alLL'nlna, on silica gel, or on activated carbon in preferred embodiments. Of these catalysts, palladium and nickel are preferred. Pal 1 adi~,y-n or. activated carbon Gnd r:ickel en kieselguhr are especially preferred. ':he hydrcger.aticn reGctior. is carried cut in t:e presence or absence ef solvents. Selverts are necess~r;~ or:ly to increase the volume. Examples of suitable solvents are hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclohexane, methycyclohexane and cyclooctane aromatic hydrocarbons such as toluene, xylene or benzene.
The temperature of the hydrogenation reaction may range, for example, from about 150°C to about 500°C, preferably from about 250° to about 350°C. The, hydrogenation reaction pressure may be, for example, in the range of 250-1090 ~sig hydrogen. The hydrogenated polymeric product is then recovered by conventional procedures. In the hydrogenated product, the double bonds formed in the cracking step have been hydrogenated so that the polymer is a separate type of product. The hydrogenated product will have a number average molecular weight ranging from about 300 to 1000 and a kinematic viscosity @ 100°C of about 6-16 centistokes.
In a further embodiment of the present invention, the resulting ethylene-olefin polymer or terpolymer .can be hydroisomerized in the presence of a catalytic amount (0.1 to 5 wt.~) of an acidic hydroisomerization catalyst. The hydroisomerization temperature used in this process ra~rges from about 250°C to about 550°C, preferably from about l5fl°C
to about 300°C.
The pressure in the hydroisomerization process may range, for example, from about 17 to 68 atm (250 to 1000 psig) hydrogen pressure, preferably from about 20.4 to about 34 atm (300 to about 500 psig) hydrogen pressure. In the resulting hydroisomerized product, the carbon moieties have been rearranged into a different molecular structure.
Examples of the acidic hydroisomerizatian catalysts include transition metals of Groups VI to VIII of the Periodic Table, their cxides, or the combination of metal and metal oxide supported on acidic molecular sieves. The metals include Pd, Ni, Ft, Mc~. Metal oxides include PdC, NiO, MoC:.
Molecular sieves includE synthetic zeelites, such ZEOllte ~:, L, X, ~', and riaturcl ZcGI i tes, Such o~ mGrd~n tie, .,° ;: '=.~C, j .~= f rr C.aabaZl ~e, iCml ~.., cnC C ~:lC;r _ 1 tE . a E E,~
~hydroisomerization catalysts include Pd supported on acidic zeolite X, Ni/Mo03 on zeolite and Ni/Ni0 on zeolite:
The polymer products of the invention are useful as synthetic lubricating base oils. The base oils of the invention are comparable or improved in lubricating properties, but are less expensive to produce, than poly-alpha-olefins which are currently used commercially as synthetic lubricants.
The synthetic base oils of the invention may be formulated with from about 0.1% up to aboutl5 wt.% of one or more conventional lubricating oil additives. Such adds-tives comprise detergent packages, pour point depressants, viscosity index improvers and other additives such as anti-oxidants, additives with a detergent action, viscosity increasing compounds, anti-corrosi~res, anti-foaming agents, agents to improve the lubricating effect and other compounds which are usually added to lubricating oils.
The following examples are presented to further illustrate the invention but are not considered to limit the scope of the invention in any manner whatsoever.
p~naration of ethylene-propylene s~,y~ne_r A 4-liter autoclave reactor (using two 2-liter autoclave reactors connected in series) was thoroughly purged with nitrogen and was charged with 300 ml of dried toluene (dried over potassium). Ethylene, propylene and hydrogen were simultaneously and continuously fed through a mass flow controller into the bottom of the reactor at a ratio of 2000 cc/min, 1900 cc/min, and 240 cc/min, respectively.
~0 Methylaluminoxane 1.5 mg-atom/hour based on A1 content in toluene solution and bis(isopropyl-cyclopentadienyl)zirconium dichloride 15x10-' mg-atom/hour based on Zr content in toluene solution were simultaneously and continuously pumped into the reactor. The ethylene and propylene were polymerized at 50°C
and 1.02 atm(15 psig) pressure. Throughout the reaction run, the temperature was maintained at +/-2°C by a heat transfer fluid being circulated through a coil tubing inside the reactor. The excess monomers and hydrogen were continuously vented out at 11.33 x 10'' m3 (0.9 cubic .feet) per hour to maintain a constant gas concentration in the reactor.
5 The resulting polymer solution was continuously transferred from the reactor to a collection vessel. The pressure was controlled by a back-pressure valve 1.02 atm (15 psig). The product, along with toluene, was withdrawn from the collector, and the toluene was removed on a rota-evaporator.
The polymerization temperature in this first step of the process of the invention may range, for example, from about 0C to about 200C, preferably from about 40C to about 120C.
When the polymerization reaction in the process of this invention is carried out in the absence of hydrogen, a liguid copolymer having a high bromine value is obtained which contains unsaturation (double bonds). This copolymer is usually a high molecular weight copolymer. When the polymerization is carried out in the presence of hydrogen, a liquid polymer having a low bromine value or a bromine value of substantially zero may be obtained. Some unsaturation may be present. The hydrogen is used to control (lower) the molecular weight of the copolymer.
Excess solvent may be removed by evaporation and a light copolymer (boiling point below 371C (700F) in ASTM D-2887 Simulated Distillation) is recovered by distillation under vacuum.
The product resulting from this copolymerization reaction of ethylene monomer and an olefin monomer different from ethylene is a copolymer suitable as a base oil for synthetic lubricants. The polymer may be characterized as containing from 50 to 75 mole % ethylene, having a number average molecular weight in exc-es=_ of 1000, a molecular weight distribution in excess of 2, a bromine number in excess of 2, and'~a molecular structure which is head to tail with a random monomer distribution.
In a further aspect, the present invention provides vinylidene olefin polymers, copolymers, and terpolymers from vinylidene monomers alone or copolymerized with other non vinylidene monomers. Vinylidene monomers are characterized by the formula:
CHZ=CR1R2 wherein R, and RZ are independently selected from the group consisting of C,-C2o aliphatic groups, alicyclic groins and aromatic groups. Preferred vinylidene monomers are 2-methyl propene (isobutylene) and 4-methylpentene.
Homopolymers of vinylidene monomers may be produced or a vinlidene monomer may be reacted with one or more comot~ome rs which may be a second vinylidene monomer or an alpha-olefin.
Suitable alpha-olefin comonomers comprise ethEne, propene, styrene, ethylidene, norbornene, non-conjugated dienes, norbornene, and the like.
These vinylidene polymers are produced in generally the same manner and under the same conditions as the other polymers of the invention. however, it is preferred to use a tri-catalyst system comprising a catalytic amount of triisobutyl aluminum (TIBA) , a TeCl catalyst, ( (CSM.e~) Si~iez_ ~N(T-Bu)TiCl2" and a borate, triphenyl carbenium tetrakis (pentafluorophenyl) borate. The monomers are contacted with this catalyst system at a termperature ranging from a3~out 20°C to 40°C, a polymerization pressure of about x.34 to 1.7 atm (5 to 25 psig) and a residence time of .about 0.5 to 2 hour" and preferably in the presence of hydrogen. Preferred ratios of reactants comprise olefin to vinylidene olefin ranging from about 5-50 mole ~: olefins to 50-95 mole ~
vinylidene olefin, and optionally about 0-2 percent hydrogen.
In a preferred fur then embodiment of the invention, a third monomeric reactant different from ethylene and the Glefin polymer, :;;ay be included in the initial polymerization.
reaCtlGn t0 fCriCi c :.Cr''jJG!1~'~le~ ; rGW:Ct. i'hi5 tr:lrd ~O!ilpC::Erit must contain unsaturation so that polymerization can occur and is selected from the group consisting of olefins having 4 to 20 carbon atoms.
Preferred reactants are olefins of 4 to 12 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-hepter~e, 1- ., octene, 1-decene, 1-undecene and 1-dodecene, 2-methyl-1-pentene, styrene, «-methylstyrene, 2-methyl-1-butene, 3-methyl-1-butene, 9-methyl-1-pentene, 2-methyl-1-pentene, 2-methyl-1-propene.
In conducting the reaction with the third monomeric reactant, it is preferred to use about 0.1 up to ~40 mole percent, preferably about 1 to 20 mole percent of the third monomer, based on the total composition.
The terpolymer produced in this embodiment of the invention may be characterized as a liquid terpolymer of ethylene, a first olefin different from ethylene, and a second olefin different from ethylene and the first olefin, preferably having 4 to about 2;0 carbon atoms; and characterized by:
(a) mole ~ ethylene of from 10 to 80~;
(b) mole ~ of said first olefin of from 19 to 80~;
(c) mole ~ of said second olefin of from 1~ to 10$;
(d) number average molecular weight of 3D0-l0,fla0;
(e) molecular weight distribution of < 2.5; and a (f) bromine number in the range of 0 to 53.
The terpolymer resulting from reaction using the third monomer reactant is also useful as a synthetic base oil for synthetic lubricants and as a white oil for use in cosmetics and medicines. The third monomer provides a beneficial effect by lowering the pour point of the final base oil.
The presence of the third monomer during the polymerization reaction may reauire a change in catGlyst or polymerization reaction conditions. Obviously, ether and additional different r~~cnomers may be included in t~:e reaCt~On tQ ~:I'~vui7Ce ~e~:alr'..Oil~~.aer~~ etC.
In a further embodiment of the invention, the intermediate copolymer or terpolymer resulting from the polymerization reaction, is subjected to cracking, prefer-ably thermal cracking. As noted above, once tie polymerization reaction is completed, excess solvent is removed and those polymers having boiling points below about 371°C (700°F) in ASTM D-2887 Simulated Distillation are recovered by distillation. The catalyst may be washed from the copolymer or terpolymer with an aqueous base (e. g., 1M NaOH) or acid (e. g., 1M HC1). The resulting copolymer or terpolymer product is then subjected to . cracking, preferably under thermal conditions but catalytic cracking could be used as is known in the art. The thermal cracking process is carried at a temperature range of from about 250°C to about 550°C, preferably from about 350°C
to about 950°C.
The pressure in the cracking step of the invention may range, for example, from about 0.1 to 30 mm Hg vacuum pressure, preferably from about fl.2 to about 10 mm Hg vacuum pressure.
The cracked product in liquid form may optionally be washed with an aqueous base or aqueous acid, and water.
Preferably, the cracked feed is washed with aqueous 1M
NaOH, followed by large quantities of water.
r_ As a result of the thermal cracking process, there is produced a copolymer or terpolymer or segments thereof which contain unsaturation (double bonds). The thermally cracked polymeric product is Glso useful as a synthetic base oil for synthetic lubricants.
The cracked liquid copolymer may be described as a liquid Copolymer of ethylene and an olefin, said copolymer being characterized by:
(a) mole ~ ethylene of from 10 to 75~;
(b) nu~~iber average molecular weight of < 2000;
(c) molecular weic:l~ cistributior. of < 2;
~'rC.iTIIiZE rluJ~~r vl < .~.~.: ~ Gnd e) G ~:EG~ tJ tell mVleCL:~Gr eC..trlJVtur~.
The cracked liquid terpolymer may be described as a liquid terpolymer of ethylene, a first olefin, and a second olefin having 3 to about 20; carbon atoms: said terpolymer being characterized by:
(a) mole $ ethylene of from 10 to 80$;
(b) mole $ of said first olefin of from 14 to 80$:
(c) mole $ of said second olefin of from 1$ to 10~~
(d) number average molecular weight of 300-10,000;
(e) molecular weight distribution of < 2.5: and a (f) bromine number in the range of 0 to 53.
In the thermal cracking process, the polymer appears to crack or separate substantially in the center of the i ' polymer. These are narrow molecular weight range products particularly useful as 2, 4 and 6 centistoke oils. For I5 example, in a polymer having a number average molecular weight of about 1200, the resulting cracked products will have two segments of about 600 number average molecular weight each. Also, after cracking the segments will not exclusively exhibit vinylidene unsaturation but rather will have allyl unsaturates and some internal double bonds .
The bromine number of a preferred hydrogenated cracked hydrocarbon product will range from 0 up to 1.0, the kinematic viscosity at 100C will range from 2 to 16 cSt, the viscosity index will range from 140 to 160, and the .
pour point will be below 0C.
In a further embodiment, the cracked product is then hydrogenated by reaction with hydrogen gas in the presence of a catalytic amount (0.1 to 5 wt.~) of a catalyst.
Examples of suitable hydrogenating catalysts are metals of Group VIII of the Periodic Table such as iron, cobalt, nickel, rhodium, palladium and platinum. These catalysts are deposited on alLL'nlna, on silica gel, or on activated carbon in preferred embodiments. Of these catalysts, palladium and nickel are preferred. Pal 1 adi~,y-n or. activated carbon Gnd r:ickel en kieselguhr are especially preferred. ':he hydrcger.aticn reGctior. is carried cut in t:e presence or absence ef solvents. Selverts are necess~r;~ or:ly to increase the volume. Examples of suitable solvents are hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclohexane, methycyclohexane and cyclooctane aromatic hydrocarbons such as toluene, xylene or benzene.
The temperature of the hydrogenation reaction may range, for example, from about 150°C to about 500°C, preferably from about 250° to about 350°C. The, hydrogenation reaction pressure may be, for example, in the range of 250-1090 ~sig hydrogen. The hydrogenated polymeric product is then recovered by conventional procedures. In the hydrogenated product, the double bonds formed in the cracking step have been hydrogenated so that the polymer is a separate type of product. The hydrogenated product will have a number average molecular weight ranging from about 300 to 1000 and a kinematic viscosity @ 100°C of about 6-16 centistokes.
In a further embodiment of the present invention, the resulting ethylene-olefin polymer or terpolymer .can be hydroisomerized in the presence of a catalytic amount (0.1 to 5 wt.~) of an acidic hydroisomerization catalyst. The hydroisomerization temperature used in this process ra~rges from about 250°C to about 550°C, preferably from about l5fl°C
to about 300°C.
The pressure in the hydroisomerization process may range, for example, from about 17 to 68 atm (250 to 1000 psig) hydrogen pressure, preferably from about 20.4 to about 34 atm (300 to about 500 psig) hydrogen pressure. In the resulting hydroisomerized product, the carbon moieties have been rearranged into a different molecular structure.
Examples of the acidic hydroisomerizatian catalysts include transition metals of Groups VI to VIII of the Periodic Table, their cxides, or the combination of metal and metal oxide supported on acidic molecular sieves. The metals include Pd, Ni, Ft, Mc~. Metal oxides include PdC, NiO, MoC:.
Molecular sieves includE synthetic zeelites, such ZEOllte ~:, L, X, ~', and riaturcl ZcGI i tes, Such o~ mGrd~n tie, .,° ;: '=.~C, j .~= f rr C.aabaZl ~e, iCml ~.., cnC C ~:lC;r _ 1 tE . a E E,~
~hydroisomerization catalysts include Pd supported on acidic zeolite X, Ni/Mo03 on zeolite and Ni/Ni0 on zeolite:
The polymer products of the invention are useful as synthetic lubricating base oils. The base oils of the invention are comparable or improved in lubricating properties, but are less expensive to produce, than poly-alpha-olefins which are currently used commercially as synthetic lubricants.
The synthetic base oils of the invention may be formulated with from about 0.1% up to aboutl5 wt.% of one or more conventional lubricating oil additives. Such adds-tives comprise detergent packages, pour point depressants, viscosity index improvers and other additives such as anti-oxidants, additives with a detergent action, viscosity increasing compounds, anti-corrosi~res, anti-foaming agents, agents to improve the lubricating effect and other compounds which are usually added to lubricating oils.
The following examples are presented to further illustrate the invention but are not considered to limit the scope of the invention in any manner whatsoever.
p~naration of ethylene-propylene s~,y~ne_r A 4-liter autoclave reactor (using two 2-liter autoclave reactors connected in series) was thoroughly purged with nitrogen and was charged with 300 ml of dried toluene (dried over potassium). Ethylene, propylene and hydrogen were simultaneously and continuously fed through a mass flow controller into the bottom of the reactor at a ratio of 2000 cc/min, 1900 cc/min, and 240 cc/min, respectively.
~0 Methylaluminoxane 1.5 mg-atom/hour based on A1 content in toluene solution and bis(isopropyl-cyclopentadienyl)zirconium dichloride 15x10-' mg-atom/hour based on Zr content in toluene solution were simultaneously and continuously pumped into the reactor. The ethylene and propylene were polymerized at 50°C
and 1.02 atm(15 psig) pressure. Throughout the reaction run, the temperature was maintained at +/-2°C by a heat transfer fluid being circulated through a coil tubing inside the reactor. The excess monomers and hydrogen were continuously vented out at 11.33 x 10'' m3 (0.9 cubic .feet) per hour to maintain a constant gas concentration in the reactor.
5 The resulting polymer solution was continuously transferred from the reactor to a collection vessel. The pressure was controlled by a back-pressure valve 1.02 atm (15 psig). The product, along with toluene, was withdrawn from the collector, and the toluene was removed on a rota-evaporator.
10 The product was washed with aqueous 1M NaOH, followed by washing with a large quantity of water. A clear liquid polymer (245 grams per hour) was obtained. The obtained liquid polymer had a kinematic viscosity of 90 cSt at 100°C and viscosity index of 173, Mn of 1400, Mw/Mn of 2.49, bromine number of 4.7.
15 The obtained copolymer contained 62 mole ~ ethylene.
E?~AMPLE 2 The procedure was essentially the same as Example 1, except the polymerization conditions and the feed ratio of ethylene/propylene were changed. The results and properties of the product are summarized in Table 1.
is Polymerization conditions arid roducts ro erties E=am le ! 2 Rcaclor Vol. L 4 2 lerre cclmin 1990 2000 Ethylene, cclmin 2000 1400 H dro en, cc/mia 240 ' 20 MAO A1 m -atom /h 1.5 1.5 i-PrC 1, Zr m atom/h 1.5x10'' 1.5x10'' Polymerization Tem ature,50 90 C
Polymerization Pressure 1.02 (15 2.04 (30 atm si ) Mn 1400 1300 Mw/Mn 2.37 2.41 Ethylene mole % in Co 62 63 lvmer Yield, ams/hour 245 153 Simulated Distillation off at 371 C 700F 10 8,6 Kinematic Viscosity ra7 40 33 100C, cSt Visc~itv lndcx 173 176 2 Bromine Number 4.7 8.5 Then_nal Cracki~Q
The light polymers produced in Example 1 (boiling point below 371°C (700°F) in ASTM D-2887 Simulated Distillation) were distilled under vacuum. The remaining viscous oils (5aa grams) were placed in a round-bottom flask connected to a short-path distillation column and a receiver. The contents were heated at 350° to 45D°C at 0.2 to 2 mm Hg vacuum pressure. The liquid polymers were thermally cracked inside the flask. Once the polymer pyrolized, the cracked polymers were simultaneously evaporated at this temperature range under . reduced pressure, and condensed in the receiver to give 420 grams of clear oil. About 15 grams of polymer were left in the flask with the remaining catalysts. The condensed tracked product was characterized by Mn, 797; Mw/Mn, 1.34: kinematic viscosity at 100°C, 7.29 cSt; VI, 160; bromine number, 18.9.
ljydrooenatian j~pt-hod A
A portion of the cracked product from Example 1 and 1 weight percent of Fd/C powder were placed in a Zipperclave rEactor and filled with 34 arm (500 psig) hydrogen. After 2' aeitGtion for 7 hour Gt 250'C, the reactor was cooled at room;
temperature. The catalyst was filtered through a filter agent available under the trade designGtion "cellitE" under reducEd pressure to give a ciEar colorless liquid oil #~aving a bromine number of less than 0.1. C-13 hlNR: peak at b 11.4 FFn~- Frove~ the prESEncE cf iso-butyl group .
.J
F
A ~ ic1n1E55 StEE CG_~ L.'t1''1 1 . c % C311 X ~' . 61 :a: ( ~ i L In X ~ fEEt ) we .;i~EU wiu: ~~.~ Crcs'i'.~ Cr TV::-KiE~E!Q'1.:f1: TJEI.~.Et~. A ~v~tlOW ~.~f ~itE
cracked oils from Example 2 were continuously pumped upward at a rate of 1.5 ml/min. through the column at 35fl°~ (inside temperature) and 51.05 atm (750 prig) hydrogen. The hydrogen also flowed upward through the column from a separate line.
The hydrogenated products Were collected at the other end of column to give a clear colorless liquid oil having a bromine number of less than 0.1. The C-13 NMR. peak at a T1.4 ppm.
proves the presence of iso-butyl groups.
Hydroisomgrizati"Qin rlethod A
Hydroisomerization on a portion of the cracked product of Example 1 was performed in the same equipment using the same procedure as described in Method B of Example 4, except the Ni-Kieselguhr catalyst was replaced by 32 grams of Pd supported acidic molecular sieve (an x-type zeolite). The Pd supported zeolite was prepared by thetreatment of molecular s i eve X13 ( 50 grams ) wi th NH4C1 ( I 3 grams ) and ~d (NH3 ) 2C12 ( I
gram) in aqueous solution at 90°C. After the separation of the water, the treated zeolite was then calcined at 450° for 4 hours. The hydroisomerization was carried out at 284°C and 23.8°C (350 psig) of hydrogen pressure. The hydroisamerized product is a clear colorless liquid having a bromine number of <0.1; C-13 NMR showed the characteristic internal ethyl group at b 10.9 ppm and the characteristic terminal ethyl .group at b 11.4 ppm. High resolution C-13 NMR also revealed that there are at least six different methyl-carbon signals at 14.16, 14.21, 14.42, 14.95, 14.58, and 14.63 ppm.
Method B
Method A was repeGted or. a potion of the cracked product ef Example _ but using tine cc:~~rercially available Pd supported zeolite. There was obtained an isomerized colorless liquid having a bromine number of <0.1.
The hydrogenated cracked oil obtained in Example 4 was formulated by the addition of commercial additives into a SW30 grade motor oil. The formulation and the resulting physical properties are shown in Table II and compared with a commercial slrnthetic SW-30 oil made from poly-alpha-olefins. In Table II, DI is a detergent inhibitor package and a vI improver is a viscosity index improver.
SW30 From Commercial E=ample 4 Synthetic SW
Com ncnts Wt % Wt %
S thetie Basestock - Exam le 71:29 0 5 S thetic Ester 11'.39 12.06 PAO 8 0 39.17 PAO 4 0 30.79 DI Packa a 11.40 11.56 VIIm rover 5.82 6.32 10 Pow Point ressant 0.1 0.1 Ph sical Pro erties Kinematic Viscosity 100C 11.6 cSt 11.3 cSt Kincmatic Viscosity na 40C 64.5 St 65.3 cSt Viscosity index 177 166 15 Cold Crankin Simulator, -25C 2628 cP 2486 cP
Minirotarv Viscometer TP-1 (ci,-30C6600 eP 5400 eP
Minirotarv Viscometer TP-1 Y.S.0 0 Scannin Brooideld Viscosin at -39.9C <-40C
30.000 cP
Pout Point, C -54C <-57C
2 0 Simulated Distillation. % ofI'at10.90% 2.60%
371 C (700F) Noack 11.89% N.D. I
4-Ball Wear Scar, mm 0.37 0.38 Friction Coellicient na, 100C 0.71 0.11 The data in Table II shows that the~~motor oil formed from the base oil of Example 9 is comparable in characteristics and performance to the more expensive synthetic PAO oil.
E~BM~ ~
The hydrogenated cracked oil obtained in Example 4 was further fractionated into 2 cSt, 4 cSt and 6 cSt base oils.
Their physical properties are shown in Table III.
TABLE III
Pro_ party 2 cSt 4 cSt Oil 6 cSt Oil Oit Viscosity, cSt 100 C 1.9 4.05 6.1 40C 5.98 17.3 31.6 Viscosih~ Index 106 137 145 Cold Cranking Simulator,N.D. 670 1930 Pow Point. C <-60 -27 -27 Flash Point, C 146 207 246 Fire Point, C N.D. 259 282 . ~ Sp. Gr. 0.797 0.815 0.823 Bromine Number <0.1 <0.1 <0.1 GPC, Mn 326 606 761 2 5 GPC, Mw/Mn 1.07 1.05 1.15 NOACK. N~t% 99.6 15.2 7.1 Simulated 96.5 0 1.2 Distillation, oti"at X71 C1700Fl :s 0 1% 561 730 694 5% 577 7S2 747 10% 592 761 786 20% 604 77S 838 50% 637 804 883 90% 680 820 927 95% 693 ; 853 972 99% 730 869 1101 PDSC Oxidation Tit 20 18.4 18.8 34 atm Oz (500 psig O~
Base oil. @ 50.1 165C,minuta 25.8 49.9 Containing 10%
[ Dl, (~ l 95 1 I
C, min J
This experiment was carried out in a similar manner as Example 1, except that the reaction was a batch reaction. A
1-liter autoclave reactor was thoroughly purged with nitrogen and then charged with 300 ml of dried toluene. Through the mass flow controller, ethylene, propylene, 1-butene and hydrogen were fed into the reactor at a ratio of 4fl 00 cc/min, 3600 cc/min, 900 cc/min, and 400 cc/min, respectively. Methyl aluminoxane in toluene solution, 46.9 mg-atom, as aluminum atom, and 0.015 mg-atom, as Zr atom, of bis(isopropylcyclo-pentadienyl)zirconium dichloride in toluene solutions were injected at 50°C and 1.02 atm (15 prig) pressure. After 3 hours, the :Eaction was auerched with 1~. Gc. HC1, then washed with aquEO~ss 1 M NaOH, followed by a large quar:tity of water .
After tripping off tcluEnE, the reaction gavE a48 grams cf liquid tErpoiymer. ThE polymerization conditions end physiCci p:cpertl.e5 G? the :EaCtOr pr0.~.uCt c2r.e S'~:.'Tlmc~iZEG
~n Ta.~.iE 1'V. ThE C~L7CtE =EBCtGi pr~vdi:Ct wa8 thEr:ua.:~~y' cracked as described in Example 3, followed by distilling off the light polymer through a Vigreux column. The residue was hydrogenated with 1 wt% of i0% Pd on active carbon. The final hydrogenated liquid terpolymer had a ksnemat.'ic viscosity at 100°C of 9.6 cSt and viscosity index of 358; Mn of 1006, Mw/Mn of 1.24. The composition of the terpolymer, determined by C-13 NMR, was '72 mole % of ethylene, 25 mole %
of propylene, and 3 mole % of butene. The physical properties are summarized in Table V.
The liquid terpoiymer was prepared in the same manner as in Example e, except that the reactor was fed ethylene, propylene, 1-butene and hydrogen at a rate of 4000 cc/min, 3980 cc/min, 995 cc/min, and 540 cc/min, respectively. The polymerization conditions and physical properties ef the product are summarized in Table IV.
The reactor product was cracked and ~~.ydrogenated ir. the same manner as in Example a to give a colorless liquid of kinematic viscosity at 100°C of 9.9 cSt and v;scosity index of 150. Tre ~cmposi~ion and the physical properties of terocl~,rn:er are summar=zed _.. '='able V.
Ethylene/.~-:ccv:e.~.e,rl-~ecene Teroolvmer The 1_quid terpol;ym,er was prepared is the same manner as Exa~':r,le 8, except that ~-:tc t~-:e reactor was infected 25 mL of i-decene anc ethylene, propylene, and hydrogen at a rats of 4000 cc/min, 3980 cc,'~~=::, and 480 cc/mi:~, respect=vely. The reaction =an fc: _ !-:curs and nave 444 grams cf liqu_d ~erpe,,m'~er. The :.; _-~-:er=tatic : condition s and physical crct~e:;=es c: ~:~e ~rcc::c_ ~re st:";:::armed in Table V.
T."le ~ EaC: 'r :'- ::.;:~ _ 'w'a~ ~ ~ r.~ KeC anC :':Yur CgervGt~Q _.. t.::E
same T,a-Lne: as =xa~-c~e~ _ ~..~ . _~ .;me a ccc:'_ess ~ _ _ w..
having a kinematic viscosity at 100°C of 9.8 cSt and viscosity index of 159. The ,terpolymer contained 4.2$ by weight of 1-decene. The physical properties, summarized in Table V, show the terpolymer has a better (lower) pour point than the copolymer in comparative Example A.
som~arat?ve Exam lie A, The same procedure as Example 10'was followed, except the polymerization was conducted without adding a third olefin.
The physical properties of the reactor product and the final hydrogenated cracked liquid terpolymer are outlined in Tables IV and V.
,AMPLE 11 ~ylene/ProRylene/1-Rexene Term er Ethylene, propylene, and hydrogen were mixed in ratio of 97:53.3:5.2 in a 7 L cylinder to a total pressure of 7.16 atm (105.2 psig). The temperature of thel~,cylinder was heated to and maintained at 50°C for at least 2 hours to mix the gases.
Into a 0.5 L autoclave reactor was placed 100 ml of toluene, followed by the gas mixture at 50°C, 1.02 atm (15 psig) pressure. Two ml of 1-hexene, dried over 9A molecular sieves, was injected into the reactor, followed by the injection of 15 r~
mg-atom, as aluminum atom, of methyl aluminoxane and O.D15 mg atom, as zirconium atom, of Bis(i-propylcyclopentadienyl) zirconium dichloride in toluene solution. After 3 hours, the polymerization product was quenched with 1~ HC1/MeOH, washed with 100 ml 0.5 M aq.NaOH, then water. The solvent was rota evaporated to give 156 grams of liquid terpolvmer. The terpolymer contained 0.9~ 1-hexane by weight.
The crude reactor product wGs cracked in the same rnar~r.er as described in Example ... F: hear t cut of terpolymer was collected overhead at ~ temperature of 150'C to 275°C at 1.' mm Ha vacuum. The product, 1i4 crams (82~), was hydrogenated with 1 wt.~ o' Fd/C Gs descrih~ed in Example ~ to give ..
25 ' colorless liquid polymer. The physical properties of the final hydrogenated liquid terpolymer are outlined in Table VI.
Example 11 was repeated, except that 4 ml l-hexer~e was injected as the third mc-~omer . The physical properties of the final hydrogenated liquid terpolymer are outlined in Table VI.
Example 11 was repeated, except that 20 ml 1-hexene was injected as the third monomer. The physical properties of the final hydrogenated liquid terpolymer are outlined in Table VI.
Comparative Examnie H
For comparison, the etrylene/propylene copolymer was prepared witrout adding ~-:~exene using the same procedure as described ~~ Exampie 1~. The physical properties of the final hydroge:~ated licuid cepci.,r~~er are outlined in Tabie VI.
TABLE IV
Conditions and 'Pro ertiese Reactoroducts of th Pr E=periment Comparative Ei. A 8 9 10 Rcacta Volume 1 L 1 L 1 L 1 L
Solvent, ml 300 ~ 300 300 300 T, C 50 50 50 50 Pressure, atm (psig) 1.02 ( 1 1.02 1.02 ( 1.02 {
~ S) ( 15) I 5) i 5) Foed: Monomers Ethylene, cc/min 4000 4000 4000 4000 Propylene, cc/min 3980 3600 3980 3980 1-Butene, cc/min 0 400 995 0 1-Decene, ml 0 0 0 25 Hvdro cn. cc/min 480 400 540 480 Catalysts MAO, A1 mg-atom 31.3 .!.46.9 62.6 31.3 (i-PrCp)~ZrCIz, Zr mg-atom/h0.01 0.015 0.02 0.01 Time, hours 3 3 3 3 Yield, dams 311 348 394 444 Kin. Vis., at I00C, 113 86 53 43 cSt 2 0 Kin. Vis., at 40 C 1 I O I 897 496 302 Viscosity Index 202 181 172 200 - 72 71.5 67 NIA
Cz, mole % in pol5zner 28 25.4 27 NIA
mole % in polymer 0 3 6 0 . 2196 2339 1784 2129 -C,, mole /~ in pohzner 2.27 2 2.14 2.02 2 .8 2.1 2.5 22 2 5 Mn 3.8 4.3 6.4 6.5 Mw/Mn Bromine Number Sim. Dist.% ofl'at 371 C (700F) 2?
Ph sical Pro erties of the H dro coated Li uid Ter olymer ' Comparative E: riment Ei. A 8 9 10 Fend: Monomers Ethylene, cc/min 4000 4000 4000 4000 Propylene, cc/min 3980 3600 3980 3980 1-BuLene, cc/min 0 400 995 0 l -Decene, ml 0 0 0 25 Hydro en, cc/m 480 400 540 480 Molt % of Cz 72 72 67 N.D.
Mole % of C3 28 25 27 N.D.
Mole%ofC 0 3 6 0 Vet % of C 4.2 lCinematic Viscosity at 100C, cSt 11.4 9.6 9.9 9.8 at 40 C, cSt 66.1 55.8 60.3 56.5 Viscosih~ Index 166 158 150 159 2 0 Pour Point, C -3 - I -24 -12 Simulated Dist., % off@ 371 3.6 2.2 5.1 3.1 C (700F) Mn 1086 1006 1001 1028 Mw/Mn 1.34 I .24 1.31 1.25 Bromine Number 0.1 0. I 0.1 0.1 n 00 h ~ t~.N w r N O ~ ~ r'~U ov~'o G. ~ c~ a ~ h ooc w ~ ~ ~ x ~ ~ o vc ~ rn '~ ~
~ o ocC r,; ,..op rr, ~ N Q' U '~? N ~ ~D ' c h M ~ n Q
0. 1 ~ o rw ~ V ~p ~ a'iv ~ ~',M U M 01 E v o vc "_ = n = ~ a v N o~.N
a C ~ ~ N v~ ~p ~ en C
h U
U E
E
r, r v, U ~ ' v ~ n ~ v v r.v~ N U ~nC
V IC v O M 00 c n W C '~ ~ C~ ~ ~ ~ M oc It ~ N N W O
N
C
'a h 00 "r N
v t r .r C U N N cryN ~ ~ o_..__N '~ ~ U o ~ t~ .~ ~ ~ N tT N C
N ocC V M N C et ~ M
h V ' C
_u H
S
a ' :.
u- ' o ~ o ~ ' U ~ 0 .5 c ~ 'J o v C V ~ o C .F
~ . a a a v c ~
.c ~ .a~ r' D ~ V N
._ o z J CV >_' O C a ~ ~3 c~ m m ~I ~ .o 'c ~ ~ = H Q ' C
= ~ > a. U v ~ vr,LL O w- .a N
3 L~ 3C r7V: r ~J
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0. V
~''7 C ~ O
.-i r-! N
EXAMPLES 14-17 ' Ethylene/ProDViene/1-8utene Ter~olvmer These examples were carried out in a manner similar to Example 8, except that the feed rates of the monomers.were ~s set forth below in Table VII. Also set forth iw Table VII
are physical and chemical characteristics of the terpolymers produced.
~BL~ VII
E:ample 14 IS 16 17.
Feed Ethylene, mllmin3600 3880 4000 4000 Propylene, m1/tnin4000 4000 3000 3200 1-Huuae, mUtnin 200 200 1000 l 800 Hydrogen mhmin 312 240 480 600 Products Composition Ethylene, % mole65.2 69.7 73.6 73.5 Propylene. o 33.2 28.9 i9.9 ~ 21.3 mole 2 0 Butene..'o mole I s 1.3 6.4 ~ 5.1 Pour Point, C -33 _21 _9 -6 iVln 2477 2694 2'547 2x55 V1w/Mn :.12 I ?.23 2.01 2.16 Hromtne Number 2.3 3.2 1.3 1.0 Kin. ''vs. at 107 ~ 188 1 106 70.4 100'C. cSt at 40C, cSt ~ 1 140 I 2286 1096 625 ~'iscosm~ Index 189 ~ Z04 ( 193 ~ 191 i o Lvsaturanon ?5 6 53.9 I ?0.', 12.fi I
F!,_r~m~1_ Q 1 8 A 1-liter autoclave reactor was thoroughly purged with nitrogen and then charged with 200 ml of toluene. Through mass flow controller, ethylene, propylene, 1-butene and hydrogen were fed into the reactor at a ratio of 9000 ml/min, 312 ml/min, 135 ml/min, and 89 m./min, respectively. The molar ration of ethylene/propylene/.1-butene were 90/7/3.
Methyl aluminoxane in toluene solution, 30 mg-atom, as aluminum atom,. and 0.03 mg-atom, as Zr atom, of bis(cyclopentadienyl)zirconium dichloride in toluene solution were injected at 50°C, 2.04 atm (30 prig) pressure. After 1 hour, the reactor was dismounted. The solid polymer was washed in a blender with 5$ aq.HCl. The solid polymer was filtered. re-washed with water. The filtered solid was then oven dried overnight at 50°C/10 mm Hg. total 233 grams of a white powder was obtained. Drop melting point 103.8°C: DSC
melting point, 103°C.
Exan~~l a 1 ~
The solid terpolymer was prepared in the same manner as in Example I8, except that the fees contain no hydrogen.
total 181 grams of white solid was obtained. Capillary melting point, 91-111°C.
2 S Fop? ~ 2 0 The slid terpolymer was prepared in the same manner as in Example 18, except that the reactor pressure was maintained at 3.4 atm (50 prig): and the reaction was run for 2 hours.
total 423 grams of white fine solid was obtained. Drop melting point, 105°C.
Example 21 The semi-solid terpclymer w~~ prepared in the slime r;~Gnrer as in Example ~~, except that =t~,yie.~.e, propyle.~.e, i-butene ?~ anC hydrooer_~ wEre fed into the reactor at a ratio ef 31 ' 4000 ml/min, 1176 ml/min, 160 ml/min, and 107 ml/min, respectively. The molar ratio of ethylene/propylene/1-butene were 75/22/3. The reaction was run for 2 hours. AFter worked up, 563 grams of white semi-slid was obtained. Drop melting point 64.5°C; Brookfiled viscosity (Spindle TF at 5 RPM; 21°C), 387,000 CP.
Examol~, Z2 A rubber semi-slid terpolymer was prepared in the sam manner as in Example 2i, except that the fees contain no hydrogen. The reaction was run for 2 hours. After worked up, 303 grams of a rubber semi-slid was obtained. Drop melting point, 103.3°C.
EXAMPhE 23 Pre~araticn of ethylene-isobutene conolvmer At 250 ml pressure reaction bottle with a magnetic stir bar was thoroughly purged with argon and was charged with 50 ml of dried tcluene (distilled over potassium). Ethylene, isobutene and hydrogen were premixed in a 7 Liter cylinder at a ratic cf 8~, 82°x, and :0%, respectively, and then heated at 70°C ever~lcht . :'.-.e gas mixture was fed intc t.e reaction bcttie :._ a5°C under ~ pressure cf .0 psig. Then 1.~ :,~1 of 0.05 M triisobutylalumir.um (TIEAi ir. toluene solution was injected into the bottle with « syringe fclicwed by 1 ;,il of 3 .75 x 10'' M Dcw IZSite'~ catalyst ( [ (CSMe,; SiM.e~.~N(t-8u) JTiC:,, Me = methyl i _.~. toluene sclution and finally 1 ml of 3.~5 x :0- M triphenylcarbenium tetr3kis (Fer.taflucrcphe~,,~1) berate (P!-~,CH(C6F5),) ir. toluene solution as cocata~~rst. Folvmerization of ethylene and iscbutene was iritiatec ;:pen ;njecticn ef cotatalyst ~01ut1Cn. ThrCZ:CI:C::_ ...'.° =°aCt_.'.':t :~.:.~., ~~'le te!':pe:atur° WdS
,~,lalntaineC .i",Y a Ce~Sta::t _~~'L~e:at::=° .~''"at:: Wltll a ClrCUlater.
The excel= merome== ~nc =:rrcce~ v~ere ccntiruous:y vented at ,. =ate cf «be;:: :: ..~'-,-._:: _~ ~;ai.~.tai.~. a c;.r:star.t oa=_ Cc~Ce::t:a~~C:. ~.. _.'.E :°3___~:: :Ct_-E.
~2 After one hour the reaction was quenched by injecting 10 ml of 2$ acidic methanol into. the bottle and the resulted solution was stirred for an extra hour. The product, along with toluene, was then washed with 3 x 200 ml of deionized water in a 500 mi separatory funnel. the organic layer was filtered through a filter agent available under the trade designation "ceilite" to get a clear solution. Toluene was subsequently removed into a rots-evaporator to obtain an opaque, viscous liquid. Activity of the polymerization. was 1.97 x 10 5 g of polymer/(mol Ti-hr). Quantitative 'C NMR
analysis of the liquid showed an ethylene-isobutene copolymer was formed and it contained 46rs of ethylene.
The procedure was essentially the same as Example 23, except that polymerization conditions and the feed ratio of ethylene/isobutene were changed and ,the gas phase of t>ze reaction system was nonvented. The polymerization conditions are summarized in Table VIII. waxy solid material was obtained from the polymerization and '3C NMR analysis of the solid showed formation of ethylene-isobutene copolymer.
TABLE VIII
Polvmcrization conditions 2 Exam lc 2~ 24 Ethviene in feed % 8 9 lsobutenc in feed. % 82 91 Hvdroeen in feed. % 10 0 PohzneriZation Tem erature.?5 25 'C
0 PohTnerization Pressure, 0.68 ( 1D 0.68 ( 10) J
atm ( siel Poh~rneriZation Time. hr. J ~ 1 Toluene, ml. 50 ~ s0 TIBA 1.5 ml of ~O.OSM l .i ml of O.fl~?~9 i Insite~ catalyst 1 ml of 3,75 2 ml of 7.5 x x l 0'3M 10'3M
Ph3C8(C6Fs), 1 ml of 3.75 2 ml of 7.5 x x 10'3M 10''M
Activity, g of I .97 x l Os 2.4 x l Os of er/(mol Ti - hr E XAMPI~E 2 5 Preparation of ~ro,~,ylene-isobLtene ccyy~~
The procedure was essentially the same as Example 23. A
propylene, isobutene and hydrogen gas mixture at a ratio of 9$, 82$, and 9~, respectively, was fed into the reaction bottle containing 50 ml of toluene at 60°C under a pressure of psig. 2 ml of 0.05 M TIBA , 9 ml of 15 x 10'3 M Insite~
15 catalyst and 4 ml of 15 x. 10'3 M PhjCB (C6F5) 4 solutions were used to initiate polymerization. The gas phase of the reaction system was continuously vented at a rate of about 20 ml/min. After one hour of reaction, a clear liquid was obtained with an activity of 0.73 x 10 5 g of polymer/(mol Ti 20 - hr) . The liquid has M" of 3, 316 and M"/M~ of 3.flfl. "C NMR
analysis of the licruid showed formation of propylene-isobutene copolymer.
!ALE 2 6 The procedure was essentially the same as Example 25 except a monomer gas mixture at a ratio of 26~, 65~a, and 9$
for propylene, isobutene and hydrocen, respectively, was fed into the reacticn bottle and ~ m~ cf 0.05 M TINA was used to r:itiate polymerization. one hour of reaction s clear liquid ::,0 was obtained witr: Gii activity of 0.53 x lOr g of polymer/ (mol Ti - hr. ) . ==C MN~ ar:alysi s c: the =iauid showed formati.or: ef propylene-isobutEne copcl_,rmer.
~"~LE 2 7 The procedure was essentially the same as Example 23. An ethylene, propylene, isobutene and hydrogen gas mixture at a ratio of 9$, 4$, 78$ and 9$, respectively, was fed into the reaction bottle containing 50 ml of toluene at 40°C under a pressure of 1.36 atm (20 psig). 2 ml.~of 0.05 M TIBA, 2 ml of 3.75 x 10-' M Insite~ catalyst under 2 ml of 3.75 x 10'3 M
Ph3C8 (C6F5), solutions were used to initiate polymerization.
The gas phase of the reaction system was continuously vented at a rate of about 20 ml/min. After one hour of reaction a .
clear liquid was obtained with an activity of 4.89 x 105 g of polymer/mol Ti - hr). '3C NMR analysis of the liquid showed formation of ethylene-propylene-isobutene terpolymer.
Ea~,~gLE 2 8 The procedure was essentially the same as Example 27 except for the monomer gas mixture was at a ratio of 13.4, 18$, 55.2 and 13.4 for ethylene, propylene, isobutene and hydrogen, respectively. After one hour of reaction a clear liquid was obtained with an activity of 3.47 x 10= g of polymer/(mol Ti - rr). '3C NMR analysis of the liquid showed formation of ethylene-propylene-isobutene terpolymer.
2 5 EXf~MPL~ 2 9 r The procedure was similar to that in Example 23. The reaction bottle was charged with 50 ml of dried toluene and 10 ml cf styrene. 0.68 atm t10 psig) of a gas mixture of a ratio of 10~ and 90~. for ethylene and isobutene, respectively, was fed into the bottle at 50'C. .. ml cf 0.05 M TIFF, 9 ml Gf 0.015 M Insite~ catalyst and 4 mi of 0.01_'. M F:~_Cb (CEF~) ~ solutions were used tG
;vitiate pe::_.~e:izatiGr:. ThE cas phase of the reaction:
5'_ system was CG.~.tI~.UGi.SI'J VE:l~Ed ct c ratE Gf oGGUt iv ~ll/mi::. TiftEr G:iE :1G;:~ of rEaCtiGn c Semi-SGlid wb5 CJ.~,ta_'~:E.~.
with an activity of 2.92 x 105 g of polymer/(mol Ti - hr).
The product has Mw of 3, 127 and I~j",/M" of 3.06. DSC study of the material indicated an ethylene-styrene-isobutene, terpolymer was formed.
The procedure was similar to example 29. 10 psig of a gas mixture at a ratio of 10$ and 90$ for ethylene and 10 isobutene, respectively, was fed into the bottle containing with 1 . 04 x 10'° mole of (CSMeS) TiCl3 and 10 ml of a a-methylstyrene at 25°C. 3 m1 of 0.05 M TIBA and 5 ml of 0. 028 M Ph3CB (CbF°) ° solutions were used to initiate polymerization. The gas phase of the reaction system was 15 continuously vented at a rate of about 1D ml/min. AFter one hour of reaction solid product was obtained with an activity of 0.24 x 10 5 g of polymer/ (mol Ti - hr) . DSC
study of the material indicated an ethylene-a-methylstyrene-isobutene terpolymer was formed.
The procedure was essentially the same as Example 30 except for 1.04 x IO'~ mole of Insite~ catalyst instead of (C=Me5) TiCl3 was used as a catalyst for polymerization.
one hour of reaction. solid product was obtained with an activity of 0.41 x 10= g of polymer/(mol Ti - hr). DSC
study of the material indicated an ethylene-a-.0 methylstyrene-isobutene terpolymer was formed.
In additic:: tc their use ~~ base oils, th.e products Gf the inventcr_ Gre Gist useful in appliCation5 such as air care, skin cGre, i-.~~r cGre, cosmetics, household products, cleaners, polishes, ~~ric care, textile coatings and textile _.. .lUbr1C8T1t5, cutGITtGtl~'E JrGdllCtS, :.cr C l ecWers and p011Si7es, fuel additives, cii additives, candles, phar:raceuticals, suspending agents, sun care, insecticides, gels, hydraulic fluids,, transmission fluids, modifier fcr polymers, biodegradable applications and 2-cycle oils.
The invention has been described with reference to certain preferred embodiments. However, as obvious variations thereon will become apparent to those skilled in the art, the invention is not to be considered as limited thereto.
15 The obtained copolymer contained 62 mole ~ ethylene.
E?~AMPLE 2 The procedure was essentially the same as Example 1, except the polymerization conditions and the feed ratio of ethylene/propylene were changed. The results and properties of the product are summarized in Table 1.
is Polymerization conditions arid roducts ro erties E=am le ! 2 Rcaclor Vol. L 4 2 lerre cclmin 1990 2000 Ethylene, cclmin 2000 1400 H dro en, cc/mia 240 ' 20 MAO A1 m -atom /h 1.5 1.5 i-PrC 1, Zr m atom/h 1.5x10'' 1.5x10'' Polymerization Tem ature,50 90 C
Polymerization Pressure 1.02 (15 2.04 (30 atm si ) Mn 1400 1300 Mw/Mn 2.37 2.41 Ethylene mole % in Co 62 63 lvmer Yield, ams/hour 245 153 Simulated Distillation off at 371 C 700F 10 8,6 Kinematic Viscosity ra7 40 33 100C, cSt Visc~itv lndcx 173 176 2 Bromine Number 4.7 8.5 Then_nal Cracki~Q
The light polymers produced in Example 1 (boiling point below 371°C (700°F) in ASTM D-2887 Simulated Distillation) were distilled under vacuum. The remaining viscous oils (5aa grams) were placed in a round-bottom flask connected to a short-path distillation column and a receiver. The contents were heated at 350° to 45D°C at 0.2 to 2 mm Hg vacuum pressure. The liquid polymers were thermally cracked inside the flask. Once the polymer pyrolized, the cracked polymers were simultaneously evaporated at this temperature range under . reduced pressure, and condensed in the receiver to give 420 grams of clear oil. About 15 grams of polymer were left in the flask with the remaining catalysts. The condensed tracked product was characterized by Mn, 797; Mw/Mn, 1.34: kinematic viscosity at 100°C, 7.29 cSt; VI, 160; bromine number, 18.9.
ljydrooenatian j~pt-hod A
A portion of the cracked product from Example 1 and 1 weight percent of Fd/C powder were placed in a Zipperclave rEactor and filled with 34 arm (500 psig) hydrogen. After 2' aeitGtion for 7 hour Gt 250'C, the reactor was cooled at room;
temperature. The catalyst was filtered through a filter agent available under the trade designGtion "cellitE" under reducEd pressure to give a ciEar colorless liquid oil #~aving a bromine number of less than 0.1. C-13 hlNR: peak at b 11.4 FFn~- Frove~ the prESEncE cf iso-butyl group .
.J
F
A ~ ic1n1E55 StEE CG_~ L.'t1''1 1 . c % C311 X ~' . 61 :a: ( ~ i L In X ~ fEEt ) we .;i~EU wiu: ~~.~ Crcs'i'.~ Cr TV::-KiE~E!Q'1.:f1: TJEI.~.Et~. A ~v~tlOW ~.~f ~itE
cracked oils from Example 2 were continuously pumped upward at a rate of 1.5 ml/min. through the column at 35fl°~ (inside temperature) and 51.05 atm (750 prig) hydrogen. The hydrogen also flowed upward through the column from a separate line.
The hydrogenated products Were collected at the other end of column to give a clear colorless liquid oil having a bromine number of less than 0.1. The C-13 NMR. peak at a T1.4 ppm.
proves the presence of iso-butyl groups.
Hydroisomgrizati"Qin rlethod A
Hydroisomerization on a portion of the cracked product of Example 1 was performed in the same equipment using the same procedure as described in Method B of Example 4, except the Ni-Kieselguhr catalyst was replaced by 32 grams of Pd supported acidic molecular sieve (an x-type zeolite). The Pd supported zeolite was prepared by thetreatment of molecular s i eve X13 ( 50 grams ) wi th NH4C1 ( I 3 grams ) and ~d (NH3 ) 2C12 ( I
gram) in aqueous solution at 90°C. After the separation of the water, the treated zeolite was then calcined at 450° for 4 hours. The hydroisomerization was carried out at 284°C and 23.8°C (350 psig) of hydrogen pressure. The hydroisamerized product is a clear colorless liquid having a bromine number of <0.1; C-13 NMR showed the characteristic internal ethyl group at b 10.9 ppm and the characteristic terminal ethyl .group at b 11.4 ppm. High resolution C-13 NMR also revealed that there are at least six different methyl-carbon signals at 14.16, 14.21, 14.42, 14.95, 14.58, and 14.63 ppm.
Method B
Method A was repeGted or. a potion of the cracked product ef Example _ but using tine cc:~~rercially available Pd supported zeolite. There was obtained an isomerized colorless liquid having a bromine number of <0.1.
The hydrogenated cracked oil obtained in Example 4 was formulated by the addition of commercial additives into a SW30 grade motor oil. The formulation and the resulting physical properties are shown in Table II and compared with a commercial slrnthetic SW-30 oil made from poly-alpha-olefins. In Table II, DI is a detergent inhibitor package and a vI improver is a viscosity index improver.
SW30 From Commercial E=ample 4 Synthetic SW
Com ncnts Wt % Wt %
S thetie Basestock - Exam le 71:29 0 5 S thetic Ester 11'.39 12.06 PAO 8 0 39.17 PAO 4 0 30.79 DI Packa a 11.40 11.56 VIIm rover 5.82 6.32 10 Pow Point ressant 0.1 0.1 Ph sical Pro erties Kinematic Viscosity 100C 11.6 cSt 11.3 cSt Kincmatic Viscosity na 40C 64.5 St 65.3 cSt Viscosity index 177 166 15 Cold Crankin Simulator, -25C 2628 cP 2486 cP
Minirotarv Viscometer TP-1 (ci,-30C6600 eP 5400 eP
Minirotarv Viscometer TP-1 Y.S.0 0 Scannin Brooideld Viscosin at -39.9C <-40C
30.000 cP
Pout Point, C -54C <-57C
2 0 Simulated Distillation. % ofI'at10.90% 2.60%
371 C (700F) Noack 11.89% N.D. I
4-Ball Wear Scar, mm 0.37 0.38 Friction Coellicient na, 100C 0.71 0.11 The data in Table II shows that the~~motor oil formed from the base oil of Example 9 is comparable in characteristics and performance to the more expensive synthetic PAO oil.
E~BM~ ~
The hydrogenated cracked oil obtained in Example 4 was further fractionated into 2 cSt, 4 cSt and 6 cSt base oils.
Their physical properties are shown in Table III.
TABLE III
Pro_ party 2 cSt 4 cSt Oil 6 cSt Oil Oit Viscosity, cSt 100 C 1.9 4.05 6.1 40C 5.98 17.3 31.6 Viscosih~ Index 106 137 145 Cold Cranking Simulator,N.D. 670 1930 Pow Point. C <-60 -27 -27 Flash Point, C 146 207 246 Fire Point, C N.D. 259 282 . ~ Sp. Gr. 0.797 0.815 0.823 Bromine Number <0.1 <0.1 <0.1 GPC, Mn 326 606 761 2 5 GPC, Mw/Mn 1.07 1.05 1.15 NOACK. N~t% 99.6 15.2 7.1 Simulated 96.5 0 1.2 Distillation, oti"at X71 C1700Fl :s 0 1% 561 730 694 5% 577 7S2 747 10% 592 761 786 20% 604 77S 838 50% 637 804 883 90% 680 820 927 95% 693 ; 853 972 99% 730 869 1101 PDSC Oxidation Tit 20 18.4 18.8 34 atm Oz (500 psig O~
Base oil. @ 50.1 165C,minuta 25.8 49.9 Containing 10%
[ Dl, (~ l 95 1 I
C, min J
This experiment was carried out in a similar manner as Example 1, except that the reaction was a batch reaction. A
1-liter autoclave reactor was thoroughly purged with nitrogen and then charged with 300 ml of dried toluene. Through the mass flow controller, ethylene, propylene, 1-butene and hydrogen were fed into the reactor at a ratio of 4fl 00 cc/min, 3600 cc/min, 900 cc/min, and 400 cc/min, respectively. Methyl aluminoxane in toluene solution, 46.9 mg-atom, as aluminum atom, and 0.015 mg-atom, as Zr atom, of bis(isopropylcyclo-pentadienyl)zirconium dichloride in toluene solutions were injected at 50°C and 1.02 atm (15 prig) pressure. After 3 hours, the :Eaction was auerched with 1~. Gc. HC1, then washed with aquEO~ss 1 M NaOH, followed by a large quar:tity of water .
After tripping off tcluEnE, the reaction gavE a48 grams cf liquid tErpoiymer. ThE polymerization conditions end physiCci p:cpertl.e5 G? the :EaCtOr pr0.~.uCt c2r.e S'~:.'Tlmc~iZEG
~n Ta.~.iE 1'V. ThE C~L7CtE =EBCtGi pr~vdi:Ct wa8 thEr:ua.:~~y' cracked as described in Example 3, followed by distilling off the light polymer through a Vigreux column. The residue was hydrogenated with 1 wt% of i0% Pd on active carbon. The final hydrogenated liquid terpolymer had a ksnemat.'ic viscosity at 100°C of 9.6 cSt and viscosity index of 358; Mn of 1006, Mw/Mn of 1.24. The composition of the terpolymer, determined by C-13 NMR, was '72 mole % of ethylene, 25 mole %
of propylene, and 3 mole % of butene. The physical properties are summarized in Table V.
The liquid terpoiymer was prepared in the same manner as in Example e, except that the reactor was fed ethylene, propylene, 1-butene and hydrogen at a rate of 4000 cc/min, 3980 cc/min, 995 cc/min, and 540 cc/min, respectively. The polymerization conditions and physical properties ef the product are summarized in Table IV.
The reactor product was cracked and ~~.ydrogenated ir. the same manner as in Example a to give a colorless liquid of kinematic viscosity at 100°C of 9.9 cSt and v;scosity index of 150. Tre ~cmposi~ion and the physical properties of terocl~,rn:er are summar=zed _.. '='able V.
Ethylene/.~-:ccv:e.~.e,rl-~ecene Teroolvmer The 1_quid terpol;ym,er was prepared is the same manner as Exa~':r,le 8, except that ~-:tc t~-:e reactor was infected 25 mL of i-decene anc ethylene, propylene, and hydrogen at a rats of 4000 cc/min, 3980 cc,'~~=::, and 480 cc/mi:~, respect=vely. The reaction =an fc: _ !-:curs and nave 444 grams cf liqu_d ~erpe,,m'~er. The :.; _-~-:er=tatic : condition s and physical crct~e:;=es c: ~:~e ~rcc::c_ ~re st:";:::armed in Table V.
T."le ~ EaC: 'r :'- ::.;:~ _ 'w'a~ ~ ~ r.~ KeC anC :':Yur CgervGt~Q _.. t.::E
same T,a-Lne: as =xa~-c~e~ _ ~..~ . _~ .;me a ccc:'_ess ~ _ _ w..
having a kinematic viscosity at 100°C of 9.8 cSt and viscosity index of 159. The ,terpolymer contained 4.2$ by weight of 1-decene. The physical properties, summarized in Table V, show the terpolymer has a better (lower) pour point than the copolymer in comparative Example A.
som~arat?ve Exam lie A, The same procedure as Example 10'was followed, except the polymerization was conducted without adding a third olefin.
The physical properties of the reactor product and the final hydrogenated cracked liquid terpolymer are outlined in Tables IV and V.
,AMPLE 11 ~ylene/ProRylene/1-Rexene Term er Ethylene, propylene, and hydrogen were mixed in ratio of 97:53.3:5.2 in a 7 L cylinder to a total pressure of 7.16 atm (105.2 psig). The temperature of thel~,cylinder was heated to and maintained at 50°C for at least 2 hours to mix the gases.
Into a 0.5 L autoclave reactor was placed 100 ml of toluene, followed by the gas mixture at 50°C, 1.02 atm (15 psig) pressure. Two ml of 1-hexene, dried over 9A molecular sieves, was injected into the reactor, followed by the injection of 15 r~
mg-atom, as aluminum atom, of methyl aluminoxane and O.D15 mg atom, as zirconium atom, of Bis(i-propylcyclopentadienyl) zirconium dichloride in toluene solution. After 3 hours, the polymerization product was quenched with 1~ HC1/MeOH, washed with 100 ml 0.5 M aq.NaOH, then water. The solvent was rota evaporated to give 156 grams of liquid terpolvmer. The terpolymer contained 0.9~ 1-hexane by weight.
The crude reactor product wGs cracked in the same rnar~r.er as described in Example ... F: hear t cut of terpolymer was collected overhead at ~ temperature of 150'C to 275°C at 1.' mm Ha vacuum. The product, 1i4 crams (82~), was hydrogenated with 1 wt.~ o' Fd/C Gs descrih~ed in Example ~ to give ..
25 ' colorless liquid polymer. The physical properties of the final hydrogenated liquid terpolymer are outlined in Table VI.
Example 11 was repeated, except that 4 ml l-hexer~e was injected as the third mc-~omer . The physical properties of the final hydrogenated liquid terpolymer are outlined in Table VI.
Example 11 was repeated, except that 20 ml 1-hexene was injected as the third monomer. The physical properties of the final hydrogenated liquid terpolymer are outlined in Table VI.
Comparative Examnie H
For comparison, the etrylene/propylene copolymer was prepared witrout adding ~-:~exene using the same procedure as described ~~ Exampie 1~. The physical properties of the final hydroge:~ated licuid cepci.,r~~er are outlined in Tabie VI.
TABLE IV
Conditions and 'Pro ertiese Reactoroducts of th Pr E=periment Comparative Ei. A 8 9 10 Rcacta Volume 1 L 1 L 1 L 1 L
Solvent, ml 300 ~ 300 300 300 T, C 50 50 50 50 Pressure, atm (psig) 1.02 ( 1 1.02 1.02 ( 1.02 {
~ S) ( 15) I 5) i 5) Foed: Monomers Ethylene, cc/min 4000 4000 4000 4000 Propylene, cc/min 3980 3600 3980 3980 1-Butene, cc/min 0 400 995 0 1-Decene, ml 0 0 0 25 Hvdro cn. cc/min 480 400 540 480 Catalysts MAO, A1 mg-atom 31.3 .!.46.9 62.6 31.3 (i-PrCp)~ZrCIz, Zr mg-atom/h0.01 0.015 0.02 0.01 Time, hours 3 3 3 3 Yield, dams 311 348 394 444 Kin. Vis., at I00C, 113 86 53 43 cSt 2 0 Kin. Vis., at 40 C 1 I O I 897 496 302 Viscosity Index 202 181 172 200 - 72 71.5 67 NIA
Cz, mole % in pol5zner 28 25.4 27 NIA
mole % in polymer 0 3 6 0 . 2196 2339 1784 2129 -C,, mole /~ in pohzner 2.27 2 2.14 2.02 2 .8 2.1 2.5 22 2 5 Mn 3.8 4.3 6.4 6.5 Mw/Mn Bromine Number Sim. Dist.% ofl'at 371 C (700F) 2?
Ph sical Pro erties of the H dro coated Li uid Ter olymer ' Comparative E: riment Ei. A 8 9 10 Fend: Monomers Ethylene, cc/min 4000 4000 4000 4000 Propylene, cc/min 3980 3600 3980 3980 1-BuLene, cc/min 0 400 995 0 l -Decene, ml 0 0 0 25 Hydro en, cc/m 480 400 540 480 Molt % of Cz 72 72 67 N.D.
Mole % of C3 28 25 27 N.D.
Mole%ofC 0 3 6 0 Vet % of C 4.2 lCinematic Viscosity at 100C, cSt 11.4 9.6 9.9 9.8 at 40 C, cSt 66.1 55.8 60.3 56.5 Viscosih~ Index 166 158 150 159 2 0 Pour Point, C -3 - I -24 -12 Simulated Dist., % off@ 371 3.6 2.2 5.1 3.1 C (700F) Mn 1086 1006 1001 1028 Mw/Mn 1.34 I .24 1.31 1.25 Bromine Number 0.1 0. I 0.1 0.1 n 00 h ~ t~.N w r N O ~ ~ r'~U ov~'o G. ~ c~ a ~ h ooc w ~ ~ ~ x ~ ~ o vc ~ rn '~ ~
~ o ocC r,; ,..op rr, ~ N Q' U '~? N ~ ~D ' c h M ~ n Q
0. 1 ~ o rw ~ V ~p ~ a'iv ~ ~',M U M 01 E v o vc "_ = n = ~ a v N o~.N
a C ~ ~ N v~ ~p ~ en C
h U
U E
E
r, r v, U ~ ' v ~ n ~ v v r.v~ N U ~nC
V IC v O M 00 c n W C '~ ~ C~ ~ ~ ~ M oc It ~ N N W O
N
C
'a h 00 "r N
v t r .r C U N N cryN ~ ~ o_..__N '~ ~ U o ~ t~ .~ ~ ~ N tT N C
N ocC V M N C et ~ M
h V ' C
_u H
S
a ' :.
u- ' o ~ o ~ ' U ~ 0 .5 c ~ 'J o v C V ~ o C .F
~ . a a a v c ~
.c ~ .a~ r' D ~ V N
._ o z J CV >_' O C a ~ ~3 c~ m m ~I ~ .o 'c ~ ~ = H Q ' C
= ~ > a. U v ~ vr,LL O w- .a N
3 L~ 3C r7V: r ~J
~ ~ O
0. V
~''7 C ~ O
.-i r-! N
EXAMPLES 14-17 ' Ethylene/ProDViene/1-8utene Ter~olvmer These examples were carried out in a manner similar to Example 8, except that the feed rates of the monomers.were ~s set forth below in Table VII. Also set forth iw Table VII
are physical and chemical characteristics of the terpolymers produced.
~BL~ VII
E:ample 14 IS 16 17.
Feed Ethylene, mllmin3600 3880 4000 4000 Propylene, m1/tnin4000 4000 3000 3200 1-Huuae, mUtnin 200 200 1000 l 800 Hydrogen mhmin 312 240 480 600 Products Composition Ethylene, % mole65.2 69.7 73.6 73.5 Propylene. o 33.2 28.9 i9.9 ~ 21.3 mole 2 0 Butene..'o mole I s 1.3 6.4 ~ 5.1 Pour Point, C -33 _21 _9 -6 iVln 2477 2694 2'547 2x55 V1w/Mn :.12 I ?.23 2.01 2.16 Hromtne Number 2.3 3.2 1.3 1.0 Kin. ''vs. at 107 ~ 188 1 106 70.4 100'C. cSt at 40C, cSt ~ 1 140 I 2286 1096 625 ~'iscosm~ Index 189 ~ Z04 ( 193 ~ 191 i o Lvsaturanon ?5 6 53.9 I ?0.', 12.fi I
F!,_r~m~1_ Q 1 8 A 1-liter autoclave reactor was thoroughly purged with nitrogen and then charged with 200 ml of toluene. Through mass flow controller, ethylene, propylene, 1-butene and hydrogen were fed into the reactor at a ratio of 9000 ml/min, 312 ml/min, 135 ml/min, and 89 m./min, respectively. The molar ration of ethylene/propylene/.1-butene were 90/7/3.
Methyl aluminoxane in toluene solution, 30 mg-atom, as aluminum atom,. and 0.03 mg-atom, as Zr atom, of bis(cyclopentadienyl)zirconium dichloride in toluene solution were injected at 50°C, 2.04 atm (30 prig) pressure. After 1 hour, the reactor was dismounted. The solid polymer was washed in a blender with 5$ aq.HCl. The solid polymer was filtered. re-washed with water. The filtered solid was then oven dried overnight at 50°C/10 mm Hg. total 233 grams of a white powder was obtained. Drop melting point 103.8°C: DSC
melting point, 103°C.
Exan~~l a 1 ~
The solid terpolymer was prepared in the same manner as in Example I8, except that the fees contain no hydrogen.
total 181 grams of white solid was obtained. Capillary melting point, 91-111°C.
2 S Fop? ~ 2 0 The slid terpolymer was prepared in the same manner as in Example 18, except that the reactor pressure was maintained at 3.4 atm (50 prig): and the reaction was run for 2 hours.
total 423 grams of white fine solid was obtained. Drop melting point, 105°C.
Example 21 The semi-solid terpclymer w~~ prepared in the slime r;~Gnrer as in Example ~~, except that =t~,yie.~.e, propyle.~.e, i-butene ?~ anC hydrooer_~ wEre fed into the reactor at a ratio ef 31 ' 4000 ml/min, 1176 ml/min, 160 ml/min, and 107 ml/min, respectively. The molar ratio of ethylene/propylene/1-butene were 75/22/3. The reaction was run for 2 hours. AFter worked up, 563 grams of white semi-slid was obtained. Drop melting point 64.5°C; Brookfiled viscosity (Spindle TF at 5 RPM; 21°C), 387,000 CP.
Examol~, Z2 A rubber semi-slid terpolymer was prepared in the sam manner as in Example 2i, except that the fees contain no hydrogen. The reaction was run for 2 hours. After worked up, 303 grams of a rubber semi-slid was obtained. Drop melting point, 103.3°C.
EXAMPhE 23 Pre~araticn of ethylene-isobutene conolvmer At 250 ml pressure reaction bottle with a magnetic stir bar was thoroughly purged with argon and was charged with 50 ml of dried tcluene (distilled over potassium). Ethylene, isobutene and hydrogen were premixed in a 7 Liter cylinder at a ratic cf 8~, 82°x, and :0%, respectively, and then heated at 70°C ever~lcht . :'.-.e gas mixture was fed intc t.e reaction bcttie :._ a5°C under ~ pressure cf .0 psig. Then 1.~ :,~1 of 0.05 M triisobutylalumir.um (TIEAi ir. toluene solution was injected into the bottle with « syringe fclicwed by 1 ;,il of 3 .75 x 10'' M Dcw IZSite'~ catalyst ( [ (CSMe,; SiM.e~.~N(t-8u) JTiC:,, Me = methyl i _.~. toluene sclution and finally 1 ml of 3.~5 x :0- M triphenylcarbenium tetr3kis (Fer.taflucrcphe~,,~1) berate (P!-~,CH(C6F5),) ir. toluene solution as cocata~~rst. Folvmerization of ethylene and iscbutene was iritiatec ;:pen ;njecticn ef cotatalyst ~01ut1Cn. ThrCZ:CI:C::_ ...'.° =°aCt_.'.':t :~.:.~., ~~'le te!':pe:atur° WdS
,~,lalntaineC .i",Y a Ce~Sta::t _~~'L~e:at::=° .~''"at:: Wltll a ClrCUlater.
The excel= merome== ~nc =:rrcce~ v~ere ccntiruous:y vented at ,. =ate cf «be;:: :: ..~'-,-._:: _~ ~;ai.~.tai.~. a c;.r:star.t oa=_ Cc~Ce::t:a~~C:. ~.. _.'.E :°3___~:: :Ct_-E.
~2 After one hour the reaction was quenched by injecting 10 ml of 2$ acidic methanol into. the bottle and the resulted solution was stirred for an extra hour. The product, along with toluene, was then washed with 3 x 200 ml of deionized water in a 500 mi separatory funnel. the organic layer was filtered through a filter agent available under the trade designation "ceilite" to get a clear solution. Toluene was subsequently removed into a rots-evaporator to obtain an opaque, viscous liquid. Activity of the polymerization. was 1.97 x 10 5 g of polymer/(mol Ti-hr). Quantitative 'C NMR
analysis of the liquid showed an ethylene-isobutene copolymer was formed and it contained 46rs of ethylene.
The procedure was essentially the same as Example 23, except that polymerization conditions and the feed ratio of ethylene/isobutene were changed and ,the gas phase of t>ze reaction system was nonvented. The polymerization conditions are summarized in Table VIII. waxy solid material was obtained from the polymerization and '3C NMR analysis of the solid showed formation of ethylene-isobutene copolymer.
TABLE VIII
Polvmcrization conditions 2 Exam lc 2~ 24 Ethviene in feed % 8 9 lsobutenc in feed. % 82 91 Hvdroeen in feed. % 10 0 PohzneriZation Tem erature.?5 25 'C
0 PohTnerization Pressure, 0.68 ( 1D 0.68 ( 10) J
atm ( siel Poh~rneriZation Time. hr. J ~ 1 Toluene, ml. 50 ~ s0 TIBA 1.5 ml of ~O.OSM l .i ml of O.fl~?~9 i Insite~ catalyst 1 ml of 3,75 2 ml of 7.5 x x l 0'3M 10'3M
Ph3C8(C6Fs), 1 ml of 3.75 2 ml of 7.5 x x 10'3M 10''M
Activity, g of I .97 x l Os 2.4 x l Os of er/(mol Ti - hr E XAMPI~E 2 5 Preparation of ~ro,~,ylene-isobLtene ccyy~~
The procedure was essentially the same as Example 23. A
propylene, isobutene and hydrogen gas mixture at a ratio of 9$, 82$, and 9~, respectively, was fed into the reaction bottle containing 50 ml of toluene at 60°C under a pressure of psig. 2 ml of 0.05 M TIBA , 9 ml of 15 x 10'3 M Insite~
15 catalyst and 4 ml of 15 x. 10'3 M PhjCB (C6F5) 4 solutions were used to initiate polymerization. The gas phase of the reaction system was continuously vented at a rate of about 20 ml/min. After one hour of reaction, a clear liquid was obtained with an activity of 0.73 x 10 5 g of polymer/(mol Ti 20 - hr) . The liquid has M" of 3, 316 and M"/M~ of 3.flfl. "C NMR
analysis of the licruid showed formation of propylene-isobutene copolymer.
!ALE 2 6 The procedure was essentially the same as Example 25 except a monomer gas mixture at a ratio of 26~, 65~a, and 9$
for propylene, isobutene and hydrocen, respectively, was fed into the reacticn bottle and ~ m~ cf 0.05 M TINA was used to r:itiate polymerization. one hour of reaction s clear liquid ::,0 was obtained witr: Gii activity of 0.53 x lOr g of polymer/ (mol Ti - hr. ) . ==C MN~ ar:alysi s c: the =iauid showed formati.or: ef propylene-isobutEne copcl_,rmer.
~"~LE 2 7 The procedure was essentially the same as Example 23. An ethylene, propylene, isobutene and hydrogen gas mixture at a ratio of 9$, 4$, 78$ and 9$, respectively, was fed into the reaction bottle containing 50 ml of toluene at 40°C under a pressure of 1.36 atm (20 psig). 2 ml.~of 0.05 M TIBA, 2 ml of 3.75 x 10-' M Insite~ catalyst under 2 ml of 3.75 x 10'3 M
Ph3C8 (C6F5), solutions were used to initiate polymerization.
The gas phase of the reaction system was continuously vented at a rate of about 20 ml/min. After one hour of reaction a .
clear liquid was obtained with an activity of 4.89 x 105 g of polymer/mol Ti - hr). '3C NMR analysis of the liquid showed formation of ethylene-propylene-isobutene terpolymer.
Ea~,~gLE 2 8 The procedure was essentially the same as Example 27 except for the monomer gas mixture was at a ratio of 13.4, 18$, 55.2 and 13.4 for ethylene, propylene, isobutene and hydrogen, respectively. After one hour of reaction a clear liquid was obtained with an activity of 3.47 x 10= g of polymer/(mol Ti - rr). '3C NMR analysis of the liquid showed formation of ethylene-propylene-isobutene terpolymer.
2 5 EXf~MPL~ 2 9 r The procedure was similar to that in Example 23. The reaction bottle was charged with 50 ml of dried toluene and 10 ml cf styrene. 0.68 atm t10 psig) of a gas mixture of a ratio of 10~ and 90~. for ethylene and isobutene, respectively, was fed into the bottle at 50'C. .. ml cf 0.05 M TIFF, 9 ml Gf 0.015 M Insite~ catalyst and 4 mi of 0.01_'. M F:~_Cb (CEF~) ~ solutions were used tG
;vitiate pe::_.~e:izatiGr:. ThE cas phase of the reaction:
5'_ system was CG.~.tI~.UGi.SI'J VE:l~Ed ct c ratE Gf oGGUt iv ~ll/mi::. TiftEr G:iE :1G;:~ of rEaCtiGn c Semi-SGlid wb5 CJ.~,ta_'~:E.~.
with an activity of 2.92 x 105 g of polymer/(mol Ti - hr).
The product has Mw of 3, 127 and I~j",/M" of 3.06. DSC study of the material indicated an ethylene-styrene-isobutene, terpolymer was formed.
The procedure was similar to example 29. 10 psig of a gas mixture at a ratio of 10$ and 90$ for ethylene and 10 isobutene, respectively, was fed into the bottle containing with 1 . 04 x 10'° mole of (CSMeS) TiCl3 and 10 ml of a a-methylstyrene at 25°C. 3 m1 of 0.05 M TIBA and 5 ml of 0. 028 M Ph3CB (CbF°) ° solutions were used to initiate polymerization. The gas phase of the reaction system was 15 continuously vented at a rate of about 1D ml/min. AFter one hour of reaction solid product was obtained with an activity of 0.24 x 10 5 g of polymer/ (mol Ti - hr) . DSC
study of the material indicated an ethylene-a-methylstyrene-isobutene terpolymer was formed.
The procedure was essentially the same as Example 30 except for 1.04 x IO'~ mole of Insite~ catalyst instead of (C=Me5) TiCl3 was used as a catalyst for polymerization.
one hour of reaction. solid product was obtained with an activity of 0.41 x 10= g of polymer/(mol Ti - hr). DSC
study of the material indicated an ethylene-a-.0 methylstyrene-isobutene terpolymer was formed.
In additic:: tc their use ~~ base oils, th.e products Gf the inventcr_ Gre Gist useful in appliCation5 such as air care, skin cGre, i-.~~r cGre, cosmetics, household products, cleaners, polishes, ~~ric care, textile coatings and textile _.. .lUbr1C8T1t5, cutGITtGtl~'E JrGdllCtS, :.cr C l ecWers and p011Si7es, fuel additives, cii additives, candles, phar:raceuticals, suspending agents, sun care, insecticides, gels, hydraulic fluids,, transmission fluids, modifier fcr polymers, biodegradable applications and 2-cycle oils.
The invention has been described with reference to certain preferred embodiments. However, as obvious variations thereon will become apparent to those skilled in the art, the invention is not to be considered as limited thereto.
Claims (19)
1. A cracked liquid copolymer of ethylene and an olefin, said copolymer being characterized by:
(a) mol % of ethylene from 50 to 75%;
(b) number average molecular weight of < 2000:
(c) molecular weight distribution of < 2;
(d) random monomer distribution; and (e) a head-to-tail molecular structure.
(a) mol % of ethylene from 50 to 75%;
(b) number average molecular weight of < 2000:
(c) molecular weight distribution of < 2;
(d) random monomer distribution; and (e) a head-to-tail molecular structure.
2. A cracked copolymer according to claim 1, wherein said olefin contains from 3 to 20 carbon atoms.
3. A cracked copolymer according to claim 1, wherein said olefin is propylene.
4. A cracked copolymer according to claim 1, wherein said olefin is 2-methyl-1-propene, 2-methyl-1-butene, 2-methyl-1-pentene, or 2-methyl-1-hexene.
5. A cracked copolymer according to claim 1, wherein said olefin is alpha-methylstyrene.
6. A process for the production of a cracked copolymer, comprising the steps of:
(a) polymerizing ethylene and at least one olefin in the presence of a single-site catalyst comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane to produce a precursor copolymer; and (b) cracking at least a portion of the precursor copolymer to produce a cracked copolymer at a temperature above 300°C.
(a) polymerizing ethylene and at least one olefin in the presence of a single-site catalyst comprising a compound of a transition metal of Group IVb of the Periodic Table and an aluminoxane to produce a precursor copolymer; and (b) cracking at least a portion of the precursor copolymer to produce a cracked copolymer at a temperature above 300°C.
7. A process according to claim 6, wherein said olefin has from about 3 to 20 carbon atoms.
8. A process according to claim 6, wherein the olefin is propylene.
9. The cracked copolymer obtained according to the process of claim 6, which comprises a copolymer or segments thereof and having greater unsaturation than said precursor copolymer.
10. A process according to claim 6, wherein the transition metal is selected from the group consisting of titanium, zirconium and hafnium.
11. A process according to claim 6, wherein the aluminoxane is polymethylaluminoxane.
12. A process according to claim 6, wherein said cracking step is thermal cracking.
13. A process according to claim 6, wherein said cracking step is carried out at a temperature range of about 350°C
to about 550°C and a pressure of from about 0.1 to 30 mm Hg vacuum pressure.
to about 550°C and a pressure of from about 0.1 to 30 mm Hg vacuum pressure.
14. The process according to claim 6, which comprises the additional step of hydrogenating said cracked copolymer product to produce a hydrogenated product.
15. A process according to claim 14, wherein the hydrogenation is carried out by reaction of the cracked copolymer with hydrogen gas in the presence of a hydrogenation catalyst, a temperature of about 150°C to about 500°C, and a pressure of about 17-68 atm hydrogen.
16. The hydrogenated cracked copolymer produced according to the process of claim 15, wherein the bromine number ranges about 0 to about 1.5.
17. A lubricating oil comprising a polymer of claim 1 as the base oil and effective amount of at least one oil additive.
18. A lubricating oil comprising a polymer of claim 9 as the base oil and an effective amount of at least one oil additive.
19. A lubricating oil comprising a polymer of claim 16 as the base oil and an effective amount of at least one oil additive.
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- 1998-06-22 EP EP04100330A patent/EP1426389B1/en not_active Expired - Lifetime
- 1998-06-22 DK DK98930331T patent/DK0990005T3/en active
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- 1998-06-22 KR KR19997012032A patent/KR20010014004A/en not_active Application Discontinuation
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- 1998-06-22 CN CNB021318182A patent/CN1239532C/en not_active Expired - Lifetime
- 1998-06-22 WO PCT/US1998/012621 patent/WO1998058972A1/en not_active Application Discontinuation
- 1998-06-22 EP EP04100327A patent/EP1426388B1/en not_active Expired - Lifetime
- 1998-06-22 EP EP04100329A patent/EP1428842A3/en not_active Withdrawn
- 1998-06-22 BR BRPI9816215-2A patent/BR9816215B1/en not_active IP Right Cessation
- 1998-06-22 DE DE69841284T patent/DE69841284D1/en not_active Expired - Lifetime
- 1998-06-22 CA CA002479859A patent/CA2479859A1/en not_active Abandoned
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- 1998-06-22 AU AU79745/98A patent/AU747054B2/en not_active Ceased
- 1998-06-22 CA CA002479850A patent/CA2479850A1/en not_active Abandoned
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2001
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