USRE28475E - Process for copolymerization of maleic anhydride with 1-olefins - Google Patents

Process for copolymerization of maleic anhydride with 1-olefins Download PDF

Info

Publication number
USRE28475E
USRE28475E US45082274A USRE28475E US RE28475 E USRE28475 E US RE28475E US 45082274 A US45082274 A US 45082274A US RE28475 E USRE28475 E US RE28475E
Authority
US
Grant status
Grant
Patent type
Prior art keywords
polymerization
mixture
reaction
anhydride
maleic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Research and Technology Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/04Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of anhydrides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/04Anhydrides, e.g. cyclic anhydrides

Abstract

Maleic anhydride and polymerizable liquid 1-olefins having from 4 to 14 carbon atoms are copolymerized employing a liquid-liquid dispersion as the reaction mixture by use of excess liquid 1olefin as a diluent and a minor amount of a copolymer of maleic anhydride with an aliphatic 1-olefin having from 14 to 18 carbon atoms as a dispersing agent. Maleic anhydride and a polymerization initiator becomes dispersed in the mixture of olefin and dispersing agent and polymerization takes place when the temperature is raised to about 80* C. with agitation.

Description

United States Patent 11 1 Blecke et al.

[ PROCESS FOR COPOLYMERIZATION OF MALElC ANHYDRIDE WITH l-OLEFINS [75] Inventors: Ronald G. Blecke, Lower Salford Twp, Montgomery County; Robert W. Hill, Gibsonia, both of Pa.

[73] Assignee: Gulf Research & Development Company, Pittsburgh, Pa.

[22] Filed: Mar. 13, 1974 [21] Appl. No.: 450,822

Related U.S. Patent Documents Reissue of: [64] Patent No.: 3,729,451

Issued: Apr. 24, 1973 Appl. No.: 270,331

Filed: July 10, 1972 [52] U.S. Cl 260/78.5 R; 260/875; 260/878;

[51] Int. CL... C08F 2/02; C08F 2/08; C08F 222/06 [58] Field of Search 260/785 R 11 E Re. 28,475

[45] Reissued July 8, 1975 [56] References Cited UNITED STATES PATENTS 3,249,454 5/l966 Williams 106/309 3,46] ,l08 S/l969 Heilman et al. 260/785 3,553,183 l/l97l Field et al 260/785 3,560,456 2/l97l Hazen et al 260/785 Primary Examiner-Joseph L. Schofer Assistant Examiner-John Kight 57] ABSTRACT 6 Claims, No Drawings PROCESS FOR COPOLYMERIZATION OF MALEIC ANHYDRIDE WITH l-OLEFINS Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

DESCRIPTION OF THE INVENTION The preparation of copolymers of maleic anhydride with various unsaturated monomers, particularly ethylene and styrene is well known in the art. More recently, copolymers of maleic anhydride with various branched and linear aliphatic l-olefins have been prepared, some of which are finding uses in industry. It has been found however, that in the preparation of a copolymer of maleic anhydride and such l-olefins that the recovery of the copolymers presents some fairly difficult problems. The use of an excess of olefin in solution polymerization processes so as to obtain more complete reaction increases the difficulty of separating the product.

A satisfactory practice which has been used as disclosed for example, in U.S. Pat. 3,46] ,lOS, is to employ certain efficient solvents for the polymerization step, keeping the monomers and in some instances the poly mers also in solution during the polymerization, and then adding to the resulting solution another liquid, which causes precipitation of the polymer products in finely divided filterable solid form. The selection of the combination of reaction solvent and precipitating solvent is critical. A very limited choice of solvent combinations exists, no completely satisfactory precipitating agent having been found for some copolymers. Furthermore, the solvents are expensive and for this reason must be separated and recovered. The solvent separation, polymer filtration and washing steps require bulky equipment and are time consuming.

It has been found in accordance with the present invention that copolymers of maleic anhydride with a variety of polymerizable l-olefins having from 4 to 14 carbon atoms can be produced in the form of dispersions of solid particles in excess l-olefin as a diluent, provided there is employed as dispersing agent an equimolecular copolymer of maleic anhydride with an aliphatic l-olefin having from M to l8 carbon atoms and the reaction mixture is heated to the vicinity of 80 C. with agitation to generate a liquid-liquid dispersion as a polymerization reaction mixture.

Briefly, the present invention consists ofa liquid dispersion process for manufacturing a copolymer of maleic anhydride with an aliphatic l-olefin comprising the steps:

a. forming a reaction mixture by mixing together at least one polymerizable liquid l-olefin having from 4 to 14 carbon atoms, a minor amount of an equimolecular copolymer of maleic anhydride with an aliphatic l-olefin having from 14 to 18 carbon atoms as a dispersing agent, a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of l-olefin present,

b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the reaction mixture becomes a liquid-liquid dispersion and the polymerization reaction is initiated,

c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid l-olefin is obtained as a polymerization product mixture, and

d. recovering the solid particles of product from the polymerization product mixture by filtration or vaporization of the liquid l-olefin.

The procedure outlined above eliminates the usual precipitation step in solution polymerization which requires costly separation of solvent and precipitant when recycled, yields a liquid-liquid dispersion type of reaction mixture which has a low viscosity and is easily stirred, pumped and handled and permits operation at higher solids content in the product mixture. This results in greater throughput capacity and lower process costs for equipment of a size comparable to that employed in solution polymerization. The dispersion copolymerization process of this invention is characterized by a combination of features which include the use of a l-olefin comonomer as the dispersing medium, a unique dispersing agent and a temperature program which allows the dispersion to develop. The process is discussed in greater detail below.

In carrying out the process there are some critical features which must be taken into account. One of the most critical features is selection of the polymeric dispersing agent. Only the copolymers of the maleic anhydride with the higher l-olefin appear to have good dispersion efficiency. Equimolecular copolymers of maleic anhydride with 14 to 18 carbon l-olefins may be used for the purpose, preferably at a concentration of l to 2 weight percent. The copolymers, which may be made by published methods, for example the method of U.S. Pat. 3,560,456, are characterized in the following discussion.

The dispersing agents employed in the method of this invention are linear, low molecular weight copolymers of straight chain l-olefins and maleic anhydride, The olefin and maleic anhydride are present in a l:l molar ratio, as shown in the following structural formula. R represents a linear alkyl substituent, the length of which is determined by the choice of the olefin comonomer. In the tetradecene copolymer, for example, the R substituent is dodecyl.

The copolymer dispersing agents are white solids with melting ranges which center from about l l7 C. (l-octadecene copolymer) to about 129 C. (ltetradecene copolymer). Typical physical properties are summarized below:

-Continued l-tclral-octadecenc deccnc Property copolymer copolymer Inherent viscosity 3 0.147 0.144

Theoretical values. lgnoring end group effect 2 True density 5 g rdl in methyl isobutyl ketone at 7? F SOLUBILITY OF COPOLYMER DISPERSING AGENTS l-Octadecene copolymer l-tetradecene copolymer Chiorinated solvents:

Carbon tetrachloride l.2-dichloroethane Esters: Ethylacctatc Hydrocarbons:

Benzene Ligroin Dccalin Kelones:

Acetone Methyl isobutyl kctonc Ethers: Bis( Z-methoxyethyllether Vim S S S S SI SI S S S V i/H1 wmm MUM/1 Note S suluble, g (I00 ml. SlS=slightly soluble; l5 g ltlll ml ln carrying on the heating program it is desirable to have the solid maleic anhydride entirely mixed with liquid prior to raising the temperature to the melting point of the maleic anhydride. The temperature should be increased slowly enough so that the mixing or stirring device employed in the reactor is able to maintain a condition of efficient mixing during the rise in tempera ture. lf raising the temperature to the decomposition temperature of the initiator is carried out too quickly, without efficient stirring. polymer may adhere to the walls of the reactor. Although the process will operate and a polymer dispersion does form. the solid coating of polymer on the wall of the reactor will necessitate a cleaning operation. The speed with which the temperature can be raised to the decomposition temperature of the initiator depends to a great extent upon the efficiency of the mixing apparatus in the reactor. This is largely a matter of choice from among the many types of mixing devices which are now available. A compromise will have to be reached between mixing speed, power consumption, residence time in the reactor and various cost factors.

Selection of the polymerization initiator is made mainly on the basis of the decomposition temperature at which the compound produces free radicals. This temperature should be above the melting point of maleic anhydride but below the softening temperature of the copolymer product. Peroxide initiators such as ditertbutyl peroxide and benzoyl peroxide and azobisist butyronitrile are among those initiators which are available commercially.

Unlike the dispersing agents. the choice of polymerizable l-olefin is not critical. Pure compounds or mix tures may be used in which there is a polymerizable vinyl group. The balance of the molecule may be straight chain. branched or cyclic in structure, including vinyl aromatic monomers such as styrene.

The polymer products obtained by the present process may be used for all the purposes to which corresponding products have been used in the past and have no observable deficiencies in chemical or physical properties. The solid particles of polymer obtained by this technique appear to have a very desirable physical structure, which render them easily handled in conventional processing equipment. The operation of the process is illustrated by the following specific examples.

EXAMPLE 1 To 2.5 moles of l-hexene there is added 1.8 g. oftert- .butyl peroctoate as a polymerization initiator and 2.8 g. of an l-octadecene-maleic anhydride copolymer as a dispersing agent and 1 mole of solid maleic anhydride. The mixture is then heated with stirring. As the temperature rises above the melting point of the maleic anhydride (53 C.) the anhydride forms a second liquid phase underneath the liquid hexane. There is little tendency of the two liquid phases to intermix, even with vigorous agitation, until the temperature reaches the vicinity of C. and then only when the unique dispersing agent is present in the mixture. When the two liquid phases begin to intermix and form a liquid-liquid dispersion there is evidence that the copolymerization reaction has begun. With continued stirring for a sufficient time period at a temperature of about 80 C. the polymerization procedure yields a dispersion of solid copolymer particles in the excess liquid l-hexene employed as a diluent. When the polymerization reaction is judged to be complete, the excess olefin employed as a liquid reaction diluent is separated from the polymer by evaporation or filtration, yielding finely divided nontacky. solid copolymer.

EXAMPLE 2 The procedure employed in this specific example is essentially the same as described in Example l. The reaction vessel is charged with 29.4 g. (0.3 mole) of maleic anhydride, 250 ml. of l-hexene, 2.0 g. of benzoyl peroxide, and 2 g. of maleic anhydride-l-octadecene copolymer. The temperature profile from 60 C. to 90 C. requires one hour. The dispersion develops normally and the reaction is allowed to proceed at 90 C. for an additional 5 hours. A powdery white solid, MP. 136-140 C. is isolated in 96% yield after filtration and drying. The copolymer has a solution viscosity of 0.10 dl./g.

EXAMPLE 3 The procedure and apparatus employed in this example was the same as described in Example l. The reaction vessel was charged with 29.4 g. (0.3 mole) of maleic anhydride, 250 ml. of l-hexene, 2.0 ml. of tert.butyl peroctoate, and 2 g. of maleic anhydride-l tetradecene copolymer. The temperature profile from s0-s0 C. required one hour and the reaction was allowed to proceed for 2 hours at 86 C. Filtration and drying as before gave a white solid. M.P. l42-l60 C.. in yield. The copolymer had a solution viscosity of 0.13 dl/g.

EXAMPLE 4 The procedure and apparatus employed in this example were the same as described in Example 1. The reaction vessel was charged with 29.4 g. (0.3 mole) of maleic anhydride. 250 ml. of l-decene. 2.0 ml. of tert.butyl peroctoate. and 2 g. of maleic anhydride-loctadecene copolymer. The temperature profile from 60-90 C. was slower as the dispersion developed slowly. The resultant dispersion after filtration gave a white granular solid. M.P. 105-113 C.

EXAMPLES 5 and 6 Two batches of polymer were manufactured in a 50- gallon pilot plant reactor using the dispersion copolymerization procedure. The reaction charge for the two batches was:

l-hexene lbs 193 Maleic anhydride lbs 67 Tertbutyl peroctoate cc 520 Maleic anhydride l octadecene copolymer dispersant lbs 2.3

Each batch was heated to 194 F. (90 C.), held two hours and cooled. The excess hexene was evaporated from the product using a Patterson-Kelly rotary vacuum dryer. Dried product was passed through a inch screen. The quantities of products of two batches and their properties are tabulated below.

PILOT PLANT SYNTHESIS OF l-HEXENE prising the steps:

a. forming a reaction mixture by mixing together at least one polymerizable liquid l-olefin having from 4 to l4 carbon atoms. a minor amount of an equimolecular copolymer of maleic anhydride with a linear aliphatic l-olefin having from 14 to l8 carbon atoms as a dispersing agent. a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of lolefin present.

b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated.

c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid l-olefin is obtained as a polymerization product mixture. and

d. recovering the solid particles of product from the polymerization product mixture by filtration or evaporation of the liquid l-olefin.

2. A dispersion process for manufacturing a copoly mer of maleic anhydride with l-hexene consisting essentially of the steps:

a. forming a reaction mixture by mixing together 1- hexene. a minor amount, between 1 and 2 weight percent concentration. of an equimolar copolymer of maleic anhydride with a linear aliphatic l-olefin having from 14 to 18 carbon atoms as a dispersing agent. a polymerization initiator and a quantity of maleic anhydride which is less than a molar equiva lent of the amount of l -hexene present.

b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated.

c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid l-hexene is obtained as a polymerization product mixture, and

d. recovering the solid particles of product from the polymerization product mixture by filtration or vaporization of the liquid l-hexene.

3. A dispersion process for manufacturing a copolymer of maleic anhydride with l-decene consisting essentially of the steps:

a. forming a reaction mixture by mixing together I decene, a minor amount. between I and 2 weight percent concentration, of an equimolecular copolymer of maleic anhydride with a linear aliphatic l-olefin having from 14 to l8 carbon atoms as a dispersing agent. a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of l-decene present, agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated.

c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid l-decene is obtained as a polymerization product mixture. and

d. recovering the solid particles of product from the polymerization product mixture by filtration or vaporization of the liquid l-decene.

4. A dispersion process for manufacturing a copolymer of maleic anhydride with l'hexene consistinj. essentially ofthe steps:

a. forming a reaction mixture by mixing together at least one polymerizahle liquid l-olefin having from 4 to 14 carbon atoms. a minor amount ofan equimolecular copolymer of maleic anl'rvdride with a linear aliphatic l-olefin havingjrom 14 to 18 carbon atoms as a dispersing agent. a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of l-olefin present.

b. agitating the reaction mixture ofstep (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated. and

c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid l-olefin is obtained as a polymerization product mixture.

5. A dispersion process for manufacturing a copolymer of maleic anhydride with l-hexene consisting essen tially of the steps:

a. forming a reaction mixture by mixing together 1- hexene, a minor amount. between I and 2 weight percent concentration. of an equimolerular copolymer of maleic anhydride with a linear aliphatic olefin having from 14 to 18 carbon atoms as a dispersing agent. a polymerization initiator and a quantit of maleic anhydride which is less than a molar equivalent of the amount of I-hexene present,

b agitating the reaction mixture ofstep (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated, and

c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid I-hexene is obtained as a polymerization product mixture.

6. A dispersion process for manufacturing a copolymer of maleic anhydride with l-decene consisting essentially ofthe steps:

a. forming a reaction mixture by mixing together decene, a minor amount. between I and 2 weight continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid ldecene is obtained as a polymerization product mixture.

* k 1F l INVENTUMM UNITED STATES PATENT OFFICE (IElHlFlCATE U1 CORRECTION PATENT NU. Re. 28,475

0mm July 8, 1975 Ronald G. Blecke, Robert W. Hill it IS cerhfled that enor appears m The above-menhfaed patent and that said Letters Patent are hemby (.OHECIEU as shown below,

COL. 4, line 21, "hexane" should read -hexene.

COL. 5 line 67, "equimolar" should read equimolecular-.

COL. 6, lines 41 & 42, "l-hexene consisting essentially of" should read an aliphatic lolefin comprising-.

Signed and Scaled this eighreenlh D a y Of Noren lber I9 75 [SE ALI Arrest.

RUTH C. MASON ('mnmlssmmv u; lurvnlx and TruJmnurM

Claims (6)

1. A DISPERSION PROCESS FOR MANUFACTURING A COPOLYMER OF MALEIC ANHYDRIDE WITH AN ALIPHATIC 1-OLEFIN COMPRISING THE STEPS: A. FORMING A REACTION MIXTURE BY MIXING TOGETHER AT LEAST ONE POLYMERIZABLE LIQUID 1-OLEFIN HAVING FROM 4 TO 14 CARBON ATOMS, A MINOR AMOUNT OF AN EQUIMOLECULAR COPOLYMER OF MALEIC ANHYDRIDE WITH A LINEAR ALIPHATIC 1-OLEFIN HAVING FROM 14 TO 18 CARBON ATOMS AS A DISPERSING AGENT, A POLYMERIZATION INITIATOR AND A QUANTITY OF MALEIC ANHYDRIDE WHICH IS LESS THAN A MOLAR EQUIVALENT OF THE AMOUNT OF 1-OLEFIN PRESENT, B. AGITATING THE REACTION MIXTURE OF STEP (A) AND HEATING TO INCREASE THE TEMPERATURE TO THE POINT AT WHICH THE POLYMERIZATION REACTION IS INITIATED, C. CONTINUING AGITATION OF THE REACTION MIXTURE AT A TEMPERATURE NEAR THE DECOMPOSITION TEMPERATURE OF THE POLYMERIZATION INITIATOR UNTIL A DISPERSION OF SOLID COPOLYMER PARTICLES IN LIQUID 1-OLEFIN IS OBTAINED AS A POLYMERIZATION PRODUCT MIXTURE, AND D. RECOVERING THE SOLID PARTICLES OF PRODUCT FROM THE POLYMERIZATION PRODUCT MIXTURE BY FILTRATION OR EVAPORATION OF THE LIQUID 1-OLEFIN.
2. A dispersion process for manufacturing a copolymer of maleic anhydride with 1-hexene consisting essentially of the steps: a. forming a reaction mixture by mixing together 1-hexene, a minor amount, between 1 and 2 weight percent concentration, of an equimolar copolymer of maleic anhydride with a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of 1-hexene present, b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated, c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid 1-hexene is obtained as a polymerization product mixture, and d. recovering the solid particles of product from the polymerization product mixture by filtration or vaporization of the liquid 1-hexene.
3. A dispersion process for manufacturing a copolymer of maleic anhydride with 1-decene consisting essentially of the steps: a. forming a reaction mixture by mixing together 1-decene, a minor amount, between 1 and 2 weight percent concentration, of an equimolecular copolymer of maleic anhydride with a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of 1-decene present, b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated, c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid 1-decene is obtained as a polymerization product mixture, and d. recovering the solid particles of product from the polymerization product mixture by filtration or vaporization of the liquid 1-decene.
4. A dispersion process for manufacturing a copolymer of maleic anhydride with an aliphatic 1-olefin comprising the steps: a. forming a reaction mixture by mixing together at least one polymerizable liquid 1-olefin having from 4 to 14 carbon atoms, a minor amount of an equimolecular copolymer of maleic anhydride with a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of 1-olefin present, b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated, and c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid 1-olefin is obtained as a polymerization product mixture.
5. A dispersion process for manufacturing a copolymer of maleic anhydride with 1-hexane consisting essentially of the steps: a. forming a reaction mixture by mixing together 1-hexane, a minor amount, between 1 and 2 weight percent concentration, of an equimolecular copolymer of maleic anhydride with a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a polymerization initiator and a Quantity of maleic anhydride which is less than a molar equivalent of the amount of 1-hexane present, b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated, and c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid 1-hexane is obtained as a polymerization product mixture.
6. A dispersion process for manufacturing a copolymer of maleic anhydride with 1-decane consisting essentially of the steps: a. forming a reaction mixture by mixing together 1-decane, a minor amount, between 1 and 2 weight percent concentration, of an equimolecular copolymer of maleic anhydride with a linear aliphatic 1-olefin having from 14 to 18 carbon atoms as a dispersing agent, a polymerization initiator and a quantity of maleic anhydride which is less than a molar equivalent of the amount of 1-decene present, b. agitating the reaction mixture of step (a) and heating to increase the temperature to the point at which the polymerization reaction is initiated, and c. continuing agitation of the reaction mixture at a temperature near the decomposition temperature of the polymerization initiator until a dispersion of solid copolymer particles in liquid 1-decene is obtained as a polymerization product mixture.
USRE28475E 1972-07-10 1974-03-13 Process for copolymerization of maleic anhydride with 1-olefins Expired USRE28475E (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US27033172 true 1972-07-10 1972-07-10
USRE28475E USRE28475E (en) 1972-07-10 1974-03-13 Process for copolymerization of maleic anhydride with 1-olefins

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
USRE28475E USRE28475E (en) 1972-07-10 1974-03-13 Process for copolymerization of maleic anhydride with 1-olefins

Publications (1)

Publication Number Publication Date
USRE28475E true USRE28475E (en) 1975-07-08

Family

ID=26954215

Family Applications (1)

Application Number Title Priority Date Filing Date
USRE28475E Expired USRE28475E (en) 1972-07-10 1974-03-13 Process for copolymerization of maleic anhydride with 1-olefins

Country Status (1)

Country Link
US (1) USRE28475E (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795792A (en) * 1987-05-25 1989-01-03 Kao Corporation Process for preparing particles of olefin-maleic anhydride copolyer
US5175225A (en) * 1989-09-29 1992-12-29 Chevron Research And Technology Company Process for preparing polymeric dispersants having alternating polyalkylene and succinic groups
WO1999056718A1 (en) 1998-05-04 1999-11-11 Schering-Plough Healthcare Products, Inc. Sunscreen having disappearing color indicator
US6719053B2 (en) 2001-04-30 2004-04-13 Bj Services Company Ester/monoester copolymer compositions and methods of preparing and using same
US6919473B2 (en) 2002-09-17 2005-07-19 Cph Innovations Corporation Photostabilizers, UV absorbers, and methods of photostabilizing a sunscreen composition
US20050186152A1 (en) * 2004-02-25 2005-08-25 Bonda Craig A. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US20050207578A1 (en) * 2000-08-31 2005-09-22 Sony Corporation Content distribution system, content distribution method, information processing apparatus, and program providing medium
US20050210599A1 (en) * 2004-03-24 2005-09-29 Yanhui Sun Stain-resist compositions
US20050222307A1 (en) * 2002-11-22 2005-10-06 Cph Innovations Corp. Method of decreasing the UV light degradation of polymers
US20060002869A1 (en) * 2004-07-01 2006-01-05 Bonda Craig A Diesters containing two crylene or fluorene moieties, sunscreen compositions containing the same, and methods of photostabilizing a sunscreen compositions containing the same
US20060228311A1 (en) * 2005-04-07 2006-10-12 Bonda Craig A Photoabsorbing, highly conjugated compounds of cyanoacrylic esters, sunscreen compositions and methods of use
US20080206506A1 (en) * 2007-02-23 2008-08-28 Invista North America S.Ar.I. New stain resistant barrier fabric
WO2018081780A2 (en) 2016-10-31 2018-05-03 Cabot Corporation Polymers for inkjet ink compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249454A (en) * 1964-06-04 1966-05-03 Monsanto Co Organic dispersants for organic pigments in liquid organic systems
US3461108A (en) * 1965-10-14 1969-08-12 Gulf Research Development Co Process of forming copolymers of maleic anhydride and an aliphatic olefin having six carbon atoms
US3553183A (en) * 1969-03-27 1971-01-05 Gaf Corp Interpolymeric anti-clumping additives
US3560456A (en) * 1969-05-26 1971-02-02 Gulf Research Development Co Process of forming copolymers of maleic anhydride and an aliphatic olefin having from 16 to 18 carbon atoms

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3249454A (en) * 1964-06-04 1966-05-03 Monsanto Co Organic dispersants for organic pigments in liquid organic systems
US3461108A (en) * 1965-10-14 1969-08-12 Gulf Research Development Co Process of forming copolymers of maleic anhydride and an aliphatic olefin having six carbon atoms
US3553183A (en) * 1969-03-27 1971-01-05 Gaf Corp Interpolymeric anti-clumping additives
US3560456A (en) * 1969-05-26 1971-02-02 Gulf Research Development Co Process of forming copolymers of maleic anhydride and an aliphatic olefin having from 16 to 18 carbon atoms

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795792A (en) * 1987-05-25 1989-01-03 Kao Corporation Process for preparing particles of olefin-maleic anhydride copolyer
US5175225A (en) * 1989-09-29 1992-12-29 Chevron Research And Technology Company Process for preparing polymeric dispersants having alternating polyalkylene and succinic groups
WO1999056718A1 (en) 1998-05-04 1999-11-11 Schering-Plough Healthcare Products, Inc. Sunscreen having disappearing color indicator
US20050207578A1 (en) * 2000-08-31 2005-09-22 Sony Corporation Content distribution system, content distribution method, information processing apparatus, and program providing medium
US7644443B2 (en) 2000-08-31 2010-01-05 Sony Corporation Content distribution system, content distribution method, information processing apparatus, and program providing medium
US6719053B2 (en) 2001-04-30 2004-04-13 Bj Services Company Ester/monoester copolymer compositions and methods of preparing and using same
US6919473B2 (en) 2002-09-17 2005-07-19 Cph Innovations Corporation Photostabilizers, UV absorbers, and methods of photostabilizing a sunscreen composition
US7544350B2 (en) 2002-11-22 2009-06-09 Hallstar Innovations Corp. Method of decreasing the UV light degradation of polymers
US20050222307A1 (en) * 2002-11-22 2005-10-06 Cph Innovations Corp. Method of decreasing the UV light degradation of polymers
US20050186153A1 (en) * 2004-02-25 2005-08-25 Bonda Craig A. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US20050186152A1 (en) * 2004-02-25 2005-08-25 Bonda Craig A. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US20050186154A1 (en) * 2004-02-25 2005-08-25 Bonda Craig A. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US7560098B2 (en) 2004-02-25 2009-07-14 Hallstar Innovations Corp. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US7648697B2 (en) 2004-02-25 2010-01-19 Hallstar Innovations Corp. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US7550134B2 (en) 2004-02-25 2009-06-23 Hallstar Innovations Corp. Compounds derived from polyanhydride resins with film-forming, UV-absorbing, and photostabilizing properties, compositions containing same, and methods of using the same
US20050210599A1 (en) * 2004-03-24 2005-09-29 Yanhui Sun Stain-resist compositions
US7879112B2 (en) 2004-03-24 2011-02-01 Invista North America S.Ar.L. Stain-resist compositions
US7166236B2 (en) 2004-03-24 2007-01-23 Invista North America S.A.R.L. Stain-resist compositions
US20070101510A1 (en) * 2004-03-24 2007-05-10 Invista North America S.Ar.L. Stain-resist compositions
US7235587B2 (en) 2004-07-01 2007-06-26 Cph Innovations Corporation Diesters containing two crylene or fluorene moieties, sunscreen compositions containing the same, and methods of photostabilizing a sunscreen compositions containing the same
US20060002869A1 (en) * 2004-07-01 2006-01-05 Bonda Craig A Diesters containing two crylene or fluorene moieties, sunscreen compositions containing the same, and methods of photostabilizing a sunscreen compositions containing the same
US20060228311A1 (en) * 2005-04-07 2006-10-12 Bonda Craig A Photoabsorbing, highly conjugated compounds of cyanoacrylic esters, sunscreen compositions and methods of use
US8158678B2 (en) 2005-04-07 2012-04-17 Cph Innovations Corp. Photoabsorbing, highly conjugated compounds of cyanoacrylic esters, sunscreen compositions and methods of use
US20080206506A1 (en) * 2007-02-23 2008-08-28 Invista North America S.Ar.I. New stain resistant barrier fabric
WO2018081780A2 (en) 2016-10-31 2018-05-03 Cabot Corporation Polymers for inkjet ink compositions

Similar Documents

Publication Publication Date Title
US3620988A (en) Method of preparing bead-type polymers
US3541059A (en) Novel reaction products of glycidyl esters and alkali metal sulfite or bisulfite,and polymers thereof
US3285949A (en) Carboxyl-terminated butadiene polymers prepared in tertiary butanol with bis-azocyano acid initiation
Dekking Propagation of vinyl polymers on clay surfaces. II. Polymerization of monomers initiated by free radicals attached to clay
US3382297A (en) Polymer dispersions
US3183217A (en) Copolymerization of polar with nonpolar monomers in the presence of a friedel-craftsand a free radical initator
US3342787A (en) Resinous compositions
US3509110A (en) Vinyl aryl monomer-half ester copolymers by suspension polymerization
US3056771A (en) Polymerization process
US5773534A (en) Preparing crosslinkable polymers employing macromonomer chain transfer agents
US3390206A (en) Process for preparing polymers having one terminal functional group capble of condensation reaction
US3062792A (en) Polymers derived from tetraalkyl vinylidenediphosphonates
US3403122A (en) Emulsion polymerization of water insoluble omega-(n-perfluoroalkanesulfonyl) aminoalkyl acrylates or methacrylates
US3099636A (en) Polymeric acid salts of alkylaminoethyl methacrylate
US3393168A (en) Crosslinked olefin/maleic anhydride interpolymers
US5362826A (en) Method of preparing macrmonomer compositions
US3658772A (en) Acrylic acid polymers
US3441545A (en) Modification of olefin-carboxylic acid halide copolymers
US3284393A (en) Water-in-oil emulsion polymerization process for polymerizing watersoluble monomers
US3055873A (en) Preparation of polyitaconic acid
US2396785A (en) Process for polymerizing olefins with other polymerizable organic compounds
US2971939A (en) Process for preparing homogeneous copolymers of a vinylidene monomer and a maleic monomer and product thereof
US3580893A (en) Process for the preparation of cyclic acid anhydrides
US3336267A (en) Continuous preparation of thermoplastic copolymers and terpolymers of unsaturated cyclic anhydrides
US3085994A (en) Chain terminated copolymer of styrene and maleic anhydride of low solution viscosity

Legal Events

Date Code Title Description
AS Assignment

Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.;REEL/FRAME:004610/0801

Effective date: 19860423

Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.;REEL/FRAME:004610/0801

Effective date: 19860423