Processes to control fouling and improve compositions

Patent metadata

Field	Value
Publication number	US-9932425-B2
Application number	US-201414569956-A
Country	US
Kind code	B2
Filing date	Dec 15, 2014
Priority date	Jun 18, 2008
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

Improved reaction processes comprise reacting a mixture to form a product comprising a metal alkyl, metal oxide, or mixture thereof and then passing said product to a post-reactor heat exchanger. The improvement comprises one or more of the following:
(1) reacting said metal alkyl compound with an acid to produce a soluble metal ester; or (2) adding an ionic surfactant; or (3) adding a mixture comprising an antioxidant to the product under conditions sufficient to avoid formation of significant amounts of insoluble metal or metal compounds derived from said metal alkyl compound; or (4) purging said post-reactor heat exchanger with an inert gas under conditions to remove metal oxide from the post-reactor heat exchanger.

First claim

The invention claimed is:

1. A reaction process comprising:
(1) reacting a mixture via a reaction to form at least one product comprising:
(a) an ethylene/α-olefin multiblock interpolymer comprising at least 50 mole percent ethylene which is characterized before any crosslinking by one or more of the following characteristics:
(1) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; or
(2) at least one molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1; or
(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
T m >−6553.3+13735( d )−7051.7( d ) 2 ; or

(4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
Δ T>− 0.1299(Δ H )+62.81

for ΔH greater than zero and up to 130 J/g,
ΔT≥48° C.

for Δ H greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or
(5) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin multiblock interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin multiblock interpolymer is substantially free of a cross-linked phase:
Re> 1481−1629( d ); or

(6) has a comonomer content of a TREF fraction which elutes between 40° C. and 130° C. greater than or equal to the quantity (0.2013)T+21.07, where T is the numerical value of the peak ATREF elution temperature of the TREF fraction, measured in ° C.; or
(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in the range of about 1:1 to about 9:1; and

(b) a metal alkyl compound, a metal oxide, or a mixture thereof; and
(2) deactivating any catalyst in the at least one product; and
(3) passing said at least one product to at least one post-reactor heat exchanger;
wherein the process comprises, after the step (2) of deactivating any catalyst and prior to step (3), the following steps:
(i) optionally, adding a soluble carboxylic acid to the at least one product to react said metal alkyl compound with the soluble carboxylic acid to produce a soluble complex metal ester;
(ii) adding calcium stearate to the at least one product in a ratio of calcium stearate to metal in the at least one product of from about 1.5:1 to about 3:1 on a mass basis; and
(iii) adding a mixture comprising an antioxidant to the at least one product at a temperature of from 120° C. to 200° C. to avoid formation of significant amounts of insoluble metal or metal compounds derived from said metal alkyl compound, wherein the antioxidant is selected from the group consisting of di-octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate; benzenepropanoic acid; pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); tertiary butyl phenyl phosphate; and mixtures thereof;

wherein, performing the steps (i), (ii) or (iii) results in the at least one product characterized by a whiteness index of above 50.

2. The reaction process of claim 1 wherein step (i) is performed and soluble carboxylic acid of (i) is a saturated or unsaturated aliphatic carboxylic acid having from about 6 to about 20 carbon atoms.

3. The reaction process of claim 2 wherein the soluble carboxylic acid of (i) is stearic acid, octanoic acid, or a mixture thereof.

4. The reaction process of claim 1 wherein step (i) is performed and soluble complex metal ester of (i) is a substituted or unsubstituted aliphatic metal ester comprising from about 6 to about 30 carbon atoms wherein the metal of the metal alkyl compound is a transition metal, a Group IIIA metal, or a combination thereof.

5. The reaction process of claim 4 wherein the metal of the metal alkyl compound is selected from the group consisting of zinc, aluminum, and gallium.

6. The reaction process of claim 1 wherein step (i) is performed and resulting soluble complex metal ester of (i) is a metal ester having the formula Zn 4 O(C n H 2n+1 CO 2 ) 6 wherein n is from about 5 to about 20.

7. The reaction process of claim 1 wherein step (i) is performed and soluble carboxylic acid of (i) is mixed with water before reacting the soluble carboxylic acid with the metal alkyl compound.

8. The reaction process of claim 1 wherein the calcium stearate of (ii) is mixed with an antistatic agent.

9. A reaction process comprising:
(1) reacting a mixture via a reaction to form at least one product comprising:
(a) an ethylene/α-olefin multiblock interpolymer comprising at least 50 mole percent ethylene which is characterized before any crosslinking by one or more of the following characteristics:
(1) an average block index greater than zero and up to about 1.0 and a molecular weight distribution, Mw/Mn, greater than about 1.3; or
(2) at least one molecular fraction which elutes between 40° C. and 130° C. when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to about 1; or
(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter, wherein the numerical values of Tm and d correspond to the relationship:
T m >−6553.3+13735( d )−7051.7( d ) 2 ; or

(4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius defined as the temperature difference between the tallest DSC peak and the tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have the following relationships:
Δ T>− 0.1299(ΔH)+62.81

for ΔH greater than zero and up to 130 j/g,
ΔT≥48° C.

for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5 percent of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or
(5) an elastic recovery, Re, in percent at 300 percent strain and 1 cycle measured with a compression-molded film of the ethylene/α-olefin multiblock interpolymer, and has a density, d, in grams/cubic centimeter, wherein the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin multiblock interpolymer is substantially free of a cross-linked phase:
Re> 1481−1629( d ); or

(6) has a comonomer content of a TREF fraction which elutes between 40° C. and 130° C. greater than or equal to the quantity (0.2013)T+21.07, where T is the numerical value of the peak ATREF elution temperature of the TREF fraction, measured in ° C.; or
(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in the range of about 1:1 to about 9:1; and

(b) a metal alkyl compound, a metal oxide, or a mixture thereof; and
(2) deactivating any catalyst in the at least one product; and
(3) passing said at least one product to at least one post-reactor heat exchanger;
wherein the process comprises, after the step (2) of deact

Assignees

• Dow Global Technologies Llc

Inventors

• Castelluccio Anthony J
• Dean Jeffrey J
• Wang Alec Y
• Clark Lindsey A
• Jain Pradeep
• Kuhlman Roger L
• Taha Angela N
• Green Larry S
• Marchand Gary R
• Ewart Sean W
• Sims Jeffrey A
• Blaschke Chris E
• Fails Brandon

Classifications

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08L23/0815

  with aliphatic 1-olefins containing one carbon-to-carbon double bond · CPC title

• C08F6/02 Primary

  Neutralisation of the polymerisation mass, e.g. killing the catalyst (short-stopping C08F2/42 ){also removal of catalyst residues} · CPC title

• C08K5/098

  Metal salts of carboxylic acids · CPC title

• C08F2500/03

  Narrow molecular weight distribution, i.e. Mw/Mn < 3 · CPC title