MXPA97003576A - Polymers and copolymers of para-alquilestirenofuncionaliza - Google Patents
Polymers and copolymers of para-alquilestirenofuncionalizaInfo
- Publication number
- MXPA97003576A MXPA97003576A MXPA/A/1997/003576A MX9703576A MXPA97003576A MX PA97003576 A MXPA97003576 A MX PA97003576A MX 9703576 A MX9703576 A MX 9703576A MX PA97003576 A MXPA97003576 A MX PA97003576A
- Authority
- MX
- Mexico
- Prior art keywords
- para
- copolymer
- carbon atoms
- polymer
- group
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 125000004432 carbon atoms Chemical group C* 0.000 claims abstract description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims abstract description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229920001002 functional polymer Polymers 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910014033 C-OH Inorganic materials 0.000 claims 2
- 229910014570 C—OH Inorganic materials 0.000 claims 2
- 230000002378 acidificating Effects 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 125000004429 atoms Chemical group 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 6
- 150000001266 acyl halides Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- -1 isobutyryl Chemical group 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N Boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon bisulphide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ALZLTHLQMAFAPA-UHFFFAOYSA-N 3-Methylbutyrolactone Chemical compound CC1COC(=O)C1 ALZLTHLQMAFAPA-UHFFFAOYSA-N 0.000 description 1
- 229940117389 Dichlorobenzene Drugs 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229940023488 Pill Drugs 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000001154 acute Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003139 buffering Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- ZTHNOZQGTXKVNZ-UHFFFAOYSA-L dichloroaluminum Chemical compound Cl[Al]Cl ZTHNOZQGTXKVNZ-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N β-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N γ-Valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N γ-lactone 4-hydroxy-butyric acid Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a functionalized para-alkylstyrene polymer or copolymer containing randomly placed in the polymer chain, monomer units of the formula: wherein R1, R2 and R3 are independently selected from the group consisting of hydrogen, primary and secondary alkyl and haloalkyl and R 4 is selected from the group consisting of: wherein x is an integer from 2 to about 10 and is an integer from 0 to about 20 and A is a linear hydrocarbyl group from 2 to about 10 atoms of carbon or a branched hydrocarbyl group of 3 to about 10 carbon atoms
Description
FUNCTIONALIZED PARA-ALOUILESTIRENE POLYMERS AND COPOLYMERS
Field of the Invention This invention relates to copolymers functioning from para-alkylstyrene and an isoolefin.
BACKGROUND OF THE INVENTION Polymers containing styrene, especially para-alkylstyrene copolymers and an isoolefin having from about 4 to 7 carbon atoms are well known in the art. In fact, the para-alkylestyrene and isobutylene copolymers are low Tg elastomers possessing low air permeability, unique buffering properties, excellent resistance to environmental aging and low surface energy which makes them particularly desirable in many applications. Unfortunately, these polymers also have low reactivity and low co-compatibility with most other polymers. In this way, there is a need to functionally hoist polymers and copolymers containing para-alkyl and styrene units with more compatible units for mixing. An object of the present invention, therefore, is to functionalize polymers containing para-alkyl styrene with reactants that allow the functionalized polymer to be co-geared or compatibilized with other polymers by grafting techniques. .
SUMMARY OF THE INVENTION Accordingly, the present invention provides a styrenically functional polymer or copolymer containing para-alkylated styrene functional moiety having the formula:
wherein R1, R2 and R3 are independently selected from hydrogen, halide, alkyl and primary and secondary haloalkyl and R4 is selected from the group having the formula:
- (A) -COOH, -C II -CH = CH-C00H
wherein x is an integer from 2 to about 10, and is an integer ranging from 0 to about 20, and A is a linear hydrocarbyl group of 2 to about 10 carbon atoms or a branched hydrocarbyl group of 3 to about 10 carbon atoms. The novel copolymers of the present invention have particular utility in forming polymer blends. For example, the functional polymer reacted with acid can be used as a compatibilizer by reacting it with a polyol, polyane, or the like.
Detailed Description of the Invention Polymers containing para-alkylstyrene can be functionalized in accordance with the process of the present invention. Particularly polymers containing para-alkyl styrene suitable for functionalization are copolymers of a -isoolefin having from about 4 to 7 carbon atoms and a fraction of para-alkyl styrene represented by the formula
R C-R, wherein R 1, R and R 3 are independently selected from hydrogen, halide, alkyl and primary and secondary haloalkyl groups. In the practice of the present invention, however - it is particularly preferred to use a copolymer of isobutylene and para-ethylstyrene. The above polymers are functionalized by reacting the para-alkylsterrene-containing polymer or copolymer with an acid anhydride, acylhalide or lactone in the presence of a Lewis acid. Particularly useful anhydrides include succinic, maleic and italic anhydrides. Particularly useful acylhalides include acetyl, isobutyryl and propionyl halides, especially chloride. Particularly useful lactones include gamma-butyrolactone, beta-butyrolactone, alpha-methyl-1-gamma-butyrolactone, beta-methyl-gamma-butyrolactone, gamma-valerolactone, delta-va-lero-lactone, epsi-lon-caprolactone. Any Lewis acid catalyst can be used-in preparing para-alkylated polystyrene-containing polymers; however, the preferred Lewis acid catalysts are based on metals such as boron, aluminum, gallium, indium, titanium, zirconium, tin, arsenic, antimony and bismuth. Especially preferred are halide-containing compounds of the foregoing metals, such as boron trifluoride, aluminum trihalide, aluminum dichloride and the like.
Typically, the functionalization will be carried out in the presence of a hydrocarbon diluent such as aliphatic or aromatic hydrocarbons or in the presence of a polar solvent such as carbon disulfide, nitrobenzene, methylene chloride, 1,2-dichloroethane and the like. . It is particularly preferred - in the practice of the present invention to carry out the process in the presence of a solvent. Functionalization of the polymers will typically be carried out at temperatures of about -50 ° C to about 100 ° C, for sufficient time to add the functional group, i.e., alkylcarbonyl, alkyl or alkenylcarboxylic acid, aromatic ring of the polymer containing para-alkyne thyrene. The ratio of acylhalide, acid anhydride, or lactone to the styrenic units in the para-alkylaryl-containing polymer can vary widely. In general, however, from about 0.01 to 10 moles of acylhalide, acid anhydride or lacto per 1 mole of styrenic moieties in the para-alkylsterrene-containing polymer will be employed. In general, the acylhalide will have from 2 to about 14 carbon atoms, the acid anhydride will have from 4 to about 12 carbon atoms; and the lactone used will have from 3 to about 11 carbon atoms. The following examples illustrate the invention.
EXAMPLE 1 The para-methyl-styrene-isobutylene copolymer used in this example contained 15.0% by weight of para-methyl-styrene, the remainder being isobutylene. The copolymer had a weight average molecular weight (Mw) of 377,500 and a number average molecular weight (Mn) of 149,600 with a polydispersity of 2.52. 5.00 grams of copolymer were dissolved in 50 ml. of dichloromethane in a 3-necked flask equipped with a condenser, nitrogen sparger and a dropping funnel. 0.64 g. of succinic anhydride were added and the solution was stirred at room temperature for one hour under nitrogen. 1.70 grams of A1C13 were added and the mixture was stirred at room temperature for 6 hours. The viscous, colorless solution became viscous red-brown in 5 minutes after the addition of A1C. The product was precipitated by adding the reaction mixture to 200 ml of acetone. The product was stirred with 200 ml of HCl diluted at 0.1N for one hour, filtered, washed with 200 ml. of water and then with 100 mi. of acetone. The product was dried under vacuum. The infrared spectrum of the product was similar to the starting pore with additional crests due to carboxyl and carbonyl functionality. The fin-infrared spectrum of the product showed a broad crest at 3500-3000 cm "1 due to the carboxylic acid group and two characteristic crests of carbonyl, an acute crest at 1690 cm-1 and a broad subtraction at 1630 cm- 1 Example 2 3.00 grams of para-methyl-styrene and iso-butylene copolymer containing 15.0% by weight of para-methyl-styrene as discussed in Example 1, were dissolved in 20 ml of dichloromethane in a 3-necked flask equipped with condenser, nitrogen sparger and a drip funnel, then 0.38 g of aleic anhydride was added and the solution was stirred at room temperature for 30 minutes under nitrogen, 1.00 g of A 1 C 1 was added and the mixture was stirred at room temperature for one hour. Viscous, colorless material became viscose red-brown immediately after the addition of AIC The product was isolated by adding the reaction mixture to 100 ml of methanol The product was washed with acetone and then dried under vacuum. The infrared spectrum of the product was similar to a starting pill with additional crests due to carboxylic acid and carbonyl functionality. The infrared spectrum of the product showed a broad ridge at 3500-3000 cm due to the carboxylic acid group and two carbonyl crests characteristic 1707 cm "1 and 1674 cm" 1.
Example 3 5.00 grams of para-methyl-styrene-isobutylene copolymer containing 15.0% by weight of para-methyl-styrene as discussed in Example 1, were dissolved in 50 ml of dichloromethane in a 250 ml 3 neck flask, equipped with a condenser, nitrogen sparger and a dropping funnel. 1.70 13 grams of A1C13 and 1 gram of acetyl-1-C chloride were added at room temperature under nitrogen. The solution was stirred at room temperature for 6 hours. The clear, colorless solution became viscous red-brown in 5 minutes after the addition of AlClg. The product was precipitated by adding the reaction mixture to 200 ml of acetone mixture and water (50:50). The product was washed with acetone and dried under vacuum. The infrared spectrum of the product showed a crest character! It is 1647 cm high due to the carbonyl of the functionalized polymer.
EXAMPLE 4 The copolymer of para-methyl-styrene and isobutylene used in this example contained 15.0% by weight of para-methyl no, the remainder being isobutylene. The copolymer had a weight average molecular weight (Mw) of 377,500 and a number-average molecular weight (Mn) of 149,600 polymers (Mw / Mn) of 2.52. 3.00 grams of copolymer were dissolved in 50 ml of dichlorobenzene in a 3-necked flask equipped with a condenser, nitrogen sparger and a dropping funnel. Then 0.75 grams of gamma-buti ol actone was added and the solution was stirred at room temperature for one hour under nitrogen. 2.00 grams of A1C12 were added and the mixture was stirred at room temperature. Immediately the product became dark red. The product was precipitated after 15 minutes, adding the reaction mixture to 200 ml of acetone / methanol mixture (50:50). The product was stirred with 200 ml of water, decanted, washed with 200 ml of acetone. The product was dried under vacuum. The infrared spectra of the product showed a broad ridge at 3500-3000 cm due to the carboxylic acid group.
Example 5 This example illustrates the reactivity of the functionalized polymer of this invention with a compound that contains alcohol. 1.00 grams of functional acid-laced copolymer is prepared by the procedure described in Example 1 and dissolved in 25 ml. of toluene in a 100-ml 3-necked flask equipped with condenser, no nitrogen bubbler and a dropping funnel. 25 ml was added. of ethyl alcohol and then 2 ml. of concentrated sulfuric acid. The solution was heated in an oil bath, with a bath temperature of 85 ° C for six hours under nitrogen. The product was isolated by adding the reaction mixture to 200 ml of water. The product was washed with water three times and then cohn acetone. The product was dried under vacuum. The infrared spectrum of the product showed disappearance from a broad ridge at 3500-3000 cm due to the carboxylic acid group and our characteristic ester crests at 1738
- 1 - 1 - 1 cm and 1718 cm along with carbonyl crest at 1690 cm. Gel chromatography chromatography (GPC) of THF solution analysis, using ultraviolet (UV) detectors and refractive index (RI) of the resulting ester-functional copolymer with the resulting ester, showed that the functionality with paramethylstyrene is distributed very uniformly to through the full scale of molecular weight. The
13 NMR C of the product ester showed two carbonyl crests at -173 ppm and 202 ppm due to ester and ketone carbonyl, respectively.
Claims (10)
1. - A para-alkylstryrene polymer or copolymer functions 1-containing containing, randomly placed in the polymer chain, monomeric units of the formula: wherein R ^ R2 and R ^ are independently selected from the group consisting of hydrogen, primary and secondary alkyl and haloalkyl, and R4 is selected from the group consisting of 0 II - (A) -COOH, -C -CH = CH-C00H, 0 0 II -C- (CH2) and CH3 and • C- (CH2)? - C-0H where x is an integer from 2 to about 10, and is an integer from 0 to about 20 and A is a linear hydrocarbyl group from 2 to about 10 carbon atoms or a branched hydrocarbyl group of 3 to about 10 carbon atoms. 2. The functional polymer as claimed in claim 1, wherein the para-alkylstyrene polymer is a copolymer of -para-alkylstyrene and an isoolefin of about 4 to about 7 carbon atoms. 3. The copolymer fune ion 1 raised of claim 2, wherein R "is:
• C (CH2)? - C-OH
The raised functional copolymer of the claim 2, where R. is:
-C-CH = CH-C00H
5. - The functional copolymer hoisted in the claim 2, wherein R4 is - (A) -COOH. 6.- The functional copolymer hoisted in the claim 2, where R. is:
-C- (CH) and CH3
7. - A polymer works by lifting an isoolefin having from about 4 to about 7 carbon atoms and a para-alkylstyrene, wherein the para-alkylstyrene is represented by the formula and the functionalized para-alkylstyrene fraction raised is represented by the formula: wherein R ^ R2, and R3 are independently selected from the group of hydrogen alkyl and primary and secondary alkyl halo, and R? is selected from the group consisting of
- (- A -) - COOH, -C-CH = CH-C00H,
• C (CH2) CH3 -C- (CH2)? -C-OH wherein x is an integer from 2 to about 10, and y is an entity of from about 0 to about 20, and A is a linear hydrocarbyl group of 2 to about 10 carbon atoms or a branched hydrocarbyl group of 3 to about 10 carbon atoms. 8. The functional polymer raised from claim 7, wherein the isoolefin is isobutylene and R., R2 and R3 are hydrogens. 9. A method for operating a polymer or copolymer containing para-alkylstyrene, which comprises: reacting the polymer or copolymer with a reagent selected from the group consisting of acid halides of about 2 to about 22 carbon atoms, acidic acids of about 4 to 12 carbon atoms, and lac -ones of 3 to about 11 carbon atoms, the reaction being conducted in the presence of a Lewis acid catalyst at temperatures around 50 ° C at about 100 ° C and for a sufficient time to functionalize the polymer or copolymer.
10. The method of claim 9, wherein the reaction is conducted in the presence of a hydrocarbon diluent and the molar ratio of reactant to para-alkylstyrene fraction in the polymer or copolymer ranges from 0.01: 1 to 10: 1. SUMMARY OF THE INVENTION The present invention provides a styrenically functional polymerized copolymer or copolymer containing para-alkyl styreno-functionalized moiety having the formula: where R1? R2 and R3 are independently selected from hydrogen, alkyl and halo primary and secondary alkyl, and R. is selected from the group having the formula: (A) -COOH -C-CCH = CH-C00H C- (CH2)? - C-0H • C- (CH2) and CH3 wherein x is an integer from 2 to about 10, and is an enter ranging from 0 to about 20 and A is a linear hydrocarbyl group of 2 to about 10 carbon atoms or a branched hydrocarbyl group of 3 to about 10 carbon atoms carbon
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/346,972 US5498673A (en) | 1994-11-29 | 1994-11-29 | Functional para alkylstyrene polymers and copolymers |
| US08346972 | 1994-11-29 | ||
| PCT/US1995/014935 WO1996016995A1 (en) | 1994-11-29 | 1995-11-14 | Functionalized para-alkylstyrene polymers and copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA97003576A true MXPA97003576A (en) | 1997-08-01 |
| MX9703576A MX9703576A (en) | 1997-08-30 |
Family
ID=23361808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9703576A MX9703576A (en) | 1994-11-29 | 1995-11-14 | Functionalized para-alkylstyrene polymers and copolymers. |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US5498673A (en) |
| EP (1) | EP0794969B1 (en) |
| JP (1) | JPH10510314A (en) |
| KR (1) | KR960017708A (en) |
| CN (1) | CN1066457C (en) |
| BR (1) | BR9509837A (en) |
| CA (1) | CA2206823A1 (en) |
| CZ (1) | CZ288415B6 (en) |
| DE (1) | DE69517703T2 (en) |
| ES (1) | ES2148584T3 (en) |
| HU (1) | HU216157B (en) |
| MX (1) | MX9703576A (en) |
| PL (1) | PL183673B1 (en) |
| RU (1) | RU2157383C2 (en) |
| TW (1) | TW503243B (en) |
| WO (1) | WO1996016995A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6015862A (en) * | 1994-11-18 | 2000-01-18 | The Penn State Research Foundation | Functionalized α-olefin/para-alkylstyrene terpolymers |
| EP1527127B1 (en) * | 2002-07-05 | 2009-02-11 | Exxonmobil Chemical Patents Inc. | Functionalized elastomer nanocomposite |
| CN100489021C (en) * | 2002-07-05 | 2009-05-20 | 埃克森美孚化学专利公司 | Functionalized elastomer nanocomposite |
| CN103492425B (en) * | 2011-04-14 | 2016-08-31 | 索理思科技开曼公司 | The preparation method of the polymer containing acylated vinylamine and the application as additive for paper making thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642398A (en) * | 1947-02-26 | 1953-06-16 | Monsanto Chemicals | Acylated polystyrene |
| US2962485A (en) * | 1957-12-03 | 1960-11-29 | Monsanto Chemicals | Preparation of acetylated styrene polymers |
| US3222323A (en) * | 1962-06-27 | 1965-12-07 | Dow Chemical Co | Carboxy ethylene keto polymers |
| FR1521362A (en) * | 1966-11-16 | 1968-04-19 | Wolfen Filmfab Veb | Process for preparing ion exchange resins and resins thus obtained |
| US3474159A (en) * | 1966-12-28 | 1969-10-21 | Standard Oil Co | Synthetic rubber compositions containing oxidized polymer tackifiers |
| US4025580A (en) * | 1972-12-18 | 1977-05-24 | Owens-Illinois, Inc. | Modified styrenepolymers |
| SU713873A1 (en) * | 1973-12-04 | 1980-02-05 | Сумгаитский Филиал Ордена Трудового Красного Знамени Института Нефтехимических Процессов Им. Академика Ю.Г.Мамедалиева Ан Азербайджанской Сср | Method of preparing modified polystyrene |
| US4145490A (en) * | 1975-09-25 | 1979-03-20 | E. I. Du Pont De Nemours And Company | Carboxylated copolymers of isobutylene and a vinylbenzene |
| FR2506773B1 (en) * | 1981-05-26 | 1986-02-21 | Charbonnages Ste Chimique | AROMATIC HYDROCARBON RESINS CONTAINING VINYLCETONE GROUPS AND THEIR APPLICATION FOR OBTAINING POLYMERS BY ANIONIC ROUTE |
-
1994
- 1994-11-29 US US08/346,972 patent/US5498673A/en not_active Expired - Lifetime
-
1995
- 1995-11-14 JP JP8518852A patent/JPH10510314A/en active Pending
- 1995-11-14 CN CN95196511A patent/CN1066457C/en not_active Expired - Fee Related
- 1995-11-14 CA CA002206823A patent/CA2206823A1/en not_active Abandoned
- 1995-11-14 HU HUP9701829A patent/HU216157B/en not_active IP Right Cessation
- 1995-11-14 CZ CZ19971645A patent/CZ288415B6/en not_active IP Right Cessation
- 1995-11-14 BR BR9509837A patent/BR9509837A/en not_active IP Right Cessation
- 1995-11-14 WO PCT/US1995/014935 patent/WO1996016995A1/en active IP Right Grant
- 1995-11-14 ES ES95940011T patent/ES2148584T3/en not_active Expired - Lifetime
- 1995-11-14 MX MX9703576A patent/MX9703576A/en not_active IP Right Cessation
- 1995-11-14 PL PL95320478A patent/PL183673B1/en unknown
- 1995-11-14 EP EP95940011A patent/EP0794969B1/en not_active Expired - Lifetime
- 1995-11-14 DE DE69517703T patent/DE69517703T2/en not_active Expired - Fee Related
- 1995-11-14 RU RU97112481/04A patent/RU2157383C2/en not_active IP Right Cessation
- 1995-11-29 KR KR1019950044783A patent/KR960017708A/en not_active Application Discontinuation
- 1995-12-07 TW TW084113039A patent/TW503243B/en not_active IP Right Cessation
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