Polymer compositions allowing easier handling

Patent metadata

Field	Value
Publication number	US-10889773-B2
Application number	US-201616065249-A
Country	US
Kind code	B2
Filing date	Dec 1, 2016
Priority date	Dec 23, 2015
Publication date	Jan 12, 2021
Grant date	Jan 12, 2021

Abstract

The invention relates to a polymer composition that can be obtained by means of the free radical polymerisation of A) 95-40 wt. % of alkyl (meth)acrylate containing Ai) 20-95 wt. % of at least one alkyl (meth)acrylate with 16 to 40 C-atoms in the alcohol group, and Aii) 5-80 wt. % of at least one (meth)acrylic acid ester of a C8-C22 alcohol carrying a C6-C20 alkyl group in the 2-position relative to the hydroxyl group, in the presence of B) 5-60 wt. % ethylene copolymer. The invention also relates to a method for producing same and to the use of same as a flow improver for mineral oils and mineral oil distillates.

First claim

The invention claimed is:

1. A polymer composition prepared by free-radical polymerization of
A) 95-40% by weight of alkyl (meth)acrylate comprising
Ai) 20-95% by weight of at least one alkyl (meth)acrylate having 16 to 40 carbon atoms in the alkyl radical and
Aii) 5-80% by weight of at least one (meth)acrylic ester of a C 5 -C 22 alcohol having a C 6 -C 20 -alkyl radical in the 2 position to the hydroxyl group, where Ai) and Aii) are different than one another, in the presence of

B) 5-60% by weight of an ethylene copolymer.

2. The polymer composition as claimed in claim 1 , wherein the alkyl (meth)acrylates Ai) are according to the general formula (1)
H 2 C═C(R 2 )—COOR 3   (1)

where
R 2 is hydrogen or a methyl group,
R 3 is a linear alkyl radical having 16 to 40 carbon atoms.

3. The polymer composition as claimed in claim 1 , wherein the alkyl (meth)acrylates Aii) are according to the general formula (2)

where
R 2 is hydrogen or a methyl group,
R 4 and R 5 are independently a saturated linear alkyl radical having 6 to 20 carbon atoms and the sum total of the carbon atoms in R 4 and R 5 is between 16 and 40.

4. The polymer composition as claimed in claim 1 , wherein the alkyl (meth)acrylate A) contains 25% to 90% by weight, of at least one alkyl (meth)acrylate Ai) based on the total weight of A).

5. The polymer composition as claimed in claim 1 , wherein the alkyl (meth)acrylate A) contains 10% to 60% by weight, of at least one alkyl (meth)acrylate Aii) based on the total weight of A).

6. The polymer composition as claimed in claim 1 , wherein the alkyl (meth)acrylate A) contains up to 40% by weight of one or more further monomers Aiii).

7. The polymer composition as claimed in claim 6 , wherein the further monomers Aiii) are selected from the group consisting of vinyl esters of carboxylic acids having 1 to 20 carbon atoms, α-olefins having 6 to 40 carbon atoms, vinylaromatics, ethylenically unsaturated dicarboxylic acids and the anhydrides and esters thereof with C 10 -C 30 fatty alcohols, acrylic acid, methacrylic acid, ethylenically unsaturated compounds beating further functional groups, and vinyl and allyl polyglycols.

8. The polymer composition as claimed in claim 6 , wherein the further monomers Aiii) according to the formula (3)
H 2 C═C(R 2 )—COOR 6   (3)

where
R 2 is hydrogen or a methyl group,
R 6 is a linear alkyl radical having 1 to 11 carbon atoms, is a branched alkyl radical having 4 to 17 carbon atoms or is a cyclic alkyl radical having 5 to 20 carbon atoms.

9. The polymer composition as claimed in claim 6 , wherein the further monomers Aiii) are vinyl or allyl polyglycols of the formula (4)

in which
R 7 is hydrogen or methyl,
Z is C 1 -C 3 -alkylene or a single bond between the R 7 -bearing carbon atom and the oxygen atom,
R 8 is hydrogen, C 1 -C 30 -alkyl, cycloalkyl, aryl or —C(O)—R 10 ,
R 9 is hydrogen or C 1 -C 20 -alkyl,
R 10 is C 1 -C 30 -alkyl, C 3 -C 30 -alkenyl, cycloalkyl or aryl and
m is a number from 1 to 50.

10. The polymer composition as claimed in claim 1 , wherein the ethylene copolymer contains, as well as ethylene, 4 to 18 mol % of at least one vinyl ester, acrylic ester, methacrylic ester, alkyl vinyl ether and/or alkene.

11. The polymer composition as claimed in claim 1 , wherein the ethylene copolymer is a copolymer of ethylene and the vinyl ester of a C 1 -C 24 carboxylic acid, a C 1 -C 22 -alkyl (meth)acrylate and/or a C 3 -C 24 olefin.

12. The polymer composition as claimed in claim 1 , wherein the ethylene copolymer is a copolymer of ethylene and at least one vinyl ester of the formula (6)
CH 2 ═CH—OCOR 11   (6)

in which
R 11 is C 1 - to C 30 -alkyl.

13. The polymer composition as claimed in claim 1 , wherein the ethylene copolymer contains vinyl acetate as comonomer.

14. The polymer composition as claimed in claim 1 , wherein the ethylene copolymer is a copolymer of ethylene and at least one acrylic or methacrylic ester of the formula (7)
CH 2 ═CR 12 —COOR 13   (7)

in which
R 12 is hydrogen or methyl and
R 13 is C 1 - to C 30 -alkyl.

15. The polymer composition as claimed in claim 1 , wherein the ethylene copolymer has an MFI190 value measured according to DIN 53735 at 190° C. and an applied load of 2.16 kg of between 0.1 and 1200 g/10 min.

16. The polymer composition as claimed in claim 1 , prepared by free-radical polymerization of A and B in the presence of a solvent, where the proportion thereof in the total amount of A, B and solvent and of any further auxiliaries is between 35% and 80% by weight.

17. The polymer composition as claimed in claim 6 , in which the alkyl (meth)acrylates A) contain 20% to 93% by weight of monomers Ai).

18. The polymer composition as claimed in claim 6 , in which the alkyl (meth)acrylates A) contain 5% to 78% by weight of monomers Aii).

19. The polymer composition as claimed in claim 6 , in which the alkyl (meth)acrylates A) contain 2% to 40% by weight of monomers Aiii).

20. A process for preparing a polymer composition in which a mixture of
A) 95-40% by weight of alkyl (meth)acrylate (A) comprising
Ai) 20-95% by weight of at least one alkyl (meth)acrylate having 16 to 40 carbon atoms in the alkyl radical and
Aii) 5-80% by weight of at least one (meth)acrylic ester of a C 5 -C 22 alcohol having a C 6 -C 20 -alkyl radical in the 2 position to the hydroxyl group, where Ai) and Aii) are different than one another, in the presence of

B) 5-60% by weight of an ethylene copolymer,
is copolymerized by adding a free-radical chain initiator.

21. The process as claimed in claim 20 , in which the polymerization is conducted in the presence of 0.1 to 10 times the amount of solvent based on the amount of A) and B).

22. The process as claimed in claim 20 , in which the solvent is an aliphatic hydrocarbon or an aliphatic hydrocarbon mixture having a flashpoint of at least 60° C.

23. A concentrate comprising 10% to 80% by weight of the polymer composition as claimed in claim 1 , and 90% to 20% by weight of organic solvent.

24. The concentrate as claimed in claim 23 , wherein the organic solvent is a mixture of aliphatic and aromatic hydrocarbons.

25. The concentrate as claimed in claim 23 , wherein the organic solvent contains at least 20% by weight of aromatic hydrocarbons.

26. The concentrate as claimed in claim 23 , further comprising, in addition to the polymer composition, a wax dispersant and/or an asphaltene dispersant.

27. A process for improving the cold properties of a paraffin-containing mineral oil selected from the group consisting of crude oils, residue oils and products from mineral oil distillation, comprising the step of adding at least one polymer composition according to claim 1 to paraffin-containing mineral oil.

28. The process as claimed in claim 27 , wherein the paraffin-containing mineral oil is crude oil.

29. The process as claimed in claim 27 , wherein 10 to 10 000 ppm by weight of the polymer composition is added to the paraffin-containing mineral oil.

Assignees

• Clariant Int Ltd

Inventors

• Feustel Michael
• Krull Matthias
• Siggelkow Bettina
• Mörscher Michael
• Greger Ingo
• Haferkamp Sebastian

Classifications

• C08F220/1818

  C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate · CPC title

• C10L2200/0461

  Fractions defined by their origin · CPC title

• C10L2200/0438

  Middle or heavy distillates, heating oil, gasoil, marine fuels, residua · CPC title

• C10L1/1985

  polyethers, e.g. di- polygylcols and derivatives; ethers - esters · CPC title

• C10L1/195

  obtained by reactions involving only carbon-to-carbon unsaturated bonds · CPC title