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EP-4739719-A1 - GRADIENT POLYMER

EP4739719A1EP 4739719 A1EP4739719 A1EP 4739719A1EP-4739719-A1

Abstract

Gradient polymer is provided comprising: 5-35 wt% structural units of (meth)acrylic acid monomer; 35-65 wt% structural units of C 1-8 alkyl (meth) acrylate monomer; >10-30 wt% structural units of specialized associative monomer having structure (I) wherein R 1 is selected from a linear saturated C 12-26 alkyl group; R 2 is selected from a hydrogen and a methyl group and n is 10-30; 0.01-2 wt% structural units of multiethylenically unsaturated monomer; wherein the gradient polymer comprises <0.05 wt% structural units of sulfonated monomer; wherein the gradient polymer comprises <0.02 wt% structural units of monomer having structure (II) wherein R 3 is selected from -H and -CH 3 ; wherein R 4 is selected from -H and a -C 1-4 alkyl group; wherein R 5 is selected from -C 1-4 alkyl group; wherein α is 0-50; wherein b is 0-20; wherein c is 0-50; wherein α+c is 1 to 100 and wherein d is 1-4; and wherein the gradient polymer has a gradient polymeric morphology.

Inventors

  • ZENG, FANWEN
  • ZHANG, SHILING
  • SHULMAN, INNA
  • LU, XIADONG
  • O'CONNOR, YING

Assignees

  • DOW GLOBAL TECHNOLOGIES LLC
  • Rohm and Haas Company

Dates

Publication Date
20260513
Application Date
20230706

Claims (10)

  1. A gradient polymer comprising: (a) 5 to 35 wt%, based on dry weight of the gradient polymer, of structural monomer units of (meth) acrylic acid monomer; (b) 35 to 65 wt%, based on dry weight of the gradient polymer, of structural monomer units of C 1-8 alkyl (meth) acrylate monomer; (c) > 10 to 30 wt%, based on dry weight of the gradient polymer, of structural monomer units of a specialized associative monomer having structure I wherein each R 1 is independently selected from a linear saturated C 12-26 alkyl group; wherein each R 2 is independently selected from a hydrogen and a methyl group and wherein n is 10 to 30; (d) 0.01 to 2 wt%%, based on dry weight of the gradient polymer, of structural monomer units of multiethylenically unsaturated monomer; wherein the gradient polymer comprises ＜ 0.05 wt%, based on dry weight of the gradient polymer, of structural monomer units of sulfonated monomer; wherein the gradient polymer comprises ＜ 0.02 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer having structure II wherein each R 3 is independently selected from -H and -CH 3 ; wherein each R 4 is independently selected from -H and a -C 1-4 alkyl group; wherein each R 5 is independently selected from a -C 1-4 alkyl group; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50;wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymeric morphology.
  2. The gradient polymer of claim 1, wherein the structural monomer units of specialized associative monomer having structure I is a blend of a first specialized associative monomer having structure Ia wherein each R 1a is independently selected from a linear saturated C 12-19 alkyl group; wherein each R 2a is independently selected from a hydrogen and a methyl group and wherein na is 10 to 30; and a second specialized associative monomer having structure Ib wherein each R 1b is independently selected from a linear saturated C 20-26 alkyl group; wherein each R 2b is independently selected from a linear saturated hydrogen and a methyl group; and wherein nb is 10 to 30.
  3. The gradient polymer of claim 1, wherein the structural monomer units of (meth) acrylic acid monomer include structural monomer units of both methacrylic acid and acrylic acid.
  4. The gradient polymer of claim 1, wherein the gradient polymer comprises ＜ 0.01 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate and mixtures thereof.
  5. The gradient polymer of claim 1, wherein the gradient polymer comprises ＜ 2 wt%, based on dry weight of the gradient polymer, of monomer selected from the group consisting of alkyl (meth) acrylate having 6 to 18 carbon, vinyl alkanoate having 6 to 18 carbon atoms, N-vinyl alkylamide having 6 to 18 carbon atoms, N-alkyl (meth) acrylamide having 6 to 18 carbon atoms and mixtures thereof.
  6. The gradient polymer of claim 1, wherein the gradient polymer comprises 90 to 100 wt%of the structural monomer units present in the gradient polymer are structural monomers units of (a) - (d) .
  7. The gradient polymer of claim 2, wherein the gradient polymer comprises ＜ 0.01 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate and mixtures thereof.
  8. The gradient polymer of claim 2, wherein R 1a and R 1b differ by less than 8 carbon atoms.
  9. The gradient polymer of claim 2, wherein the gradient polymer comprises ＜ 2 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer selected from the group consisting of alkyl (meth) acrylate having 6 to 18 carbon, vinyl alkanoate having 6 to 18 carbon atoms, N-vinyl alkylamide having 6 to 18 carbon atoms, N-alkyl (meth) acrylamide having 6 to 18 carbon atoms and mixtures thereof.
  10. The gradient polymer of claim 2, with any one or more of the following provisos (i) - (v) : (i) wherein R 1a and R 1b differ by less than 8 carbon atoms; (ii) wherein the structural monomer units of (meth) acrylic acid monomer include structural monomer units of both methacrylic acid and acrylic acid; (iii) wherein the gradient polymer comprises ＜ 0.01 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer selected from the group consisting of styrene, butyl acrylate, ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, butyl acrylate and mixtures thereof; (iv) wherein the gradient polymer comprises ＜ 2 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer selected from the group consisting of alkyl (meth) acrylate having 6 to 18 carbon, vinyl alkanoate having 6 to 18 carbon atoms, N-vinyl alkylamide having 6 to 18 carbon atoms, N-alkyl (meth) acrylamide having 6 to 18 carbon atoms and mixtures thereof; and/or (v) wherein the gradient polymer comprises 90 to 100 wt%of the structural monomer units present in the gradient polymer are structural monomers units of (a) - (d) .

Description

GRADIENT POLYMER The present invention relates to a gradient polymer. In particular, the present invention relates to a gradient polymer comprising: (a) 5 to 35 wt%, based on dry weight of the gradient polymer, of structural monomer units of (meth) acrylic acid monomer; (b) 35 to 65 wt%, based on dry weight of the gradient polymer, of structural monomer units of C1-8 alkyl (meth) acrylate monomer; (c) ＞ 10 to 30 wt%, based on dry weight of the gradient polymer, of structural monomer units of a specialized associative monomer having structure I wherein each R1 is independently selected from a linear saturated C12-26 alkyl group; wherein each R2 is independently selected from a hydrogen and a methyl group and wherein n is 10 to 30; (d) 0.01 to 2 wt%%, based on dry weight of the gradient polymer, of structural monomer units of multiethylenically unsaturated monomer; wherein the gradient polymer comprises ＜ 0.05 wt%, based on dry weight of the gradient polymer, of structural monomer units of sulfonated monomer; wherein the gradient polymer comprises ＜ 0.02 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer having structure II wherein each R3 is independently selected from -H and -CH3; wherein each R4 is independently selected from -H and a -C1-4 alkyl group; wherein each R5 is independently selected from a -C1-4 alkyl group; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50;wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymeric morphology. Amino acid based surfactants have an array of desirable properties for use in personal care products (e.g., shampoos) . Such surfactants are often naturally derived and readily biodegradable. They are very mild and cause less irritation to skin and hair compared to  more traditional sulfate and sulfonate based surfactants like sodium lauryl sulfate and sodium lauryl ether sulfate. They tend to demonstrate lower toxicity and reduced negative impact on the environment than more traditional sulfate and sulfonate based surfactants. The have good cleaning and foaming properties. Notwithstanding, formulations comprising amino acid based surfactants are challenging to efficiently thicken. Some conventional thickeners achieve target viscosity at high usage levels which may negatively impact foaming performance. In other cases, conventional thickeners can provide adequate thickening, but the formulation viscosity is sensitive to changes in temperature; becoming watery at a high temperature and jelly like at low temperatures. Some conventional thickeners such as xanthan gum or cellulose esters exhibit potential compatibility issues resulting in phase separation. Accordingly, there remains a continuing need for viscosity modifiers that facilitate formulation of aqueous cleaning products, in particular amino acid surfactant containing aqueous cleaning products (e.g., shampoo) , with increased viscosity at low shear rates while maintaining desired flow properties at higher shear rates. The present invention provides a gradient polymer comprising: (a) 5 to 35 wt%, based on dry weight of the gradient polymer, of structural monomer units of (meth) acrylic acid monomer; (b) 35 to 65 wt%, based on dry weight of the gradient polymer, of structural monomer units of C1-8 alkyl (meth) acrylate monomer; (c) ＞ 10 to 30 wt%, based on dry weight of the gradient polymer, of structural monomer units of a specialized associative monomer having structure I wherein each R1 is independently selected from a linear saturated C12-26 alkyl group; wherein each R2 is independently selected from a hydrogen and a methyl group and wherein n is 10 to 30; (d) 0.01 to 2 wt%%, based on dry weight of the gradient polymer, of structural monomer units of multiethylenically unsaturated monomer; wherein the gradient polymer comprises ＜ 0.05 wt%, based on dry weight of the gradient polymer, of structural monomer units of sulfonated monomer; wherein the gradient polymer comprises ＜ 0.02 wt%, based on dry weight of the gradient polymer, of structural monomer units of monomer having structure II wherein each R3 is independently selected from -H and -CH3; wherein each R4 is independently selected from -H and a -C1-4 alkyl group; wherein each R5 is independently selected from a -C1-4 alkyl group; wherein a is 0 to 50; wherein b is 0 to 20; wherein c is 0 to 50;wherein a + c is 1 to 100; and wherein d is 1 to 4; and wherein the gradient polymer has a gradient polymeric morphology. The present invention provides a gradient polymer comprising: (a) 5 to 35 wt%, based on dry weight of the gradient polymer, of structural monomer units of (meth) acrylic acid monomer; (b) 35 to 65 wt%, based on dry weight of the gradient polymer, of structural monomer units of C1-8 alkyl (meth) acrylate monomer; (c) ＞ 10 to 30 wt%, based on dry weight of the gradient polymer, of structural monomer units of a specialized associative monomer