Process of manufacturing thickeners and use of thus produced thickeners in high-viscosity unsaturated polyester containing formulations

Patent metadata

Field	Value
Publication number	US-9546252-B1
Application number	US-201615189584-A
Country	US
Kind code	B1
Filing date	Jun 22, 2016
Priority date	Jun 22, 2016
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

The invention relates to the use of at least one mixed mineral organoclay rheology additive, which comprises or consists of a quaternary alkyl-ammonium salt treated mineral clay mixture prepared by forming an aqueous hormite clay slurry (a), forming an aqueous smectite clay slurry (b), combining the aqueous hormite clay slurry (a) with the aqueous smectite clay slurry (b) to form a combined clay slurry (c), treating the combined clay slurry (c) with one or more quaternary alkyl-ammonium salts, separating the thus produced quaternary alkyl-ammonium salt treated mineral clay mixture from the aqueous medium, in which the aqueous hormite clay slurry (a) being formed by (i.1) dispersing a fraction of one or more hormite clays selected from the group of sepiolites and palygorskites in an aqueous medium to form a dispersion, and the aqueous smectite clay slurry (b) being formed by (ii.1) dispersing a fraction of one or more smectite clays in an aqueous medium to form a dispersion, and in that the weight of the hormite clay content exceeds the weight of the smectite clay content in the combined clay slurry (c), and subjecting the dispersions formed in (i.1) and (ii.1) to high speed fluid shear before carrying out step iii. and/or after having carried out step and wherein the fraction of one or more hormite clays employed in the formation of the aqueous hormite clay slurry (a) has an integral breadth B defined according of the reflection with Miller indices (110) of less than 0.800 scan units in an X-ray powder pattern recorded on an oriented glycolated sample of the hormite clay fraction using Cu-K α1 -radiation, in a liquid composition comprising at least one unsaturated polyester. The invention also relates to a process for producing a mixed mineral organoclay rheology additive and the use of the thus produced additive as a thickening agent in liquid compositions.

First claim

The invention claimed is:

1. A process comprising mixing
at least one mixed mineral organoclay rheology additive, which comprises or consists of a quaternary alkyl-ammonium salt treated mineral clay mixture prepared by
i. forming an aqueous hormite clay slurry (a)
ii. forming an aqueous smectite clay slurry (b)
iii. combining the aqueous hormite clay slurry (a) with the aqueous smectite clay slurry (b) to form a combined clay slurry (c)
iv. treating the combined clay slurry (c) with one or more quaternary alkyl-ammonium salts
v. separating the thus produced quaternary alkyl-ammonium salt treated mineral clay mixture from the aqueous medium,

in which
the aqueous hormite clay slurry (a) being formed by
(i.1) dispersing a fraction of one or more hormite clays selected from the group of sepiolites and palygorskites in an aqueous medium to form a dispersion,

and
the aqueous smectite clay slurry (b) being formed by
(ii.1) dispersing a fraction of one or more smectite clays in an aqueous medium to form a dispersion,

and
in that the weight of the hormite clay content exceeds the weight of the smectite clay content in the combined clay slurry (c); and
subjecting the dispersions formed in (i.1) and (ii.1) to high speed fluid shear before carrying out step iii. and/or after having carried out step ii.1; and
wherein the fraction of one or more hormite clays employed in the formation of the aqueous hormite clay slurry (a) has an integral breadth B defined according to formula (I)
B =(net area of reflection)/(net height of reflection)  (I)

of the reflection with Miller indices (110) of less than 0.800 scan units in an X-ray powder pattern recorded on an oriented glycolated sample of the hormite clay fraction using Cu-K α1 -radiation,
in a liquid composition comprising at least one unsaturated polyester.

2. The process according to claim 1 , wherein the liquid composition further comprising at least one ethylenically unsaturated monomer.

3. The process according to claim 2 , the at least one ethylenically unsaturated monomer being selected from the group of styrene, alpha-methylstyrene, methyl acrylate, methyl methacrylate, vinyl acetate, divinyl benzene, diallyl phthalate, triallylcyanurate, and triallyl phosphate and mixtures thereof.

4. The process according to claim 1 , wherein the mixed mineral organoclay rheology additive is contained in an amount from 0.1 to 10 wt.-% based on the total weight of the liquid composition.

5. A process for producing a mixed mineral organoclay rheology additive, which comprises or consists of a quaternary alkyl-ammonium salt treated mineral clay mixture, the process being characterized by:
i. forming an aqueous hormite clay slurry (a)
ii. forming an aqueous smectite clay slurry (b)
iii. combining the aqueous hormite clay slurry (a) with the aqueous smectite clay slurry (b) to form a combined clay slurry (c)
iv. treating the combined clay slurry (c) with one or more quaternary alkyl-ammonium salts, and
v. optionally separating the thus produced quaternary alkyl-ammonium salt treated mineral clay mixture from the aqueous medium,
in which
the aqueous hormite clay slurry (a) being formed by
(i.1) dispersing a fraction of one or more hormite clays selected from the group of sepiolites and palygorskites in an aqueous medium to form a dispersion,

and
the aqueous smectite clay slurry (b) being formed by
(ii.1) dispersing a fraction of one or more smectite clays in an aqueous medium to form a dispersion,

and
in that the weight of the hormite clay content exceeds the weight of the smectite clay content in the combined clay slurry (c); and
subjecting the dispersions formed in (i.1) and (ii.1) to highspeed fluid shear before carrying out step iii. and/or after having carried out step iii;
and
wherein the fraction of one or more hormite clays employed in the formation of the aqueous hormite clay slurry (a) has an integral breadth B defined according to formula (I)
B =(net area of reflection)/(net height of reflection)  (I)

of the reflection with Miller indices (110) of less than 0.800 scan units in an X-ray powder pattern recorded on an oriented glycolated sample of the hormite clay fraction using Cu-K α1 -radiation.

6. The process according to claim 5 , wherein the weight of the fraction of one or more hormite clays (i) based on the total weight of the clays in the combined clay slurry is from 60 to 95 wt. %.

7. The process according to claim 5 wherein the weight of the fraction of one or more smectite clays (ii) based on the total weight of the clays in the combined clay slurry is from 5 to 40 wt. %.

8. The process according to claim 5 , wherein the one or more smectite clays are selected from the group consisting of hectorites, montmorillonites, bentonites, beidelites, saponites, stevensites and mixtures thereof.

9. The process according to claim 8 , wherein the smectite clay is selected from the group consisting of hectorites, saponites and mixtures thereof.

10. The process according to claim 5 , wherein the quaternary alkyl-ammonium salt contains the same or different straight-chain or branched, saturated or unsaturated alkyl groups having 1 to 22 carbon atoms and the counter-ion moiety is selected from the group consisting of chloride, bromide, methylsulfate, nitrate, hydroxide, acetate, phosphate and mixtures thereof.

11. The process according to claim 10 , wherein the quaternary alkyl-ammonium salt is selected from the group consisting of dimethyl di(C 14-18 alkyl) ammonium chloride, methyl benzyl di(C 14-18 alkyl) ammonium chloride, dimethyl benzyl C 14-18 -alkyl ammonium chloride, dimethyl C 14-18 -alkyl 2-ethylhexyl ammonium methylsulfate and mixtures thereof.

12. The process according to claim 5 , wherein the mineral clay mixture is treated with about 5 to 80 mmol of the quaternary alkyl-ammonium salt per 100 g of clay in the combined clay slurry.

13. The process according to claim 5 , wherein subsequently to step (i.1) the aqueous slurry (a) and subsequently to step (ii.1) the aqueous slurry (b) are screened through an at least 100 mesh screen (U.S. standard mesh) to remove coarse particles.

14. The process according to claim 5 , wherein the aqueous slurry (a) and the aqueous slurry (b) are subjected to high speed fluid shear by passing the respective slurry or a mixture of the slurries through a narrow gap, across which a pressure differential is maintained.

15. A process comprising mixing the mixed mineral organoclay rheology additives as obtained by the process according to claim 5 in a composition as thickening agent.

16. The process according to claim 15 , wherein the mixed mineral organoclay rheology additives are used as thickening agents in a liquid composition.

17. The process according to claim 16 , wherein the liquid composition is a liquid organic composition.

18. The process according to claim 17 wherein the liquid organic composition is selected from the group consisting of coating materials, sealants, adhesives, oil drilling fluids, gas drilling fluids, composite materials, moulding compounds and liquid organic compositions which contain besides the mixed mineral organoclay rheology additive only one or more organic solvents.

19. The process according to claim 16 , wherein the mixed mineral organoclay rheology additive is contained in an amount from 0.1 to 10 wt.-% based on the total weight of the liquid composition.

20. The process according to claim 17 wherein the liquid organic composition is an oil drilling

Assignees

• Byk Chemie Gmbh
• Byk Additives Inc
• Byk Chemie Gmbh
• Byk Additives Inc

Inventors

• Dziwok Klaus
• Coutelle Helmut
• Briell Robert G
• Nash Tyler

Classifications

• C01B33/44

  Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material · CPC title

• C08K9/04 Primary

  Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)} · CPC title

• C09J167/06

  Unsaturated polyesters having carbon-to-carbon unsaturation · CPC title

• C09J11/06 Primary

  organic · CPC title

• C08K3/346

  Clay · CPC title